CA2136125A1 - Heat-stable, highly resilient, abrasion-resistant polyurethane/polyester three-block polyadducts, their preparation and their use - Google Patents
Heat-stable, highly resilient, abrasion-resistant polyurethane/polyester three-block polyadducts, their preparation and their useInfo
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- CA2136125A1 CA2136125A1 CA002136125A CA2136125A CA2136125A1 CA 2136125 A1 CA2136125 A1 CA 2136125A1 CA 002136125 A CA002136125 A CA 002136125A CA 2136125 A CA2136125 A CA 2136125A CA 2136125 A1 CA2136125 A1 CA 2136125A1
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- polyester
- polyurethane
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- thermoplastic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Heat-stable, highly resilient, abrasion-resistant polyurethane/
polyester three-block polyadducts are obtainable by reacting A) at least one thermoplastic polyester and B) at least one thermoplastic polyurethane elastomer which pre-ferably has a content of free NCO groups of from 0.5 to 4% by weight and a total content of NCO groups of from 0.75 to 5 %
by weight, based in each case on the total weight of the thermoplastic polyurethane, and in turn is obtainable by reacting organic diisocyanates (Ba) with relatively high molecular weight polyhydroxy compounds (Bb) and low molecular weight chain extenders (Bc) with the use of an NCO index of more than 115, advantageously at from 180 to 300°C, and are used for the production of moldings.
polyester three-block polyadducts are obtainable by reacting A) at least one thermoplastic polyester and B) at least one thermoplastic polyurethane elastomer which pre-ferably has a content of free NCO groups of from 0.5 to 4% by weight and a total content of NCO groups of from 0.75 to 5 %
by weight, based in each case on the total weight of the thermoplastic polyurethane, and in turn is obtainable by reacting organic diisocyanates (Ba) with relatively high molecular weight polyhydroxy compounds (Bb) and low molecular weight chain extenders (Bc) with the use of an NCO index of more than 115, advantageously at from 180 to 300°C, and are used for the production of moldings.
Description
Heat-stable, highly re9ilient, abrasion-resistant polyurethane/
polyester three-block polyadducts, their preparation and their use Heat-stable, highly resilient, abrasion-resistant polyurethane/
polyester three-block polyadducts are obtainable by reacting A) at least one thermoplastic polyester, abbreviated below to PES, and B) at least one thermoplastic polyurethane elastomer, referred to below as TPU, which preferably has a content of free NC0 y~U~ of from 0.5 to 4~ by weight and a total content of NC0 y~Up~ of from 0.75 to 5~ by weight, based in each case on the total weight of the TPU, and in turn is obtainable by reacting organic diisocyanates (Ba) with relatively high molecular weight polyhydroxy compounds (~b) and low molecular weight chain extenders (~c) with the use of an i~ocyanàte index greater than 115, and are used for the production of moldings.
Thermoplastic polymer mixtures comprising at least one PES, for 25 example an aromatic polycarbonate or polyalkylene terephthalate, and one TPU are known. Such polymer mixtures comprising at least 2 completely reacted thermoplastics, for example (co)polymers, polycondensates o~ polyadducts, which are usually mixed as dry granules at room temperature and then compounded by kneading or 30 extruding at elevated temperatures, for example at from 1~0 to 250 C, are also referred to as blends. In blends, the individual thermoplastics used are present in separate phases without there being any chemical bond. Where there are sufficiently great dif-ferences in polarity between the individual plastics phases, the 35 latter can be di~solved out of the blend using suitable solvents.
In contrast, block copolymers, polyadducts, ~uch as TPU, or poly-condensates, for example polyetheramides, consist of different segments or phases linked by a chemical bond. TPU consists, for 40 example, of a flexible phase comprising relatively high molecular weight polyhydroxy compound~, for example of polyester or poly-ether segments, and of a rigid phase comprising urethane groups, formed from low molecular weight chain extenders and polyiso-cyanates. Similarly, polyetheramides contain a polyether flexible 45 phase and a polyamide rigid phase.
`' - 22l36125 ~ TPUs are u6ually prepared by reacting a prepared, relatively high molecular weight, essentially linear polyhydroxy compound with an organic diisocyanate and a low molecular weight chain extender by the one-shot or prepolymer process in a suitable apparatus. De-5 pending on the chemical structure and reactivity of the starting materials used, the reaction temperature employed and the reac-tion rate dependent thereon, TPUs having a more or less pro-nounced block-type binding of the flexible and rigid segments are obtained. In the case of TPU, a well defined block structure re-10 sults in, inter alia, high resilience. If the block structure isadversely affected, for example by excessively high reaction tem-peratures or excessively long reaction times, this leads to a dramatic deterioration in the mechanical properties of the TPU.
15 As stated above, PES/TPU blends are known. According to DE-A-26 46 947 ~GB-A 1 513 197), polymer blends having excellent flexibility at low temperatures and high impact strength are obtained by thorough mixing of from 50 to 25 parts by weight of polybutylene terephthalate and from 50 to 75 parts by weight of 20 TPU. To improve the hardness of TPU or the moldability of poly-butylene terephthalate, according to CA-A 1 111 984 PES/TPU
blends which contain from 5 to 95% by weight of polybutylene terephthalate and from 95 to 5% by weight of TPU, based on the total weight, are prepared. Thermoplastic polymer blends having a 25 high modulus of elasticity, a high Shore D hardness, a high elongation at break and excellent low-temperature impact strength consist, according to EP-A 0 334 186, of from 70 to 95 parts by weight of a TPU, prepared from a diisocyanate (Ba), a hydroxyl-or amino-containing compound (~b) and a short-chain chain 30 extender (~c), the amount of (Bb) being from 5 to 20~ by weight, based on the sum (Ba) to (Bc), and the ratio of NCO groups of component (Ba) to the Zerewitinoff-active groups of components (Bb) and (Bc) being from 0.9 to 1.15, and from 30 to 5 parts by weight of a thermoplastic terephthalate which may be mixed with 35 at least one further thermoplastic component. EP-A 0 420 016 (CA-A 20 24 715) describes toughened polyurethane/polyester molding materials which contain from 30 to 90 parts by weight of TPU, from 5 to 65 parts by weight of PES and from 5 to 30 part6 by weight of at least one graft rubber based on a polybutadiene 40 or on a polyacrylate, the percentages being based on 100 parts by weight. The disadvantage of these molding materials is that, although their low-temperature flexibility is considerably improved, at the same time their heat 6tability is reduced.
polyester three-block polyadducts, their preparation and their use Heat-stable, highly resilient, abrasion-resistant polyurethane/
polyester three-block polyadducts are obtainable by reacting A) at least one thermoplastic polyester, abbreviated below to PES, and B) at least one thermoplastic polyurethane elastomer, referred to below as TPU, which preferably has a content of free NC0 y~U~ of from 0.5 to 4~ by weight and a total content of NC0 y~Up~ of from 0.75 to 5~ by weight, based in each case on the total weight of the TPU, and in turn is obtainable by reacting organic diisocyanates (Ba) with relatively high molecular weight polyhydroxy compounds (~b) and low molecular weight chain extenders (~c) with the use of an i~ocyanàte index greater than 115, and are used for the production of moldings.
Thermoplastic polymer mixtures comprising at least one PES, for 25 example an aromatic polycarbonate or polyalkylene terephthalate, and one TPU are known. Such polymer mixtures comprising at least 2 completely reacted thermoplastics, for example (co)polymers, polycondensates o~ polyadducts, which are usually mixed as dry granules at room temperature and then compounded by kneading or 30 extruding at elevated temperatures, for example at from 1~0 to 250 C, are also referred to as blends. In blends, the individual thermoplastics used are present in separate phases without there being any chemical bond. Where there are sufficiently great dif-ferences in polarity between the individual plastics phases, the 35 latter can be di~solved out of the blend using suitable solvents.
In contrast, block copolymers, polyadducts, ~uch as TPU, or poly-condensates, for example polyetheramides, consist of different segments or phases linked by a chemical bond. TPU consists, for 40 example, of a flexible phase comprising relatively high molecular weight polyhydroxy compound~, for example of polyester or poly-ether segments, and of a rigid phase comprising urethane groups, formed from low molecular weight chain extenders and polyiso-cyanates. Similarly, polyetheramides contain a polyether flexible 45 phase and a polyamide rigid phase.
`' - 22l36125 ~ TPUs are u6ually prepared by reacting a prepared, relatively high molecular weight, essentially linear polyhydroxy compound with an organic diisocyanate and a low molecular weight chain extender by the one-shot or prepolymer process in a suitable apparatus. De-5 pending on the chemical structure and reactivity of the starting materials used, the reaction temperature employed and the reac-tion rate dependent thereon, TPUs having a more or less pro-nounced block-type binding of the flexible and rigid segments are obtained. In the case of TPU, a well defined block structure re-10 sults in, inter alia, high resilience. If the block structure isadversely affected, for example by excessively high reaction tem-peratures or excessively long reaction times, this leads to a dramatic deterioration in the mechanical properties of the TPU.
15 As stated above, PES/TPU blends are known. According to DE-A-26 46 947 ~GB-A 1 513 197), polymer blends having excellent flexibility at low temperatures and high impact strength are obtained by thorough mixing of from 50 to 25 parts by weight of polybutylene terephthalate and from 50 to 75 parts by weight of 20 TPU. To improve the hardness of TPU or the moldability of poly-butylene terephthalate, according to CA-A 1 111 984 PES/TPU
blends which contain from 5 to 95% by weight of polybutylene terephthalate and from 95 to 5% by weight of TPU, based on the total weight, are prepared. Thermoplastic polymer blends having a 25 high modulus of elasticity, a high Shore D hardness, a high elongation at break and excellent low-temperature impact strength consist, according to EP-A 0 334 186, of from 70 to 95 parts by weight of a TPU, prepared from a diisocyanate (Ba), a hydroxyl-or amino-containing compound (~b) and a short-chain chain 30 extender (~c), the amount of (Bb) being from 5 to 20~ by weight, based on the sum (Ba) to (Bc), and the ratio of NCO groups of component (Ba) to the Zerewitinoff-active groups of components (Bb) and (Bc) being from 0.9 to 1.15, and from 30 to 5 parts by weight of a thermoplastic terephthalate which may be mixed with 35 at least one further thermoplastic component. EP-A 0 420 016 (CA-A 20 24 715) describes toughened polyurethane/polyester molding materials which contain from 30 to 90 parts by weight of TPU, from 5 to 65 parts by weight of PES and from 5 to 30 part6 by weight of at least one graft rubber based on a polybutadiene 40 or on a polyacrylate, the percentages being based on 100 parts by weight. The disadvantage of these molding materials is that, although their low-temperature flexibility is considerably improved, at the same time their heat 6tability is reduced.
