CA2030735A1 - Thermoplastic polyurethanes with improved flow - Google Patents
Thermoplastic polyurethanes with improved flowInfo
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- CA2030735A1 CA2030735A1 CA 2030735 CA2030735A CA2030735A1 CA 2030735 A1 CA2030735 A1 CA 2030735A1 CA 2030735 CA2030735 CA 2030735 CA 2030735 A CA2030735 A CA 2030735A CA 2030735 A1 CA2030735 A1 CA 2030735A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- Chemical Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Mo3492 LeA 27,149 THERMOPLASTIC POLYURETHANES WITH IMPROVED FLOW
ABSTRACT OF THE DISCLOSURE
The present invention is directed to thermoplastic molding compounds which comprise mixtures of thermoplastic polyurethanes and polyphenols. The molding compounds have greatly improved flowability.
Mo3492
ABSTRACT OF THE DISCLOSURE
The present invention is directed to thermoplastic molding compounds which comprise mixtures of thermoplastic polyurethanes and polyphenols. The molding compounds have greatly improved flowability.
Mo3492
Description
.~ 7 ~ ~
Mo3492 LeA 27,149 THERMOPLASTIC POLYURETHANES WITH IMPROVED FLOW
BACKGROUND OF THE~I~VENTION
The present invention relates to thermoplastic polyurethane molding compounds with improved flow and to the use of these molding compounds for the production of molded articles9 sheet products, fibers and other products.
Thermoplastic polyurethane elastomers (nTPU"~ are known as materials characterized by a block structure of hard segments (urethane blocks) and soft segments (polyether, polyester and poly(ether) carbonate blocks). A wide field of appli~ation has been opened TPUs due to their attractive profile of properties.
TPUs may, however, have insufficient flowability, for example, due to their overall composition and amount of filler and, in the case of ~olded products, the shape of the mold.
This lack of flowability may be partly overcome by increasing the temperature employed for processing. However, since, in many cases, the processing temperature of TPU is already close to a critical level at which the urethane group may be decomposed by heat, this method is generally not advisable.
Lubricants for TPU are known (see, e.g., German Auslegeschriften 3,7~3,752 and 2,901,774~. However, in many cases such lubricants are not sufficiently effective.
Polyurethanes containing a synergistically active stabilizer combination of sterically hindered phenols, alkylidene bisphenols and optionally certain nitrogen compounds are described in Japanese Patent Applications 43754/1973 and 43755/1973. It is disclosed in the said patent applications that the alkyl;dene bisphenols have no significant stabilizing effect on their own and the said applications contain no indication of processiny in the molten, solvent free state nor of any flow improving action of the polyphenols. This is all the more understandable in view of the fact that the hard segments in the polymers used in the examples consist 2 ~ 3 ~
exclusively of urea groups. The polymers are therefore polyureas which, as is well known, are virtually impossible to work up from the melt (see C.R. McMiliu~ Elastomerics 1988 (11), 22; S. Gogelewski, Coll. & Polymer Science 267. 757 (19~9)).
Mixtures of certain polyurethanes and phenols and optionally special polymeric alloying components are disclosed in German Auslegeschriften 3,810,567 and 3,810,568. These polyurethanes have molar ratios of chain lengthening agents o to soft segments of at most 1.1.1 and may be soluble in organic so~vents su~h as acetone and methylene chloride and there-fore constitute typical adhesive polyurethanes of the type conventionally used inter alia as solutions in the above mentioned solvents. Further, the references give no indication of the flow improving action of polyphenols in the thermoplastic polyurethanes.
It was an object of the present invention to provide thermop1astic polyurethanes with improved flowability.
~escription of the Invention 20 . The present invention therefore relates to thermoplastic polyurethane molding compounds with improved flow, containing 1) from 85 to 99.5% by weight of thermoplastic polyurethanes (TPU) having a molar ratio of chain lengthening agents to soft segments of at least 1.5:1 and 2) from 0.5 to 15% by weight of polyphenols correspondiny to the general formula (IJ
l ~R1 (OH) ¦~-R1 (HO)p ~ I ~ ~ (OH)p (R)s (R~s (R)s _ _ t Mo3492 203~73~i with the sum of 1~ and 2) being 100%, wh~rein R may be the same or different and represents H, a C
to C20 alkyl or alkoxy, a C7 to C20 aralkyl or aralkoxy, a C6 to C18 aryl or aryloxy, or a C7 to C18 alkaryl or alkaryloxy, (the Rs are preferably H
and/or C1 to C5 alkyl, and/or phenyl), Rl may be the same or different and represent a chemical bond, a C1 to C20 alkylene groupS a C2 to C20 alkylidene group, a C3 to C2~ ~ycloalkylidene group, an ester group, an amide group, -O-, -SO-, -SO2-s -S-, -CO-, -P~ jP;O-, or a condensation of two or more rings ~the Rls are preferably C1 to C10 alkylene, C2 to ClO alkylidene, C3 to ClO
cycloalkylidene, -SO2, -S-, or a chemical bond), p denotes the number 1 or 2 (preferably 1), r denotes the numbers O, 1 or 2 (preferably 1~, s denotes the numbers O, 1 or 2 (preferably O or 1~, and t has an average value of from 0 to 15 (preferably 0 to 8), with the proviso that no R which is in the ortho position to a phenolic OH group is a tertiary alkyl group, and 3) from 0 to 200% by weight, based on the combined weight of components 1) and 2), and, preferably from 0.01 to 100% by weight, of conventional additives.
