FI118337B - New polymers and process for their preparation - Google Patents

Description

118337

NEW POLYMERS AND METHOD FOR MANUFACTURING THEM

This invention relates to the field of electrically conductive polymers, and more particularly to novel conductive polyurethanes and processes for their preparation.

U.S. Patent No. 5,925,893 also discloses electrically conductive materials such as charge and copy ropes and attachment pressure rollers containing a resistance component layer of polyurethane ionomer. The ionomer molecule has an ionic moiety that is a sulfonic acid group, a carboxylic acid group, or a tertiary amino radical.

For the production of polyurethane, a first polyol component consisting of a condensation product of 1,4-butanediol and adipic acid and a second polyol component consisting of 1,4-butanediol, adipic acid and dimethyl isophthalate 5-sodium sulfonate are required. The latter component introduces an ionic segment into the polyurethane obtained by solution polymerization of the first and second polyol components.

The coupling agent used is diphenylmethane-4,4-diisocyanate (MDI). The reaction mixture is diluted repeatedly with a solvent to reduce the increase in viscosity. In another. . ·. in the embodiment, the known polyurethane ionomer is prepared from a polyisocyanate which contains * * 20 polyethylene glycol and TDI (2,4-toluene diisocyanate) and. . ·. which reacts with a chain extender, namely 2,2-dimethylol-propionic acid (DMPA).

Volume specific for polyurethane disclosed in U.S. Patent No. 5,925,893. ***. the resistance factor is nom 10 'Measured from the membrane.

··· 25. As is well known, polyurethanes have strong hydrogen bonds in their urethane bonds and generally ♦ · · phase-separate into a so-called hard segment. When using DMPA in final • · ·. *. however, polyurethanes have an acid group a few carbons away from urethane linkages, and interfere with the formation of a hard segment by preventing phase separation. This • ·. As a result, the mechanical properties of the polyurethane suffer and the material becomes easily brittle and weak. According to patent examples, the cross-linking of the 118357 resistance control layer means that the materials cannot be utilized e.g. In addition, solvent polymerization requires lengthy work-up of the reaction mixtures and is quite expensive In addition, 5 ionizable functional groups are used as charge carriers in the present invention. for thermoplastic polymers containing functional groups.

US Patent 6,680,149 proposes the use of polyether poly (N- [substituted urethane) as a solid polymer electrolyte. Such polyether poly (N-substituted in urethane) has side chains of oligoethylene oxide and has an average molecular weight of 50,000 to 2,000,000, preferably 200,000 to 1,500,000. The side chain of low molecular weight polyethylene oxide is internally plasticized, resulting in increased electrolyte dissociation.

Neither of these documents describes a polyurethane ionomer having excellent electrical conductivity properties, good mechanical resistance and,. can still be produced economically.

• · · 20 • ·. It is an object of the present invention to eliminate at least some of the problems of the prior art inventions in this field and to provide novel polyurethane ionomers.

• · * · · • · · ·. · · ·. Another object of the invention is to provide a process for the preparation of such polyurethane ionomers.

• · · • * · • · ·. * * *. These and other aspects, and their advantages over known polymers and processes, which will be apparent from the following specification, are achieved by the present invention. as follows from the following descriptions and claims.

e · 30 • · · • · · · · · · · · · · 118337 3

The invention is based on the idea of producing a thermoplastic urethane polymer having a ionizable acid group in the polymer backbone and having a surface resistance of less than 108 µm / cm as defined by ASTM-2S7. The polyurethane contains a soft segment consisting predominantly of a polyether, such as S polyalkylene oxide, which occurs in an amorphous state.

Polymers can be prepared by melt processing whereby the starting materials, namely the diol, the coupling agent (diisocyanate) and the chain extender containing the carboxylic acid group (s) are mixed and reacted dynamically to the polyurethanes by melt reactions, for example in an extruder, e.g.

The novel polymers are characterized by what is set forth in the characterizing part of claim 1.

15

The process for preparing polyurethanes, in turn, is characterized by what is stated in the characterizing part of claim 17.

,. ·. The present invention achieves considerable advantages. Thus, the properties of polyurethanes **** ....: 20 can be greatly improved by the formation of ionomeric · ·,, ·. polyurethanes. Such ionomers can be formed from carboxylated Flaps functionalized polyols or polyurethanes by neutralization of acid groups with a base.

The base forms ionic groups on the polyurethane backbone, which makes polyurethane. more polar, provides potentially better solvent resistance and may lead to · · · hydrophilia or hydrophobia, depending on the selected base. Exporting Ionic Bonds • · · /. polyurethane also significantly improves the thermal stability of the polymer.

The novel polyurethane ionomer is very readily miscible with other polymers and can be used in the manufacture of electrically conductive and antistatic polymeric components. Because it contains acid groups, it is fully compatible with other types of ionomers, namely polyethylene-based or any other carboxylic or sulfonic acid-containing polymers. This is a significant advantage over known polyurethane-based IDP-5 polymers such as the Noveon Inc. Stat-Rite RTM.

The molten processing method disclosed herein provides significant economic and technical advantages due to its simplicity and efficiency.

In the following, the polyurethane ionomer of the present invention will be described in more detail with the aid of a detailed description and application examples.

The molecular weights given below are all average weights of the molecular weights.