- The stated PES/TPU blends furthermore have the disadvantage that, owing to the use of TPU having an index of, usually, from 90 to 110, no chemical bonding takes place between the PES and TPU
phase.
According to DE-A 41 28 274, thermoplastic materials having high strength, a high modulus of elasticity and improved heat distor-tion resistance consi~t of from 99.5 to 60/o by weight of TPU and from 0.5 to 40% by weight of a PES, which are prepared at from 10 180 to 250 C with the addition of from 0.05 to 5% by weight of an organic polyisocyanate. The disadvantage of this process is the high concentration of monomeric, often gaseous di- or triiso-cyanates in the preparation of the polymer blend. The added mono-meric di- or triisocyanate undergoes only incomplete reaction 15 during the residence time in, for example, the reaction extruder and escapes in the form of vapor at the extrusion head.
It is an object of the present invention to prepare materials having very good heat stability, high resilience and good abra-20 sion resistance by a process which is technically easy to handle.
We have found that this object i8 achieved, surprisingly, bythree-block polyadducts based on a PES and on a modified TPU, in which the polyester blocks of the PES and the rigid and flexible 25 segments of the TPU are linked to one another by a chemical bond.
The present invention therefore relates to polyurethane/polyester three-block polyadducts which are obtainable by reacting 30 A) at least one thermoplastic polyester, preferably polybutylene terephthalate and/or polyethylene terephthalate, and B) at least one thermoplastic polyurethane elastomer which in turn is obtainable by reacting Ba) organic diisocyanates with Bb) relatively high molecular weight polyhydroxy compounds and Bc) low molecular weight chain extenders, with the use of an NCo index (isocyanate index) greater than 115, preferably from 116 to 135.
phase.
According to DE-A 41 28 274, thermoplastic materials having high strength, a high modulus of elasticity and improved heat distor-tion resistance consi~t of from 99.5 to 60/o by weight of TPU and from 0.5 to 40% by weight of a PES, which are prepared at from 10 180 to 250 C with the addition of from 0.05 to 5% by weight of an organic polyisocyanate. The disadvantage of this process is the high concentration of monomeric, often gaseous di- or triiso-cyanates in the preparation of the polymer blend. The added mono-meric di- or triisocyanate undergoes only incomplete reaction 15 during the residence time in, for example, the reaction extruder and escapes in the form of vapor at the extrusion head.
It is an object of the present invention to prepare materials having very good heat stability, high resilience and good abra-20 sion resistance by a process which is technically easy to handle.
We have found that this object i8 achieved, surprisingly, bythree-block polyadducts based on a PES and on a modified TPU, in which the polyester blocks of the PES and the rigid and flexible 25 segments of the TPU are linked to one another by a chemical bond.
The present invention therefore relates to polyurethane/polyester three-block polyadducts which are obtainable by reacting 30 A) at least one thermoplastic polyester, preferably polybutylene terephthalate and/or polyethylene terephthalate, and B) at least one thermoplastic polyurethane elastomer which in turn is obtainable by reacting Ba) organic diisocyanates with Bb) relatively high molecular weight polyhydroxy compounds and Bc) low molecular weight chain extenders, with the use of an NCo index (isocyanate index) greater than 115, preferably from 116 to 135.
4 2l36l2s Such TPUs (B) which can be used according to the invention advan-tageously have a content of free NC0 yLOu~S of from 0-5 to 4% by weight and a total content of NC0 y-OU~S of from 0.75 to 5% by weight, based on the total weight of the TPU.
The present invention furthermore relates to a process for the preparation of the novel TPU/PES three-block polyadducts by reacting the PES (A) and the special TPU (B) which can be used according to the invention at from 180 to 300 C, as claimed in 10 claim 9, and the use of the novel TPU/PES three-block polyadducts for the production of extruded products, preferably of moldings as claimed in claims 10 and 11.
The novel TPU/PES three-block polyadducts consist of two rigid 15 phase blocks, the PES rigid phase comprising, preferably, poly-butylene terephthalate, also abbreviated to PBT, or polyethylene terephthalate, also abbreviated to PET, or of mixtures of PBT and PET, and the TPU rigid phase, consisting of the urethane rigid segment, the oligomeric or polymeric reaction product of an 20 organic diisocyanate and a low molecular weight chain extender, preferably an alkanediol and/or dialkylene glycol, and the resilient urethane flexible segment, consisting of the relatively high molecular weight polyhydroxy compound, preferably a relatively high molecular weight polyesterdiol and/or polyether-25 diol, which are chemically bonded to one another in the form ofblocks by urethane and/or amide bonds. The urethane or amide bonds are formed on the one hand from terminal hydroxyl or carboxyl groups of the PES and on the other hand from terminal isocyanate groups of the TPU. The novel TPU/PES three-block poly-30 adducts have a virtually ideal combination of mechanicalproperties, consisting of high heat stability, resilience and abrasion resistance, the excellent long-term heat stability at high storage temperatures, for example at from 150 to 170 C, being particularly noteworthy.
If the PES are reacted with corresponding amounts of TPU which may be used according to the invention, three-block polyadducts which have high heat stability, high elongation at break and high toughness and in which the individual structural blocks are 40 chemically bonded are obtained.
The PES (A) and TPU (B) which may be used in the preparation of the novel TPU/PES three-block polyadducts correspond to the prior art.
_ A) PES (A) suitable for this ~ul~ose are described in the literature and contain at least one aromatic ring which is bonded in the polycondensate main chain and iB derived from an aromatic dicarboxylic acid. The aromatic ring may further-more be substituted, for example by halogen, eg. chlorine or bromine, and/or by linear or branched alkyl of, preferably, 1 to 4, in particular 1 or 2, carbon atoms, eg. methyl, ethyl, isopropyl, n-propyl and/or n-butyl, isobutyl or tert-butyl.
The PES (A) may be prepared by polycondensation of aromatic dicarboxylic acids or mixture~ of aromatic and aliphatic and/
or cycloaliphatic dicarboxylic acids and the corresponding ester-forming derivatives, such as dicarboxylic anhydrides, monoe~ters and/or diesters where the alcohol radical is advantageously of not more than 4 carbon atoms, with aliphatic dihydroxy cG~.~ounds at elevated temperatures, for example from 160 to 260 C, in the presence or absence of esterification catalysts.
Examples of preferably used aromatic dicarboxylic acids are the naphthalenedicarboxylic acids, isophthalic acid and in particular terephthalic acid or mixtures of these dicarboxylic acids. If mixtures of aromatic and (cyclo)aliphatic dicarboxylic acids are used, up to 10 mol%
of the aromatic dicarboxylic acids may be replaced by aliphatic and/or cycloaliphatic dicarboxylic acid~ of, advan-tageously, 4 to 14 carbon atoms, eg. succinic, adipic, azelaic, sebacic, dodecanedioic and/or cyclohexanedicarboxyl-ic acid.
Preferred aliphatic dihydroxy compounds are alkanediols of 2 to 6 carbon atoms and cycloalkanediols of 5 to 7 carbon atoms. 1,2-Ethanediol, 1,4-butanediol, 1,6-hexanediol, neo-pentylglycol and 1,4-cyclohexanediol or mixtures of at least two of the stated diols may be mentioned by way of example and are preferably used.
In particular, the polyalkylene terephthalates of alkanediols of 2 to 6 carbon atoms have proven excellent as PES (A), so that preferably PET and particularly preferably PBT or mixtures of PET and P~T are used.
The relative viscosity of the PES (A) is usually from 0.8 to 1.8, preferably from 1.0 to 1.8, in particular from 1.2 to 1.6, measured in a 0. 5% strength by weight solution in a ` ` 6 2 1 3 6I 2 5 - phenol/1,2-dichlorobenzene mixture having a weight ratio of 1:1, at 25-C.
B) The TPU (B) which may be used for the preparation of the novel TPU/PES three-block polyadducts may be prepared, for example, by reacting Ba) organic, preferably aromatic diisocyanates, in particular diphenylmethane 4,4'-diisocyanate, with Bb) at least one relatively high molecular weight polyhydroxy compound, preferably an essentially bifunctional poly-hydroxy coll,pound having a molecular weight of from 500 to 8000, in particular polyalkylene glycol polyadipates where the alkylene radical i8 of 2 to 6 carbon atoms and which have molecular weights of from 500 to 6000, or polyoxytetramethylene glycol having a molecular weight of from 500 to 3200, and Bc) at least one low molecular weight chain extender, advan-tageously having a molecular weight of less than 400, preferably from 60 to 300, in particular 1,4-butanediol, in the absence or, preferably, presence of Bd) catalysts and, if required, Be) additives at elevated temperatures.
Regarding the TPU components (Ba) to (Bc) and, if required, (Bd) and/or (Be), the following may be stated: -35 Ba) exAmrles of suitable organic diisocyanates (Ba) are aliphatic, cycloaliphatic and, preferably, aromatic diiso-cyanates. Specific examples are: aliphatic diisocyanates, such as hexamethylene 1,6-diisocyanate, 2-methylpenta-methylene 1,5-diisocyanate, 2-ethyl-2-butylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate or mixtures of at least two of the stated aliphatic diiso-cyanates, cycloaliphatic diisocyanates, such as isophorone diisocyanate, cyclohexane 1,4-diisocyanate, l-methylcyclo-hexane 2,4- and 2,6-diisocyanate and the corresponding isomer mixtures, dicyclohexylmethane 4,4'-, 2,4'- and 2,2'-diiso-cyanate and the corresponding isomer mixtures and, pre-ferably, aromatic diisocyanates, such as toluylene ~ 2,4-diisocyanate, mixtures of toluylene 2,4- and 2,6-diiso-cyanate, diphenylmethane 4,4'-, 2,4'- and 2,2'-diisocyanate, mixtures of diphenylmethane 2,4'- and 4,4'-diisocyanate, urethane-modified liquid diphenylmethane 4,4'- and/or 2,4'-diisocyanates, 4,4'-diisocyanato-1,2-diphenylethane and mixtures of 4,4'-, 2,4'- and/or 2,2'-diiso-cyanato-1,2-diphenylethane, advantageously those having a 4,4'-diisocyanato-1,2-diphenylethane content of at least 95 by weight. Diphenylmethane diisocyanate isomer mixtures having a diphenylmethane 4,4'-diisocyanate content of more than 96% by weight and in particular substantially pure diphenylmethane 4,4'-diisocyanate are preferably uced.