Thermoplastic polyurethanes 13 are known (see e.g. J.H.
Saunders, K.C. Fresch: Polyurethanes, Part I, High Polymer Series XVI, Interscience Publishers, New York, 1962).Examples of suitable isocyanates for the preparation of these 30 . polyurethanes include (cyclo)aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and 1-methyl-2,4- and -2,6-cyclohexane diisocyanate (or mixtures of these two) and aromatic diisocyanates such as 4s4'-diphenylmethane diisocyanate (or Mo3492 ~3~73~
isomeric mixtures of various diphenylmethane diisocyanates), toluene-2,4- and -2,6-diisocyanate (or mixtures of these two), 1,5-naphthylene diisocyanate and 1,4-phenylene diisocyanate.
The following are preferred: 4,4'-diphenylmethane diisocyanate (and mixtures thereof with the 2,4-isomers), isophorone diisocyanate, hexamethylene diisocyanate, 2,4- and 2,6-toluene diisocyanate ~and mixtures of these two), 1,5-naphthylene diisocyanate and 4,4 dicyclohexylmethane diisocyanate.
Diphenylmethane diisocyanate containing at least 95~ of the o 4,4'-isomer is particularly preferred.
The following are examples of suitable chain lengthening agents (optionally used as mixtures): aliphatic diols such as 1,4-butane diol, 1,6-hexane diol, 1,2-ethylene glycol, and the like; diethylene glycol, triethylene glycol and in some cases also diamines such as ethylene diamine, hexamethylene diamine, diaminodiphenyl methanes, toluene diamines, and the like. It is generally not suitable to use diamines as the only chain lengthening agents because the resulting polyureas generally cannot be worked up thermoplastically.
Alkane diols having 2 to 6 carbon atoms are preferred chain lengthening agents, particularly butane~l,4-diol. The TPU~ 1) should contain only enough urea groups to enable them to be thermoplastically processed or none at all. They preferably contain less than 20 mol% of urea groups (based on the urethane groupsJ but most preferably contain no urea groups.
The known polyesters, poly(ether)carbonates and polyethers are suitable soft segments. Relatively high molecular weight compounds containing hydrnxyl groups, such as polyester diols 30 . of straight chained or branched aliphatic and/or cycloaliphatic diols and aliphatic dicarboxylic acids, in particular adipic acid, are preferred soft segments of the TPUs but the TPUs may also contain minor quantities of aromatic dicarboxylic acids, in particular phthalic acid, and optionally also terephthalic acid and products of hydrogenation of these acids.
Mo3492 ~3~5 Hydroxypoly(ether)carbonates, hydroxypolycaprolactones and hydroxy-polyether diols based on ethylene oxide, propylene oxide, tetrahydrofuran or mixed polyethers of propylene oxide and/or ethylene oxide and/or tetrahydrofuran are also suitable.
Soft segments such as polyether polyols which have been grafted with vinyl monomers such as styrene or acrylonitrile are also suitable.
The soft segments normally have molecular weights (Mn) ranging from several hundred (e.g. 200 to 300) to about 6000, preferably from 500 to 3,500. They ~ay carry amino end groups.
Monofunctional compounds known in the art may be used as so called chain terminating agents in minor quantities, e.g.
from 0.01 to 3% by weight, based on the TPU solids content.
Examples of such compounds include monohydric alcohols such as butanol, 2-ethylene hexanol, isobu~yl alcohol, octanol-1 and stearyl alcohol and monoamines such as aniline, dibutylamine, N-methylstearylamine and piperidine.
Catalysts and processes for the preparation of the TPUs 1), e.g. the band process and the extrusion process, are known.