As mentioned briefly above, the present invention consists of a thermoplastic urethane polymer having a ionizable acid group in the polymer backbone and having a surface resistance of less than 109 Ω / cm according to ASTM-257. The polyurethane hard segment contains at least one ionizable acid group. Ionic hard segments. the polyurethane content is about 5 to 50% by weight, preferably less than 35% by weight, preferably less than 30% by weight.

• * • * * • · · • · ·

Although the various components of the polyurethane in question will be discussed in more detail below, the following will first provide a summary of its composition and the properties of some preferred embodiments: • 25. . ·. According to a first preferred embodiment, the ionizable acid group of the polyurethane is a sulfonic acid group, a carboxylic acid group, a mixture thereof or a mixture thereof. salt, and carboxyl groups and their salts are particularly preferred.

The polyurethane contains a soft segment which is in an amorphous state. According to a preferred embodiment, the polyurethane soft segment contains a polyether, for example a polyalkylene oxide-type polyether (the alkylene chain has 2 - 10 carbon atoms, preferably 2 to 6 carbon atoms) .This type of polyether has excellent conductive properties as it allows the movement of charges / ions along the chain.The combination of a chain extender containing an ionizable acid group and a soft segment 5 of a polyether makes it possible to add significant amounts of polyether to the polyurethane. Thus, the content of the soft segment is generally 20 to 95% by weight of the polymer, more preferably the polyether content is 50 to 95% by weight, particularly 70 to 85% by weight of the polymer.

According to a preferred embodiment of the invention, the ether urethane polymer contains a residue from a long chain polyol having a molecular weight in the range of 400 to 10,000, in particular 600 to 5,000. This polyether is preferably derived from polypropylene oxide (PPG) and / or polyethylene oxide (PEG). In particular, the polyether is derived from PEG having a molecular weight of 600-4000, preferably 1000-3000.

15

Polyurethane or poly (ether urethane) is an optically brightener in a transparent or translucent film form. In addition, this polyurethane ionomer has a glass transition temperature of 20 ° C or less.

E # 20 In this type of conductive polymers, coupling agents (diisocyanates) e ·. . ·. are mainly based on aliphatic, linear or cyclic (»functional ·» · ....: isocyanates. A particularly preferred embodiment of the diisocyanate is the hexamethylene diisocyanate HDI. Another example is cyclohexamethylene di- «« ··. ***. isocyanate (CHDI).

«·· 25. In order to obtain the desired properties, the polyurethane should have a molecular weight of «« ·. »** greater than 50,000, particularly more than 80,000, preferably about 100,000 and * ·. *. 2,500,000.

The polymers of the present invention are prepared by condensation polymerization. using an amine or organometallic catalyst in a concentration of about 0.005 to 2 · 118337 6% by weight based on the total reaction weight. Polymer polymerization is challenging due to the narrow temperature range of the processing step. Most preferred is catalysis using an environmentally friendly, highly selective titanium based catalyst, such as a ligated titanium based catalyst. These catalysts can be used in concentrations ranging from 0005 to 3% by weight based on the total reaction weight.

Metal ions that ionize acid groups can be monovalent or divalent - or even trivalent - ions that are alkali metal or alkaline earth metals such as Li, Na, K, Rb, Cs, Ca, Mg or Al inonic. Transition metal ions are also included in the invention. Organic ions can also be used as neutralizing components.

The polymers can be produced by melt processing, e.g. extruder process, dynamically or by melt blending statically. In one embodiment, the long chain polyol (polyether), the short chain diol containing acidic groups 15 (chain extender), and the catalyst are mixed and heated to about 30-80 ° C.

to a temperature, preferably 40 to 60 ° C. A calculated amount of diisocyanate HDI (coupling agent), 120 to 200 molar parts, relative to 100 parts polyol and diol, is then added, either once or in several parts, for example 2 to 5 parts, and the reaction is carried out under exothermic conditions, preferably under vigorous stirring. The result is an isocyanate-terminated polyurethane prepolymer having a molecular weight of about 500 to about. , ·, 10,000 g / mol. The prepolymer may additionally be polymerized with another chain extender 9 · · · * · ....: (a diol such as a conventional alkylenediol (ethylene glycol, 1,4-di-butanediol)) to give a final polymer of molecular weight Exceeds 50,000 g / mol.

····, * ·. The preparation of the polymer may also be carried out partly by melt blending in the blender (particularly the preparation of the prepolymer) and partly in the extruder.

• · · • · · ··. * · *. As mentioned above, one important feature of the present invention is to provide • ♦ ·. *. acid functionality of the polyurethane molecular chain. This functionality will be added · · * ♦ *! polyurethane, preferably using a chain extender (diol) containing an acid group.

. 30 Thus, the polyurethanes or poly (ether urethane) in question have in practice one • · · * · * hard segment formed by diols having an acid side group attached to one of the diisocyanates, in particular aliphatic isocyanates, and further comprising soft segments represented by polyethers, for example of the poly (alkylene oxide) type, which are essentially free of acid side groups.

