DE4112805A1 - Using bis:methoxy-ethoxy-ethyl phthalate as plasticiser - for poly:isocyanate polyaddition prods., partic. soft rubber-elastic cellular or compact polyurethane elastomers - Google Patents

Abstract

Polyurethane (PU) elastomers (I) contg. bis (methoxyethoxyethyl) phthalate (II) are used as plasticisers. (I) is prepd. by reacting (A) organic polyisocyanates with (B) polyhydroxy cpds. of mol.wt. 500-8,000 and (C) chain lengthening and/or crosslinking agents of mol.wt. 60-400, opt. in the presence of (D) blowing agents, (E) catalysts, (F) auxiliaries and/or additives. (II) is incorporated in (A)-(F) before reaction, in the reaction mixt. or in a thermoplastic PU prepd. from (A)-(C) and opt. (E) and (F) by a belt or extrusion process. Pref. (I) comprise 1-50 pts. (all pts.wt.) (II) and 99-50 pts. PU elastomer. Rubber-elastic (I) with Shore AS hardness 85-60 contain 1-50 pts. (II) and 99-50 pts. thermoplastic PU, partic. PU with Shore A hardness 95-80, main melting peak of hard segment 210-220 deg.C (DSC), and melt viscosity corresp. to MFI (melt flow index) at 190 deg.C/212 N, of 0.1-200. Thermoplastic PU elastomer has been prepd. by reaction of aromatic diisocyanate as (A) with (B) and chain lengthening agent of mol.wt. 60-400 as (C), opt. in presence of (D), (E) and (F). Partic. thermoplastic PU prepd. by a belt process is used. USE/ADVANTAGE - (I) are used for prepn. of films, shaped articles, tubes or profiles, partic. sealing profiles (claimed), esp. for prepn. of cellular mouldings (claimed). (II) is incorporated relatively rapidly, reducing prodn. costs and does not exude or migrate. Residual tensile deformation value and water vapour permeability of (I) are improve

Description

Objects of the invention are soft, rubber-elastic, cellular or compact polyurethane elastomers used as plasticizers bis (methoxyethoxy ethyl) phthalate of the formula

contain a process for their preparation and their use.

The production of compact or cellular polyisocyanate polyadditions products, preferably polyurethanes, hereinafter also abbreviated PU called, for example of thermoplastic polyurethanes (TPU) or compact or cellular PU cast elastomers, has long been numbered known patent and literature publications. Your technical Importance is based on the combination of high quality mechanical properties with the advantages of inexpensive processing methods. By using different chemical components in Different proportions can be processed thermoplastically or cross-linked, compact or cellular PU elastomers and PU foams are manufactured, which differ in terms of their processability and their differentiate mechanical properties. An overview of Polyurethanes, their properties and applications are used e.g. B. in plastic Handbuch, Volume 7, Polyurethane, 1st edition, 1966, published by Dr. R. Vieweg and Dr. A. Höchtlen, and 2nd edition, 1983, published by Dr. G. Oertel (Carl Hanser Verlag, Munich, Vienna).

Polyurethane elastomers can be discontinuous or continuous various methods can be produced.

PU cast elastomers can be introduced, e.g. B. by pouring or Inject a reaction mixture into an open or closed one Molding tool and its curing can be obtained.

TPU are usually continuous according to the so-called band ver drive, e.g. B. according to GB-A-10 57 018, or extrusion process, for. B. according US-A-36 42 964.  

TPU, which consists of essentially linear polyhydroxyl compounds, aromatic diisocyanates and low molecular weight dihydroxy compounds, such as B. alkane diols or dialkylene glycols are built, the Hardness about the content of so-called hard phase, which essentially consists of Diisocyanate-diol segments exist. By an appropriate choice the molar ratios of the structural components can TPU with hardness of Shore A 80 to Shore D 74 can be easily produced. TPU with one Shore A hardness less than 80 can theoretically be done in the same way be preserved; the disadvantage, however, is that the products at Make production difficult to handle because they solidify only slowly and become firm.

PU elastomers can also be modified by additives. For verb Hydrolysis resistance are substituted in the ortho position Diarylcarbodiimides in amounts up to a maximum of 2% by weight for use. PU elastomers with a low coefficient of friction are added by adding suitable lubricants, such as. B. graphite or molybdenum disulfide, receive. In addition, PU elastomers can be made using the rubber technique Fillers of all kinds can be incorporated in large quantities.

According to US-A-37 88 882, breathable laminates can be used as Upper material for shoes are made of an open-cell foam and a top layer, e.g. B. made of PVC or TPU. To Improvement of vapor permeability and resistance to Water can the top layer, for. B. made of thermoplastic polyester urethanes, plasticizers, such as. B. trialkoxyalkyl phosphates or Di (alkoxyethyl) phthalates are incorporated.

EP-A-01 34 455 also describes the addition of di (methoxyethyl) phthalate, tricresyl phosphate, diphenyl cresyl phosphate and polyester polyurethanes with a molecular weight of 4,000 to 10,000 based on 1,4-butanediol polyadipate and 4,4'-diphenylmethane diisocyanate for formation known from soft, rubber-elastic TPU. By adding this With TPU, plasticizers can increase the hardness from Shore A 95 to 80 to values of Shore A 80 to 60 can be lowered. Such TPU have improved Remnants of compression and tension.