20 . Preferred TPUs 1) are obtained from 4,4'-diphenylmethane diisocyanate (295% of the 4,4'-isomer), 1,4-butane diol and polyester or poly(ether)carbonate soft segments (or soft segment mixtures). They are most preferably prepared by the extrusion/reaction screw process.
~5 The phenolic compounds 2) corresponding to formula (IJ are generally known or may be prepared by known processes.
The following are examples of compounds corresponding to formula (1): alkylidene bisphenols such as 2,2-~bis(4-hydroxy-phenyl)]-propane, bis(4-hydroxyphenyl)methane, 1,1-[bis(4-hydroxyphenyl)]-cyclohexane, 1,1-[bis(4-hydroxyphenyl)]-ethane, 1,2-[bis(4-hydroxyphenyl)]-ethane, 2,2-[bis(4-hydroxy-3,5-dimethylphenyl~]-propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, phenol- or alkylphenolformaldehyde condensates (Novolaks) preferably having an average of 3 to 10 rings per molecule, and 4,4'-dihydroxy-diphenyl sulphone.
Mo3492 2(~3~7~
The following are preferred phenols 23: 2,2-bis(4-hydroxy-phenyl)-propane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenylJ-3,3,5-trimethyl cyclohexane, 4,4'-dihydroxy-diphenyl sulphone and Novolaks corresponding to formula III) ~2 1 ~ CH2 ~ (Il), R R
t lS wherein R represents hydrogen and/or a C1 to C5 alkyl group and/or a phenyl group (preferably hydrogen~, and t represents a number (average value) with a value from 1 to 8, so that the molecular weight (Mn) of the Novolak is approximately from 300 to 1500. These Novolaks may also be branched, i.e. they may carry more than two CH2 groups per nucleus.
The phenols 2~ may be used singly or as mixtures (including isomeric mixtures). The phenols 2) are preferably used in quantities from 2.5 to 12% by weight, most preferably from ~ to 10% by weight (based on the combined amount of 1) and 2) .
The additives 3) used may in particular be antistatic agents, stabili~ers, flame retardants, fillers, glass fibers and other reinforcing materials, dyes, pigments, polymeric alloying components and nucleating agents. Mold release agents, both external and internal, may also be present.
The molding compounds according to the invention are preferably prepared by mixing the components as solvent free liquids, optionally after preliminary mixing or in several Mo3492 2~735 stages. It should also be possible to incorporate components after a reaction for the preparation of the compounds, e.g. in part of a reaction screw, and they may also be added immediately before processing.
The molding compounds are processed as solvent free melts, in which the phenols 2) lower the melt viscosity. The flow improvement of thermoplastic polyurethanes obtained according to the invention by the addition of polyphenolic compounds is unexpected and cannot be deduced from the state of the art.
The TPUs 1) used in the present invention have molar ratios of chain lengthening agents to soft segments of at least 1.5:1 preferably at least 1.8:1 and most preferably at least 2.0:1.
Such TPUs are generally insoluble in the solvents noted in German Auslegeschriften 3,810,567 and 3,810,568. At most the TPUs would swell in such solvents.
The flowability of the polyurethane elastomers according to the invention is dramatically increased. They may therefore be worked up even into complicated molded parts under milder conditions, possibly at lower temperatures. For large parts, it may be possible to reduce the number of injection openings and therefore also the number of joint lines. The mechanical properties are generally only slightly influenced by the phenols 2) but the elongation under tension may be significantly increased and the resistance to UV light may also be increased.
The new molding compounds therefore constitute a valuable enrichment in the state of the art. They are suitable for the production of non-tacky molded products, in particular sheet products, fibers, injection molded parts and composite materials.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
Mo3492 2~a735 ~XAMPL~S
The abbreviations used in the Examples have the following meanings:
TPU-1: polye~ter urethane elastomer prepared from 100 parts by weight of an adipic aoid/butane diol polyester (~n = 2250 g mol 1), 10.5 parts by weight of butane-1,4-diol and 40 parts by weight of 4,4'-diphenyl-methane diisocyanate.
TPU-2: polyester urethane elastomer prepared from 85 parts by weight of adipic acid/butane diol polyester (Mn = 2250 9 mol 1), 15 parts by weight of adipic acid/butane diol/ethylene glycol polyester (Mn =
2000 9 mol 1), 31.5 parts by weight of butane-1,4-diol, 96 parts by weight of 4,4'-diphenylmethane diisocyanate and 0.76 parts by weight of l-octanol.
Phenol 1: 2,2-[bis(4-hydroxyphenyl)]-propane.