The diols containing acid groups are preferably selected from diols having 3 to 10, preferably 4 to 7 carbon atoms in the main chain. In an exemplary embodiment, the carboxylic acid groups are attached to the polymer backbone using dimethylol propionic acid (DMPA) or dimethylolbutanoic acid (DMBA). DMPA has a molecular weight of 136, has two hydroxyl groups and one carboxylic acid group. DMBA has a molecular weight of 148, has two hydroxyl groups and one carboxylic acid group.

Since molten processing represents an economically interesting application, a diol chain extender such as DMBA is preferably used and can be dissolved in other starting materials at low temperatures. This is necessary as the polymerization-15 temperature must be low.

It should be noted that the acid groups of the diol may be in free form or in the form of salts formed with metal ions.

• i · • · · • · *,.,.; Generally, when forming polyurethane, DMPA / DMBA is reacted with · ·. . ·. starting polyol and diisocyanate to form an isocyanate terminated prepolymer. The prepolymer is made at a temperature at which the hydroxyl groups can react with excess isocyanate without using acid groups. The acid groups ····. ··· could be neutralized with metal ions prior to the diisocyanate reactions. The difficulty with using DMPA ·· ♦ 25 is that it has a high melting point solid. . ·. a material that has limited solubility in polyols. Because of these features ···. ** ·. DMPA is generally pre-dissolved in polyol with a solvent above 100 ° C ···. *. temperature. This step is demanding because the temperature should be below 100 ° C in order for the di-• * ♦ I isocyanate to react selectively and release the hydroxyl groups »·. 30 carboxylic acids. In addition, the above step increases processing time and costs for polyurethane production, and increases the need for organic solvents. Using DMBA • 118337 s instead of DMPA provides advantages in polyol dissolution, giving DMBA a wider production gap.

Polyurethanes have urethane bonds with strong hydrogen bonds and are phase-separated into so-called hard segments. However, when using DMPA, the final polyurethanes have an acid group a few carbons away from the urethane linkages and interfere with the formation of a hard segment by preventing phase separation. As a result, the mechanical properties of the polyurethane may be impaired.

A particularly preferred polyurethane ionomer consists of an amorphous, soft segment derived from PEG having a molecular weight of 1500-2000, HDI used as a coupling agent and DMBA used as a chain splitter. It has a PEG content of about 60-85% by weight and a DMBA content of about 5-10%.

15 The various components of the new polymers will now be slightly more generally considered.

Polyurethane / polyurea ionomers. The polyurethane and polyurea ionomers of this invention include anionic moieties or groups of 999:20. Such groups are typically attached to the polyurethane or polyurea ionomers 9 ·, · ·. diisocyanate or diisocyanate component. The anionic group is preferably based on a 4 9 9 999 ,,: sulfonic, carboxylic or phosphoric acid group. In addition, several types of anionic groups can be attached to the polyurethane or polyurea 9 9.

9 9999 999 9 9 9 9 919 25 By attaching ionic groups to the urethane backbone, the polymer can be made more polar,,, ·, which can improve its solvent resistance and, depending on the base used, can lead to 999 .1 · 1. either hydrophilic or hydrophobic properties. Ionic groups become molecules 999, '. intracellular and intermolecular attraction sites that increase the polymer 9 9 9 9 9 9 * I cohesive energy. Joints work in the same way as covalent 9 9. 30 crosslinks, but they can disintegrate or merge under load, while the 9 9 9 9 9 t covalent bond breaks under load and is unable to re-form.

9 99999 9 9 118337 9

As the polyurethane ionomer described above, for example, the reaction product obtained by reacting the polyisocyanate and the long chain polyol and chain extender in the presence of a catalyst can be used. Further, an ionic segment is preferably added as an ingredient in the long chain polyol and / or chain extender.

5

Possible organic polyisocyanates include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene i-diisocyanate, 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate and the like, alicyclic diisocyanates. , such as isophorone diisocyanate, hydrotoluene diisocyanate, hydroxylene diisocyanate, hydrotetramethylxylene diisocyanate, hydrodiphenyl methane diisocyanate and the like, aromatic diisocyanates such as m-phen -phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-xylene diisocyanate, diphenyl 4,4-diisocyanate, 2-nitrodiphenyl-4 , 4-diisocyanate, 3,3-dimethoxydiphenyl-4,4-diisocyanate, 1S diphenylmethane-2,4-diisocyanate, di-phenylmethane-4,4-diisocyanate, 3,3-dimethyldiphenylmethane -4,4-diisocyanate, b-diphenylpropane-4,4-diisocyanate, diphenyl ether-4,4-diisocyanate, 1,4-naphthalene diisose yanate, 1,5-naphthalene diisocyanate and the like, polymers thereof; substances to which polyols have been added, such as tri-, .1. methylolpropane and the like; as well as prepolymers of polyols and polyisocyanates with ··· 20 ends having an isocyanate group.

• · · • · · ···

Long chain polyols include a) polyether polyols, b) polyester polyols, and copolymer polyols thereof.

The polyether polyols (a) include polyethylene glycol, polypropylene glycol and. · 1 · polytetramethylene glycol and the like, obtained from ethylene oxide, propylene oxide ··· · “1: and tetrahydrofuran and the like, their copolymers and ··. polymerization of polyester ether polyols having copolymer components with polyester polyols, where the ring is opened.