The organic diisocyanates may be replaced in minor amounts, for example in amounts of up to 3, preferably up to 1, mol~, based on the organic diisocyanate, by a polyisocyanate having a functionality of 3 or higher, the amounts of which, however, must be limited so that polyurethanes which can be processed by a thermoplastic method are still obtained. A
larger amount of such isocyanates having a functionality of more than 2 is advantageously compensated by the presence of compounds having a functionality of less than 2 and posses-sing reactive hydrogen atoms, 80 that excessive chemical crosslink;ng of the polyurethane is avoided. Examples of iso-cyanates having a functionality of more than 2 are mixtures of diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates, ie. crude MDI, and liquid diphenylmethane 4,4'- and/or 2,4'-diisocyanates modified with isocyanurate, urea, biuret, allophanate, urethane and/or carbodiimide group~.
Examples of suitable monofunctional compounds which have a reactive hydrogen atom and may also be used as molecular weight regulators are: monoamines, eg. butylamine, dibutyl-amine, octylamine, stearylamine, N-methylstearylamine, pyrro-lidone, piperidine and cyclohexylamine, and monoalcohols, eg.
butanol, amyl alcohol, l-ethylhexanol, octanol, dodecanol, cyclohexanol and ethylene glycol monoethyl ether.
40 Bb) Preferred relatively high molecular weight polyhydroxy com-pounds (B) having molecular weights of from 500 to 8000 are polyetherols and in particular polyesterols. However, other hydroxyl-cont~; n; ng polymers having ether or ester groups as bridge members, for example polyacetals, such as polyoxy-methylenes, and especially water-insoluble formal~, for example polybutanediol formal and polyhexanediol formal, and polycarbonates, in particular those obtained from diphenyl ~ carbonate and 1,6-hexanediol and prepared by transesterifica-tion, are also suitable. The polyhydroxy compounds must be at least predominantly linear, ie. must be bifunctional for the ~u.~o~es of the isocyanate reaction. The stated polyhydroxy c~ Gund~ may be used as individual components or in the form of mixtures.
Suitable polyetherols can be prepared by known processes, for example by anionic polymerization with Al kAl 1 metal hydroxides, such as sodium hydroxide or potassium hydroxide, or alkali metal alcoholates, such as sodium methylate, sodium ethylate, potassium ethylate or potassium isopropylate, as catalysts and with the addition of at least one initiator molecule which preferably contains 2 bound reactive hydrogen atoms, or by cationic polymerization with Lewis acids, such as antimony pentachloride, boron fluoride etherate, etc., or bleaching earth as catalysts, from one or more alkylene oxides where the alkylene radical is of 2 to 4 carbon atoms.
Examples of suitable alkylene oxide~ are 1,3-propylene oxide, 1,2- and 2,3-butylene oxide and preferably tetrahydrofuran, ethylene oxide and 1,2-propylene oxide. The alkylene oxides may be used individually, alternately in succession or as mixtures. Examples of suitable initiator molecules are: wa-ter, organic dicarboxylic acids, such as succinic acid, adipic acid and/or glutaric acid, N-alkyldialkanolamines, eg.
N-methyl- and N-ethyldiethanolamine, and preferably dihydric alcohols which may contain bound ether bridges, eg. ethane-diol, 1,2- and 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, 2-methyl-1,5-pentanediol and 2-ethyl-1,4-butanediol. The initiator molecules may be u~ed individually or a~ mixtures.
Polyetherols obtained from 1,2-propylene oxide and ethylene oxide and in which more than 50%, preferably from 60 to 80%, of the OH groups are primary hydroxyl groups and at least some of the ethylene oxide is arranged as a terminal block are preferably used. Such polyetherols may be obtained, for example, by polymerizing first the 1,2-propylene oxide and then the ethylene oxide with the initiator molecule or first copolymerizing the total amount of 1,2-propylene oxide as a mixture with some of the ethylene oxide and then polymerizing on the remainder of the ethylene oxide, or gradually polymer-izing first some of the ethylene oxide, then the total amount of 1,2-propylene oxide and thereafter the remainder of the ethylene oxide with the initiator molecule.
9 213612~
In particular, the hydroxyl-cont~ n; ng polymers of tetra-hydrofuran, the polyoxytetramethylene glycols, are very suitable.
~he essentially linear polyetherols have molecular weights of from 500 to 8000, preferably fro~ 600 to 6000, and in par-ticular from 800 to 3500, the polyoxytetramethylene glycols preferably having molecular weights of from 500 to 3200, in particular from 600 to 2200. The polyetherols may be used both individually and in the form of mixtures with one another.
Suitable polyesterols may be prepared, for example, from dicarboxylic acids of 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 tereph-thalic acid. The dicarboxylic acids may be used individually or as mixtures, for example in the form of a mixture of succinic, glutaric and adipic acid. For the preparation of the polyesterols, it may be advantageous to use the corres-ponding dicarboxylic acid derivatives, such as dicarboxylic mono- or diesters where the alcohol radical is of 1 to 4 carbon atoms, dicarboxylic anhydrides or dicarbonyl dichlorides, instead of the dicarboxylic acids. Examples of polyhydric alcohols are alkanediols of 2 to 10, preferably 2 to 6, carbon atoms, such as ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decane-diol, 2,2-dimethyl-1,3-propanediol, 1,2-propanediol and dialkylene glycols, eg. diethylene glycol and dipropylene glycol. Depending on the desired properties, the polyhydric alcohols may be used alone or, if required, as mixtures with one another.
Polyesters of carbonic acid with the stated polyhydric alcohols, in particular alkanediols of 4 to 6 carbon atoms, such as 1,4-butanediol and/or 1,6-hexanediol, condensates of w-hydroxycarboxylic acids, for example w-hydroxycaproic acid, and preferably polymers of lactones, for example unsubsti-tuted or substituted ~-caprolactones, are also suitable.
Preferably used polyesterols are polyalkylene glycol poly-adipates where the alkylene radical is of 2 to 6 carbon atoms, eg. ethanediol polyadipates, 1,4-butanediol poly-adipates, ethanediol 1,4-butanediol polyadipates, hexanediol neopentylglycol polyadipates, or 1,~-hexane-diol 1,4-butanediol polyadipates, and polycaprolactones.
The polyesterols have molecular weights of from 500 to 6000, preferably from 800 to 3500.
Bc) Preferred chain extenders (Bc) having molecular weights of less than 400, preferably from 60 to 300, are alkanediols of 2 to 12, preferably 2, 4 or 6, carbon atoms and/or alkylene glycols, eg. ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol. However, diesters of terephthalic acid with glycols of 2 to 4 carbon atoms, eg. bis-ethylene glycol or bis-1,4-butanediol tereph-thalate, and hydroxyalkylene ethers of hydroquinone, eg.
1,4-di-(b-hydroxyethyl)-hydroquinone, and polytetramethylene glycols having molecular weights of from 162 to 378 are also suitable.
In order to establish the hardness and melt flow index, the components may be varied in relatively wide molar ratios, the hardness and the melt viscosity increasing with increasing content of chain extender (c) while the melt flow index decreases.
For the preparation of more flexible TPUs (B), for example those having a Shore A hardness of less than 95, preferably from 95 to 75 Shore A, for example, the substantially bifunc-tional polyhydroxy ~-~...pounds (Bb) and alkanediols (Bc) may advantageously be used in molar ratios of from 1:1 to 1:5, preferably from 1:1.5 to 1:4.5, so that the resulting mixtures of (Bb) and (Bc) have a hydroxyl equivalent weight of more than 200, in particular from 230 to 450, whereas for the preparation of more rigid TPUs (B), for example those having a Shore A hardness of more than 98, preferably from 55 to 75 Shore D, the molar ratios of (Bb) to (Bc) are from 1:5.5 to 1:15, preferably from 1:6 to 1:12, BO that the resulting mixtures of (Bb) and (Bc) have a hydroxyl equiva-lent weight of from 110 to 200, preferably from 120 to 180.
40 Bd) The TPUs (B) may be prepared in the absence or, preferably, presence of catalysts (Bd). Suitable catalysts, which in par-ticular accelerate the reaction between the NCO yL ~U~S of the diisocyanates (Ba) and the hydroxyl groups of the components (Bb) and (Bc), are the conventional tertiary amines known from the prior art, for example triethylamine, dimethylcyclo-hexyl~ine, N-methylmorpholine, N,N'-dimethylpiperazine, diazabicyclo[2.2.2]octane and the like, and in particular `t ` 11 ` 2136125 - organometallic compounds, ~uch as titanates, iron co~pounds, tin cG...~o~rlds~ eg. tin diacetate, tin dioctoate, tin dilaurate or the dialkyltin salts of aliphatic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate or the like. The catalysts are usually used in amounts of from 0.001 to 0.1 part by weight per 100 parts by weight of the mixture of polyhydroxy compounds (Bb) and chain extenders (Bc).
10 In addition to catalysts (Bd), additives (Be) may also be incorporated into the components. Examples are lubricants, inhibitors, hydrolysis stabilizers, light stabilizers, heat stabilizers or stabilizers against discoloration, flameproofing agents, dyes, pigments, inorganic and/or organic fillers and 15 reinforcing agents.
For this purpose, the additives (Be) may be introduced into the components or into the reaction mixture for the preparation of the TPUs (B). In another process variant, the additives (Be) can, 20 however, be mixed with the PES (A) and the TPU (B) and then melted, or they are incorporated directly into the melt of PES
(A) and TPU (B). The last-mentioned method i5 used in particular for introducing fibers and/or particulate fillers.
25 When no further information is given below about the additives which may be used, this information may be obtained from the technical literature, for example from the monograph by J.H. Saunders and K.C. Frisch, High Polymers, Volume XVI, Poly-urethane, Parts 1 and 2 (Interscience Publishers 1962 and 1964), 30 Kunststoff-Handbuch, Volume 7, Polyurethane, 1st and 2nd editions (carl Hanser Verlag, 1966 and 1983) or DE-A 29 01 774.