Phenol 2: phenol-formaldehyde-Novolak (phenol: CH20 ratio was about 1:0.78).
Examples 1 and ?
TPU-2 was mixed dry with 10% by weight of Phenol I
(example 1) and 10% by weight of Phenol 2 texample 2) and extruded from a ZSK 53-double shaft extruder at 220C and at a throughput rate of 30 kg h-l. Energy absorption values of the extruder are shown in Table 1.
ComParison Example l The unmodified TPU-2 was extruded in the same manner. The data are again shown in Table I
Mo3492 _ ~ ~ J~ 5 Table 1 Example Phenol Quantity (%) A (A) 1) Comparison 1 - - 37 1) A denotes the energW in ampere in the extruder needed to extrudate the material at the given through=put rate and is a measure of the flowability. The lower the value for A, the better i 5 the flowability ~ ples 3 and 4 TPU-1 was mixed with 5% by weight and 10% by weight, respectively (based on the mixture) of Phenol 1 in a ZSK-53 double shaft extruder and worked up into test samples. The mechanical properties and MVI values are summarized in Table 2, Comparison Example 2 Pure TPU was tested in the same manner (Table 2).
Example % Phenol 1 ~z1) ~2) ~w3) Shore MVI4) (MPa) (%) (kN/m) Hardness A D
3 5 29.9 654 76.8 84 32 136.0 4 10 25.3 707 49.2 8~3 31 209.7 Compari-son 2 - 37.8 582 70.3 85 34 25.5 1) tensile strength; DIN 53 504 2) elongation under tension; DIN 53 504 3) tear propagation resistance; DIN 53 515 4) Melt Viscosity Index (9/10 min, 190C, 10 kg).
Examples 5 and 6 and Comparison Example 3 The compounds of Examples 3 and 4 and Comparison Example 2 were processed in a film blowing apparatus (50~ film thickness) with the object of determining the degree to which the Mo3492 ~0~5 processing temperature may be lowered as a result of the increase in flowability.
Under comparable conditions, the samples which had been modified according to the invention could he processed at 184C
(Example 3) and 180-C ~Example 4) while Comparison Example 2 required a temperature of 200C. This marked lowering in the processing temperature is a particularly valuable aspect of the inventicn.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3492
Mo3492 LeA 27,149 THERMOPLASTIC POLYURETHANES WITH IMPROVED FLOW
BACKGROUND OF THE~I~VENTION
The present invention relates to thermoplastic polyurethane molding compounds with improved flow and to the use of these molding compounds for the production of molded articles9 sheet products, fibers and other products.
Thermoplastic polyurethane elastomers (nTPU"~ are known as materials characterized by a block structure of hard segments (urethane blocks) and soft segments (polyether, polyester and poly(ether) carbonate blocks). A wide field of appli~ation has been opened TPUs due to their attractive profile of properties.
TPUs may, however, have insufficient flowability, for example, due to their overall composition and amount of filler and, in the case of ~olded products, the shape of the mold.
This lack of flowability may be partly overcome by increasing the temperature employed for processing. However, since, in many cases, the processing temperature of TPU is already close to a critical level at which the urethane group may be decomposed by heat, this method is generally not advisable.
Lubricants for TPU are known (see, e.g., German Auslegeschriften 3,7~3,752 and 2,901,774~. However, in many cases such lubricants are not sufficiently effective.
Polyurethanes containing a synergistically active stabilizer combination of sterically hindered phenols, alkylidene bisphenols and optionally certain nitrogen compounds are described in Japanese Patent Applications 43754/1973 and 43755/1973. It is disclosed in the said patent applications that the alkyl;dene bisphenols have no significant stabilizing effect on their own and the said applications contain no indication of processiny in the molten, solvent free state nor of any flow improving action of the polyphenols. This is all the more understandable in view of the fact that the hard segments in the polymers used in the examples consist 2 ~ 3 ~
exclusively of urea groups. The polymers are therefore polyureas which, as is well known, are virtually impossible to work up from the melt (see C.R. McMiliu~ Elastomerics 1988 (11), 22; S. Gogelewski, Coll. & Polymer Science 267. 757 (19~9)).
Mixtures of certain polyurethanes and phenols and optionally special polymeric alloying components are disclosed in German Auslegeschriften 3,810,567 and 3,810,568. These polyurethanes have molar ratios of chain lengthening agents o to soft segments of at most 1.1.1 and may be soluble in organic so~vents su~h as acetone and methylene chloride and there-fore constitute typical adhesive polyurethanes of the type conventionally used inter alia as solutions in the above mentioned solvents. Further, the references give no indication of the flow improving action of polyphenols in the thermoplastic polyurethanes.