30 • · • · · • ·· • ♦ e ίο 118337

It is desirable that these long chain polyols have a molecular weight of 600 to 5000. "" Molecular weight "refers to any molecular weight, including mean molecular weight, average molecular weight, etc., as determined by known methods. At a molecular weight of less than 600, the functional groups of the charge-carrying polyol component of the polyurethane-5 ionomer in which the ionic segment is configured may be insufficient and the resistance may increase. On the other hand, if the molecular weight is greater than 1000, partial crystallization by the polyol component may occur, but binding by suitable ionic segments significantly reduces the crystallization of the polyether segment. By using magnesium, zinc or other divalent or trivalent cations, it is possible to crosslink the polyurethane ionomer ionically, internally, or to any other suitable polar or ionizable polymer. Ionic crosslinking reduces the crystallization of the polyether segment.

Even in the long-chain polyol described above, aliphatic long-chain polyalkylene glycol and polyethylene glycol and polypropylene glycol having molecular weights within the above-described ranges, or mixtures thereof, are preferably used as the optimal polyol blend. Ethylene oxide and propylene oxide are also among the most desirable polyol components.

The chain extender is generally a compound containing two or more active hydrogens in a ***** molecule and having a molecular weight of less than 300, and used as polyols. polyamines and amino alcohols and the like. Again, "molecular weight", * ···. ···, refers here to any molecular weight, by any means.

• · «· 25. Specific examples may include ethylene glycol, propylene glycol, 1,3- ·· *. · **. propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentylene glycol, ·· *. *. 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol,

* M

diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexane-dimethanol • · 30 and bisphenol A additive ethylene oxide or propylene oxide; glycerin, • * * * · * trimethylol propane and other polyols; hexamethylamine, · hexamethylamine; Xylenamine, methylene bis (chloroaniline) and other polyamines, ethanolamine, propanolamine, ε-aminohexanol and other amino alcohols, and water or urea can be used as chain extenders.

S When using a chain extender, it would be desirable to keep the number of moles lower than the total molar amount of the long chain polyol, preferably half or less than half thereof.

The ionic segment is selected from a sulfonic acid group or a carboxyl group.

The value of the neutralizing cation is one, two or more.

As described above, at least one type of ionic segment is introduced into the urethane polymer, preferably by reaction between the organic polyisocyanate and the long-chain polyol, and the chain-extinguishing agent which has triggered the ionic segment described above. When the ionic segment is a salt, the sulfonic acid group and the carboxyl group are neutralized in different salts either before or after the polyurethane production reaction.

,. ·. Of the monomeric component of the long chain polyol contained in the sulfonic acid group or of the 9 · chain extending agents, 1,4-butanediol-2-sulfonic acid, 5 · * may be mentioned. ., Sulfoisobutylic acid, succinic or carboxylic acid monomethyl or · · · dimethyl ester or the like, or their ammonium salts, or alkali metal salts of sodium or potassium.

Examples of chain extenders containing carboxylic acid include 2,3-. dihydroxypropionic acid, 2,2-dimethylolpropionic acid, tartaric acid, 2- ···. * * *: methyl tartaric acid, 2,3-dihydroxyisobutanoic acid, 2,3-dihydroxy-2- · * · /. isopropylbutanoic acid, 3,11-dihydroxymyristic acid, 9,10- • ·· dihydroxystearic acid, 2,6-dihydroxy-1,2-dihydro-4-pyridinecarboxylic acid, · · · · · dimethylolbutanoic acid and the like, or their alkali metal salts or ammonium salts.

* · · • · · · · 118337 12

The organic polyisocyanate, long chain polyol, chain extender and the above ionic chain extender may be used alone or in admixture with two or more types. In addition, the long chain polyol introduced into the ionic segment preferably has a molecular weight of between 600 and 5000 for the same reasons mentioned above.

In addition, examples of catalysts include tertiary amines such as triethylamine or the like, potassium acetate, zinc stearate and other carboxylic acid metal salts, dibutyl tin laurate, dioctyl tin laurate, dibutyl tin oxide and other organic metal compounds.

For the polyurethane ionomer of this invention, it is convenient to introduce the ionic segment into the molecule at a concentration of 0.1 to 1 mmol / g. If the ionic segment described above is less than 0.1 millimeter, the crystallinity of the long chain polyether may not be very reduced and will have little effect on compatibility. If the ionic segment described above is more than 1.0 millimole per gram of polyurethane, the excess crosslinking density does not reduce the crystallization of the long chain polyether segment.

• · · • · ·

• M

The specific resistance value of the polyurethane ionomer as described above is. . *. preferably 106 to 109 Ω / cm. The polyurethane ionomer has a glass transition temperature (Tg) preferably of 10 ° C or less. The reason for this is that polyurethane • i. the electrically conductive mechanism of an ionomer is caused by the movement of ions caused by

»» M

. * * '. the lower the Tg of the polymer backbone, the more favorable it is for conducting ions, so it is particularly recommended at 0 ° C or lower. . *; temperature.