Plasticizers are used proportionately for the production of PU elastomers rarely used, as these are insoluble in the hard phase and only a few Plasticizers are compatible with the PU elastomers at all. Rollable PU elastomers generally take the plasticizers slowly and in limited quantities. In addition, the plasticizer must not be chemical Have a side effect. Therefore z. B. from the use of phosphorus  acid esters are discouraged, often due to their traces of acid Impact the aging resistance of the end product.

Polymers and plasticizers vary in polarity and must therefore be optimally coordinated. Phthalic acid di (methoxyethyl ester) and phthalic acid di (butoxyethyl ester) show compared to the Polyurethane matrix has a limited tolerance, which is reflected in a time-consuming familiarization level and a high level of volatility expresses that due to their relatively low molecular weights is reinforced. By evaporating the plasticizer, the so-called Fogging, an undesirable creeping increase in shore hardness occurs a.

A low tolerance of the has a particularly disadvantageous effect Plasticizer with the TPU matrix on the swelling rate and the required swelling temperature in mixing devices, one being too high temperature stress on the TPU can lead to undesired discoloration can.

PU casting elastomers containing plasticizers are described in GB-A-15 84 780 described. The crosslinked PU cast elastomers are u. a. produced using more than difunctional organic polyisocyanates and polyhydroxyl compounds and are therefore not thermoplastic processable.

The object of the present invention was to make soft rubber elastic polyurethane elastomers, preferably those with Shore hardness of equal to or less than 85 A to produce the disadvantages mentioned above do not show. With an increased swelling rate, the Production costs can be reduced. One should also be reduced Blooming, exudation or emigration of the plasticizer. The mechanical Properties of the PU elastomers should at least not be added deteriorate. Rather, the Zugver residual shape and the water vapor permeability of the PU elastomer be improved.

Surprisingly, this task could be accomplished by using a selected plasticizer can be solved.

The invention thus relates to soft, rubber-elastic, cellular or compact polyurethane elastomers used as plasticizers bis (methoxyethoxy contain ethyl) phthalate.  

Other objects of the invention are a method for producing the soft, rubber-elastic, cellular or compact PU elastomers Claim 7, the use of the compact PU elastomers according to the invention for the production of preferably films, moldings, for. B. tubes and Profiles according to claim 8, the use of the invention PU elastomers for the production of cellular moldings according to claim 9 and the use of the bis (methoxyethoxyethyl) phthalates as plasticizers for polyisocyanate polyaddition products according to claim 10.

The bis (methoxyethoxyethyl) used as plasticizer according to the invention Phthalate can be made from a wide variety of PU elastomers Starting materials are introduced. It stands out in any TPU, especially in thermoplastic polyester urethanes, by an essential Lich higher swelling speed with a relatively low swelling temperature and a significantly reduced volatility with increased Temperature, compared to conventional known plasticizers. Through the low swelling temperature can cause TPU discolouration during application processing almost completely avoided.

One showed up in thermoplastic polyether urethanes, for special ones Applications extremely positive, greatly increased water vapor permeability in the Compared to other soft TPU. This was also possible in this polyether TPU Fogging can be significantly reduced. The PU elastomers also had one improved train deformation remainder.

The soft, rubber-elastic, cellular or compact PU elastomers that preferably a Shore A hardness equal to or less than 85, in particular have in particular from 80 to 60, contained in 100 parts by weight, 1 to 50 parts by weight, preferably 15 to 35 parts by weight and in particular 18 up to 31 parts by weight of bis (methoxyethoxyethyl) phthalate and 99 to 50 parts by weight, preferably 85 to 65 parts by weight and in particular 82 to 69 parts by weight of a polyurethane elastomer, preferably one compact or cellular PU cast elastomers or in particular a TPU.

The soft, rubber-elastic TPU according to the invention with a Shore hardness A of preferably 85 or less suitably have as base plastic a TPU with a Shore hardness A of 95 to 80, preferably from 85 to 80, a main melting peak of the hard segments, measured by differential calorimetry (DSC) from 210 to 220 ° C, preferably from 212 to 218, and a melt viscosity, an MFI (melt flow index) at 190 ° C and a bearing weight of 212 N corresponding to 0.1 to 200, preferably from 0.5 to 50, after the extruder and be produced in particular by the belt process.  

The PU elastomers according to the invention, preferably TPU, can according to known methods by implementing

• a) organic polyisocyanates, preferably aromatic diisocyanates With
• b) polyhydroxyl compounds, preferably essentially linear Polyhydroxyl compounds with molecular weights from 500 to 8000, preferably polyalkanediol polyadipates with 2 to 6 carbon atoms in the Alkylene radical and molecular weights from 500 to 6000, hydroxyl groups containing polytetrahydrofuran with a molecular weight of 500 to 3500 or polyoxybutylene-polyoxyalkylene glycols with one molecular weight from 500 to 3500 and
• c) crosslinking agents and / or preferably chain extenders with molecular weights of 60 to 400, especially diols and particularly preferably 1,4-butanediol

in the presence or absence of

• d) blowing agents,
• e) catalysts and
• f) auxiliaries and / or additives

getting produced.