It was an object of the present invention to provide thermop1astic polyurethanes with improved flowability.
~escription of the Invention 20 . The present invention therefore relates to thermoplastic polyurethane molding compounds with improved flow, containing 1) from 85 to 99.5% by weight of thermoplastic polyurethanes (TPU) having a molar ratio of chain lengthening agents to soft segments of at least 1.5:1 and 2) from 0.5 to 15% by weight of polyphenols correspondiny to the general formula (IJ
l ~R1 (OH) ¦~-R1 (HO)p ~ I ~ ~ (OH)p (R)s (R~s (R)s _ _ t Mo3492 203~73~i with the sum of 1~ and 2) being 100%, wh~rein R may be the same or different and represents H, a C
to C20 alkyl or alkoxy, a C7 to C20 aralkyl or aralkoxy, a C6 to C18 aryl or aryloxy, or a C7 to C18 alkaryl or alkaryloxy, (the Rs are preferably H
and/or C1 to C5 alkyl, and/or phenyl), Rl may be the same or different and represent a chemical bond, a C1 to C20 alkylene groupS a C2 to C20 alkylidene group, a C3 to C2~ ~ycloalkylidene group, an ester group, an amide group, -O-, -SO-, -SO2-s -S-, -CO-, -P~ jP;O-, or a condensation of two or more rings ~the Rls are preferably C1 to C10 alkylene, C2 to ClO alkylidene, C3 to ClO
cycloalkylidene, -SO2, -S-, or a chemical bond), p denotes the number 1 or 2 (preferably 1), r denotes the numbers O, 1 or 2 (preferably 1~, s denotes the numbers O, 1 or 2 (preferably O or 1~, and t has an average value of from 0 to 15 (preferably 0 to 8), with the proviso that no R which is in the ortho position to a phenolic OH group is a tertiary alkyl group, and 3) from 0 to 200% by weight, based on the combined weight of components 1) and 2), and, preferably from 0.01 to 100% by weight, of conventional additives.
Thermoplastic polyurethanes 13 are known (see e.g. J.H.
Saunders, K.C. Fresch: Polyurethanes, Part I, High Polymer Series XVI, Interscience Publishers, New York, 1962).Examples of suitable isocyanates for the preparation of these 30 . polyurethanes include (cyclo)aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and 1-methyl-2,4- and -2,6-cyclohexane diisocyanate (or mixtures of these two) and aromatic diisocyanates such as 4s4'-diphenylmethane diisocyanate (or Mo3492 ~3~73~
isomeric mixtures of various diphenylmethane diisocyanates), toluene-2,4- and -2,6-diisocyanate (or mixtures of these two), 1,5-naphthylene diisocyanate and 1,4-phenylene diisocyanate.
The following are preferred: 4,4'-diphenylmethane diisocyanate (and mixtures thereof with the 2,4-isomers), isophorone diisocyanate, hexamethylene diisocyanate, 2,4- and 2,6-toluene diisocyanate ~and mixtures of these two), 1,5-naphthylene diisocyanate and 4,4 dicyclohexylmethane diisocyanate.
Diphenylmethane diisocyanate containing at least 95~ of the o 4,4'-isomer is particularly preferred.
The following are examples of suitable chain lengthening agents (optionally used as mixtures): aliphatic diols such as 1,4-butane diol, 1,6-hexane diol, 1,2-ethylene glycol, and the like; diethylene glycol, triethylene glycol and in some cases also diamines such as ethylene diamine, hexamethylene diamine, diaminodiphenyl methanes, toluene diamines, and the like. It is generally not suitable to use diamines as the only chain lengthening agents because the resulting polyureas generally cannot be worked up thermoplastically.
Alkane diols having 2 to 6 carbon atoms are preferred chain lengthening agents, particularly butane~l,4-diol. The TPU~ 1) should contain only enough urea groups to enable them to be thermoplastically processed or none at all. They preferably contain less than 20 mol% of urea groups (based on the urethane groupsJ but most preferably contain no urea groups.
The known polyesters, poly(ether)carbonates and polyethers are suitable soft segments. Relatively high molecular weight compounds containing hydrnxyl groups, such as polyester diols 30 . of straight chained or branched aliphatic and/or cycloaliphatic diols and aliphatic dicarboxylic acids, in particular adipic acid, are preferred soft segments of the TPUs but the TPUs may also contain minor quantities of aromatic dicarboxylic acids, in particular phthalic acid, and optionally also terephthalic acid and products of hydrogenation of these acids.