♦ · · * · · • · • »* · * /. The chain extender in question is typically a low molecular weight (less than 400, preferably less than? »T t J 300) hydrocarbon having two functional groups capable of reacting with? 30 diisocyanate. The chain extender is preferably an aliphatic or cycloaliphatic compound having up to 15 carbon atoms and having two functional groups selected from hydroxyl and amino groups. The number of carbon atoms in the chain extender is preferably 1 to 14, most preferably 2 to 8. The chain extender is preferably a diol or diamine, for example a diol selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,6-hexanediol, 1,4-dihydroxycyclohexane and 1,4-butanediol or diamine selected from ethyl diamine, 4,4-methylene-bis (o-chloroaniline), 4,4-diamine diphenylmethane, p-phenylenediamine, or derivatives thereof. Most preferably the chain extender is a diol, preferably a saturated alpha-diol, and 1,4-butanediol is particularly suitable.

The ratio of the isocyanate moiety of the reactants to the hydroxyl and amino moieties of the reactants may be at least 0.90 and most preferably at least 0.98. The ratio may be less than 1.10, in particular less than 1.03.

In the process for preparing the polyurethanes in question, 15 catalysts can be used. Suitable catalysts include organic and inorganic organic salts of bismuth, lead, tin, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, titanium, manganese and zirconium. . as well as phosphines and tertiary organic amines. Organic tin compounds most suitable ··· ....; The catalysts include tin octoate, tin oleate, dibutyltin dioctoate, dibutyltin. dilaurate and the like. Particularly preferred are ligand-based titanium-based catalysts. The amount of catalyst used in the process is generally from 0.005 to 2.0. % by weight based on the total weight of the reactants.

As noted above, the polyurethanes of the present invention may:; : '· Be ionic hard segments of less than 35% by weight, in particular less than 10 * ··: ***; weight-%.

According to the process of this invention, the polymerization of some reactants may be carried out prior to the use of a reactive extruder. For example, * · · * * j can be prepared by a prepolymer, preferably by the solvent-free prepolymer process.

♦ · 14 118337

In this process, some or preferably all of the isocyanate is mixed with some or preferably all of the polydienediol at elevated temperature, usually 70-100 ° C, for 30 minutes or more, and in an inert atmosphere, for example, hydrogen.

5

The prepolymer heated to 30-70 ° C, preferably 40-60 ° C, can then be introduced into the inlet of said reactive extruder. The extender, which may be heated but which is also suitable for ambient temperature, may also be fed to the inlet at this stage, preferably to the same inlet of the reaction extruder in question.

According to a preferred embodiment, the process comprises: - mixing at least a portion of the calculated amount of diisocyanate with at least a portion of the polydienediol at an elevated temperature for at least 30 minutes under an inert atmosphere to produce a prepolymer having a molecular weight of 5000-15000 g / mol; - the prepolymer is recovered, - the prepolymer is heated, - the prepolymer is fed together with the diol chain extender co-reaction *: **: 20 to the inlet of the extruder and ί:. '~ the prepolymer is reacted with a chain extender of at least 80 000 g / mol.

* · * M ··· * # ·

A suitable rotary reaction extruder is a twin-screw extruder containing a plurality of shear / mixing areas separated by screw pumps. Increasing the residence time of reactants in the extruder to produce * · · TPUs with desired properties may require additional steps. One of ordinary skill in the art can: easily do this, for example, by connecting • • transport / mixing zones in opposite directions to the extruder.

30 • · · «ti • · • · 118337 15

The polyurethane ionomer in question may be blended, for example, by melt blending with a polymer formed of olefun and an alpha or beta-unsaturated carboxylic acid having from 3 to 8 carbon atoms and having an acid group content of 0.5 to 15 mol%. Typical such co- or terblock polymers are, for example, ethylene-5-butyl acrylate-methacrylic acid terpolymers. According to the invention, the polyurethane is thus blended with the olefinic copolymer or terpolymer at elevated temperature, and 90-10% by weight of the resulting copolymer is composed of an olefinic copolymer or terpolymer (olefin + unsaturated carboxylic acid) and 10-90% by weight of polyurethane ionomer. The alkali metal compound is generally added in an amount corresponding to 0.02 to 3.0 mmol of alkali metal ions per g of polymer blend. The mixture is stirred at elevated temperature to react the alkali metal compound with the polymer components of the mixture, and stirring is continued until the alkali metal compound has reacted substantially completely with the polymer components of the mixture.

In general, it is possible to use the materials of the invention in, for example, packaging materials, fibers, tubes, hoses, tread coatings, coatings in a variety of applications, biotechnological applications, loudspeakers, and electrically conductive additives for a variety of polymers. It is particularly advantageous. Suitable for electronic packaging cardboard coatings, iatia coatings and «· <....: 20 fiber applications. These can benefit from the good mechanical properties of the alloy,. .1 2. Capable of forming films with a thickness of approximately 10 to 500 * ·· • ··· | micrometers, typically about 15 to 200 micrometers.

Due to the good mechanical properties of these ionomers, the material can be used, for example, in packaging materials, floor coverings, other polymers, or as a coating polymer.

The particularly preferred embodiment involves the use of said polyurethane ionomers in polyether urethanes, optionally mixed with other polymers (see Example 10 below), as disappearing layers in multilayer coatings. membrane structures and • »i 2 'I fibers, such structures have been described in our prior art • 1,118337 16 in our patent applications 20041361 and 20041361, the contents of which are incorporated herein by reference.

Such multilayer films generally include a top layer, a middle layer, and possibly a base layer, the middle layer of which is made of an electrically conductive polymer. They can be used in ESD packaging, such as electronics packaging, chemical packaging, food packaging and grocery packaging, where products are easily recharged.