As suitable structural components for the production of the PU elastomers, preferably the TPU and cellular or compact PU cast elastomers the compounds known from polyurethane chemistry, to which in the following is carried out, for example:

• a) Find organic, optionally modified polyisocyanates (a) expediently aliphatic, cycloaliphatic and preferably aromatic diisocyanates use. In particular, are exemplary called: aliphatic diisocyanates, such as 1,6-hexamethylene diisocyanate, 2-methyl-pentamethylene-diisocyanate-1,5, 2-ethyl-butylene-diiso cyanate-1,4 or mixtures of at least two of the ali mentioned phatic diisocyanates, cycloaliphatic diisocyanates such as Iso phoron diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and -2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate and the ent  speaking isomer mixtures and preferably aromatic diisocyanates, such as 2,4-tolylene diisocyanate, mixtures of 2,4- and 2,6-tolylene diisocyanate, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate, Mixtures of 2,4′- and 4,4′-diphenylmethane diisocyanate, urethane-modified liquid 4,4′- and / or 2,4′- diphenylmethane diisocyanates, 4,4'-diisocyanato-diphenylethane-1,2, mixtures of 4,4'-, 2,4'- and 2,2'-diisocyanato-diphenylethane-1,2, advantageously those with a 4,4'-diisocyanato-diphenylethane-1,2 content of at least 95% by weight and 1,5-naphthylene diisocyanate. Preferably Diphenylmethane diisocyanate isomer mixtures with a 4,4'-diphenylmethane diisocyanate content of greater than 96 wt .-% and in particular essentially pure 4,4'-diphenylmethane diisocyanate.
• The organic diisocyanates can optionally be subordinate Quantities, e.g. B. in amounts up to 3 mol%, preferably up to 1 mol%, based on the organic diisocyanate, by a tri or higher functional polyisocyanate are replaced, the amounts of which the production of TPU must be limited so that thermoplastically processable polyurethanes can be obtained. A larger amount of such more than difunctional isocyanates expediently by using less than di functional compounds with reactive hydrogen atoms, out same, so that a too extensive chemical crosslinking of the poly urethans is avoided. Examples of more than difunctional iso cyanates are mixtures of diphenylmethane diisocyanates and poly phenyl polymethylene polyisocyanates, so-called raw MDI and liquid, with Isocyanurate, urea, biuret, allophanate, urethane and / or Carbodiimide groups modified 4,4'- and / or 2,4'-diphenyl methane diisocyanates.
• As suitable monofunctional compounds with a reactive Hydrogen atom, which can also be used as a molecular weight regulator, be z. B. called: monoamines such. B. butyl, dibutyl, octyl, Stearyl, N-methylstearylamine, pyrrolidone, piperidine and cyclohexyl amine, and mono alcohols such as. B. butanol, amyl alcohol, 1-ethylhexanol, Octanol, dodecanol, cyclohexanol and ethylene glycol monoethyl ether.
• b) As higher molecular weight polyhydroxyl compounds (b) with molecular weight from 500 to 8000 - that in the description of the invention and in The molecular weights mentioned in the claims relate to the Number average - polyetherols are particularly suitable and in particular Polyesterols. However, other hydroxyl groups are also possible containing polymers with ether or ester groups as bridge members,  for example polyacetals, such as polyoxymethylene and above all water-insoluble formals, e.g. B. Polybutanediol formal and polyhexane diol formal, and polycarbonates, especially those made from diphenyl carbonate and hexanediol-1,6, e.g. B. by transesterification. The Polyhydroxyl compounds must be at least predominantly linear, i.e. H. in the Be difunctional in terms of the isocyanate reaction. The called Polyhydroxyl compounds can be used as individual components or in form of mixtures are used.
• Suitable polyetherols can by known methods, for example by anionic polymerization with alkali hydroxides, such as Sodium or potassium hydroxide or alkali alcoholates such as sodium methylate, sodium or potassium ethylate or potassium isopropoxide as Catalysts and the addition of at least one starter molecule the 2nd contains up to 3, preferably 2 reactive hydrogen atoms bound, or by cationic polymerization with Lewis acids such as antimony penta chloride, boron fluoride etherate u. a. or bleaching earth as catalysts one or more alkylene oxides having 2 to 4 carbon atoms in the Alkylene radical can be produced.
• Suitable alkylene oxides are preferably, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide and particularly preferred Ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be individually can be used alternately in succession or as mixtures. As Starter molecules can be considered, for example: water, organic Dicarboxylic acids, such as succinic acid, adipic acid and / or glutaric acid, Alkanolamines, e.g. B. ethanolamine, N-alkylalkanolamines, N-alkyl dialkanolamines, such as. B. N-methyl and N-ethyl-diethanolamine and preferably divalent, optionally linked ether bridges containing alcohols, such as. B. ethanediol, 1,2-propanediol and 1,3, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, di propylene glycol, 2-methylpentanediol-1,5 and 2-ethyl-butanediol-1,4. The Starter molecules can be used individually or as mixtures.
• Polyetherols of 1,2-propylene oxide and are preferably used Ethylene oxide in which more than 50%, preferably 60 to 80% of the OH Groups are primary hydroxyl groups and at least some of them of the ethylene oxide is arranged as a terminal block. Such Polyetherols can be obtained by e.g. B. to the starter Molecule first the 1,2-propylene oxide and then the Ethylene oxide polymerizes or initially all 1,2-propylene oxide copolymerized in a mixture with part of the ethylene oxide and the The rest of the ethylene oxide subsequently polymerized or gradually  first part of the ethylene oxide, then all of the 1,2-propylene oxide and then anpoly the rest of the ethylene oxide onto the starter molecule merized.