For the preparation of the TPUs (B), the components (Ba), (Bb) and (Bc) are reacted, preferably in the presence of catalysts 35 (Bd) and, if required, additives (Be), in amounts guch that the ratio of the number of equivalents of NC0 groups of the diiso-cyanates to the sum of the hydroxyl groups of components (Bb) and (Bc) is greater than 1.15:1, preferably from 1.16:1 to 1.35:1, and in particular from 1.20:1 to 1.35:1.
The TPUs ( B) which may be used according to the invention advan-tageously have a content of free NC0 groups of 0.5 to 4, pre-ferably from 1.0 to 2.5, % by weight and a total content of NC0 groups of from 0.75 to 5, preferably from 1.25 to 3.5, in par-45 ticular from 1.25 to 3.0, % by weight, based in each case on thetotal weight of the TPU (B). The total content of NCo groups is defined as the sum of the free NC0 groups plus the NC0 groups ,~ bound in allophanate, biuret and uretdione groups. The TPUs may be prepared, for example, by the extruder or, preferably, belt method by batchwise or continuous mixing of the components (Ba) to (Bc) and, if required, (Bd) and/or (Be), complete reaction of 5 the reaction mixture in the extruder or on a supporting belt at from 60 to 250 C, preferably from 70 to 150 C, and subsequent granulation of the resulting TPU (B). It may be advantageous to heat the resulting TPUs (B) at from 80 to 120 C, preferably from 100 to 110 C, over a period of from 1 to 24 hours before further 10 processing to the novel TPU/PES three-block polyadducts.
The TPUs (B) are preferably prepared by the belt method, as stated above. For this purpose, the ~-G".~onents (Ba) to (Bc) and, if required, (Bd) and/or (Be) are continuously mixed at above the 15 melting point of ~-o".~onents (Ba) to (Bc) with the aid of a mixing head. The reaction mixture is applied to a support, preferably a conveyor belt, for example of metal, and is passed at a speed of from 1 to 20, preferably from 4 to 10, m/minute through a heated zone having a length of from 1 to 20 m, preferably from 3 to 20 10 m. The reaction temperature in the heated zone is from 60 to 200 C, preferably from 80 to 180 C. Depending on the diisocyanate content of the reaction mixture, the reaction is controlled by cooling or heating in such a way that at least 70%, preferably at least 80~, of the isocyanate groups of the diisocyanates are con-25 verted and the reaction mixture solidifies at the chosen reactiontemperature. Owing to the free isocyanate groups in the solidi-fied reaction product, TPUs (B) having a very low melt viscosity or a high melt index are obtained.
30 For the preparation of the novel TPU/PES three-block polyadducts, the components PES (A) and TPU (B) may be varied within wide ratios, for example in PES/TPU weight ratios of from 95:5 to 5:95. In a preferred embodiment, the TPU/PES three-block poly-adducts contain or, preferably, consist of A) from 70 to 5, preferably from 50 to 10, % by weight of at least one PES (A) and B) from 30 to 95, preferably from 50 to 90, ~ by weight of at least one TPU (B), the percentages being based on the total weight.
The novel TPU/PES polyadducts may be prepared by any processes 45 under reaction conditions under which the free NCO groups of the TPU (B) react with the hydroxyl and/or carboxyl groups of the PES
(A). For example, the storage-stable PES (A) and TPU (B), in granular or powder form, may be mixed at up to about 150 C, pre-ferably from 0 to 50 C, and then melted, or the PES (A) and the TPU (B) can be mixed directly in the melt.
5 The novel TPU/PES three-block polyadducts are advantageously pre-pared at from 180 to 300 C, preferably from 190 to 260 C, and in particular from 220 to 245 C, and in a residence time from 1 to 30, preferably from 2 to 10, minutes using, for example, the free-flowing, softened or, preferably, molten state of the PES
10 (A) and TPU (B), for example by stirring, treating in a roll mill, kneading or, preferably, extrusion, for example with the use of conventional plastication apparatuses, such as Brabender or Banbury mills, kneaders and extruders, preferably a single-screw extruder, double-screw extruder or transfer molding/mixing 15 extruder.
In the most advantageous and therefore preferably used prepara-tion process, the PES (A) and TPU (B) are melted together at from 220 to 245 C, preferably in an extruder, additives (Be) are, if 20 required, incorporated into the melt, the latter is then allowed to cool and the TPU/PES three-block polyadducts obtained are com-minuted.
In contrast to TPU and TPU-contA~ n; ng polymer blends, the novel 25 TPU/PES three-block polyadducts are essentially insoluble in sol-vents conventionally used for polyurethanes, for example dimethylformamide or dimethylformamide/amine mixtures. In con-trast to TPU-cont~i ni ng polymer blends, the TPU cannot be dis-solved out of the novel TPU/PES three-block polyadduct with the 30 stated solvents. Apart from the virtual insolubility of the TPU~
PES three-block polyadducts in the solvents suitable for TPU, the decrease in the content of free NC0 groups in the end product also demonstrates the reaction between PES (A) and TPU (B).
35 As stated above, the novel TPU/PES three-block polyadducts have high heat stability, in particular long-term heat stability, high resilience and abrasion resistance and can readily be processed to give moldings, separation into the components PES and TPU
taking place neither in the melt nor in the molding.
Ex~ples The following components were used for the preparation of the novel TPU/PES three-block polyadducts and of the TPU/PES blends 45 as C~mrA rative products:
` ` 14 2 1 3 61 2 S
A) Thermoplastic PES
A1: Polybutylene terephthalate having terminal hydroxyl groups and a relative viscosity of 130, measured in a 0.5%
strength by weight solution in 1:1 (w/w) phenol/1,2-dichlorobenzene at 25 C (molecular weight about . 35,000).
A2: Polybutylene terephthalate having terminal hydroxyl groups and a relative viscosity of 140, measured as described in A1 (molecular weight about 40,000).
A3: Polyethylene terephthalate having terminal hydroxyl groups and a relative viscosity of 90, measured as described in A1.
B) Thermoplastic polyurethane elastomers Comparative products:
BI: TPU, prepared by reacting a mixture consisting of 1000 parts by weight of a polycaprolactonediol having an average molecular weight of 2000 (calculated from the hydroxyl number determined), 133 parts by weight of 1,4-butanediol and 10 parts by weight of 2,2',6,6'-tetraisopropyldiphenyl-carbodiimide with 520 parts by weight of diphenylmethane 4,4'-diisocyanate (MDI) at from 80 to 170 C by the belt method.
The ratio of NCO to OH groups was 1.05:1, corresponding to an NCO index of 105.
35 BII: TPU, prepared by reacting a mixture consisting of 1000 parts by weight of a polyoxytetramethylene glycol having an average molecular weight of 1000 (calcu-lated from the hydroxyl number determined) and 126 parts by weight of 1,4-butanediol with 600 parts by weight of 4,4'-MDI, similarly to BI.
The ratio of NCO to OH groups was 1.1:1, corresponding to an NCO index of 100.1.
- BIII: TPU, prepared by reacting a mixture consisting of t 1000 parts by weight of a poly(ethanediol 1,4-butanediol adipate) having an average molecular weight of 2000 (calculated from the hydroxyl number determined)~
112 parts by weight of 1,4-butanediol and 10 parts by weight of 2,2',6,6'-tetraisopropyldiphenyl-carhs~;;~;de with 440 parts by weight of 4,4'-MDI, similarly to BI.
The ratio of NCO to OR groups was 1.008:1, corresponding to an NCO index of 100.8.
Thermoplastic polyurethanes which may be used according to the 15 invention Bl: TPU prepared similarly to BI but with the use of 111 parts by weight of 1,4-butanediol.
The ratio of NCO to OH groups was 1.2:1, corresponding to an NCO index of 120. The TPU had an analytically determined con-tent of free NCO groups of 2.0% by weight and a total content of NCO groups of 2.1% by weight.
25 B2: TPU prepared similarly to BII but with the uQe of 90 parts by weight of 1,4-butanediol.
The ratio of NCO to OH groups was 1.2:1, corresponding to an NCO index of 120. The TPU had an analytically determined con-tent of free NCO groups of 1.7% by weight and a total content of NCO groups of 1.9% by weight.
B3: TPU prepared similarly to BIII but with the use of 87 parts by weight of 1,4-butanediol.
The ratio of NCO to OH groups was 1.2:1, corresponding to an NCO index of 120. The TPU had a content of free NCO groups of 2.4% by weight and a total content of NCO groups of 2.5% by weight.
B4: TPU prepared by reacting a mixture consi~ting of 1000 parts by weight of a poly(l,4-butanediol adipate) having an average molecular weight of 2500 (calculated from the hydroxyl number determined), 68 parts by weight of 1,4-butanediol and , 16 2136125 ; _ 10 parts by weight of - 2,2',6,6'-tetraisopropyldiphenylcarbodiimide with 360 parts by weight of 4,4'-MDI, ~imilarly to BI.
The ratio of NCO to OH groups was 1.25:1, corresponding to an NCO index of 125.
B5: TPU, prepared similarly to BI but with the use of 10S parts by weight of 1,4-butanediol.
The ratio of NCO to OH groups wa~ 1.25:1, corresponding to an NCO index of 125.
15 B6: TPU, prepared similarly to BII but with the use of 94 parts by weight of 1,4-butanediol.
The ratio of NCO to OH groups was 1.35:1, corresponding to an NCO index of 135.
B7: TPU, prepared similarly to BIII but with the use of 96 parts by weight of 1,4-butanediol.
The ratio of NCO to OH groups was 1.16:1, corresponding to an NCO index of 116.
Comparative Examples I to III
and Examples 1 to 9 30 Process variant 1 For the preparation of the novel TPU/PES three-block polyadducts or TPU/PES blends as comparative products, the PES and TPU
granules were thoroughly mixed at 23 C and the mixture was 35 introduced into a twin-screw extruder, melted at from 220 to 240 C, reacted within a residence time of from 2 to 5 minutes and then extruded into a water bath.
After granulation and drying, the TPU/PES three-block polyadducts 40 or blends were molded with the aid of an injection molding apparatus at from 210 to 235 C, depending on the hardness, to give test specimens for which, without further aftertreatment, the density according to DIN 53 479, the Shore D hardness according to DIN 53 505, the tensile strength according to DIN 53 504, the 45 elongation at break according to DIN 53 504, the tear propagation , 17 21~fil2S
_ ~trength according to DIN 53 515 and the abrasion according to DIN 53 516 were measured.