10 Due to the high strength properties of composite films, they are also suitable for combination with thermoplastics such as LD-PE and DH-PE to give the packaging materials boundary properties, strength and impact resistance. The polyolefin packaging film is completely transparent, allowing product codes such as barcodes to be read through the film.

15

The film applications include various shrink wrap packages based on polyolefinic materials. Cellular plastics and deep-drawn packages, such as semiconductor housings, are also potential applications.

I · i • · · · · ...: 20 The fibers have a core consisting of an electrically conductive material surrounded by the outer. thermoplastic polymer protective cover layer.

·· * • ·

EXAMPLES The following examples are processed using the extrusion method. “ZSK 25: Extruder” refers to a rotary 2-piece made by Wemer & Pfeiderer

»M

screw extruder. Its screws were shaped to have a set of ··· /. massaging / mixing areas separated by screw pumps. To increase the residence time of the reactive materials, the first two massaging areas were followed by a narrow region 30 with opposite transport / mixing regions. The extruder boundary temperatures * · * · were 100-160 ° C.

• · 118337 17

Example 1 (outside the invention)

Polyethylene glycol (PEG) having a molecular weight of 1500 Mw and hexamethylene di-5 isocyanate (HDI) was reacted with 2,2-dimethylolpropionic acid (DMPA) as a chain extender and dibutyltin diacetate (DBTAC) as a catalyst. The molar proportions were: PEG 80 parts, DMPA 20 parts HDI 100 parts.

The temperature of the extruder was 100-160 ° C. The reaction product was opaque, elastic, thermoplastic polyurethane due to crystallization of the polyether component. The surface resistance of the polymer was 1010 Ω / cm according to ASTM-257.

Example 2 15

Polyethylene glycol (PEG) having a molecular weight of 1500 Mw and hexamethylene diisocyanate (HDI) reacted with a 2,2-dimethylolpropionic acid lithium salt (DMPALi) and a dibutyltin diacetate (catalyst) as the catalyst. . ·, In the presence of a 2-screw extruder. The molar proportions were: PEG 80 parts, DMPALi 20 parts · e ...: 20 and HDI 100 parts.

The temperature of the extruder was 120-160 ° C. The reaction product was a clear and flexible thermoplastic polyurethane ionomer having a surface resistance of 108 Ω / cm according to ASTM ··· 257.

• · «· · 25: Example 3 • e * • ·· • · • e ··· φ» [. Polyethylene glycol (PEG) with a molecular weight of 1500 Mw and hexamethylene di-• · ·> tit | isocyanate (HDI) reacted in the presence of a chain extender 2,2-dimethylolpropionic acid • · 30 magnesium salt (DMPAMg) and a catalyst dibutyltin diacetate • · · a a * • · a · 118337 18 (DBTAC) in a 2-screw extruder. The molar proportions were: PEG 80 parts, DMPAMg 20 parts HDI 100 parts.

The extruder temperature was 100-160 ° C. The reaction product was a clear and flexible thermoplastic polyurethane ionomer having a surface resistance of 108 Ω / cm according to ASTM-257.

Example 4 Polyethylene glycol (PEG) having a molecular weight of 1500 Mw and hexamethylene diisocyanate (HDI) was reacted with the lithium salt of 2,2-dimethylolbutanoic acid (DMBALi) as a chain extender and dibutyltin diacetate as a catalyst. The molar proportions were: PEG 80 parts, DMBAL 20 parts and HDI 100 parts.

15

The extruder temperature was 100-160 ° C. The reaction product was a clear and flexible thermoplastic polyurethane with a surface resistance of 108 Ω / cm according to ASTM-257.

. .1 2. Example S

• · · 1 • et 20 • ·. .Polyethylene glycol (PEG) having a molecular weight of 1500 Mw / hexamethylene di-··· isocyanate (HDI) reacted with two ionic chain extenders, namely 2,2- ··· dimethylolbutanoic potassium salt (DMBAK) and 2,2-dimethylolbutanoic acid ··· : 1 1 '. in the presence of magnesium salt (DMB AMg), and dibutyl acting as catalyst, in the presence of 1 tin ··· 25 diacetate (DBTAC) in a 2-screw extruder. Mole fractions were: PEG 80 µl: DMPAMg 10 parts, DMBAK 10 parts HDI 100 parts. The extruder temperature was tt · ··· 1: 120-160 1c.

«·« • · • · ·

The reaction product was clear, flexible thermoplastic polyurethane. Its surface resistance was e · 30 107Ω / αη according to ASTM-257.

• · * 1 a 2 1j Example 6 • · 118337 19

Polyethylene glycol (PEG) having a molecular weight of 2500 MW and hexamethylene diisocyanate (HD1) reacted with potassium salt of DMBAK and 2,2-dimethylolbutanoic acid (DMBAK) and magnesium salt of DMB, in the presence of dibutyltin acetate (DBTAC) as a catalyst in a 2-screw extruder. The molar proportions were: PEG 80 parts, DMPAMg 10 parts, DMBAK 10 parts and HDI 100 parts. The extruder temperature was 120-160 ° C.

The reaction product was opaque and slightly brittle thermoplastic polyurethane. Its surface resistance was 1010 / cm according to ASTM-257.