• The hydroxyl-containing polymers are also very suitable tion products of tetrahydrofuran, those with molecular weight weights from 500 to 3500 are particularly preferred.
• As higher molecular weight polyoxybutylene polyoxyalkylene glycols mentioned by way of example: polyoxybutylene-polyoxyethylene glycols, Polyoxybutylene-polyoxypropylene glycols and polyoxybutylene-polyoxy propylene-polyoxyethylene glycols or mixtures of at least two of the polyoxybutylene-polyoxyalkylene glycols mentioned. The polyoxy Butylene-polyoxyalkylene glycols usually have molecular weight weights of preferably 500 to 3500 and in particular 800 to 2200 and contain at least 50 wt .-%, preferably 50 to 90 wt .-% and in particular 65 to 80% by weight, based on the total weight of (b) Oxybutylene units. The oxybutylene units can be like that Oxyalkylene units are oxyethylene or oxypropylene or Oxyethylene and oxypropylene units, block by block or statistical Distribution. As polyoxybutylene-polyoxyalkylene polyols polyoxybutylene-polyoxyethylene glycols are preferably used with block or statistical distribution of oxybutylene and Oxyethylene units, those with molecular weights from 800 to 2200 are particularly preferred.
• The essentially linear polyetherols have molecular weights from 500 to 8000 and preferably from 500 to 3500. You can use both individually and in the form of mixtures with one another come.
• Suitable polyesterols can be produced, for example, from dicarboxylic acids having 2 to 12, preferably 4 to 6 carbon atoms and polyhydric alcohols. Examples of suitable dicarboxylic acids are: aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, e.g. B. in the form of a succinic, glutaric and adipic acid mixture, are used ver. To prepare the polyesterols, it may be advantageous to use the corresponding dicarboxylic acid derivatives, such as dicarboxylic acid mono- and / or diesters having 1 to 4 carbon atoms in the alcohol radical, dicarboxylic acid anhydrides or dicarboxylic acid dichlorides instead of the dicarboxylic acids. Examples of polyvalent alcohols are alkanediols with 2 to 10, preferably 2 to 6 carbon atoms and / or dialkylene ether glycols with 4 to 12, preferably 4 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, 1,4-butanediol and 1,5-pentanediol , 1,6-hexanediol, 1,10-decanediol, 2,2- dimethylpropanediol-1,3, 1,3-propanediol and dipropylene glycol. Depending on the properties desired, the polyhydric alcohols can be used alone or, if appropriate, in mixtures with one another.
• Also suitable are esters of carbonic acid with the above Alkanediols or dialkylene glycols, especially those with 4 to 6 carbon atoms, such as 1,4-butanediol and / or 1,6-hexanediol, Condensation products of ω-hydroxycarboxylic acids, for example ω-hydroxycaproic acid and preferably polymerization products of Lactones, for example optionally substituted ω-caprolac tone.
• Preferably used as polyesterols are ethanediol polyadipates, 1,4-butanediol polyadipate, ethanediol-1,4-butanediol polyadipate, 1,6- Hexanediol-neopentylglycol polyadipate, 1,6-hexanediol-1,4-butanediol polyadipate and polycaprolactones.
• The polyesterols have molecular weights of 500 to 6000, preferably wise from 800 to 3500.
• c) Have suitable chain extenders and / or crosslinking agents usually molecular weights less than 400, preferably 60 to 300. Alkanediols having 2 to 12 carbon atoms are preferably used, preferably 2, 4 or 6 carbon atoms, such as. B. Ethane, 1,3-propane, 1,5-pentane, 1,6-hexane, 1,7-heptane, 1,8-octane, 1,9-nonane, 1,10-decanediol and in particular 1,4-butanediol and dialkylene glycols with 4 to 8 carbon atoms, such as. B. Diethylene glycol and dipropylene glycol. However, branched chains are also suitable and / or unsaturated alkanediols usually no longer than 12 carbon atoms, e.g. B. 1,2-propanediol, 2-methyl-, 2,2-dimethyl-propanediol-1,3, 2-butyl-2-ethylpropanediol-1,3-butene-2-diol-1,4 and butyn-2-diol-1,4, diester of terephthalic acid with glycols with 2 up to 4 carbon atoms, e.g. B. terephthalic acid bis ethylene glycol or 1,4-butanediol, hydroxyalkylene ether of hydroquinone or Resorcins, such as B. 1,4-di- (β-hydroxyethyl) hydroquinone or 1,3-di- (β-hydroxyethyl) resorcinol, Alkanolamines with 2 to 12 carbon atoms, such as B. ethanolamine, 2-aminopropanol and 3-amino-2,2-dimethylpropanol, N-alkyl dialkanolamines, such as. B. N-methyl and  N-ethyl-diethanolamine, (cyclo) aliphatic diamines with 2 to 15 carbon atoms, e.g. B. ethylene, 1,2-, 1,3-propylene, 1,4-butylene and 1,6-hexamethylene diamine, isophorodiamine, 1,4-cyclohexylene diamine and 4,4'-diamino-dicyclohexylmethane, N-alkyl and N, N'-dialkylalkylene diamines such as. B. N-methyl-propylenediamine and N, N'-dimethylethylene diamine and aromatic diamines, such as. B. Methylene bis (4-amino-3-benzoic acid methyl ester), 1,2-bis (2-aminophenylthio) ethane, Trimethylene glycol di-p-aminobenzoate, 2,4- and 2,6-tolylene diamine, 3,5-diethyl-2,4- and -2,6-toluenediamine, 4,4'-diamino-diphenylmethane, 3,3'-dichloro-4,4'-diamino-diphenylmethane and primary ortho-di, tri and / or tetraalkyl substituents 4,4'-diamino-diphenylmethane, such as. B. 3,3'-di- and 3,3 ', 5,5'-tetraisopropyl, 4,4'-diamino-diphenylmethane. Find to make the TPU alkane diols, in particular, are used as chain extenders.
• As a highly functional crosslinking agent, which is expediently used for Production of the PU cast elastomers are also used exemplified: trifunctional and higher alcohols, such as. B. Glycerin, trimethylolpropane, pentaerythritol and trihydroxycyclohexane and tetrahydroxyalkylalkylene diamines such as e.g. B. Tetra- (2-hydroxyethyl) - ethylenediamine or tetra- (2-hydroxypropyl) ethylene diamine.
• Suitable chain extenders and crosslinking agents can used individually or in the form of mixtures. Are usable also mixtures of chain extenders and crosslinking agents.
• For setting the hardness of the PU elastomers and the melt index the TPU can build components (b) and (c) in relatively wide Quantity ratios can be varied, the hardness and the enamel viscosity with increasing content of difunctional chain extensions agent (c) in the TPU increases while the melt index decreases.