The tensile strength and elongation at break after storage at 5 elevated temperatures for 500 hours in a through-circulation oven at 130 C, 150 C and 170 C were also measured.
Process variant 2 - 10 The procedure was similar to that of Process variant 1, except that a single-screw extruder was u~ed instead of the twin-screw extruder.
Process variant 3 The TPU was prepared in a reaction extruder in the presence of the PES.
The components (Ba), (Bb) and (Bc) were thoroughly mixed in 20 amounts corresponding to the high ratio of the number of equiva-lents of NCO groups to that of OH groups in a twin-screw extruder and were reacted. The resulting TPU having a high NCO index was reacted, in the further course of the reaction in the twin-screw extruder, with added polybutylene terephthalate to give the 25 three-block polyadduct.
The type and amount of the PES (A) and TPU (B) used and the mechanical properties measured on the test specimens are summa-rized in Tables I and II below.
Table I
Co~para- Starting ~aterials Proces~ Density ~ard- Ten~ile Elonga- Tear Abra~ion tive variant nes~ ~trength tion Example at tion break strength P~S TPU [g/c~3J Ishorel lMPal l~] tN/mml tmn3]
A~ount Type A~ount Type lPart~3 by wt.l lPart~ by wt.]
I~ 50 Al50 8I 21.24 60 D 33 470 117 76 II~ 30 A270 BII 11.165 40 D 16 490 52 71 III~ 33 Al67 8III 31.255 47 D 18 410 61 127 Exa~ple~
1 50 Al50 - 81 21.245 64 D 50 440 149 20 2 30 A270 B2 11.17 50 D 55 600 80 27 3 33 A167 83 31.255 52 D 61 560 95 31 4 30 A270 Bl 21.21 53 D 64 560 99 26 ~_~
A250 84 21.255 63 D 50 480 145 48 C~
The present invention furthermore relates to a process for the preparation of the novel TPU/PES three-block polyadducts by reacting the PES (A) and the special TPU (B) which can be used according to the invention at from 180 to 300 C, as claimed in 10 claim 9, and the use of the novel TPU/PES three-block polyadducts for the production of extruded products, preferably of moldings as claimed in claims 10 and 11.
The novel TPU/PES three-block polyadducts consist of two rigid 15 phase blocks, the PES rigid phase comprising, preferably, poly-butylene terephthalate, also abbreviated to PBT, or polyethylene terephthalate, also abbreviated to PET, or of mixtures of PBT and PET, and the TPU rigid phase, consisting of the urethane rigid segment, the oligomeric or polymeric reaction product of an 20 organic diisocyanate and a low molecular weight chain extender, preferably an alkanediol and/or dialkylene glycol, and the resilient urethane flexible segment, consisting of the relatively high molecular weight polyhydroxy compound, preferably a relatively high molecular weight polyesterdiol and/or polyether-25 diol, which are chemically bonded to one another in the form ofblocks by urethane and/or amide bonds. The urethane or amide bonds are formed on the one hand from terminal hydroxyl or carboxyl groups of the PES and on the other hand from terminal isocyanate groups of the TPU. The novel TPU/PES three-block poly-30 adducts have a virtually ideal combination of mechanicalproperties, consisting of high heat stability, resilience and abrasion resistance, the excellent long-term heat stability at high storage temperatures, for example at from 150 to 170 C, being particularly noteworthy.
If the PES are reacted with corresponding amounts of TPU which may be used according to the invention, three-block polyadducts which have high heat stability, high elongation at break and high toughness and in which the individual structural blocks are 40 chemically bonded are obtained.
The PES (A) and TPU (B) which may be used in the preparation of the novel TPU/PES three-block polyadducts correspond to the prior art.
_ A) PES (A) suitable for this ~ul~ose are described in the literature and contain at least one aromatic ring which is bonded in the polycondensate main chain and iB derived from an aromatic dicarboxylic acid. The aromatic ring may further-more be substituted, for example by halogen, eg. chlorine or bromine, and/or by linear or branched alkyl of, preferably, 1 to 4, in particular 1 or 2, carbon atoms, eg. methyl, ethyl, isopropyl, n-propyl and/or n-butyl, isobutyl or tert-butyl.
The PES (A) may be prepared by polycondensation of aromatic dicarboxylic acids or mixture~ of aromatic and aliphatic and/
or cycloaliphatic dicarboxylic acids and the corresponding ester-forming derivatives, such as dicarboxylic anhydrides, monoe~ters and/or diesters where the alcohol radical is advantageously of not more than 4 carbon atoms, with aliphatic dihydroxy cG~.~ounds at elevated temperatures, for example from 160 to 260 C, in the presence or absence of esterification catalysts.
Examples of preferably used aromatic dicarboxylic acids are the naphthalenedicarboxylic acids, isophthalic acid and in particular terephthalic acid or mixtures of these dicarboxylic acids. If mixtures of aromatic and (cyclo)aliphatic dicarboxylic acids are used, up to 10 mol%
of the aromatic dicarboxylic acids may be replaced by aliphatic and/or cycloaliphatic dicarboxylic acid~ of, advan-tageously, 4 to 14 carbon atoms, eg. succinic, adipic, azelaic, sebacic, dodecanedioic and/or cyclohexanedicarboxyl-ic acid.
Preferred aliphatic dihydroxy compounds are alkanediols of 2 to 6 carbon atoms and cycloalkanediols of 5 to 7 carbon atoms. 1,2-Ethanediol, 1,4-butanediol, 1,6-hexanediol, neo-pentylglycol and 1,4-cyclohexanediol or mixtures of at least two of the stated diols may be mentioned by way of example and are preferably used.
In particular, the polyalkylene terephthalates of alkanediols of 2 to 6 carbon atoms have proven excellent as PES (A), so that preferably PET and particularly preferably PBT or mixtures of PET and P~T are used.
The relative viscosity of the PES (A) is usually from 0.8 to 1.8, preferably from 1.0 to 1.8, in particular from 1.2 to 1.6, measured in a 0. 5% strength by weight solution in a ` ` 6 2 1 3 6I 2 5 - phenol/1,2-dichlorobenzene mixture having a weight ratio of 1:1, at 25-C.
B) The TPU (B) which may be used for the preparation of the novel TPU/PES three-block polyadducts may be prepared, for example, by reacting Ba) organic, preferably aromatic diisocyanates, in particular diphenylmethane 4,4'-diisocyanate, with Bb) at least one relatively high molecular weight polyhydroxy compound, preferably an essentially bifunctional poly-hydroxy coll,pound having a molecular weight of from 500 to 8000, in particular polyalkylene glycol polyadipates where the alkylene radical i8 of 2 to 6 carbon atoms and which have molecular weights of from 500 to 6000, or polyoxytetramethylene glycol having a molecular weight of from 500 to 3200, and Bc) at least one low molecular weight chain extender, advan-tageously having a molecular weight of less than 400, preferably from 60 to 300, in particular 1,4-butanediol, in the absence or, preferably, presence of Bd) catalysts and, if required, Be) additives at elevated temperatures.
Regarding the TPU components (Ba) to (Bc) and, if required, (Bd) and/or (Be), the following may be stated: -35 Ba) exAmrles of suitable organic diisocyanates (Ba) are aliphatic, cycloaliphatic and, preferably, aromatic diiso-cyanates. Specific examples are: aliphatic diisocyanates, such as hexamethylene 1,6-diisocyanate, 2-methylpenta-methylene 1,5-diisocyanate, 2-ethyl-2-butylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate or mixtures of at least two of the stated aliphatic diiso-cyanates, cycloaliphatic diisocyanates, such as isophorone diisocyanate, cyclohexane 1,4-diisocyanate, l-methylcyclo-hexane 2,4- and 2,6-diisocyanate and the corresponding isomer mixtures, dicyclohexylmethane 4,4'-, 2,4'- and 2,2'-diiso-cyanate and the corresponding isomer mixtures and, pre-ferably, aromatic diisocyanates, such as toluylene ~ 2,4-diisocyanate, mixtures of toluylene 2,4- and 2,6-diiso-cyanate, diphenylmethane 4,4'-, 2,4'- and 2,2'-diisocyanate, mixtures of diphenylmethane 2,4'- and 4,4'-diisocyanate, urethane-modified liquid diphenylmethane 4,4'- and/or 2,4'-diisocyanates, 4,4'-diisocyanato-1,2-diphenylethane and mixtures of 4,4'-, 2,4'- and/or 2,2'-diiso-cyanato-1,2-diphenylethane, advantageously those having a 4,4'-diisocyanato-1,2-diphenylethane content of at least 95 by weight. Diphenylmethane diisocyanate isomer mixtures having a diphenylmethane 4,4'-diisocyanate content of more than 96% by weight and in particular substantially pure diphenylmethane 4,4'-diisocyanate are preferably uced.
The organic diisocyanates may be replaced in minor amounts, for example in amounts of up to 3, preferably up to 1, mol~, based on the organic diisocyanate, by a polyisocyanate having a functionality of 3 or higher, the amounts of which, however, must be limited so that polyurethanes which can be processed by a thermoplastic method are still obtained. A
larger amount of such isocyanates having a functionality of more than 2 is advantageously compensated by the presence of compounds having a functionality of less than 2 and posses-sing reactive hydrogen atoms, 80 that excessive chemical crosslink;ng of the polyurethane is avoided. Examples of iso-cyanates having a functionality of more than 2 are mixtures of diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates, ie. crude MDI, and liquid diphenylmethane 4,4'- and/or 2,4'-diisocyanates modified with isocyanurate, urea, biuret, allophanate, urethane and/or carbodiimide group~.
Examples of suitable monofunctional compounds which have a reactive hydrogen atom and may also be used as molecular weight regulators are: monoamines, eg. butylamine, dibutyl-amine, octylamine, stearylamine, N-methylstearylamine, pyrro-lidone, piperidine and cyclohexylamine, and monoalcohols, eg.
butanol, amyl alcohol, l-ethylhexanol, octanol, dodecanol, cyclohexanol and ethylene glycol monoethyl ether.
40 Bb) Preferred relatively high molecular weight polyhydroxy com-pounds (B) having molecular weights of from 500 to 8000 are polyetherols and in particular polyesterols. However, other hydroxyl-cont~; n; ng polymers having ether or ester groups as bridge members, for example polyacetals, such as polyoxy-methylenes, and especially water-insoluble formal~, for example polybutanediol formal and polyhexanediol formal, and polycarbonates, in particular those obtained from diphenyl ~ carbonate and 1,6-hexanediol and prepared by transesterifica-tion, are also suitable. The polyhydroxy compounds must be at least predominantly linear, ie. must be bifunctional for the ~u.~o~es of the isocyanate reaction. The stated polyhydroxy c~ Gund~ may be used as individual components or in the form of mixtures.