EXAMPLE 7 Polyethylene glycol (PEG) having a molecular weight of 600 Mw and hexamethylene diisocyanate (HDI) was reacted with two magnesium salts of dimethylolybutanoic acid (DMBAK) and 2,2-dimethylolbutanoic acid (DMBAK) and in the presence of dibutyltin diacetate (DBTAC), a catalyst, in a 2-screw extruder. The molar proportions were: PEG 80 · · · · · · 20 parts, DMPAMg 10 parts, DMBAK 10 parts HDI 100 parts. Extruder temperature was. 120-160 T.

• · 1 · «· • ·.:. The reaction product was a clear and flexible thermoplastic polyurethane with a ····. *** surface resistance of 108Ω / αη according to ASTM-257.

· <· 25 • · 1 · Example 8 ··· ··· • · · · do. This example illustrates the preparation of the polyurethane in question by melt processing on an extruder device.

• · 30 • · • 1 1 * 1 | The following materials were used: · 118337 20

Material: Quantity: PEG1500 2523.18 g (previously vacuum dried) 5 PEG2000 307.91 g

Polypropylene Glycol (PPG) 326.70 g (previously vacuum-dried) DMBA 257.52 g HDI 1293.79 g

Dibutyltin octoate DBSnOct 4.95 g Ethylene glycol (EG) 238.75 g PEG1500, PEG2000, PPG 1200, DMBA and DBSnOct catalyst were mixed together and the mixture was heated to about 50 ° C. The entire HDI was added at one time and the temperature of the mixture was maintained at 70-80 ° C by cooling it during the exothermic step of the reaction. Cooling was stopped as soon as the temperature ceased to rise significantly.

The reaction mixture was stirred for about 3 hours; towards the end of that time, the mixture was • slightly warmed to maintain its temperature at 60 ° C.

··· ...! 20 • ·; · * · A polyurethane prepolymer was obtained as described above. It was fed at a feed rate of 2.5 kg / h ····· through a liquid feeder simultaneously with a chain extender (ethylene glycol, ... EG, 2.1 kg / min) fed via a syringe pump to a tubular reactor vessel.

····; ***: The reaction mixture was passed from the tubular reactor vessel to the extruder.

· * «25 In the extruder, the temperature was 160 ° C (or 180 ° C) and the screw rotation speed was 150 rpm.

Example: Example 9 This example illustrates the preparation of the polyurethane in question by molten processing in a LÖdige blender.

• · · • ♦ · • · * • · 118337 21

The following materials were used:

Material: Quantity: PEG1500 15.7 kg 5 DMBA 1.205 kg HDI 6.256 kg DBSnOct 24 g EG 1.154 kg 10 Drying conditions: PEG 1500 and DMBA were dried for 1 hour and 0.5 hours in vacuo at 90 ° C.

After drying, the components were mixed together and HDI was added. The temperature was 45 ° C. The catalyst was then added in two portions every 15 minutes. The reaction mixture was stirred for 3 hours with occasional heating, and the temperature of the mixture was kept below 90 ° C.

After stirring for 3 hours, a chain extender was added (the temperature of the mixture was approximately, 69 ° C). Within 15 minutes, the temperature rose to 12 ° C, and as the temperature began to decline, the mixture was heated. After a predetermined 45 minutes after adding the chain extender. , *. the viscosity of the mixture had increased to such an extent that the mixer no longer rotated. The temperature of the mixture was then 98 ° C.

9,999 9,999999. ***. Example 10 ··· 25. . *. The material prepared in Example 8 was melt blended with ethylene-butyl acrylate. methacrylic acid terpolymer with a BA concentration of 10% by weight and 999 /%. 10% by weight of LAND. The urethane ionomer was mixed with the E / BA / MAA terpolymer so that the weight fraction of the urethane ionomer was 30 parts by weight and the E / BA / MAA terpolymer was 70 to 9 parts by weight. The temperature of the 2-screw extruder was 220-270 ° C and 0.6 parts by weight of 9 9 9 * sodium hydroxide and 0.4 parts by weight of zinc acetate were present.

9 9 22 118337 After mixing at 1200 rpm, a homogeneous, clear, elastic material with a surface resistance of 2 x 10 8 ohms was obtained.

The material of Example 10 can be used in very thin layers in multilayer structures of packaging materials or in dual component fibers to prevent static charges, a few examples of possible applications of this material.

• ♦ • · · «« a a a a a a

«M

• · * ··· · ** · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · 0 9 9 9 9 0 00 9 9 1 • 0

Claims (25)