• Depending on the desired hardness, the required Amounts of the structural components (b) and (c) in a simple manner be determined experimentally. Molar ratios have proven successful from polyhydroxyl compounds (b) to chain extenders (c) from 1: 1 to 1:12, preferably from 1: 1.8 to 1: 4.4.
• The production of compact PU elastomers, preferably PU casting elastomeric and TPU, is preferred in the absence of Kataly sators (e) and aids (f) performed. On the other hand, it has proven to be expedient for the production of cellular PU elastomers, preferably PU cast elastomers, in addition to those required  Blowing agents (d) mitzuver catalysts (e) and auxiliaries (f) turn. To modify the mechanical properties of the PU-Ela In addition, it may be necessary to add additives (f) put.
• d) To the blowing agents (d) which are used to produce the cellular PU elastomers can be used, preferably water, that reacts with isocyanate groups to form carbon dioxide. The Amounts of water which are expediently used are 0.01 up to 3 parts by weight, preferably 0.1 to 2 parts by weight and in particular 0.2 to 1 part by weight, based on 100 parts by weight of the higher molecular weight Polyhydroxyl compounds (b).
• In a mixture with water, physical blowing agents can also be used can be used or only physically acting Use blowing agents. Liquids are suitable, which compared to the organic, optionally modified polyiso cyanates (a) are inert and boiling points below 100 ° C, preferably below 50 ° C, especially between -50 ° C and 30 ° C at atmospheric pressure have so that they are under the influence of exothermic polyadditions vaporize reaction. Examples of such, preferably usable Liquids are hydrocarbons, such as n- and iso-pentane, techni pentane mixtures, n- and isobutane and propane, ethers, such as furan, Dimethyl ether and diethyl ether, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl formate and preferably halo Hydrogenated hydrocarbons such as methylene chloride, difluoromethane, tri chlorofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, 1,1,1- Dichlorofluoroethane, 1,1,1-chlorodifluoroethane, dichlorotetrafluoroethane, Tetrafluoroethanes, 1,1,2-trichloro-1,2,2-trifluoroethane and heptafluoro propanes, as well as noble gases, such as. B. Krypton. Mixtures of these low-boiling liquids with each other and / or with others substituted or unsubstituted hydrocarbons be used.
• The required amount of physically active blowing agents can be in Depending on the desired density of the PU elastomers can be determined in a simple manner and is approximately 1 to 15 parts by weight, preferably 2 to 11 parts by weight per 100 parts by weight of the higher moles kular polyhydroyl compounds (b), their share in the Use of water reduced proportionately. If necessary it may be expedient to modify the optionally modified polyiso mix cyanate (a) with the physical blowing agent and thereby reducing their viscosity.  
• e) In particular, compounds which are used as catalysts (e) the reaction of the compounds of the compo containing hydroxyl groups Accelerate nenten (b) and (c) with the polyisocyanates (a). In Organic metal compounds are preferred, preferably organic Tin compounds, such as tin (II) salts of organic carboxylic acids, e.g. B. tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and Tin (II) laurate and the dialkyltin - ((V) salts of organic car bonic acids, e.g. B. dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate and dioctyl tin diacetate. The organic metal compound solutions are used alone or preferably in combination with strong basic amines used. Examples include amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines such as tri ethylamine, tributylamine, dimethylbenzylamine, N-methyl, N-ethyl, N-cyclohexylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′- Tetramethylbutane diamine or hexane diamine, pentamethyl diethylene tri amine, tetramethyl-diaminoethyl ether, bis (dimethylaminopropyl) urine substance, 1,4-dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo- (3,3,0) octane and preferably 1,4-diaza-bicyclo- (2,2,2) octane and Alkanolamine compounds, such as triethanolamine, triisopropanolamine, N-methyl and N-ethyl-diethanolamine and dimethylethanolamine. Preferential 0.001 to 5% by weight, in particular 0.05 to, are used 2 wt .-% catalyst or catalyst combination based on the Ge importance of polyoxybutylene-polyoxyalkylene glycols (b).
• f) The reaction mixture for the production of the PU elastomers can be countered if necessary, auxiliaries and / or additives (f) are also incorporated will. Examples include surface-active substances, Foam stabilizers, cell regulators, fillers, flame retardants, germs Educational agents, oxidation retarders, stabilizers, slip and Ent molding aids, dyes and pigments.
• As surface-active substances such. B. consider connections which serve to support the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure. Emulsifiers such as the sodium salts of Castor oil sulfates, or of fatty acids and salts of fatty acids with Amines, e.g. B. oleic acid diethylamine, stearic acid diethanolamine, rici noleic acid diethanolamine, salts of sulfonic acids, e.g. B. alkali or Ammonium salts of dodecylbenzene or dinaphthylmethane disulfonic acid and ricinoleic acid; Foam stabilizers, such as siloxane-oxalkylene mixture polymers and other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oleic or ricinoleic acid esters, turkish red oil and peanut oil and cell regulators such as paraffins, fat  alcohols and dimethylpolysiloxanes. To improve the emulsification Kung, the cell structure and / or stabilization of the foam are suitable also oligomeric polyacrylates with polyoxyalkylene and fluoroalkane leftovers as page groups. The surface-active substances are usually in amounts of 0.01 to 5 parts by weight, based on 100 parts by weight of the polyhydroxyl compounds (b) applied.