Mo3492 ~3~5 Hydroxypoly(ether)carbonates, hydroxypolycaprolactones and hydroxy-polyether diols based on ethylene oxide, propylene oxide, tetrahydrofuran or mixed polyethers of propylene oxide and/or ethylene oxide and/or tetrahydrofuran are also suitable.
Soft segments such as polyether polyols which have been grafted with vinyl monomers such as styrene or acrylonitrile are also suitable.
The soft segments normally have molecular weights (Mn) ranging from several hundred (e.g. 200 to 300) to about 6000, preferably from 500 to 3,500. They ~ay carry amino end groups.
Monofunctional compounds known in the art may be used as so called chain terminating agents in minor quantities, e.g.
from 0.01 to 3% by weight, based on the TPU solids content.
Examples of such compounds include monohydric alcohols such as butanol, 2-ethylene hexanol, isobu~yl alcohol, octanol-1 and stearyl alcohol and monoamines such as aniline, dibutylamine, N-methylstearylamine and piperidine.
Catalysts and processes for the preparation of the TPUs 1), e.g. the band process and the extrusion process, are known.
20 . Preferred TPUs 1) are obtained from 4,4'-diphenylmethane diisocyanate (295% of the 4,4'-isomer), 1,4-butane diol and polyester or poly(ether)carbonate soft segments (or soft segment mixtures). They are most preferably prepared by the extrusion/reaction screw process.
~5 The phenolic compounds 2) corresponding to formula (IJ are generally known or may be prepared by known processes.
The following are examples of compounds corresponding to formula (1): alkylidene bisphenols such as 2,2-~bis(4-hydroxy-phenyl)]-propane, bis(4-hydroxyphenyl)methane, 1,1-[bis(4-hydroxyphenyl)]-cyclohexane, 1,1-[bis(4-hydroxyphenyl)]-ethane, 1,2-[bis(4-hydroxyphenyl)]-ethane, 2,2-[bis(4-hydroxy-3,5-dimethylphenyl~]-propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, phenol- or alkylphenolformaldehyde condensates (Novolaks) preferably having an average of 3 to 10 rings per molecule, and 4,4'-dihydroxy-diphenyl sulphone.
Mo3492 2(~3~7~
The following are preferred phenols 23: 2,2-bis(4-hydroxy-phenyl)-propane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenylJ-3,3,5-trimethyl cyclohexane, 4,4'-dihydroxy-diphenyl sulphone and Novolaks corresponding to formula III) ~2 1 ~ CH2 ~ (Il), R R
t lS wherein R represents hydrogen and/or a C1 to C5 alkyl group and/or a phenyl group (preferably hydrogen~, and t represents a number (average value) with a value from 1 to 8, so that the molecular weight (Mn) of the Novolak is approximately from 300 to 1500. These Novolaks may also be branched, i.e. they may carry more than two CH2 groups per nucleus.
The phenols 2~ may be used singly or as mixtures (including isomeric mixtures). The phenols 2) are preferably used in quantities from 2.5 to 12% by weight, most preferably from ~ to 10% by weight (based on the combined amount of 1) and 2) .
The additives 3) used may in particular be antistatic agents, stabili~ers, flame retardants, fillers, glass fibers and other reinforcing materials, dyes, pigments, polymeric alloying components and nucleating agents. Mold release agents, both external and internal, may also be present.
The molding compounds according to the invention are preferably prepared by mixing the components as solvent free liquids, optionally after preliminary mixing or in several Mo3492 2~735 stages. It should also be possible to incorporate components after a reaction for the preparation of the compounds, e.g. in part of a reaction screw, and they may also be added immediately before processing.
The molding compounds are processed as solvent free melts, in which the phenols 2) lower the melt viscosity. The flow improvement of thermoplastic polyurethanes obtained according to the invention by the addition of polyphenolic compounds is unexpected and cannot be deduced from the state of the art.
The TPUs 1) used in the present invention have molar ratios of chain lengthening agents to soft segments of at least 1.5:1 preferably at least 1.8:1 and most preferably at least 2.0:1.
Such TPUs are generally insoluble in the solvents noted in German Auslegeschriften 3,810,567 and 3,810,568. At most the TPUs would swell in such solvents.
The flowability of the polyurethane elastomers according to the invention is dramatically increased. They may therefore be worked up even into complicated molded parts under milder conditions, possibly at lower temperatures. For large parts, it may be possible to reduce the number of injection openings and therefore also the number of joint lines. The mechanical properties are generally only slightly influenced by the phenols 2) but the elongation under tension may be significantly increased and the resistance to UV light may also be increased.