Suitable polyetherols can be prepared by known processes, for example by anionic polymerization with Al kAl 1 metal hydroxides, such as sodium hydroxide or potassium hydroxide, or alkali metal alcoholates, such as sodium methylate, sodium ethylate, potassium ethylate or potassium isopropylate, as catalysts and with the addition of at least one initiator molecule which preferably contains 2 bound reactive hydrogen atoms, or by cationic polymerization with Lewis acids, such as antimony pentachloride, boron fluoride etherate, etc., or bleaching earth as catalysts, from one or more alkylene oxides where the alkylene radical is of 2 to 4 carbon atoms.
Examples of suitable alkylene oxide~ are 1,3-propylene oxide, 1,2- and 2,3-butylene oxide and preferably tetrahydrofuran, ethylene oxide and 1,2-propylene oxide. The alkylene oxides may be used individually, alternately in succession or as mixtures. Examples of suitable initiator molecules are: wa-ter, organic dicarboxylic acids, such as succinic acid, adipic acid and/or glutaric acid, N-alkyldialkanolamines, eg.
N-methyl- and N-ethyldiethanolamine, and preferably dihydric alcohols which may contain bound ether bridges, eg. ethane-diol, 1,2- and 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, 2-methyl-1,5-pentanediol and 2-ethyl-1,4-butanediol. The initiator molecules may be u~ed individually or a~ mixtures.
Polyetherols obtained from 1,2-propylene oxide and ethylene oxide and in which more than 50%, preferably from 60 to 80%, of the OH groups are primary hydroxyl groups and at least some of the ethylene oxide is arranged as a terminal block are preferably used. Such polyetherols may be obtained, for example, by polymerizing first the 1,2-propylene oxide and then the ethylene oxide with the initiator molecule or first copolymerizing the total amount of 1,2-propylene oxide as a mixture with some of the ethylene oxide and then polymerizing on the remainder of the ethylene oxide, or gradually polymer-izing first some of the ethylene oxide, then the total amount of 1,2-propylene oxide and thereafter the remainder of the ethylene oxide with the initiator molecule.
9 213612~
In particular, the hydroxyl-cont~ n; ng polymers of tetra-hydrofuran, the polyoxytetramethylene glycols, are very suitable.
~he essentially linear polyetherols have molecular weights of from 500 to 8000, preferably fro~ 600 to 6000, and in par-ticular from 800 to 3500, the polyoxytetramethylene glycols preferably having molecular weights of from 500 to 3200, in particular from 600 to 2200. The polyetherols may be used both individually and in the form of mixtures with one another.
Suitable polyesterols may be prepared, for example, from dicarboxylic acids of 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 tereph-thalic acid. The dicarboxylic acids may be used individually or as mixtures, for example in the form of a mixture of succinic, glutaric and adipic acid. For the preparation of the polyesterols, it may be advantageous to use the corres-ponding dicarboxylic acid derivatives, such as dicarboxylic mono- or diesters where the alcohol radical is of 1 to 4 carbon atoms, dicarboxylic anhydrides or dicarbonyl dichlorides, instead of the dicarboxylic acids. Examples of polyhydric alcohols are alkanediols of 2 to 10, preferably 2 to 6, carbon atoms, such as ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decane-diol, 2,2-dimethyl-1,3-propanediol, 1,2-propanediol and dialkylene glycols, eg. diethylene glycol and dipropylene glycol. Depending on the desired properties, the polyhydric alcohols may be used alone or, if required, as mixtures with one another.
Polyesters of carbonic acid with the stated polyhydric alcohols, in particular alkanediols of 4 to 6 carbon atoms, such as 1,4-butanediol and/or 1,6-hexanediol, condensates of w-hydroxycarboxylic acids, for example w-hydroxycaproic acid, and preferably polymers of lactones, for example unsubsti-tuted or substituted ~-caprolactones, are also suitable.
Preferably used polyesterols are polyalkylene glycol poly-adipates where the alkylene radical is of 2 to 6 carbon atoms, eg. ethanediol polyadipates, 1,4-butanediol poly-adipates, ethanediol 1,4-butanediol polyadipates, hexanediol neopentylglycol polyadipates, or 1,~-hexane-diol 1,4-butanediol polyadipates, and polycaprolactones.
The polyesterols have molecular weights of from 500 to 6000, preferably from 800 to 3500.
Bc) Preferred chain extenders (Bc) having molecular weights of less than 400, preferably from 60 to 300, are alkanediols of 2 to 12, preferably 2, 4 or 6, carbon atoms and/or alkylene glycols, eg. ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol. However, diesters of terephthalic acid with glycols of 2 to 4 carbon atoms, eg. bis-ethylene glycol or bis-1,4-butanediol tereph-thalate, and hydroxyalkylene ethers of hydroquinone, eg.
1,4-di-(b-hydroxyethyl)-hydroquinone, and polytetramethylene glycols having molecular weights of from 162 to 378 are also suitable.
In order to establish the hardness and melt flow index, the components may be varied in relatively wide molar ratios, the hardness and the melt viscosity increasing with increasing content of chain extender (c) while the melt flow index decreases.
For the preparation of more flexible TPUs (B), for example those having a Shore A hardness of less than 95, preferably from 95 to 75 Shore A, for example, the substantially bifunc-tional polyhydroxy ~-~...pounds (Bb) and alkanediols (Bc) may advantageously be used in molar ratios of from 1:1 to 1:5, preferably from 1:1.5 to 1:4.5, so that the resulting mixtures of (Bb) and (Bc) have a hydroxyl equivalent weight of more than 200, in particular from 230 to 450, whereas for the preparation of more rigid TPUs (B), for example those having a Shore A hardness of more than 98, preferably from 55 to 75 Shore D, the molar ratios of (Bb) to (Bc) are from 1:5.5 to 1:15, preferably from 1:6 to 1:12, BO that the resulting mixtures of (Bb) and (Bc) have a hydroxyl equiva-lent weight of from 110 to 200, preferably from 120 to 180.
40 Bd) The TPUs (B) may be prepared in the absence or, preferably, presence of catalysts (Bd). Suitable catalysts, which in par-ticular accelerate the reaction between the NCO yL ~U~S of the diisocyanates (Ba) and the hydroxyl groups of the components (Bb) and (Bc), are the conventional tertiary amines known from the prior art, for example triethylamine, dimethylcyclo-hexyl~ine, N-methylmorpholine, N,N'-dimethylpiperazine, diazabicyclo[2.2.2]octane and the like, and in particular `t ` 11 ` 2136125 - organometallic compounds, ~uch as titanates, iron co~pounds, tin cG...~o~rlds~ eg. tin diacetate, tin dioctoate, tin dilaurate or the dialkyltin salts of aliphatic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate or the like. The catalysts are usually used in amounts of from 0.001 to 0.1 part by weight per 100 parts by weight of the mixture of polyhydroxy compounds (Bb) and chain extenders (Bc).
10 In addition to catalysts (Bd), additives (Be) may also be incorporated into the components. Examples are lubricants, inhibitors, hydrolysis stabilizers, light stabilizers, heat stabilizers or stabilizers against discoloration, flameproofing agents, dyes, pigments, inorganic and/or organic fillers and 15 reinforcing agents.
For this purpose, the additives (Be) may be introduced into the components or into the reaction mixture for the preparation of the TPUs (B). In another process variant, the additives (Be) can, 20 however, be mixed with the PES (A) and the TPU (B) and then melted, or they are incorporated directly into the melt of PES
(A) and TPU (B). The last-mentioned method i5 used in particular for introducing fibers and/or particulate fillers.
25 When no further information is given below about the additives which may be used, this information may be obtained from the technical literature, for example from the monograph by J.H. Saunders and K.C. Frisch, High Polymers, Volume XVI, Poly-urethane, Parts 1 and 2 (Interscience Publishers 1962 and 1964), 30 Kunststoff-Handbuch, Volume 7, Polyurethane, 1st and 2nd editions (carl Hanser Verlag, 1966 and 1983) or DE-A 29 01 774.
For the preparation of the TPUs (B), the components (Ba), (Bb) and (Bc) are reacted, preferably in the presence of catalysts 35 (Bd) and, if required, additives (Be), in amounts guch that the ratio of the number of equivalents of NC0 groups of the diiso-cyanates to the sum of the hydroxyl groups of components (Bb) and (Bc) is greater than 1.15:1, preferably from 1.16:1 to 1.35:1, and in particular from 1.20:1 to 1.35:1.
The TPUs ( B) which may be used according to the invention advan-tageously have a content of free NC0 groups of 0.5 to 4, pre-ferably from 1.0 to 2.5, % by weight and a total content of NC0 groups of from 0.75 to 5, preferably from 1.25 to 3.5, in par-45 ticular from 1.25 to 3.0, % by weight, based in each case on thetotal weight of the TPU (B). The total content of NCo groups is defined as the sum of the free NC0 groups plus the NC0 groups ,~ bound in allophanate, biuret and uretdione groups. The TPUs may be prepared, for example, by the extruder or, preferably, belt method by batchwise or continuous mixing of the components (Ba) to (Bc) and, if required, (Bd) and/or (Be), complete reaction of 5 the reaction mixture in the extruder or on a supporting belt at from 60 to 250 C, preferably from 70 to 150 C, and subsequent granulation of the resulting TPU (B). It may be advantageous to heat the resulting TPUs (B) at from 80 to 120 C, preferably from 100 to 110 C, over a period of from 1 to 24 hours before further 10 processing to the novel TPU/PES three-block polyadducts.
The TPUs (B) are preferably prepared by the belt method, as stated above. For this purpose, the ~-G".~onents (Ba) to (Bc) and, if required, (Bd) and/or (Be) are continuously mixed at above the 15 melting point of ~-o".~onents (Ba) to (Bc) with the aid of a mixing head. The reaction mixture is applied to a support, preferably a conveyor belt, for example of metal, and is passed at a speed of from 1 to 20, preferably from 4 to 10, m/minute through a heated zone having a length of from 1 to 20 m, preferably from 3 to 20 10 m. The reaction temperature in the heated zone is from 60 to 200 C, preferably from 80 to 180 C. Depending on the diisocyanate content of the reaction mixture, the reaction is controlled by cooling or heating in such a way that at least 70%, preferably at least 80~, of the isocyanate groups of the diisocyanates are con-25 verted and the reaction mixture solidifies at the chosen reactiontemperature. Owing to the free isocyanate groups in the solidi-fied reaction product, TPUs (B) having a very low melt viscosity or a high melt index are obtained.