As fillers, in particular reinforcing fillers, are the known, conventional organic and inorganic fillers, Ver to understand tonics and weighting agents. In particular mentioned as examples: inorganic fillers such as silicate minerals, for example layered silicates such as antigorite, serpentine, hornblende, Amphibole, chrisotile, talc; Metal oxides, such as kaolin, aluminum oxides, Aluminum silicate, titanium oxides and iron oxides, metal salts such as chalk, Heavy spar and inorganic pigments such as cadmium sulfide, zinc sulfide as well Glass particles. Examples of suitable organic fillers are: Carbon black, melamine, expanded graphite, rosin, cyclopentadienyl resins and Graft polymers.

Fibers are preferably used as reinforcing fillers, for example carbon fibers or in particular glass fibers, especially then, when high heat resistance or very high rigidity is required is, the fibers equipped with adhesion promoters and / or sizes could be. Suitable glass fibers, e.g. B. also in the form of glass fabrics, mats, nonwovens and / or preferably glass silk rovings or cuts ner glass silk from low-alkali E-glasses with a diameter of 5 to 200 microns, preferably 6 to 15 microns are used, according to their Incorporation into the molding compositions generally has an average fiber length of 0.05 to 1 mm, preferably 0.1 to 0.5 mm.

The inorganic and organic fillers can be used individually or as Mixtures are used and are usually the reaction mixture in amounts of 0.5 to 50% by weight, preferably 1 to 30% by weight, based on the weight of the structural components (a) to (c).

Suitable flame retardants are, for example, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (1,3-dichlor propyl) phosphate, tris (2,3-dibromopropyl) phosphate and tetrakis (2-chloro ethyl) ethylenediphosphate.

In addition to the halogen-substituted phosphates already mentioned, inorganic flame retardants, such as red phosphorus, aluminum oxide hydrate, Antimony trioxide, arsenic trioxide, ammonium polyphosphate and calcium sulfate or  Cyanuric acid derivatives, such as. B. melamine or mixtures of at least two Flame retardants such as B. ammonium polyphosphates and melamine and optionally starch and / or expandable graphite for flame retarding the PU elastomers produced according to the invention can be used. Generally mine has proven to be useful, 5 to 50 parts by weight, preferably 5 to 25 parts by weight of the flame retardants or mixtures mentioned to be used for 100 parts by weight of the components (a) to (c).

As nucleating agents such. B. talc, calcium fluoride, sodium phenyl Phosphinate, aluminum oxide and fine-particle polytetrafluoroethylene in quantities up to 5% by weight, based on the total weight of the structural components (a) to (c).

Suitable oxidation retarders and heat stabilizers that the PU elastomers can be added, for example, halides of Group I metals of the periodic system, e.g. B. sodium, potassium, Lithium halides, optionally in combination with copper (I) Halides, e.g. B. chlorides, bromides or iodides, sterically hindered Phenols, hydroquinones, and substituted compounds from these groups and Mixtures thereof, preferably in concentrations up to 1% by weight, based on the weight of the structural components (a) to (c) used will.

Examples of UV stabilizers are various substituted resorcinols, Salicylates, benzotriazoles and benzophenones as well as sterically hindered Amines, generally in amounts up to 2.0 wt .-%, based on the Weight of the structural components (a) to (c) can be used.

Lubricants and mold release agents, which are usually also in amounts up to 1% by weight, based on the weight of the structural components (a) to (c), are added are stearic acids, stearyl alcohol, stearic acid esters and amides and the fatty acid esters of pentaerythritol.

Organic dyes such as nigrosine, pigments, e.g. B. Titan di oxide, cadmium sulfide, cadmium sulfide selenide, phthalocyanines, ultramarine blue or soot can be added.

Details of the other usual auxiliary and Additives are in the specialist literature, for example the monograph of J.H. Saunders and K.C. Fresh "High Polymers" Volume XVI, Polyurethanes, Part 1 and 2, publisher Interscience Publishers 1962 and 1964, or the Plastic manual, polyurethane, Volume VII, Carl Hanser Verlag, Munich, Vienna, 1st and 2nd editions, 1966 and 1983.  

The invention in the soft, rubber-elastic, cellular or compact PU elastomers containing bis (methoxyethoxy ethyl) phthalate can be used in technical or pure form. To Reduction in manufacturing costs are preferably the usual Manufacturing process available technical bis (methoxyethoxyethyl) - phthalate use.