The new molding compounds therefore constitute a valuable enrichment in the state of the art. They are suitable for the production of non-tacky molded products, in particular sheet products, fibers, injection molded parts and composite materials.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
Mo3492 2~a735 ~XAMPL~S
The abbreviations used in the Examples have the following meanings:
TPU-1: polye~ter urethane elastomer prepared from 100 parts by weight of an adipic aoid/butane diol polyester (~n = 2250 g mol 1), 10.5 parts by weight of butane-1,4-diol and 40 parts by weight of 4,4'-diphenyl-methane diisocyanate.
TPU-2: polyester urethane elastomer prepared from 85 parts by weight of adipic acid/butane diol polyester (Mn = 2250 9 mol 1), 15 parts by weight of adipic acid/butane diol/ethylene glycol polyester (Mn =
2000 9 mol 1), 31.5 parts by weight of butane-1,4-diol, 96 parts by weight of 4,4'-diphenylmethane diisocyanate and 0.76 parts by weight of l-octanol.
Phenol 1: 2,2-[bis(4-hydroxyphenyl)]-propane.
Phenol 2: phenol-formaldehyde-Novolak (phenol: CH20 ratio was about 1:0.78).
Examples 1 and ?
TPU-2 was mixed dry with 10% by weight of Phenol I
(example 1) and 10% by weight of Phenol 2 texample 2) and extruded from a ZSK 53-double shaft extruder at 220C and at a throughput rate of 30 kg h-l. Energy absorption values of the extruder are shown in Table 1.
ComParison Example l The unmodified TPU-2 was extruded in the same manner. The data are again shown in Table I
Mo3492 _ ~ ~ J~ 5 Table 1 Example Phenol Quantity (%) A (A) 1) Comparison 1 - - 37 1) A denotes the energW in ampere in the extruder needed to extrudate the material at the given through=put rate and is a measure of the flowability. The lower the value for A, the better i 5 the flowability ~ ples 3 and 4 TPU-1 was mixed with 5% by weight and 10% by weight, respectively (based on the mixture) of Phenol 1 in a ZSK-53 double shaft extruder and worked up into test samples. The mechanical properties and MVI values are summarized in Table 2, Comparison Example 2 Pure TPU was tested in the same manner (Table 2).
Example % Phenol 1 ~z1) ~2) ~w3) Shore MVI4) (MPa) (%) (kN/m) Hardness A D
3 5 29.9 654 76.8 84 32 136.0 4 10 25.3 707 49.2 8~3 31 209.7 Compari-son 2 - 37.8 582 70.3 85 34 25.5 1) tensile strength; DIN 53 504 2) elongation under tension; DIN 53 504 3) tear propagation resistance; DIN 53 515 4) Melt Viscosity Index (9/10 min, 190C, 10 kg).
Examples 5 and 6 and Comparison Example 3 The compounds of Examples 3 and 4 and Comparison Example 2 were processed in a film blowing apparatus (50~ film thickness) with the object of determining the degree to which the Mo3492 ~0~5 processing temperature may be lowered as a result of the increase in flowability.
Under comparable conditions, the samples which had been modified according to the invention could he processed at 184C
(Example 3) and 180-C ~Example 4) while Comparison Example 2 required a temperature of 200C. This marked lowering in the processing temperature is a particularly valuable aspect of the inventicn.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3492
Claims (8)
1. A thermoplastic polyurethane molding compound comprising:
1) from 85 to 99.5% by weight of a thermoplastic polyurethane having a molar ratio of chain lengthening agents to soft segments of at least 1.5:1 and
1) from 85 to 99.5% by weight of a thermoplastic polyurethane having a molar ratio of chain lengthening agents to soft segments of at least 1.5:1 and
2) from 0.5 to 15% by weight of polyphenols corresponding to the general formula (I) (I) with the sum of 1) and 2) being 100%, wherein R may be the same or different and represents H, a C1 to C20 alkyl or alkoxy, a C7 to C20 aralkyl or aralkoxy, a C6 to C18 aryl or aryloxy, or a C7 to C18 alkaryl or alkaryloxy, R1 may be the same or different and represent a chemical bond, a C1 to C20 alkylene group, a C2 to C20 alkylidene group, a C3 to C20 cycloalkylidene group, an ester group, an amide group, -O-, -SO-, -SO2-, -S-, -CO-, , or a condensation of two or more rings, p denotes the number 1 or 2, r denotes the numbers 0, 1 or 2, s denotes the numbers 0, 1 or 2, and t has an average value of from 0 to 15, with the proviso that no R which is in the ortho position to a phenolic OH group is a tertiary alkyl group, and Mo3492
3) from 0 to 200% by weight, based on the combined weight of components 1) and 2), of conventional additives.
2. The thermoplastic molding compound of Claim 1, wherein the polyphenol 2) is selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane,
2. The thermoplastic molding compound of Claim 1, wherein the polyphenol 2) is selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane,
4,4'-dihydroxy-diphenyl sulphone, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl cyclohexane and a Novolak corresponding to formula (II) (II), wherein R can be the same or different and represents hydrogen, a C1 to C5 alkyl, or a phenyl group and t denotes a number (average value) of from 1 to 8.
3. The thermoplastic molding compound of Claim 1 containing from 2.5 to 12% by weight of said polyphenols.
4. The thermoplastic molding compound of Claim 1 wherein said polyurethane 1) is prepared from 4,4'-diphenylmethane diisocyanate, a C2 to C6 alkylene glycol and polyester- and/or poly(ether)carbonate soft segments.
3. The thermoplastic molding compound of Claim 1 containing from 2.5 to 12% by weight of said polyphenols.
4. The thermoplastic molding compound of Claim 1 wherein said polyurethane 1) is prepared from 4,4'-diphenylmethane diisocyanate, a C2 to C6 alkylene glycol and polyester- and/or poly(ether)carbonate soft segments.
5. The thermoplastic molding compound of Claim 1 wherein the molar ratio of chain lengthening agents to soft segments in the polyurethanes 1) is at least 1.8:1.
6. The thermoplastic molding compound of Claim 1 wherein the polyurethanes 1) are prepared solvent free by an extruder/reaction screw process.
Mo3492
Mo3492
7. The thermoplastic molding compound of Claim 1 wherein said additives 3) are selected from the group consisting of fillers, mold release agents, polymeric alloying components, stabilizers and mixtures thereof.
8. A process for the preparation of the molding compounds of Claim 1 wherein said polyurethanes 1), polyphenols 2) and additives 3) are mixed together as solvent free melts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3941234.2 | 1989-12-14 | ||
| DE19893941234 DE3941234A1 (en) | 1989-12-14 | 1989-12-14 | THERMOPLASTIC POLYURETHANE WITH IMPROVED FLOWABILITY |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2030735A1 true CA2030735A1 (en) | 1991-06-15 |
Family
ID=6395422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2030735 Abandoned CA2030735A1 (en) | 1989-12-14 | 1990-11-23 | Thermoplastic polyurethanes with improved flow |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0432596A3 (en) |
| JP (1) | JPH0493352A (en) |
| CA (1) | CA2030735A1 (en) |
| DE (1) | DE3941234A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0625454A (en) * | 1992-03-30 | 1994-02-01 | Arco Chem Technol Lp | Stable polyurethane foam |
| DE19513501C2 (en) * | 1995-04-10 | 1998-10-08 | Bayer Ag | Production of TPU / copolymer mixtures with the help of flow improvers |
| JP2006199719A (en) * | 2003-05-02 | 2006-08-03 | Bridgestone Corp | Crosslinked polyurethane composition |
| JP5103140B2 (en) * | 2007-11-05 | 2012-12-19 | タイガースポリマー株式会社 | Carbonized refractory composition and refractory sheet |
| EP3131967B1 (en) * | 2014-04-15 | 2021-04-14 | SHPP Global Technologies B.V. | High heat polycarbonate compositions |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2314925A1 (en) * | 1973-03-26 | 1974-10-10 | Dow Chemical Co | Non cellular polyurethanes - from novolacs polyisocyanates and polyols |
| DD115142A1 (en) * | 1974-06-04 | 1975-09-12 | ||
| US4555552A (en) * | 1982-03-24 | 1985-11-26 | Monsanto Company | Phenolic modified urethane elastomer |
| DE3810567A1 (en) * | 1988-03-29 | 1989-10-12 | Bayer Ag | POLYURETHANE MIXTURES AND THEIR USE AS ADHESIVES |
-
1989
- 1989-12-14 DE DE19893941234 patent/DE3941234A1/en not_active Withdrawn
-
1990
- 1990-11-23 CA CA 2030735 patent/CA2030735A1/en not_active Abandoned
- 1990-12-01 EP EP19900123034 patent/EP0432596A3/en not_active Withdrawn
- 1990-12-12 JP JP2409868A patent/JPH0493352A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0493352A (en) | 1992-03-26 |
| DE3941234A1 (en) | 1991-06-20 |
| EP0432596A2 (en) | 1991-06-19 |
| EP0432596A3 (en) | 1991-10-16 |
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