30 For the preparation of the novel TPU/PES three-block polyadducts, the components PES (A) and TPU (B) may be varied within wide ratios, for example in PES/TPU weight ratios of from 95:5 to 5:95. In a preferred embodiment, the TPU/PES three-block poly-adducts contain or, preferably, consist of A) from 70 to 5, preferably from 50 to 10, % by weight of at least one PES (A) and B) from 30 to 95, preferably from 50 to 90, ~ by weight of at least one TPU (B), the percentages being based on the total weight.
The novel TPU/PES polyadducts may be prepared by any processes 45 under reaction conditions under which the free NCO groups of the TPU (B) react with the hydroxyl and/or carboxyl groups of the PES
(A). For example, the storage-stable PES (A) and TPU (B), in granular or powder form, may be mixed at up to about 150 C, pre-ferably from 0 to 50 C, and then melted, or the PES (A) and the TPU (B) can be mixed directly in the melt.
5 The novel TPU/PES three-block polyadducts are advantageously pre-pared at from 180 to 300 C, preferably from 190 to 260 C, and in particular from 220 to 245 C, and in a residence time from 1 to 30, preferably from 2 to 10, minutes using, for example, the free-flowing, softened or, preferably, molten state of the PES
10 (A) and TPU (B), for example by stirring, treating in a roll mill, kneading or, preferably, extrusion, for example with the use of conventional plastication apparatuses, such as Brabender or Banbury mills, kneaders and extruders, preferably a single-screw extruder, double-screw extruder or transfer molding/mixing 15 extruder.
In the most advantageous and therefore preferably used prepara-tion process, the PES (A) and TPU (B) are melted together at from 220 to 245 C, preferably in an extruder, additives (Be) are, if 20 required, incorporated into the melt, the latter is then allowed to cool and the TPU/PES three-block polyadducts obtained are com-minuted.
In contrast to TPU and TPU-contA~ n; ng polymer blends, the novel 25 TPU/PES three-block polyadducts are essentially insoluble in sol-vents conventionally used for polyurethanes, for example dimethylformamide or dimethylformamide/amine mixtures. In con-trast to TPU-cont~i ni ng polymer blends, the TPU cannot be dis-solved out of the novel TPU/PES three-block polyadduct with the 30 stated solvents. Apart from the virtual insolubility of the TPU~
PES three-block polyadducts in the solvents suitable for TPU, the decrease in the content of free NC0 groups in the end product also demonstrates the reaction between PES (A) and TPU (B).
35 As stated above, the novel TPU/PES three-block polyadducts have high heat stability, in particular long-term heat stability, high resilience and abrasion resistance and can readily be processed to give moldings, separation into the components PES and TPU
taking place neither in the melt nor in the molding.
Ex~ples The following components were used for the preparation of the novel TPU/PES three-block polyadducts and of the TPU/PES blends 45 as C~mrA rative products:
` ` 14 2 1 3 61 2 S
A) Thermoplastic PES
A1: Polybutylene terephthalate having terminal hydroxyl groups and a relative viscosity of 130, measured in a 0.5%
strength by weight solution in 1:1 (w/w) phenol/1,2-dichlorobenzene at 25 C (molecular weight about . 35,000).
A2: Polybutylene terephthalate having terminal hydroxyl groups and a relative viscosity of 140, measured as described in A1 (molecular weight about 40,000).
A3: Polyethylene terephthalate having terminal hydroxyl groups and a relative viscosity of 90, measured as described in A1.
B) Thermoplastic polyurethane elastomers Comparative products:
BI: TPU, prepared by reacting a mixture consisting of 1000 parts by weight of a polycaprolactonediol having an average molecular weight of 2000 (calculated from the hydroxyl number determined), 133 parts by weight of 1,4-butanediol and 10 parts by weight of 2,2',6,6'-tetraisopropyldiphenyl-carbodiimide with 520 parts by weight of diphenylmethane 4,4'-diisocyanate (MDI) at from 80 to 170 C by the belt method.
The ratio of NCO to OH groups was 1.05:1, corresponding to an NCO index of 105.
35 BII: TPU, prepared by reacting a mixture consisting of 1000 parts by weight of a polyoxytetramethylene glycol having an average molecular weight of 1000 (calcu-lated from the hydroxyl number determined) and 126 parts by weight of 1,4-butanediol with 600 parts by weight of 4,4'-MDI, similarly to BI.
The ratio of NCO to OH groups was 1.1:1, corresponding to an NCO index of 100.1.
- BIII: TPU, prepared by reacting a mixture consisting of t 1000 parts by weight of a poly(ethanediol 1,4-butanediol adipate) having an average molecular weight of 2000 (calculated from the hydroxyl number determined)~
112 parts by weight of 1,4-butanediol and 10 parts by weight of 2,2',6,6'-tetraisopropyldiphenyl-carhs~;;~;de with 440 parts by weight of 4,4'-MDI, similarly to BI.
The ratio of NCO to OR groups was 1.008:1, corresponding to an NCO index of 100.8.
Thermoplastic polyurethanes which may be used according to the 15 invention Bl: TPU prepared similarly to BI but with the use of 111 parts by weight of 1,4-butanediol.
The ratio of NCO to OH groups was 1.2:1, corresponding to an NCO index of 120. The TPU had an analytically determined con-tent of free NCO groups of 2.0% by weight and a total content of NCO groups of 2.1% by weight.
25 B2: TPU prepared similarly to BII but with the uQe of 90 parts by weight of 1,4-butanediol.
The ratio of NCO to OH groups was 1.2:1, corresponding to an NCO index of 120. The TPU had an analytically determined con-tent of free NCO groups of 1.7% by weight and a total content of NCO groups of 1.9% by weight.
B3: TPU prepared similarly to BIII but with the use of 87 parts by weight of 1,4-butanediol.
The ratio of NCO to OH groups was 1.2:1, corresponding to an NCO index of 120. The TPU had a content of free NCO groups of 2.4% by weight and a total content of NCO groups of 2.5% by weight.
B4: TPU prepared by reacting a mixture consi~ting of 1000 parts by weight of a poly(l,4-butanediol adipate) having an average molecular weight of 2500 (calculated from the hydroxyl number determined), 68 parts by weight of 1,4-butanediol and , 16 2136125 ; _ 10 parts by weight of - 2,2',6,6'-tetraisopropyldiphenylcarbodiimide with 360 parts by weight of 4,4'-MDI, ~imilarly to BI.
The ratio of NCO to OH groups was 1.25:1, corresponding to an NCO index of 125.
B5: TPU, prepared similarly to BI but with the use of 10S parts by weight of 1,4-butanediol.
The ratio of NCO to OH groups wa~ 1.25:1, corresponding to an NCO index of 125.
15 B6: TPU, prepared similarly to BII but with the use of 94 parts by weight of 1,4-butanediol.
The ratio of NCO to OH groups was 1.35:1, corresponding to an NCO index of 135.
B7: TPU, prepared similarly to BIII but with the use of 96 parts by weight of 1,4-butanediol.
The ratio of NCO to OH groups was 1.16:1, corresponding to an NCO index of 116.
Comparative Examples I to III
and Examples 1 to 9 30 Process variant 1 For the preparation of the novel TPU/PES three-block polyadducts or TPU/PES blends as comparative products, the PES and TPU
granules were thoroughly mixed at 23 C and the mixture was 35 introduced into a twin-screw extruder, melted at from 220 to 240 C, reacted within a residence time of from 2 to 5 minutes and then extruded into a water bath.
After granulation and drying, the TPU/PES three-block polyadducts 40 or blends were molded with the aid of an injection molding apparatus at from 210 to 235 C, depending on the hardness, to give test specimens for which, without further aftertreatment, the density according to DIN 53 479, the Shore D hardness according to DIN 53 505, the tensile strength according to DIN 53 504, the 45 elongation at break according to DIN 53 504, the tear propagation , 17 21~fil2S
_ ~trength according to DIN 53 515 and the abrasion according to DIN 53 516 were measured.
The tensile strength and elongation at break after storage at 5 elevated temperatures for 500 hours in a through-circulation oven at 130 C, 150 C and 170 C were also measured.
Process variant 2 - 10 The procedure was similar to that of Process variant 1, except that a single-screw extruder was u~ed instead of the twin-screw extruder.
Process variant 3 The TPU was prepared in a reaction extruder in the presence of the PES.
The components (Ba), (Bb) and (Bc) were thoroughly mixed in 20 amounts corresponding to the high ratio of the number of equiva-lents of NCO groups to that of OH groups in a twin-screw extruder and were reacted. The resulting TPU having a high NCO index was reacted, in the further course of the reaction in the twin-screw extruder, with added polybutylene terephthalate to give the 25 three-block polyadduct.
The type and amount of the PES (A) and TPU (B) used and the mechanical properties measured on the test specimens are summa-rized in Tables I and II below.
Table I
Co~para- Starting ~aterials Proces~ Density ~ard- Ten~ile Elonga- Tear Abra~ion tive variant nes~ ~trength tion Example at tion break strength P~S TPU [g/c~3J Ishorel lMPal l~] tN/mml tmn3]
A~ount Type A~ount Type lPart~3 by wt.l lPart~ by wt.]