To produce the PU elastomers, the organic ones, if necessary modified polyisocyanates (a), the polyhydroxyl compounds (b) and Chain extenders and / or crosslinking agents (c) in the presence or Absence of blowing agent (d), catalysts (e), auxiliaries and / or Additives (f) and bis (methoxyethoxyethyl) phthalate in such quantities implemented that the equivalence ratio of NCO groups of Polyisocyanates (a) for the sum of the reactive hydrogen atoms of the components ten (b) and (c) 0.90 to 1.25: 1, preferably 0.95 to 1.15: 1 and is in particular 1.00 to 1.05: 1.

The PU elastomers can be made continuously or discontinuously according to the methods described in the literature, such as. B. the one shot or Prepolymer process, produced using known mixing devices will. The TPU are expediently by the extruder method or preferably produced by the belt process.

To produce the compact PU cast elastomers, the starting components usually at a temperature of 15 to 90 ° C, preferred as homogeneously mixed from 20 to 35 ° C, the reaction mixture in one open, optionally tempered mold introduced and out let harden. To form cellular PU cast elastomers, the Structural components mixed in the same way and if necessary Tempered molding tool can be filled in the reaction Mixture to avoid a densified edge zone essentially can foam free of pressure or the molding tool is after filling closed and the reaction mixture with compression, e.g. B. with a Degree of compaction from 1.1 to 8, preferably from 1.2 to 6 and in particular let foam 2 to 4 in particular to form moldings. As soon as the Moldings have sufficient strength, they are removed from the mold. The demolding times are u. a. depending on the mold temperature, geometry and the reactivity of the reaction mixture and are more common wise in a range of 0.5 to 20 minutes.

As already stated, the TPU are preferably after the band ver drive manufactured. For this purpose, the structural components (a) to (c) and optionally (e) and / or (f) usually at temperatures above  the melting point of the structural components (a) to (c) using a Mixing head continuously mixed. The reaction mixture is on a Carrier, preferably a conveyor belt, and applied by a tempered zone. The reaction temperature in the tempered zone is suitably 60 to 200 ° C, preferably 100 to 180 ° C at a residence time of 0.05 to 1.0 hours, preferably 0.1 to 0.25 hours.

After the reaction has ended, the TPU obtained is allowed to cool, crushed or granulated, optionally tempered, and between stored or, if not already done, directly with the invention suitable bis (methoxyethoxyethyl) phthalate and optionally processed further.

The bis (methoxyethoxyethyl) phthalate usable according to the invention can PU elastomers, preferably the TPU, by various methods remains. The bis (methoxyethoxyethyl) phthalate can, for example, with the structural components (a) to (f), preferably (b) and / or (c) mixed are, so that the production of the PU elastomers according to the invention in Presence of the plasticizer is carried out. According to another ver driving variant, the bis (methoxyethoxyethyl) phthalate during the PU production of the reaction mixture which has not yet fully reacted be incorporated. The process variants mentioned are preferred Application for the production of compact or cellular PU cast elastomers.

Especially for the production of soft, rubber-elastic, compact TPU have proven their worth, however, and methods are therefore preferred, in which the bis (methoxyethoxyethyl) phthalate reacted into the optionally granulated TPU with a Shore hardness equal to or greater than 80 A is introduced. So the plasticizer by swelling, for example in a heatable horizontal mixer, under simultaneous Heating, e.g. B. incorporated at about 60 to 170 ° C granulated TPU will. The bis (methoxyethoxyethyl) phthalate can also be melted with the help of extruders, if necessary with special devices, such as B. dosing pumps are equipped, at temperatures from 180 to 220 ° C can be worked into the TPU. According to a particularly preferred applied process variant is in a 1st reaction stage in one usual mixer the fully reacted, granulated TPU the bis (methoxy Ethoxyethl) phthalate fed and the mixture is at a temperature from 75 to 120 ° C until the bis (methoxyethoxyethyl) - phthalate is essentially completely incorporated into the granules (Drying point). Depending on the type of TPU, the Granulate form u. a. usually mixing times from 1 to 20 hours,  preferably 2 to 12 hours required. Then the dry mix obtained in a second reaction stage in an extruder in molten form at 180 ° C to 220 ° C, preferably 195 to 210 ° C and a residence time of 0.5 to 5 minutes, preferably 1 to 5 minutes homogenized and then granulated.

The soft, rubber-elastic, cellular or compact according to the invention PU elastomers show reduced fogging, good water vapor permeability and depending on the composition of the base TPU an improved tension set. The high is also remarkable Rate of swelling of the bis (methoxyethoxyethyl) phthalate in the TPU.

The soft, rubber-elastic, compact PU elastomers according to the invention find use for the production of foils and compact shaped bodies, e.g. B. of pipes and profiles, preferably sealing profiles, and Production of cellular moldings with different spatial shapes.

Although the bis (methoxyethoxyethyl) phthalate is preferably a plasticizer used in PU elastomers, especially in TPU, it can be the same measure as a plasticizer for other polyisocyanate polyaddition products, e.g. B. Polyurethane foams are used.

Examples example 1

A cube granulate made of TPU with a Shore hardness of 95 A, the MFI of 7 at 190 ° C and a coating weight of 212 N, the main melting peak of the Hard segments of 215 ° C, measured by differential calorimetry, and an average edge length of about 3 to 5 mm, the was prepared by reacting a 1,4-butanediol-1,6-hexanediol polyadipates with a molecular weight of 2000 with 4,4'-diphenylmethane Diisocyanate and 1,4-butanediol was in a horizontal mixer at 80 ° C. treated with bis (methoxyethoxyethyl) phthalate until the TPU 25% by weight, based on the total weight, of the plasticizer contained. Then the bis- (methoxyethoxyethyl) phthalate containing TPU in homogenized in an extruder at 210 ° C and then granulated.

The TPU obtained had a Shore hardness of 82 A. The swelling speed at 80 ° C was 0.78 wt .-% per hour.  

Comparative Example I

The procedure was analogous to that of Example 1, but was used as Plasticizer bis (butoxyethyl) phthalate.

The TPU obtained had a Shore hardness of 85 A. The swelling rate at 80 ° C was 0.39% by weight per hour.

Example 2

80 parts by weight of a TPU, produced by reacting a butanediol 1,4-polyadipate with a molecular weight of 2000, 4,4'-diphenylmethane diisocyanate and 1,4-butanediol, which has a Shore hardness of 80 A and an MFI of 32 at 190 ° C and a coating weight of 212 N was included 20 parts by weight of bis (methoxyethoxyethyl) phthalate at 80 ° C for 15 hours mixed in a horizontal mixer. The bis (methoxy TPU containing ethoxyethyl) phthalate in an extruder at 210 ° C homo genized and then granulated.

The TPU obtained had a Shore hardness of 70 A. The relative Volatility of the bis (methoxyethoxyethyl) phthalate from the TPU at 130 ° C in a period of 24 hours (measured according to DIN 75 201, method B) was 1.3% by weight.

Comparative Example II

To produce a TPU with a Shore hardness of 70 A, in 75 parts by weight of the TPU described in Example 2 25 parts by weight Bis (methoxyethyl) phthalate introduced analogously to the information in Example 2.

The relative volatility of the bis (methoxyethyl) phthalate from the TPU 130 ° C within a period of 24 hours (measured according to DIN 75 201, Process B) was 12% by weight.

Example 3

A Shore hardness TPU of 80 A made by reaction of a polyoxytetramethylene glycol with a molecular weight of 1000, with 4,4'-diphenylmethane diisocyanate and 1,4-butanediol was analogous to Example 1 treated with bis (methoxyethoxyethyl) phthalate.

From the obtained TPU granules, the 25 wt .-%, based on the total weight, containing bis (methoxyethoxyethyl) phthalate and a Shore hardness  of 79 A, a 1 mm thick film was produced and on this at 23 ° C and 93% relative humidity according to DIN 53 122 a Water vapor permeability measured at 54 g.

Comparative Example III

A 1 mm thick film from the TPU described in Example 3 Shore hardness of 80 A resulted in relative air humidity at 23 ° C and 93 ° C according to DIN 53 122 a water vapor permeability of 18 g.

Claims (14)

1. Soft, rubber-elastic, cellular or compact polyurethane elastomers, containing bis (methoxyethoxyethyl) phthalate as plasticizer. 2. Soft, rubber-elastic, cellular or compact polyurethane elastomers, containing 100 parts by weight, 1 to 50 parts by weight of bis- (methoxyethoxyethyl) phthalate and
99 to 50 parts by weight of a polyurethane elastomer. 3. Rubber-elastic polyurethane elastomers with a Shore A hardness of 85 up to 60, containing 100 parts by weight, 1 to 50 parts by weight of bis (methoxyethoxyethyl) phthalate and 99 to 50 parts by weight of a thermoplastic polyurethane. 4. Rubber-elastic polyurethane elastomers with a Shore hardness A of 85 to 60, containing in 100 parts by weight, 1 to 50 parts by weight of bis (methoxyethoxyethyl) phthalate and
99 to 50 parts by weight of a thermoplastic polyurethane with a Shore A hardness of 95 to 80, a main melting peak of the hard segments of 210 to 220 ° C, measured by differential calorimetry, and a melt viscosity, corresponding to an MFI at 190 ° C and one Support weight from 212 N from 0.1 to 200. 5. Rubber-elastic polyurethane elastomers according to claim 3 or 4, characterized in that thermoplastic polyurethane elastomers are used for their production, which by reaction of

• a) aromatic diisocyanates with
• b) polyhydroxyl compounds with molecular weights of 500 to 8000 and
• c) chain extenders with molecular weights of 60 to 400

in the presence or absence of

• d) blowing agents
• e) catalysts and
• f) auxiliaries and / or additives

getting produced. 6. Soft, rubber-elastic polyurethane elastomers according to claim 1, characterized in that for their manufacture after Belt process thermoplastic polyurethanes used.   7. Process for the production of soft, rubber-elastic, cellular or compact polyurethane elastomers by reacting

• a) with organic polyisocyanates
• b) polyhydroxyl compounds with molecular weights of 500 to 8000 and
• c) chain extenders and / or crosslinking agents with molecular weights of 60 to 400

in the presence or absence of

• d) blowing agents,
• e) catalysts,
• f) auxiliaries and / or additives,

wherein the structural components (a) to (f) before the preparation of the Reaction mixture during manufacture or from construction components (a) to (c) and optionally (e) and (f) after Belt or extrusion process thermoplastic Polyurethane incorporates a plasticizer, characterized in that that the plasticizer consists of bis (methoxyethoxyethyl) phthalate. 8. Use of soft, rubber-elastic, compact polyurethane Elastomers according to claim 1 for the production of films, moldings, Tubes and profiles, preferably sealing profiles. 9. Use of soft, rubber-elastic polyurethane elastomers after Claim 1 for the production of cellular moldings. 10. Use of bis (methoxyethoxyethyl) phthalate as a plasticizer for Polyisocyanate polyaddition products.