1. A thermoplastic urethane polymer, which consists of a polymeric body having - a hard segment containing ionizable acid groups, and - a soft segment, which is almost composed of a polyether and which is in amorphous state, characterized by the polymer being prepared by melt blending, whereby the polyurethane is blended together react in the molten state at an elevated temperature and the surface resistance of the polymer is less than 108 Ω / cm, determined in accordance with standard ASTM-257. Polymer according to claim 1, characterized in that the ionizable acid group is a carboxylic group, a sulfonic acid group, a mixture or a salt thereof. Polymer according to claim 1 or 2, characterized in that the polyurethane is a polyurethane ionomer whose glass transition temperature rises to 20 ° C. Polymer according to any of claims 1-3, characterized in that ··· - ♦ • «. the content of ionic hard segments ranges from 5 to 50% by weight, preferably below 35%, preferably below 30% by weight. The polymer according to any one of claims 1-4, characterized in that the content of the polyether is equal to 20 - 95% by mass of the polymer weight, preferably .. 50 - 90 mass percent, preferably 60 - 85 mass percent. : Polymer according to any of claims 1-5, characterized in that the soft segment originates from a long chain polyol, whose molecular weight * ·; ** increase to 400 - 10,000, preferably to 600 - 5,000. Polymer according to claim 6, characterized in that the soft segment consists of poly (alkylene ether), the alkylene chain of which has 2 to 6 carbon atoms and 28 is 1 8337 which is preferably derived from poly (propylene glycol) (PPG) or poly (ethylene ether). glycol) (PEG). 8. Polymer according to claim 7, characterized in that the soft segment is derived from poly (ethylene glycol), whose molecular weight amounts to 1,000 to 5,000 g / mol. Polymer according to any of claims 1-8, characterized in that the polyurethane contains a residue of a chain extender, which is a diol, preferably a diol with a terminal hydroxyl group and a hydrocarbon chain consisting of 2 to 12 carbon atoms, preferably 4 -6 carbon atoms. Polymer according to claim 9, characterized by the chain extender consisting of an acidic group which may be in the form of a metal salt. Polymer according to any one of claims 1-10, characterized in that the ionizable acid group consists of a metal salt, the metal ion of which is derived from alkali metals, alkaline earth metals and aluminum. ·. ·. * 15 Polymer according to any of claims 1-11, characterized in that the polymer contains residues of a coupling agent selected from linear or cyclic. · Aliphatic diisocyanates. • * Polymer according to claim 1, characterized in that the diisocyanate is a hexamethylene diisocyanate (HDI) or a cyclohexamethylene diisocyanate (CHDI). ·· • · * M ··· Polymer according to any of claims 1-13, characterized in that the segment containing an acidic group is derived from a chain extender, which is made up of a dialkylalkanoic acid, the alkyl of which has 1-3 carbon atoms and alkanoic acid residues. 2 - ***. 12 carbon atoms. · · E ·· Polymer according to claim 14, characterized in that the chain linker is dimethylolbutanoic acid. 29 1 1 8337 16. Polymeric similarity with no prior patent claim, characterized in that the molecular weight of the polyurethane exceeds 50,000, preferably 80,000, and is most preferably between 100,000 and 2,500,000. A process for producing thermoplastic polyurethane by means of melt processing, said polyurethane comprising a polymer backbone having - a hard segment containing ionizable acid groups, - a soft segment almost consisting of a polyether and in amorphous state, and - which polyurethane surface resistance is less than 10® Ω / cm, determined in accordance with standard ASTM-257, characterized in that the polymer is prepared by melt blending, whereby the starting materials of the polyurethane are mixed together and reacted in the molten state at an elevated temperature. A process according to claim 17, characterized in that a diol, a diisocyanate and a chain extender containing a carboxylic acid group (s) are mixed together and are reacted dynamically in an extruder or static in a batch. mixer. A process according to claim 17 or 18, characterized in that • S · ·· »diisocyanate is added in a stoichiometric amount relative to the amount of compounds • 20 containing two hydroxy target groups. M ·· ·· ♦:: ··· 20, A method according to any of claims 17-19, characterized by: ·. that: · ·· · · · - at least part of the calculated diisocyanate amount is mixed with ···, Λ at least part of polydienediol at an elevated temperature of 70-100 ° C * · t · ·. ···. for 30 minutes in an inert atmosphere to prepare a prepolymer, whose molecular weight is added up to 5,000 -15,000 g / mol,: the prepolymer is used, the prepolymer is heated to a temperature of The prepolymer is measured together with a diol chain extender into the feed port of a reaction extruder, and the 118337 prepolymer is reacted with the chain extender to provide a polyurethane having a molecular weight amounting to at least 80,000 g / mole, preferably at least 50,000 g / mole. 000 g / mol. 21. Process according to any of claims 17-20, characterized in that the reaction is carried out in the presence of an amino or organometallic catalyst, the concentration of the catalyst being up to about 0.005-2% by weight based on the total reaction weight. Method according to any of claims 17-20, characterized in that the reaction is carried out in the presence of a liganded titanium-based catalyst, the concentration of the catalyst being about 0.005-3% by weight based on the total reaction weight. The use of a polyurethane ionomer according to any one of claims 1-16 for the manufacture of an electrically conductive polymeric material, wherein the ionomer is mixed with a polymer formed from an olefin and an alpha or beta unsaturated carboxylic acid with 3 -8 carbon atoms and whose amount of acid groups is up to 0.5 - 15 mol%. • • · # • i i The use according to claim 23, characterized in that poly- · ·· · • *. the urethane anomer is mixed with an olefinic block copolymer or block polymer. • i ί The use according to claim 23 or 24, characterized in that the polyurethane anomer is mixed with an olefinic polymer in a molar ratio of about 90:10 to 10:90. · ♦ • ·: ·· f: # · »♦ · · · · · · · · · ···:: ··· i ·· •« • '· ··· ··· «· • *