I~ 50 Al50 8I 21.24 60 D 33 470 117 76 II~ 30 A270 BII 11.165 40 D 16 490 52 71 III~ 33 Al67 8III 31.255 47 D 18 410 61 127 Exa~ple~
1 50 Al50 - 81 21.245 64 D 50 440 149 20 2 30 A270 B2 11.17 50 D 55 600 80 27 3 33 A167 83 31.255 52 D 61 560 95 31 4 30 A270 Bl 21.21 53 D 64 560 99 26 ~_~
A250 84 21.255 63 D 50 480 145 48 C~
6 70 Al30 85 11.27 73 D 57 480 201 22 ~,~
7 95 Al 5 i36 11.31 77 D 52 360 140 46 8 50 A350 ~1 11.22 68 D 51 370 131 32 9 10 Al90 87 21.135 41 D 42 360 39 24 Comr~rative Example9 I to III gave TPU/PES blends having inhomogeneous, poor phase adhesion Table II
MechAn;cal properties after storage at elevated temperatures for 500 hours in a through-circulation oven Examples Tensile strength [MPa] Elongation at break [%]
2 31 . 22 23 460 200 120 6 49 46 44 420 4Z0 2~0 t ~
MechAn;cal properties after storage at elevated temperatures for 500 hours in a through-circulation oven Examples Tensile strength [MPa] Elongation at break [%]
2 31 . 22 23 460 200 120 6 49 46 44 420 4Z0 2~0 t ~
Claims (11)
1. A polyurethane/polyester three-block polyadduct obtainable by reacting A) at least one thermoplastic polyester and B) at least one thermoplastic polyurethane elastomer which in turn is obtainable by reacting Ba) organic diisocyanates with Bb) relatively high molecular weight polyhydroxy com-pounds and Bc) low molecular weight chain extenders using an NCO index of more than 115.
2. A polyurethane/polyester three-block polyadduct as claimed in claim 1, wherein the thermoplastic polyurethane elastomers (B) have a content of free NCO groups of from 0.5 to 4% by weight and a total content of NCO groups of from 0.75 to 5%
by weight, based on the total weight of the thermoplastic polyurethane.
by weight, based on the total weight of the thermoplastic polyurethane.
3. A polyurethane/polyester three-block polyadduct obtainable by reacting A) at least one thermoplastic polyester and B) at least one thermoplastic polyurethane elastomer which in turn is obtainable by reacting Ba) at least one organic diisocyanate with Bb) at least one relatively high molecular weight poly-hydroxy compound and Bc) at least one chain extender having a molecular weight of less than 400 in the ratio of NCO groups of (Ba) to the sum of the hydroxyl groups of (Bb) and (Bc) of more than 1.15:1Ø
4. A polyurethane/polyester three-block polyadduct as claimed in claim 3, wherein the thermoplastic polyurethane elastomers (B) have a content of free NCO groups of from 0.5 to 4% by weight and a total content of NCO groups of from 0.75 to 5%
by weight, based on the total weight of the thermoplastic polyurethane.
by weight, based on the total weight of the thermoplastic polyurethane.
5. A polyurethane/polyester three-block polyadduct as claimed in claim 3, wherein the thermoplastic polyurethane elastomers (B) are prepared by reacting Ba) at least one aromatic diisocyanate with Bb) at least one essentially bifunctional polyhydroxy com-pound having a molecular weight of from 500 to 8000 and Bc) at least one diol having a molecular weight of from 60 to in an amount such that the ratio of the number of equivalents of NCO groups of the aromatic diisocyanates (Ba) to the sum of the hydroxyl groups of the components (Bb) and (Bc) is from 1.16:1.0 to 1.35:1Ø
6. A polyurethane/polyester three-block polyadduct as claimed in claim 3, wherein the thermoplastic polyurethane elastomers (B) are prepared by reacting Ba) diphenylmethane 4,4'-diisocyanate with Bb) polyalkylene glycol polyadipates where the alkylene radical is of 2 to 6 carbon atoms and which have molecu-lar weights of from 500 to 6000 or polyoxytetramethylene glycol having a molecular weight of from 500 to 3200 and Bc) 1,4-butanediol in amounts such that the ratio of the number of equivalents of NCO groups to that of OH groups is more than 1.15:1.
7. A polyurethane/polyester three-block polyadduct as claimed in claim 1 or 3, wherein the thermoplastic polyesters (A) have a relative viscosity of from 0.8 to 1.8, measured in a 0.5%
strength by weight solution in a 1:1 (w/w) phenol/1,2-dichlorobenzene mixture at 25°C, and are prepared by polycondensation of aromatic dicarboxylic acids or dicarboxylic acid derivatives with alkanediols where the alkylene radical is of 2 to 6 carbon atoms.
strength by weight solution in a 1:1 (w/w) phenol/1,2-dichlorobenzene mixture at 25°C, and are prepared by polycondensation of aromatic dicarboxylic acids or dicarboxylic acid derivatives with alkanediols where the alkylene radical is of 2 to 6 carbon atoms.
8. A polyurethane/polyester three-block polyadduct as claimed in claim 1 or 3, wherein the thermoplastic polyesters (A) con-sist of polyethylene terephthalate, polybutylene tereph-thalate or a mixture thereof.
9. A process for the preparation of a polyurethane/polyester three-block polyadduct by reacting A) at least one thermoplastic polyester and B) at least one thermoplastic polyurethane elastomer at from 180 to 300°C, wherein the thermoplastic polyurethane elastomers have a content of free NCO groups of from 0.5 to 4% by weight and a total content of NCO groups of from 0.75 to 5% by weight, based on the total weight of the thermo-plastic polyurethane, and in turn are prepared by reacting Ba) at least one organic diisocyanate with Bb) at least one relatively high molecular weight polyhydroxy compound and Bc) at least one low molecular weight chain extender in amounts such that the ratio of NCO groups of (Ba) to the sum of the hydroxyl groups of (Bb) and (Bc) is more than 1.15:1.
10. Use of the polyurethane/polyester three-block polyadduct as claimed in any of claims 1 to 8 for the preparation of extruded products.
11. Use of a polyurethane/polyester three-block polyadduct as claimed in any of claims 1 to 8 for the production of moldings.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4341077.4 | 1993-12-02 | ||
| DE4341077A DE4341077A1 (en) | 1993-12-02 | 1993-12-02 | Temperature-resistant, highly elastic, abrasion-resistant polyurethane-polyester triblock polyaddition products, a process for their production and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2136125A1 true CA2136125A1 (en) | 1995-06-03 |
Family
ID=6504003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002136125A Abandoned CA2136125A1 (en) | 1993-12-02 | 1994-11-18 | Heat-stable, highly resilient, abrasion-resistant polyurethane/polyester three-block polyadducts, their preparation and their use |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0656397B1 (en) |
| JP (1) | JPH0848742A (en) |
| KR (1) | KR950018119A (en) |
| CN (1) | CN1109074A (en) |
| AT (1) | ATE169051T1 (en) |
| CA (1) | CA2136125A1 (en) |
| DE (2) | DE4341077A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11267928B2 (en) | 2016-02-22 | 2022-03-08 | Basf Se | Method for producing a diblock copolymer |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1017742A1 (en) * | 1997-09-04 | 2000-07-12 | Eastman Chemical Company | Thermoplastic polyurethane additives for chain extension and reactive extrusion |
| CN1078228C (en) * | 1997-12-22 | 2002-01-23 | 黎燕 | Wear-resisting type polyester resin |
| DE10138298A1 (en) | 2001-08-10 | 2003-02-27 | Basf Ag | Thermoplastic polyurethanes |
| KR100694200B1 (en) * | 2004-03-05 | 2007-03-14 | (주)선한엠엔티 | Copolymer for manufacturing a waterproof agent and a method for preparing the same |
| CN105237964A (en) * | 2015-09-30 | 2016-01-13 | 滁州优胜高分子材料有限公司 | High-impact-resistance PBT/BOVC/TPU composite material and preparation method thereof |
| EP3394138B1 (en) * | 2015-12-22 | 2020-03-11 | Basf Se | Tpu shrinkage material |
| JP2021515839A (en) | 2018-03-14 | 2021-06-24 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | Method for manufacturing a polyether ester elastomer |
| JP2022515854A (en) | 2018-12-28 | 2022-02-22 | ビーエーエスエフ ソシエタス・ヨーロピア | Effervescent particles made of aromatic polyester-polyurethane multi-block copolymer |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4165307A (en) * | 1977-04-11 | 1979-08-21 | Dai Nippon Ink & Chemicals Incorporated | Process for preparation of molding resins |
| JPS5460395A (en) * | 1977-10-20 | 1979-05-15 | Toray Ind Inc | Preparation of modified polyester |
| NL7900022A (en) * | 1979-01-03 | 1980-07-07 | Akzo Nv | PROCESS FOR PREPARING A SEGMENTED THERMOPLASTIC ELASTANE. |
| US4542177A (en) * | 1984-06-29 | 1985-09-17 | Mobay Chemical Corporation | Thermoplastic polyester molding composition having an improved impact performance |
| DE3810078A1 (en) * | 1988-03-25 | 1989-10-05 | Bayer Ag | THERMOPLASTIC POLYMER BLEND AND METHOD FOR THE PRODUCTION THEREOF |
| ATE115973T1 (en) * | 1990-03-30 | 1995-01-15 | Fuller H B Licensing Financ | WATER CURRENT POLYURETHANE HOT MELTS ADHESIVE. |
| DE4128274A1 (en) * | 1991-08-27 | 1993-03-04 | Basf Schwarzheide Gmbh | Thermoplastic polyurethane blends with improved properties - are prepd. by compounding thermoplastic polyurethane with a polyester and small amts. of organic di;isocyanate |
| US5319039A (en) * | 1992-04-30 | 1994-06-07 | The Dow Chemical Company | Thermally processable blends of aromatic polyesters and high modulus polyurethanes |
-
1993
- 1993-12-02 DE DE4341077A patent/DE4341077A1/en not_active Withdrawn
-
1994
- 1994-11-18 CA CA002136125A patent/CA2136125A1/en not_active Abandoned
- 1994-11-23 DE DE59406557T patent/DE59406557D1/en not_active Expired - Fee Related
- 1994-11-23 EP EP94118398A patent/EP0656397B1/en not_active Expired - Lifetime
- 1994-11-23 AT AT94118398T patent/ATE169051T1/en not_active IP Right Cessation
- 1994-11-30 JP JP6296769A patent/JPH0848742A/en active Pending
- 1994-12-02 KR KR1019940032503A patent/KR950018119A/en not_active Application Discontinuation
- 1994-12-02 CN CN94119363A patent/CN1109074A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11267928B2 (en) | 2016-02-22 | 2022-03-08 | Basf Se | Method for producing a diblock copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0656397A1 (en) | 1995-06-07 |
| ATE169051T1 (en) | 1998-08-15 |
| CN1109074A (en) | 1995-09-27 |
| JPH0848742A (en) | 1996-02-20 |
| DE59406557D1 (en) | 1998-09-03 |
| KR950018119A (en) | 1995-07-22 |
| DE4341077A1 (en) | 1995-06-08 |
| EP0656397B1 (en) | 1998-07-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |