CA2012761A1 - Thermoplastic polyblends of aromatic polycarbonates and thermoplastic polyurethanes - Google Patents
Thermoplastic polyblends of aromatic polycarbonates and thermoplastic polyurethanesInfo
- Publication number
- CA2012761A1 CA2012761A1 CA002012761A CA2012761A CA2012761A1 CA 2012761 A1 CA2012761 A1 CA 2012761A1 CA 002012761 A CA002012761 A CA 002012761A CA 2012761 A CA2012761 A CA 2012761A CA 2012761 A1 CA2012761 A1 CA 2012761A1
- Authority
- CA
- Canada
- Prior art keywords
- thermoplastic
- composition
- polyurethane
- weight percent
- percent based
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Abstract
ABSTRACT
Binary thermoplastic polyblends consisting essentially of from 65 to 95 weight percent of a thermoplastic aromatic polycarbonate and from 5 to 35 weight percent of a thermoplastic polyester polyol-based polyurethane having a Shore Hardness of from 70A to 70D exhibit improved hydrocarbon solvent resistance over polycarbonate resins.
Binary thermoplastic polyblends consisting essentially of from 65 to 95 weight percent of a thermoplastic aromatic polycarbonate and from 5 to 35 weight percent of a thermoplastic polyester polyol-based polyurethane having a Shore Hardness of from 70A to 70D exhibit improved hydrocarbon solvent resistance over polycarbonate resins.
Description
7 ~ ~
THERMOPLASTIC POLYBLENDS
OF AROMATIC POLYCARBONATES
AND THERMOPLASTIC POLYURETHANES
This invention relates to a thermoplastic polymeric resin which is a polyblend of a thermoplastic aromatic polycarbonate polymer and a thermoplastic polyester polyol-ba~ed polyurethane polymer.
Thermoplastic polycarbonate polymers are readily molded at elevated temperatures to make a wide variety of articles. Exemplary of such articles are automotive parts, tool hou~ings, structural component3 and the like. The use of polycarbonate on its own for molding purposes is limited as the polycarbonate has a number oP dePiciencie~ including~sensitivity of impact toughne~s to the ambient temperature and more particu-larly thickness of the molded article, and suscepti-bility to degradation by solvents including water and hydrocarbon~.
Correction of such dePicienoy of polycarbonate polymers is known by blending the polycarbonates with other polymeric additive~, such as disclosed in U.S.~
Patent No. 3,431,224.
37,913-F
:~
. ~ ~
::: ~ , .
7?~7~
Polycarbonate polymer~ have been modified by blending with other polymers including polyethylene, Dolypropylene, copolymerq of ethylene and an alkyl acrylate, polyamide, polyvinyl acetate, alkyl cellu~
lo~e ether and polyurethane elastomer.
In U.S. Patent No. 4,03~,012 a ternary blend of polymer~ conqi~ting o~ a polycarbonate , a polybutylene terephthalate and a thermopla~tic polyurethane (hereaf-ter re~erred to a~ TPU) i9 disclosed having an improved impact ~trength at critical thickne~s. U.S. Patent No.
4,179,479 di~clo~e~ a ternary polymer blend o~ a TPU, a thermoplastic polycarbonate and an acrylio polymer; the latter functioning as a proces~ing aid to confer uni-formity of melt flow properties. U.S. Patent No.
4,350,799 disclo~e~ a ternary blend containing a TPU, apolycarbonate and a polypho~phate, the blend diqplayq reduced flammability. Ternary blends of TPU, polycarbonate and rubber~ a~ impact modifierq are disoloqed by EP 125739 and U.S. Patent No. 4,522,979.
The preparation of binary TPU/polycarbonate blends has been llttle ~tudied due to the inherent problem~ of compatibility between polycarbonate and TPU
includlng, for example9 large difference~ in melt vi~-coqitia~, prooes~ing temperatures and thermodynamic solubilities. These difference are eqpecially promi-nent with polyether-ba~sd TPU~.
In the publicat~on, U.S. Patent No. 4~743J650~
binary blend~ con~ist1ng e~entially o~ a thermoplastic aromatic polycarbonate and from 5 to 35 part~ by weight of a th~rmoplaqtio poIyether polyol-baqed polyurethane are di~closed.
37,913-F -2-. . - . .
.
;, ~ ' 3 2 ~3 ~
Accordingly, it would be de~irable to provide a binary polycarbonate /TPU blend wherein the incompat-ibility difference cf the two polymerY has been mini-mized and wherein molded article~ prepared there~rom that ~how improved reqistance to hydrocarbon ~olvents and improved impact re~istance and toughness compared to polycarbonate alone.
In one a~pect, this inventlon is a thermoplas-tic polyblend which consists es~entially oP
(a) ~rom 65 to 95 weight percent baqedon the combined weight~ oP (a~ and (b) of a thermopla~tic polycarbonate polymer; and (b) from 5 to 35 weight percent based on the combined weights of (a) and (b) of a thermoplastic polyester polyol-based poly-urethane having a Shore Hardness of from 70A
to 7OD.
Preferably the resulting thermoplastic polyblend exhibit~ an environmental crack ~tress re~istance oP from 2150 psi (15 x 103 kPa) and a flexural modulus of ~rom 2.20 x lO psi (l.5 GPa).
In a second aspeot, this invention i~ a proce3s for preparing a thermoplaqtio polyblend which oonqists es~entially oP melt-blending:
(a) from 65 to 95 weight peroent ba~ed on the combined weight~ of (a) and (b) of a thermoplastic aromatic polycarbonate polymer; and 37,913-F -3-~4_ (b) from 5 to 35 weight percent based on the combined weights of (a) and (b) of a thermoplastic polyester polyol-based polyurethane having ~ Shore Hardness from 70A to 70D, and characterized in that the melt blendlng proces~ i~ substantially free of an acrylic polymer proce~ing aid.
In a third aspect, thi~ invention is an article prepared by melt extrusion or molding of a polyblend characterized in that the polyblend consist3 esYentially of (a) from 65 to 95 weight percent based on the combined weight3 of (a) and (b) of a thermoplastic aromatic polycarbonate polymer; and tb) from 5 to 35 welght percent based on the combined weights o~ (a) and (b) of a thermoplastic polyester polyol-based polyurethane. having a Shore Hardness from 70A to 70D, and characterized in that the resulting arti¢le~ exhibit~ an environmental crack stress re~istance o~ ~rom 2150 psi ~15 MPa~ and a flexural modulus of ~rom 2.20 x 105 psi (1.5 GPa).
Surprisingly, it ha been found that by u~ing said thermoplastic polyurethane whlch ha~ a Shore Hardne~a of ~rom 70A to 70D in combination with a thermoplastio aromatic polycarbonate polymer; a thermoplastic polyblend whieh has good meohanical, proc@s~ing and chemical propertie~ includlng ~olvent resiqtance can be prepared.
`~ 37,913-F -4-.
, . . .
.
`
The polyblend consists of a thermoplastic aromatic poly-carbonate polymer in an amount of from a-t least 65, and up to 95, preferably up to 85 and more preferably up to 75 weight percent based on the combined weight of thermoplastic aromatic polycarbon-ate (a) and thermoplastic polyurethane (b) present in the polyblend.
The thermoplastic polyurethane is present in the poly-blend in an amount of from at least 5, preferably at least 15, and more preferably at least 25, but not more than 35 weight percent based on the combined weights of the thermoplastic aromatic polycarbonate and thermoplastic polyurethane present.
Mixtures of thermoplastic aromatic polycarbonate polymers and/or mixtures of thermoplastic polyester polyol-based poly-urethanes of the aforementioned hardness may be present in the polyblends.
Suitable thermoplastic aromatic polycarbonate polymers that can be used in the practice of this invention are those aromatic homopolycarbonates and aromatic copolycarbonates advan-tageouslyhaving a molecular weight of from 10,000 to 200,000, and preferably of from 15,000 to 100,000. In addition, the polycar-bonate advantageously has a melt flow rate of at least 8 g/10 minutes, preferably at least 10 g/10 minutes, and more preferably at least 12 g/10 minutes but less than 30 g/10 minutes, preferably less than 22 g/10 minutes and more preferably less than 18 g/10 minutes at 300C with 1.2 kg weight as measured by the ASTM
Procedure D-1238. However, use of polycarbonates having melt-flow rates as high as 100 g/10 minutes is possible when it is beneEicial to the overall melt processing characteristics of the polyblend and minimizes the possibility of thermal degradation of the thermo-~ .
~.
?,~27~f~
thermoplastic polyurethane.
Polycarbonate3 ~ultable for u3e ~n thl3 pres-ent invention are prepared from dlhydroxy compounds con-forming to tbe struoture of rormula I or rormula II
_ _ ~ )8 ~ -0 HO ~ (~)d (Z~d HO OH
~, , 9~
(Z)~ (Z~r whereln A denotes an alkylene group wlth 1 to 8 oarbon atom9, an alkylldene group with 2 to 8 carbon atoms, a cyoloalkylena group wlth 5 to 15 carbon atoms, a oyolo-alkylidene group with 5 to 15 carbon atoms, an aromatio group wlth 5 to 15 carbon atoms,a carbonyl group, an oxygan atom, a sul~ur atom, an -SO- or -S02- radlcal or a radical o~ the g~neral formula 37,913-F -6-. ~ .. . , ~. .-:. . . .
' ' . ' ~ '.
' ': '' ''' '' ~ ' '' ' '~ , 7H3 ~ IH3 IH3 ~ CH3 Cl ~ -C - or g denotes the number O or 1; e denotes the number O or l; Z denotes F, Cl or Br atoms or a C1_3 alkyl and if several Z radicals are substituents in one aryl radical, they may be identical or di~ferent; d denote~ O or an integer of from 1 to 4; and f denotes O or an integer of from l to 3. Preferred are the dihydroxy compounds where g is 1 and e is 1.
Among the useful dihydroxy compounds in the practice of the invention are hydroquinone, resorcinol, bis-(hydroxyphenyl~alkanes, bis-(hydroxyphenyl)cyelo-alkanes, bis-(hydroxyphenyl)ethers, bis-(hydroxyphe-nyl)ketones, bis-(hydroxyphenyl)sulfoxides, bis-(hy-droxyphenyl)sulfones and ~ bis-(hydroxyphenyl)di-isopropylbenzenes. These and further suitable aromatic dihydroxy compounds are described, for example, in U.S.
Patent Nos. 2,991,273; 2,999,835; 2,999,846; 3,014,891;
3,028,365; 3,035,021; 3,035,036; 3,036,037; 3,036~038;
3,036,039:; 3,148,172;:3,271,367; 3,271,368 and 3,280,078, in German Offenlegungsschriftens (German Published Speaifications) 1,570,703; 2,063,050;
THERMOPLASTIC POLYBLENDS
OF AROMATIC POLYCARBONATES
AND THERMOPLASTIC POLYURETHANES
This invention relates to a thermoplastic polymeric resin which is a polyblend of a thermoplastic aromatic polycarbonate polymer and a thermoplastic polyester polyol-ba~ed polyurethane polymer.
Thermoplastic polycarbonate polymers are readily molded at elevated temperatures to make a wide variety of articles. Exemplary of such articles are automotive parts, tool hou~ings, structural component3 and the like. The use of polycarbonate on its own for molding purposes is limited as the polycarbonate has a number oP dePiciencie~ including~sensitivity of impact toughne~s to the ambient temperature and more particu-larly thickness of the molded article, and suscepti-bility to degradation by solvents including water and hydrocarbon~.
Correction of such dePicienoy of polycarbonate polymers is known by blending the polycarbonates with other polymeric additive~, such as disclosed in U.S.~
Patent No. 3,431,224.
37,913-F
:~
. ~ ~
::: ~ , .
7?~7~
Polycarbonate polymer~ have been modified by blending with other polymers including polyethylene, Dolypropylene, copolymerq of ethylene and an alkyl acrylate, polyamide, polyvinyl acetate, alkyl cellu~
lo~e ether and polyurethane elastomer.
In U.S. Patent No. 4,03~,012 a ternary blend of polymer~ conqi~ting o~ a polycarbonate , a polybutylene terephthalate and a thermopla~tic polyurethane (hereaf-ter re~erred to a~ TPU) i9 disclosed having an improved impact ~trength at critical thickne~s. U.S. Patent No.
4,179,479 di~clo~e~ a ternary polymer blend o~ a TPU, a thermoplastic polycarbonate and an acrylio polymer; the latter functioning as a proces~ing aid to confer uni-formity of melt flow properties. U.S. Patent No.
4,350,799 disclo~e~ a ternary blend containing a TPU, apolycarbonate and a polypho~phate, the blend diqplayq reduced flammability. Ternary blends of TPU, polycarbonate and rubber~ a~ impact modifierq are disoloqed by EP 125739 and U.S. Patent No. 4,522,979.
The preparation of binary TPU/polycarbonate blends has been llttle ~tudied due to the inherent problem~ of compatibility between polycarbonate and TPU
includlng, for example9 large difference~ in melt vi~-coqitia~, prooes~ing temperatures and thermodynamic solubilities. These difference are eqpecially promi-nent with polyether-ba~sd TPU~.
In the publicat~on, U.S. Patent No. 4~743J650~
binary blend~ con~ist1ng e~entially o~ a thermoplastic aromatic polycarbonate and from 5 to 35 part~ by weight of a th~rmoplaqtio poIyether polyol-baqed polyurethane are di~closed.
37,913-F -2-. . - . .
.
;, ~ ' 3 2 ~3 ~
Accordingly, it would be de~irable to provide a binary polycarbonate /TPU blend wherein the incompat-ibility difference cf the two polymerY has been mini-mized and wherein molded article~ prepared there~rom that ~how improved reqistance to hydrocarbon ~olvents and improved impact re~istance and toughness compared to polycarbonate alone.
In one a~pect, this inventlon is a thermoplas-tic polyblend which consists es~entially oP
(a) ~rom 65 to 95 weight percent baqedon the combined weight~ oP (a~ and (b) of a thermopla~tic polycarbonate polymer; and (b) from 5 to 35 weight percent based on the combined weights of (a) and (b) of a thermoplastic polyester polyol-based poly-urethane having a Shore Hardness of from 70A
to 7OD.
Preferably the resulting thermoplastic polyblend exhibit~ an environmental crack ~tress re~istance oP from 2150 psi (15 x 103 kPa) and a flexural modulus of ~rom 2.20 x lO psi (l.5 GPa).
In a second aspeot, this invention i~ a proce3s for preparing a thermoplaqtio polyblend which oonqists es~entially oP melt-blending:
(a) from 65 to 95 weight peroent ba~ed on the combined weight~ of (a) and (b) of a thermoplastic aromatic polycarbonate polymer; and 37,913-F -3-~4_ (b) from 5 to 35 weight percent based on the combined weights of (a) and (b) of a thermoplastic polyester polyol-based polyurethane having ~ Shore Hardness from 70A to 70D, and characterized in that the melt blendlng proces~ i~ substantially free of an acrylic polymer proce~ing aid.
In a third aspect, thi~ invention is an article prepared by melt extrusion or molding of a polyblend characterized in that the polyblend consist3 esYentially of (a) from 65 to 95 weight percent based on the combined weight3 of (a) and (b) of a thermoplastic aromatic polycarbonate polymer; and tb) from 5 to 35 welght percent based on the combined weights o~ (a) and (b) of a thermoplastic polyester polyol-based polyurethane. having a Shore Hardness from 70A to 70D, and characterized in that the resulting arti¢le~ exhibit~ an environmental crack stress re~istance o~ ~rom 2150 psi ~15 MPa~ and a flexural modulus of ~rom 2.20 x 105 psi (1.5 GPa).
Surprisingly, it ha been found that by u~ing said thermoplastic polyurethane whlch ha~ a Shore Hardne~a of ~rom 70A to 70D in combination with a thermoplastio aromatic polycarbonate polymer; a thermoplastic polyblend whieh has good meohanical, proc@s~ing and chemical propertie~ includlng ~olvent resiqtance can be prepared.
`~ 37,913-F -4-.
, . . .
.
`
The polyblend consists of a thermoplastic aromatic poly-carbonate polymer in an amount of from a-t least 65, and up to 95, preferably up to 85 and more preferably up to 75 weight percent based on the combined weight of thermoplastic aromatic polycarbon-ate (a) and thermoplastic polyurethane (b) present in the polyblend.
The thermoplastic polyurethane is present in the poly-blend in an amount of from at least 5, preferably at least 15, and more preferably at least 25, but not more than 35 weight percent based on the combined weights of the thermoplastic aromatic polycarbonate and thermoplastic polyurethane present.
Mixtures of thermoplastic aromatic polycarbonate polymers and/or mixtures of thermoplastic polyester polyol-based poly-urethanes of the aforementioned hardness may be present in the polyblends.
Suitable thermoplastic aromatic polycarbonate polymers that can be used in the practice of this invention are those aromatic homopolycarbonates and aromatic copolycarbonates advan-tageouslyhaving a molecular weight of from 10,000 to 200,000, and preferably of from 15,000 to 100,000. In addition, the polycar-bonate advantageously has a melt flow rate of at least 8 g/10 minutes, preferably at least 10 g/10 minutes, and more preferably at least 12 g/10 minutes but less than 30 g/10 minutes, preferably less than 22 g/10 minutes and more preferably less than 18 g/10 minutes at 300C with 1.2 kg weight as measured by the ASTM
Procedure D-1238. However, use of polycarbonates having melt-flow rates as high as 100 g/10 minutes is possible when it is beneEicial to the overall melt processing characteristics of the polyblend and minimizes the possibility of thermal degradation of the thermo-~ .
~.
?,~27~f~
thermoplastic polyurethane.
Polycarbonate3 ~ultable for u3e ~n thl3 pres-ent invention are prepared from dlhydroxy compounds con-forming to tbe struoture of rormula I or rormula II
_ _ ~ )8 ~ -0 HO ~ (~)d (Z~d HO OH
~, , 9~
(Z)~ (Z~r whereln A denotes an alkylene group wlth 1 to 8 oarbon atom9, an alkylldene group with 2 to 8 carbon atoms, a cyoloalkylena group wlth 5 to 15 carbon atoms, a oyolo-alkylidene group with 5 to 15 carbon atoms, an aromatio group wlth 5 to 15 carbon atoms,a carbonyl group, an oxygan atom, a sul~ur atom, an -SO- or -S02- radlcal or a radical o~ the g~neral formula 37,913-F -6-. ~ .. . , ~. .-:. . . .
' ' . ' ~ '.
' ': '' ''' '' ~ ' '' ' '~ , 7H3 ~ IH3 IH3 ~ CH3 Cl ~ -C - or g denotes the number O or 1; e denotes the number O or l; Z denotes F, Cl or Br atoms or a C1_3 alkyl and if several Z radicals are substituents in one aryl radical, they may be identical or di~ferent; d denote~ O or an integer of from 1 to 4; and f denotes O or an integer of from l to 3. Preferred are the dihydroxy compounds where g is 1 and e is 1.
Among the useful dihydroxy compounds in the practice of the invention are hydroquinone, resorcinol, bis-(hydroxyphenyl~alkanes, bis-(hydroxyphenyl)cyelo-alkanes, bis-(hydroxyphenyl)ethers, bis-(hydroxyphe-nyl)ketones, bis-(hydroxyphenyl)sulfoxides, bis-(hy-droxyphenyl)sulfones and ~ bis-(hydroxyphenyl)di-isopropylbenzenes. These and further suitable aromatic dihydroxy compounds are described, for example, in U.S.
Patent Nos. 2,991,273; 2,999,835; 2,999,846; 3,014,891;
3,028,365; 3,035,021; 3,035,036; 3,036,037; 3,036~038;
3,036,039:; 3,148,172;:3,271,367; 3,271,368 and 3,280,078, in German Offenlegungsschriftens (German Published Speaifications) 1,570,703; 2,063,050;
2,063,052; 2,21~1,956 and 2,211,957, in French Patent Specification 1,561,518 and in the monograph, 37,913-F -7-.
. . : . ~ . . .
2/ ~
H. Schnell, ChemistryandPhysicsofPolycarbonates, Inter-science Publishers, New York (1964). Further examples of suitable dihyd;oxy compounds are ~he bisphenols including 2,2-bis-(4-hydroxyphenyl)propane, (bisphenol A), 2,4-bis~(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4 -hydroxyphenyl)cyclohexane, a,a bis-(4-hydroxyphenyl-p--diisopropylbenzene, 2,2-bis-(3-chloro-4-hydroxy--- phenyl)propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl) propane and 1,1-bis-(4-hydroxyphenyl)-1-phenylethane hydroxybenzophenone and 4,4-sulfonyl diphenol.
The aromatic polycarbonates used in preparing the polyblend of this invention may entail in their structure units derived from one or more of the suitable dihydroxy compounds.
The most preferred dihydroxy compounds are when g is 1 and e is 1 such as, for example, the bisphenols, especially 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A).
The preparation of polycarbonate resins may be carried out in accordance with any of the processes known in the art, for example, by the interfacial poly-condensation process, polycondensation in a homogeneous phase or by transesterification. The suitable processes and conditions have been disclosed in the literature and in general are described in the above-mentioned monograph by H. Schnell.
In the preparation of the aromatic polycarbonate resins used to prepare the polyblends of this invention, monofunctional reactants such as 37,913-F -8- -. . ., ~ . .
..
. . . : : .
`, ' ~.' . ', , .' . ' .',: . : ... .
monoph~nols may be used in order to limit their re~pec-tive molecular weights. Also, branching obtained by the incorpora~ion, in the re~pective proce~es, of small amountq, preferably of between about 0.05 and 2.0 molecular percent (relative to the dihydroxy compound employed) of branching agents which are at least tri-functional compound~, especially, compound~ having three - or more phenolic hydroxyl group~. Aromatic polycarbonate~ o~ this type are deqcribed, for example, in German Offenlegungs~chriftens (German Publi~hed Specifications) 1,570,533; 1,595,762; 2,116,974 and 2,113,347, British Speci~ication 1,079,ô21 and U.S.
Patent No. 3,544,5140 Thermoplaqtic polyurethaneq are subqtantially linear polymer~ and have thermoplaqtic proce~q~ng characteristics. They may be prepared from the reaction of an organia polyi~ocyanate, pre~erably a diisocyanake, with a polyahl compo~ition which comprise~ a polycaprolactone polyol, or a polye~ter polyol or a polyether polyol, and a chain extender. Hence they reqpectively are, a thermoplaqtic polycaprolactone polyol-based polyurethane, a thermoplastic polyester polyol-ba~ed polyurethane and a thermoplastic polyether polyol-ba3ed polyurethane. The thermopla~tic polyurethane can be prepared by method~ a~ di~closed in U.S. Patent Nos. 3,214,411 and 4,376,834. The thermo-plastic polyurethanes which are used in this present invention are polyester polyol based polyurethanes.
The Shore Hardnes~ of the thermoplastic poly urethane is measured according to ASTM D-2240. The thermoplastlc polyurethane has a Shore Hardnes~ of from 37,913-F _g_ .
~;J3 ~ '~
70A on the "A'l scale 9 and up to 70D on the "D" ~cale.
The thermapla3tic polyurethane preferably ha~ a Shore Hardness of Prom 70A to 100A, and more preferably from 85A to lOOA. On the "D" qcale, the thermoplastic polyurethane preferably haq a hardness of from 40D to 70D and mcre preferably ~rom 40D to 65D and most preferably from 55D to 65D. A larger number indicates a harder thermoplastic polyurethane.
The thermoplastic polyurethane i9 further characterized in that it ha~ a melt flow rate of at least 6~ preferably at leaqt 8, more preferably at least 10 and up to 40, preferably up to 35 and more pre~erably up to 30 g/10 min. Melt flow ratas are determined according to procedure ASTM D-1238.
The polyeqter polyol u~ed to prepare the thermoplastic polyurethane employed in the present invention advantageously has a molecular weight of at lea~t 500, more preferably at least 1250, and moqt pre~erably at least 1500, but less than 10,000, preferably less than 8,ooo and more preferably less than 6000. The average ~unctionality o~ the polyol (i.e. n~r of iQocyanate-reactive hydrogens per molecule~i~ in the range oP 1.8 to 4, and preferably ln the range of 1,8 to 2.5.
Particularly use~ul polyeQter polyol~ whioh may be used aq starting material for preparing the thermopla~tic polyaster polyol-based polyurathanes are those produced from divalent carboxylic acids or the anhydrides of these aolds and a glycol having at least one, pre~erably two primary hydroxyl groups. Suitable divalent carboxylic aoid~ in¢lude succ1nio acid, ~uberic : -37,913-F -10-.. . - . ' ~. ,, .. ' ', .~ , . .
.
,. . . . . .
" 2~
acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid and isophthalic acid, and anhy-drides of the above. Preferred polyester polyols for the present invention are those prepared from adipic acid.
- By way of example, adipic acid is condensed with a suitabl~ glycol or mixtures of glycols which have at least one primary hydroxyl group. The condensation is stopped when an acid number of from 0.5 to 200 iS
reached. The water formed during the reaction is simultaneously removed so that the final water content of the resulting product is from 0.01 to 0.02, preferably from 0.01 to 0.05 percent by weight.
Any suitable glycol may be used in reaction with the adipic acid such as, for example, ethylene glycol, propylene glycol, butylene glycol, hexanediol, bis-(hydroxymethylcyclohexane), 1,4-butanediol, dieth-ylene glycol, 2,2-dimethylpropylene glycol and 1,3 -propylene glycol. In addition to the glycols, a small amount of trihydric alcohol, up to about 1 percent may be used along with the glycols such as, for example, trimethylolpropane, glycerine and hexanetriol. The molecular weight of the polyester polyol can be increased, if desired, by ~urther reacting with an oxirane such as, for example, ethylene oxide or propylene oxide.
Any of the organic polyisocyanates and pre~erably diisocyanates employed in the preparation of polyurethanes can be employed in preparing the thermoplastic polyurethanes required for the present 37,913-F
?,~3 invention. Illustrative of such isocyanates are:
methylene bis(phenylisocyanates) including the 4,4~
-isomer, the 2,4'-isomer and miYtures thereof, meta- and para-phenylene diisocyanates, chlorophenylene diisocyanates, a,~'-xylylene diisocyanate, 2,4- and 2,6 -toluene diisocyanate and mixtures of these latter two isomers which are available commercially, toluidine - diisocyanate9 hexamethylene diisocyanate, 1,5-naphtha-lene diisocyanate, isophorone diisocyanate and methylene bis(cyclohexylisocyanate) including the 4,4'-isomer and 2,4'-isomer, and mixtures thereof.
Preferably, the organic polyisocyanate employed to prepare the thermoplastic polyurethanes useful In this invention is methylene bis(phenylisocyanate) in the form of the 4,4'-isomer as well as mixtures of the 4,4' -isomer with amounts o~ up to about 70 percent by weight of the 2,4'-isomer, and modified forms of these diisocyanates. By the latter are meant those forms o~
methylene bis(phenylisocyanate) which have been treated to render them stable liquids at ambient temperature.
Such products include those which have been reacted with a minor amount (up to 0.2 equivalents per equivalent o~
a polyphenyl polyisocyanate) of an aliphatic glycol or mixture of aliphatic glycols; such modified methylene bis(phenylisocyanates) are described in U.S. Patent Nos.
. . : . ~ . . .
2/ ~
H. Schnell, ChemistryandPhysicsofPolycarbonates, Inter-science Publishers, New York (1964). Further examples of suitable dihyd;oxy compounds are ~he bisphenols including 2,2-bis-(4-hydroxyphenyl)propane, (bisphenol A), 2,4-bis~(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4 -hydroxyphenyl)cyclohexane, a,a bis-(4-hydroxyphenyl-p--diisopropylbenzene, 2,2-bis-(3-chloro-4-hydroxy--- phenyl)propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl) propane and 1,1-bis-(4-hydroxyphenyl)-1-phenylethane hydroxybenzophenone and 4,4-sulfonyl diphenol.
The aromatic polycarbonates used in preparing the polyblend of this invention may entail in their structure units derived from one or more of the suitable dihydroxy compounds.
The most preferred dihydroxy compounds are when g is 1 and e is 1 such as, for example, the bisphenols, especially 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A).
The preparation of polycarbonate resins may be carried out in accordance with any of the processes known in the art, for example, by the interfacial poly-condensation process, polycondensation in a homogeneous phase or by transesterification. The suitable processes and conditions have been disclosed in the literature and in general are described in the above-mentioned monograph by H. Schnell.
In the preparation of the aromatic polycarbonate resins used to prepare the polyblends of this invention, monofunctional reactants such as 37,913-F -8- -. . ., ~ . .
..
. . . : : .
`, ' ~.' . ', , .' . ' .',: . : ... .
monoph~nols may be used in order to limit their re~pec-tive molecular weights. Also, branching obtained by the incorpora~ion, in the re~pective proce~es, of small amountq, preferably of between about 0.05 and 2.0 molecular percent (relative to the dihydroxy compound employed) of branching agents which are at least tri-functional compound~, especially, compound~ having three - or more phenolic hydroxyl group~. Aromatic polycarbonate~ o~ this type are deqcribed, for example, in German Offenlegungs~chriftens (German Publi~hed Specifications) 1,570,533; 1,595,762; 2,116,974 and 2,113,347, British Speci~ication 1,079,ô21 and U.S.
Patent No. 3,544,5140 Thermoplaqtic polyurethaneq are subqtantially linear polymer~ and have thermoplaqtic proce~q~ng characteristics. They may be prepared from the reaction of an organia polyi~ocyanate, pre~erably a diisocyanake, with a polyahl compo~ition which comprise~ a polycaprolactone polyol, or a polye~ter polyol or a polyether polyol, and a chain extender. Hence they reqpectively are, a thermoplaqtic polycaprolactone polyol-based polyurethane, a thermoplastic polyester polyol-ba~ed polyurethane and a thermoplastic polyether polyol-ba3ed polyurethane. The thermopla~tic polyurethane can be prepared by method~ a~ di~closed in U.S. Patent Nos. 3,214,411 and 4,376,834. The thermo-plastic polyurethanes which are used in this present invention are polyester polyol based polyurethanes.
The Shore Hardnes~ of the thermoplastic poly urethane is measured according to ASTM D-2240. The thermoplastlc polyurethane has a Shore Hardnes~ of from 37,913-F _g_ .
~;J3 ~ '~
70A on the "A'l scale 9 and up to 70D on the "D" ~cale.
The thermapla3tic polyurethane preferably ha~ a Shore Hardness of Prom 70A to 100A, and more preferably from 85A to lOOA. On the "D" qcale, the thermoplastic polyurethane preferably haq a hardness of from 40D to 70D and mcre preferably ~rom 40D to 65D and most preferably from 55D to 65D. A larger number indicates a harder thermoplastic polyurethane.
The thermoplastic polyurethane i9 further characterized in that it ha~ a melt flow rate of at least 6~ preferably at leaqt 8, more preferably at least 10 and up to 40, preferably up to 35 and more pre~erably up to 30 g/10 min. Melt flow ratas are determined according to procedure ASTM D-1238.
The polyeqter polyol u~ed to prepare the thermoplastic polyurethane employed in the present invention advantageously has a molecular weight of at lea~t 500, more preferably at least 1250, and moqt pre~erably at least 1500, but less than 10,000, preferably less than 8,ooo and more preferably less than 6000. The average ~unctionality o~ the polyol (i.e. n~r of iQocyanate-reactive hydrogens per molecule~i~ in the range oP 1.8 to 4, and preferably ln the range of 1,8 to 2.5.
Particularly use~ul polyeQter polyol~ whioh may be used aq starting material for preparing the thermopla~tic polyaster polyol-based polyurathanes are those produced from divalent carboxylic acids or the anhydrides of these aolds and a glycol having at least one, pre~erably two primary hydroxyl groups. Suitable divalent carboxylic aoid~ in¢lude succ1nio acid, ~uberic : -37,913-F -10-.. . - . ' ~. ,, .. ' ', .~ , . .
.
,. . . . . .
" 2~
acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid and isophthalic acid, and anhy-drides of the above. Preferred polyester polyols for the present invention are those prepared from adipic acid.
- By way of example, adipic acid is condensed with a suitabl~ glycol or mixtures of glycols which have at least one primary hydroxyl group. The condensation is stopped when an acid number of from 0.5 to 200 iS
reached. The water formed during the reaction is simultaneously removed so that the final water content of the resulting product is from 0.01 to 0.02, preferably from 0.01 to 0.05 percent by weight.
Any suitable glycol may be used in reaction with the adipic acid such as, for example, ethylene glycol, propylene glycol, butylene glycol, hexanediol, bis-(hydroxymethylcyclohexane), 1,4-butanediol, dieth-ylene glycol, 2,2-dimethylpropylene glycol and 1,3 -propylene glycol. In addition to the glycols, a small amount of trihydric alcohol, up to about 1 percent may be used along with the glycols such as, for example, trimethylolpropane, glycerine and hexanetriol. The molecular weight of the polyester polyol can be increased, if desired, by ~urther reacting with an oxirane such as, for example, ethylene oxide or propylene oxide.
Any of the organic polyisocyanates and pre~erably diisocyanates employed in the preparation of polyurethanes can be employed in preparing the thermoplastic polyurethanes required for the present 37,913-F
?,~3 invention. Illustrative of such isocyanates are:
methylene bis(phenylisocyanates) including the 4,4~
-isomer, the 2,4'-isomer and miYtures thereof, meta- and para-phenylene diisocyanates, chlorophenylene diisocyanates, a,~'-xylylene diisocyanate, 2,4- and 2,6 -toluene diisocyanate and mixtures of these latter two isomers which are available commercially, toluidine - diisocyanate9 hexamethylene diisocyanate, 1,5-naphtha-lene diisocyanate, isophorone diisocyanate and methylene bis(cyclohexylisocyanate) including the 4,4'-isomer and 2,4'-isomer, and mixtures thereof.
Preferably, the organic polyisocyanate employed to prepare the thermoplastic polyurethanes useful In this invention is methylene bis(phenylisocyanate) in the form of the 4,4'-isomer as well as mixtures of the 4,4' -isomer with amounts o~ up to about 70 percent by weight of the 2,4'-isomer, and modified forms of these diisocyanates. By the latter are meant those forms o~
methylene bis(phenylisocyanate) which have been treated to render them stable liquids at ambient temperature.
Such products include those which have been reacted with a minor amount (up to 0.2 equivalents per equivalent o~
a polyphenyl polyisocyanate) of an aliphatic glycol or mixture of aliphatic glycols; such modified methylene bis(phenylisocyanates) are described in U.S. Patent Nos.
3,394,164; 3,883,571; 4,115,429; 4,118,411 and 4,299,347; and those wherein a minor amount oP the 30 diisocyanate has been converted to the corresponding carbodiimide as described in U.S. Patent No. 3,384,653.
Mixtures of the above-described polyisocyanates can be employed i~ desired.
37,913-F -1?-:
The chain sxtenders which are uqed in making the thermoplastic polyurethanes required by the present invention include aliphatic ~traight- and branched chain diolq including cycloaliphatic diols, preferably having from 2 to 8 carbon atoms9 incluqive, in the chain.
Illustrati~e of such diolq are ethylene glycol, 1,3 propanediol, 1 9 5-pentanediol, 1,6-hexanediol, 1,2 - -propanediol, 1,3-butanediol, 1,4-butanediol, 2,3 -butanediol, 1,3-pentanediol t 1~ 2-hexanediol, 3-methylpentane-1,5-diol, 1,4-cyclohexane dimethanol, and mixtureq of two or more such diols. The chain extenders which can be used alone or in admixture with each other or any one of the above diols also inc.lude diethylene glycol, dipropylene glycol, tripropylene glycol, ethanolamine, N-methyl diethanolamine, N-ethyl diethanolamine, as well a~ ester diols obtained by e~terifying adipic, azelaic, glutarie and the aliphatic dicarboxylic acid~ with aliphatlc diols such as tho~e exemplified above utilizing from 0.01 to 0.8 mole o~
acid per mole of diol. Also inaluded ln the chaln extenderq whlch can be used in preparing the thermoplastic polyurethane~ are adducts obtained by an allphatic diol or triol such a~ 1,4-cyclohexane dlmethanol, neopentyl glycol, hexane-1,2-diol, ethylene glycol, butane-1,4-dlol, trimethylolpropane 9 Wi th caprolactone in a mole ratio o~ from 0.01 to 2 moles of oaprolactone per mole o~ diol or triol.
While any o~ the diol extendsr~ described and exemplified above can be employed in preparing the tharmoplastic polyurethane, alone, or in admixture, it is pre~erred to use 1,4-butanediol, neopentyl glycol, 1,4-cyclohexane dimethanol, ethylene glycol and dieth- ~-37,913-F -13-~ . .................................. .
",~
.
ylene glycol either alone or in admixture with each other.
The hardness of the thermoplastic polyurethane is controlled in part by the quantity and type of chain extender employed in its preparation. Larger amounts of chain extender generally give harder thermoplastic - polyurethanes.
The polyol, the organic polyisocyanate and the chain extender may be individually heated preferably to a temperature of from 60C to 135C and then the polyol and chain extender may be substantially simultaneously mixed with the polyisocyanate.
Preferably, the chain extender and the polyol, each of which has been previously heated, are first mixed and the resulting mixture is mixed with the heated polyiso-cyanate. This method is pre~erred ~or the reason that the extender and the polyester will not react prior to the introduction of polyisocyanate and rapid mixing with the polyisocyanate is thus facilitated.
Advantageously, the rate of reaction may be increased by adding any suitable catalyst to the reac-tion mixture such as tertiary amines as disclosed in, for example, U.S. Patent Nos. 2,620,516; 2,621,166 and 2,729,618.
Other techniques for the production of ther-moplastic polyurethanes useful in the context of the present invention are disclosed in the text "Polyure-thanes: Chemistry and Technology", Vol~ 2 9 pp ~ 299-452 by J. H. Saunders and K. C. Frisch, Interscience Pub-lishers, New York (1964).
37,913-F -14-, ~ ,............ . .
, The polyblends of this invention can be pre~
pared by mixing the thermoplastic aromatic polycarbonate with the thermoplastic po'yurethane and wherein the process is substantially free of a processing aid. The blending may be carried out by adding the polycarbonate and polyurethane together and mixing the components with conventional technique and apparatusO In general, the mixtures may be blended by optionally premixing in conventional mixing rolls, dough mixers, ~anbury mixers and the like and blending the premix in an extruder or fluxing it on a mill at an elevated temperature suffi-cient to achieve a melt blending. Prior to melt-blend-ing it is important that all ingredients are dried thoroughly, in for example, a dehumidifying dryer oper-ating at a temperature of greater than 95C, and areessentially water-free.
The temperature employed in the melt-blending process is sufficient to allow the preparation of the polyblend described in the present invention. Advanta-geously, the temperature does not exceed the decomposi-tion temperature of the thermoplastic polyurethane that is to be blended with the polycarbonate. Typically, initial temperatures employed in a melt-blending process will be less than 260C, preferably less than 250C and more preferably less than 240C. These temperatures can be maintained or reduced as appropriate so as to maintain an efficient melt-blending process whilst minimizing any possibility of decomposing the thermoplastic polyurethane.
' 37,913-F -15-~ ' , ~ . ;
~ ~J~ ~J
The melt-blending process is conducted sub-stantially free o~ such processing aids that consist of an acrylic polymer having a number average molecular weight of from 500,000 to 1,500,000. Typical acrylic polymers are homopolymers of methyl methacrylate;
copolymers of methyl methacrylate with n-butyl methacrylate or ethyl acrylate; or terpolymers of methyl methacrylate, n-butyl acrylate and styrene.
By "substantially free" it is meant that the processing aid is present in less than 5.0, preferably less than 3.0, and more preferably less than l.O weight percent based on the combined weight of (a? and (b), and most preferably is absent.
The thermoplastic polyblend in its melt-blended state can be used to prepare articles through extru~ion techniques with or without subsequent forming or injec-tion molding. Alternatively, the polyblend may be transformed into pellets by suitable techniques, such as disclosed by U.S. Patent Nos. 3,642,964 and 3,963,679, and stored for future use.
The thermoplastic polyblends of the present invention may also optionally contain various commonly known and used additives such as, for example, impact modifying agents; antioxidants; antistatic agents; inert fillers such as glass, talc, mica and clay, ultraviolet radiation absorbers such as benzophenones, and benzotri-azoles; hydrolytic stabilizers such as the epoxides disclosed in U.S. Patent Nos. 3,489,716; 4,138,379 and 3,839,247; color stabilizers such as organopho~phites;
thermostabilizerq such as phosphites; flame retardants and mold release agents.
37,913-F -16-: , . ~ . .. . , ~
. ' ' , ' ., : '; , ' ,. ~
. . .
-17- 2 ~
Representative of suitable impact modi~ying agents are selectively hydrogenated linear, sequential o~ radial teleblock copolymers of a vinyl aromatic com-pound and an olefinic elastomer such as described in U.S. Patent Nos. 3,281,383; 3,753,936 and 4,481,331.
The impact modifying agents, optionally, employed in preparing the polyblends of the present invention may also include rubber~ or rubber-modified polystyrene ~uch as described in European Patent No.
125,739 and U.S. Patent No. 4,101,504.
Sufficient quantities o~ the impact modi~y-ing agent is employed to give the desired increase in impact performance of the polyblend. Advantageously, the quantity of impact modi~ying agent employed is from 0.1 to 10, preferably from 2.0 to 10.0, and more pref erably from 3.0 to 8.0 weight percent of the combined weight of the thermoplastic aromatic polycarbonate (a) and thermoplastic polyurethane (b) in the polyblend.
Su~ficient quantities of the filler are employed to give a desired increase in modulus and/or a decrease in the coefficient of linear thermal expansion of the polyblend. Advantageously, the quantity o~ fil-ler employed is from 2.0 to 25.0 and is preferably from 5 to 15 weight percent of the combined weight of the thermoplastic aromatic polycarbonate (a) and thermo-plastic polyurethane (bj in the polyblend.
Impact-modifying agents and fillers can be, and advantageously are, used in combination to enhance the physical properties of the polyblend.
:
:.
37,913-F -17-- .: .: . . . .. . :
. . .
~ ~ ~ b~
~1~~ 73730-7 The polyblends of the pre~ent invention can be melt extruded or molded to form articles such as automotive parts, tool hou~ings, Ytructural component~, recreational objecta, hou~ehold appliances and enclo-sures for tran~portation or communication and the like.
The u3e o~ the polyblends of the invention in place of thermopla~ti~ polyoarbonate in ~uch applications i9 particularly advantageou~ where in the application there i9 a risk o~ the prepared article coming into contact with organic solvents, especially hydrocarbon solvent~.
The ~ollowing examples are given to illu~trate the invention and should not be interpreted a~ limiting it in any way. Unless stated otherwise, all part and percentage~ are given by weight.
The following materials are used in the exam-ple~. All thermopla~tio polyurethane~ are derlved ~rom a methanediphenylisocyanate and a polyol.
Thermo~astic Pol~urethanes (TPU) TPU-A: a thermopla~tlc polyurethane having a Shore Hardne~s of 90A (ASTM D-2240), and an eatimated trnsile ~trength of 6000 psi (40 MPa1 (ASTM D-412) and a melt flow rate (MFR)( ASTM D-1238-85) 15 g~10 minute~ at 274C/~.16 kg and a 500 percent elongatlon at break prepared from a polybutylene adipate ester polyol TPU B: a thermopla3tiQ polyurethane having a Shore Hardne~s of 55D, an e~timated ten~ile ~trangth 37,913-F -18-.
.
' " ' -19~ 2 rl ~ ~
of 6500 psi (45 MPa) and a MFR 15 g/10 minutes at 224C/2.16 kg and a 440 percent elongat~on at break prepared from a polybutylene adlpate eqter polyol.
TPU-C: a thermopla~tic polyurethane having a Shore Hardne~s oP 65D, an estimated ten~ile ~trength - of 5900 psi (40 MPa) and a MFR 30 g/10 minute~
224C/5.0 kg and a 450 percent elongation at break prepared from a polybutylene adipate e3ter polyol.
TPU-D: a thermopla~tic polyurethane having a Shore Hardne~ o~ 90A, an eQtimaked tensile ~trength o~ 6200 psi (43 MPa) and a MFR 17 g/10 minute~
at 224C/2.16 kg, and a 430 percent elongation at break prepared from a polytetramethylene glycol, polyether polyol.
TPU-E: a thermopla~ti¢ polyurethane having a~Shore Hardnes3 of 55D, an e~timated tensile strength of 6500 psi (45 MPa) and a MFR 11 g/10 minute~
at 224C/2.16 kg, and a 400 percent elongatlon break prepared ~rom a polytetramethylene glycol, polyether polyol.
TPU-F: a thermoplaQtic polyurethane having a Shore Hardness o~ 65D and an e~timated ten~ile -Qtren~th o~ 6500 psi (45 MPa~ and a MFR 20 g/10 minuteQ at 224C/5.0 kg, and a 420 percent elongation at break prepared from a polytetramethylene glycoI, polyether polyol. ~:
37.913-F -19-'.
.
- :
7~ ~
~20 Thermopla~tic Polyoarbonate PC-1: a commercially available thermopla~tic aromatic polycarbonate Calibre~ 300 15, having a melt ~low rate of 15 g/10 minute~ at 300C/1.2 kg weight (ASTM D-1238) ~old by The Dow Chemical Company, deriYed from bi~phenol A
The polyblends o~ the following exampleY are prepared in a Werner-P~leider Tw$n-Screw extruder ZSK-30 operating at 400 rpm, torque 60 to 70 percent, die pressure lO0 psi (690 kPa), ~ront zone temperature 240C, r~ar zone temperature 230C. Poly¢arbonate polymer i9 dried prior to blending ~or at lea~t 4 hours in a circulatlng air oven at 120C. Sim1larly, the thermoplastic polyurethane is dried in a dehumidiPying dryer at 99C
for at least 4 hour~.
Molded articles from the polyblend~ are pre-pared by injection molding u ing an Arbury 28 ton (25.4 tonnes)injection molder operating at injection pre~sure 4 to 5.5 MPa (600 to 800 psi), holdlng pres~ure 2 to 3 MPa (300 to 450 p9i), nozzle temperature 227C to 215C, all barrel temperaturs 23 C to 220C, mold tempera~ur~
49~C to 38C. Prior to molding the granular polyblend i~
drled at 100C Por 4 hour~ in a dehumldifying dryer.
The oompo~itions oP the poIyblends prepared and 3~ the propertieq oP the molded article~ obtained from the polyblend3 are as ind1eated in Table I.
Teqt re ult~ are ln aocordanoe with the Pol-lowing test method~. Melt flow rata~, ASTM D~1238-85;
.
37,913-F -20--.
' , , - .
flexural modulus~ ASTM D-790-84; distortion tempera-ture under load (DTUL), ASTM D-648-82; heat sag, ASTM
D-3769; notchecl izod, ASTM D-256-84; and environmental stress crack resistance (ESCR), GMR-3779.
` ;~
37,913-F -21- ~.
.
i~~ ~ o . . . . . . . O, O. O, O, n ~ A N " ~ N N O ~ O O N
a ~ ~ .. " ~ ~ N ~ ~ . . 3 o` ~ ~ ~ n a --I ~ N a~
~?
a L I N N N N ~ N N r~
; G
N N N ~ ~ ~ N ,.~
d q ~5 Ul o ~ ~ ~ ~ ~ I` ~r N 0 ~ r1 ,~
~ U') r :3 ~t ~ N ~`i ~ oi ~'i ~ r~ N ~ ~
N ~ ~q U3 ~ ~ C n o ~ ~o o 9 1 o ~ 1~ ~ , ., . . , o O r1 t~ t~ ~ t`1~'~D t'' ~ Q :I t l~
~ ~ 61 la ~It Ei p~ 4 ~ t q 1~ N ~ `1 ~~ t~ 7 at ~t ~ O ~
E~ Cl. ~ ~ ~S m ~U U a W o,. R- r~ v ~ c ~ ~
qJ ~ 3 0 ~ at ~ a ~ ~ # # ¢ 4l ~
~ ~ Gt * 3~ 3 `
` :` ' :
~'; ,~ ` ' :`
: ' `
J 3' ~
As can be seen from the data presented in Table I, the melt Plow rate properties oP the polyhlends improve with the increa~ing quantity oP thermoplas~ic polyurethane incorporated therein.
With respect to flexural modulus it is to be observed that as more thermoplastic polyurethane is incorporated into the blend the resulting blend exhibits more flexibility as seen by a lower flexural modulus.
When the blended thermoplastic polyurethane is a harder polyurethane, then the increase in flexibility of the resulting blend is somewhat lower than when a similar percentage oP a softer thermoplastic polyurethane is present in the polyblend.
The Plexural modulus of the resulting poly-blend will also be dependent on the post-injection, extruding, and mold thermal history to which the poly-blend ha~ been subjected. If the polyblend is allowed to oool slowly, hard segments contained within the ther-moplastic polyurethane can more ea~ily align into crys-talline ~ormations inPluencing the flexural modulus oP
the Pinal product. If the polyblend is cooled quickly, there is insufficient time to obtain crystalline Porma-tions. The presence of crystalline formation can enhance the flexural modulus.
Distortion temperatures under load become rela-tively lower as the quantity oP the thermoplasticpolyurethane in the polyblend increases.
The polyblends of this present invention show an optimum notched izod impact perPormance when they contain about 30 weight percent of the thermoplastic 37,913-F -23-", polyurethane. Surprisingly, this optimum performance is associated with the softer thermoplastic polyester polyol-hased polyurethanes.
Again, as with the impact strength properties, optimum ESCR performance is observed when using the softer thermoplastic polyurethanes. The data suggests that optimum solvent resistance is obtained when the thermoplastic polyurethane is present in about 25 weight percent based on combined weights of (a) and (b) in the polyblend.
Comparative Examples B, C and D are polyblends prepared from thermoplastic polyether polyol-based polyurethanes. As can be seen from the table, the polyblends of this invention offer better modulus, DTUL
and ESCR performance.
37,913-F -24--:, ~. . ;
. , .
~' ,
Mixtures of the above-described polyisocyanates can be employed i~ desired.
37,913-F -1?-:
The chain sxtenders which are uqed in making the thermoplastic polyurethanes required by the present invention include aliphatic ~traight- and branched chain diolq including cycloaliphatic diols, preferably having from 2 to 8 carbon atoms9 incluqive, in the chain.
Illustrati~e of such diolq are ethylene glycol, 1,3 propanediol, 1 9 5-pentanediol, 1,6-hexanediol, 1,2 - -propanediol, 1,3-butanediol, 1,4-butanediol, 2,3 -butanediol, 1,3-pentanediol t 1~ 2-hexanediol, 3-methylpentane-1,5-diol, 1,4-cyclohexane dimethanol, and mixtureq of two or more such diols. The chain extenders which can be used alone or in admixture with each other or any one of the above diols also inc.lude diethylene glycol, dipropylene glycol, tripropylene glycol, ethanolamine, N-methyl diethanolamine, N-ethyl diethanolamine, as well a~ ester diols obtained by e~terifying adipic, azelaic, glutarie and the aliphatic dicarboxylic acid~ with aliphatlc diols such as tho~e exemplified above utilizing from 0.01 to 0.8 mole o~
acid per mole of diol. Also inaluded ln the chaln extenderq whlch can be used in preparing the thermoplastic polyurethane~ are adducts obtained by an allphatic diol or triol such a~ 1,4-cyclohexane dlmethanol, neopentyl glycol, hexane-1,2-diol, ethylene glycol, butane-1,4-dlol, trimethylolpropane 9 Wi th caprolactone in a mole ratio o~ from 0.01 to 2 moles of oaprolactone per mole o~ diol or triol.
While any o~ the diol extendsr~ described and exemplified above can be employed in preparing the tharmoplastic polyurethane, alone, or in admixture, it is pre~erred to use 1,4-butanediol, neopentyl glycol, 1,4-cyclohexane dimethanol, ethylene glycol and dieth- ~-37,913-F -13-~ . .................................. .
",~
.
ylene glycol either alone or in admixture with each other.
The hardness of the thermoplastic polyurethane is controlled in part by the quantity and type of chain extender employed in its preparation. Larger amounts of chain extender generally give harder thermoplastic - polyurethanes.
The polyol, the organic polyisocyanate and the chain extender may be individually heated preferably to a temperature of from 60C to 135C and then the polyol and chain extender may be substantially simultaneously mixed with the polyisocyanate.
Preferably, the chain extender and the polyol, each of which has been previously heated, are first mixed and the resulting mixture is mixed with the heated polyiso-cyanate. This method is pre~erred ~or the reason that the extender and the polyester will not react prior to the introduction of polyisocyanate and rapid mixing with the polyisocyanate is thus facilitated.
Advantageously, the rate of reaction may be increased by adding any suitable catalyst to the reac-tion mixture such as tertiary amines as disclosed in, for example, U.S. Patent Nos. 2,620,516; 2,621,166 and 2,729,618.
Other techniques for the production of ther-moplastic polyurethanes useful in the context of the present invention are disclosed in the text "Polyure-thanes: Chemistry and Technology", Vol~ 2 9 pp ~ 299-452 by J. H. Saunders and K. C. Frisch, Interscience Pub-lishers, New York (1964).
37,913-F -14-, ~ ,............ . .
, The polyblends of this invention can be pre~
pared by mixing the thermoplastic aromatic polycarbonate with the thermoplastic po'yurethane and wherein the process is substantially free of a processing aid. The blending may be carried out by adding the polycarbonate and polyurethane together and mixing the components with conventional technique and apparatusO In general, the mixtures may be blended by optionally premixing in conventional mixing rolls, dough mixers, ~anbury mixers and the like and blending the premix in an extruder or fluxing it on a mill at an elevated temperature suffi-cient to achieve a melt blending. Prior to melt-blend-ing it is important that all ingredients are dried thoroughly, in for example, a dehumidifying dryer oper-ating at a temperature of greater than 95C, and areessentially water-free.
The temperature employed in the melt-blending process is sufficient to allow the preparation of the polyblend described in the present invention. Advanta-geously, the temperature does not exceed the decomposi-tion temperature of the thermoplastic polyurethane that is to be blended with the polycarbonate. Typically, initial temperatures employed in a melt-blending process will be less than 260C, preferably less than 250C and more preferably less than 240C. These temperatures can be maintained or reduced as appropriate so as to maintain an efficient melt-blending process whilst minimizing any possibility of decomposing the thermoplastic polyurethane.
' 37,913-F -15-~ ' , ~ . ;
~ ~J~ ~J
The melt-blending process is conducted sub-stantially free o~ such processing aids that consist of an acrylic polymer having a number average molecular weight of from 500,000 to 1,500,000. Typical acrylic polymers are homopolymers of methyl methacrylate;
copolymers of methyl methacrylate with n-butyl methacrylate or ethyl acrylate; or terpolymers of methyl methacrylate, n-butyl acrylate and styrene.
By "substantially free" it is meant that the processing aid is present in less than 5.0, preferably less than 3.0, and more preferably less than l.O weight percent based on the combined weight of (a? and (b), and most preferably is absent.
The thermoplastic polyblend in its melt-blended state can be used to prepare articles through extru~ion techniques with or without subsequent forming or injec-tion molding. Alternatively, the polyblend may be transformed into pellets by suitable techniques, such as disclosed by U.S. Patent Nos. 3,642,964 and 3,963,679, and stored for future use.
The thermoplastic polyblends of the present invention may also optionally contain various commonly known and used additives such as, for example, impact modifying agents; antioxidants; antistatic agents; inert fillers such as glass, talc, mica and clay, ultraviolet radiation absorbers such as benzophenones, and benzotri-azoles; hydrolytic stabilizers such as the epoxides disclosed in U.S. Patent Nos. 3,489,716; 4,138,379 and 3,839,247; color stabilizers such as organopho~phites;
thermostabilizerq such as phosphites; flame retardants and mold release agents.
37,913-F -16-: , . ~ . .. . , ~
. ' ' , ' ., : '; , ' ,. ~
. . .
-17- 2 ~
Representative of suitable impact modi~ying agents are selectively hydrogenated linear, sequential o~ radial teleblock copolymers of a vinyl aromatic com-pound and an olefinic elastomer such as described in U.S. Patent Nos. 3,281,383; 3,753,936 and 4,481,331.
The impact modifying agents, optionally, employed in preparing the polyblends of the present invention may also include rubber~ or rubber-modified polystyrene ~uch as described in European Patent No.
125,739 and U.S. Patent No. 4,101,504.
Sufficient quantities o~ the impact modi~y-ing agent is employed to give the desired increase in impact performance of the polyblend. Advantageously, the quantity of impact modi~ying agent employed is from 0.1 to 10, preferably from 2.0 to 10.0, and more pref erably from 3.0 to 8.0 weight percent of the combined weight of the thermoplastic aromatic polycarbonate (a) and thermoplastic polyurethane (b) in the polyblend.
Su~ficient quantities of the filler are employed to give a desired increase in modulus and/or a decrease in the coefficient of linear thermal expansion of the polyblend. Advantageously, the quantity o~ fil-ler employed is from 2.0 to 25.0 and is preferably from 5 to 15 weight percent of the combined weight of the thermoplastic aromatic polycarbonate (a) and thermo-plastic polyurethane (bj in the polyblend.
Impact-modifying agents and fillers can be, and advantageously are, used in combination to enhance the physical properties of the polyblend.
:
:.
37,913-F -17-- .: .: . . . .. . :
. . .
~ ~ ~ b~
~1~~ 73730-7 The polyblends of the pre~ent invention can be melt extruded or molded to form articles such as automotive parts, tool hou~ings, Ytructural component~, recreational objecta, hou~ehold appliances and enclo-sures for tran~portation or communication and the like.
The u3e o~ the polyblends of the invention in place of thermopla~ti~ polyoarbonate in ~uch applications i9 particularly advantageou~ where in the application there i9 a risk o~ the prepared article coming into contact with organic solvents, especially hydrocarbon solvent~.
The ~ollowing examples are given to illu~trate the invention and should not be interpreted a~ limiting it in any way. Unless stated otherwise, all part and percentage~ are given by weight.
The following materials are used in the exam-ple~. All thermopla~tio polyurethane~ are derlved ~rom a methanediphenylisocyanate and a polyol.
Thermo~astic Pol~urethanes (TPU) TPU-A: a thermopla~tlc polyurethane having a Shore Hardne~s of 90A (ASTM D-2240), and an eatimated trnsile ~trength of 6000 psi (40 MPa1 (ASTM D-412) and a melt flow rate (MFR)( ASTM D-1238-85) 15 g~10 minute~ at 274C/~.16 kg and a 500 percent elongatlon at break prepared from a polybutylene adipate ester polyol TPU B: a thermopla3tiQ polyurethane having a Shore Hardne~s of 55D, an e~timated ten~ile ~trangth 37,913-F -18-.
.
' " ' -19~ 2 rl ~ ~
of 6500 psi (45 MPa) and a MFR 15 g/10 minutes at 224C/2.16 kg and a 440 percent elongat~on at break prepared from a polybutylene adlpate eqter polyol.
TPU-C: a thermopla~tic polyurethane having a Shore Hardne~s oP 65D, an estimated ten~ile ~trength - of 5900 psi (40 MPa) and a MFR 30 g/10 minute~
224C/5.0 kg and a 450 percent elongation at break prepared from a polybutylene adipate e3ter polyol.
TPU-D: a thermopla~tic polyurethane having a Shore Hardne~ o~ 90A, an eQtimaked tensile ~trength o~ 6200 psi (43 MPa) and a MFR 17 g/10 minute~
at 224C/2.16 kg, and a 430 percent elongation at break prepared from a polytetramethylene glycol, polyether polyol.
TPU-E: a thermopla~ti¢ polyurethane having a~Shore Hardnes3 of 55D, an e~timated tensile strength of 6500 psi (45 MPa) and a MFR 11 g/10 minute~
at 224C/2.16 kg, and a 400 percent elongatlon break prepared ~rom a polytetramethylene glycol, polyether polyol.
TPU-F: a thermoplaQtic polyurethane having a Shore Hardness o~ 65D and an e~timated ten~ile -Qtren~th o~ 6500 psi (45 MPa~ and a MFR 20 g/10 minuteQ at 224C/5.0 kg, and a 420 percent elongation at break prepared from a polytetramethylene glycoI, polyether polyol. ~:
37.913-F -19-'.
.
- :
7~ ~
~20 Thermopla~tic Polyoarbonate PC-1: a commercially available thermopla~tic aromatic polycarbonate Calibre~ 300 15, having a melt ~low rate of 15 g/10 minute~ at 300C/1.2 kg weight (ASTM D-1238) ~old by The Dow Chemical Company, deriYed from bi~phenol A
The polyblends o~ the following exampleY are prepared in a Werner-P~leider Tw$n-Screw extruder ZSK-30 operating at 400 rpm, torque 60 to 70 percent, die pressure lO0 psi (690 kPa), ~ront zone temperature 240C, r~ar zone temperature 230C. Poly¢arbonate polymer i9 dried prior to blending ~or at lea~t 4 hours in a circulatlng air oven at 120C. Sim1larly, the thermoplastic polyurethane is dried in a dehumidiPying dryer at 99C
for at least 4 hour~.
Molded articles from the polyblend~ are pre-pared by injection molding u ing an Arbury 28 ton (25.4 tonnes)injection molder operating at injection pre~sure 4 to 5.5 MPa (600 to 800 psi), holdlng pres~ure 2 to 3 MPa (300 to 450 p9i), nozzle temperature 227C to 215C, all barrel temperaturs 23 C to 220C, mold tempera~ur~
49~C to 38C. Prior to molding the granular polyblend i~
drled at 100C Por 4 hour~ in a dehumldifying dryer.
The oompo~itions oP the poIyblends prepared and 3~ the propertieq oP the molded article~ obtained from the polyblend3 are as ind1eated in Table I.
Teqt re ult~ are ln aocordanoe with the Pol-lowing test method~. Melt flow rata~, ASTM D~1238-85;
.
37,913-F -20--.
' , , - .
flexural modulus~ ASTM D-790-84; distortion tempera-ture under load (DTUL), ASTM D-648-82; heat sag, ASTM
D-3769; notchecl izod, ASTM D-256-84; and environmental stress crack resistance (ESCR), GMR-3779.
` ;~
37,913-F -21- ~.
.
i~~ ~ o . . . . . . . O, O. O, O, n ~ A N " ~ N N O ~ O O N
a ~ ~ .. " ~ ~ N ~ ~ . . 3 o` ~ ~ ~ n a --I ~ N a~
~?
a L I N N N N ~ N N r~
; G
N N N ~ ~ ~ N ,.~
d q ~5 Ul o ~ ~ ~ ~ ~ I` ~r N 0 ~ r1 ,~
~ U') r :3 ~t ~ N ~`i ~ oi ~'i ~ r~ N ~ ~
N ~ ~q U3 ~ ~ C n o ~ ~o o 9 1 o ~ 1~ ~ , ., . . , o O r1 t~ t~ ~ t`1~'~D t'' ~ Q :I t l~
~ ~ 61 la ~It Ei p~ 4 ~ t q 1~ N ~ `1 ~~ t~ 7 at ~t ~ O ~
E~ Cl. ~ ~ ~S m ~U U a W o,. R- r~ v ~ c ~ ~
qJ ~ 3 0 ~ at ~ a ~ ~ # # ¢ 4l ~
~ ~ Gt * 3~ 3 `
` :` ' :
~'; ,~ ` ' :`
: ' `
J 3' ~
As can be seen from the data presented in Table I, the melt Plow rate properties oP the polyhlends improve with the increa~ing quantity oP thermoplas~ic polyurethane incorporated therein.
With respect to flexural modulus it is to be observed that as more thermoplastic polyurethane is incorporated into the blend the resulting blend exhibits more flexibility as seen by a lower flexural modulus.
When the blended thermoplastic polyurethane is a harder polyurethane, then the increase in flexibility of the resulting blend is somewhat lower than when a similar percentage oP a softer thermoplastic polyurethane is present in the polyblend.
The Plexural modulus of the resulting poly-blend will also be dependent on the post-injection, extruding, and mold thermal history to which the poly-blend ha~ been subjected. If the polyblend is allowed to oool slowly, hard segments contained within the ther-moplastic polyurethane can more ea~ily align into crys-talline ~ormations inPluencing the flexural modulus oP
the Pinal product. If the polyblend is cooled quickly, there is insufficient time to obtain crystalline Porma-tions. The presence of crystalline formation can enhance the flexural modulus.
Distortion temperatures under load become rela-tively lower as the quantity oP the thermoplasticpolyurethane in the polyblend increases.
The polyblends of this present invention show an optimum notched izod impact perPormance when they contain about 30 weight percent of the thermoplastic 37,913-F -23-", polyurethane. Surprisingly, this optimum performance is associated with the softer thermoplastic polyester polyol-hased polyurethanes.
Again, as with the impact strength properties, optimum ESCR performance is observed when using the softer thermoplastic polyurethanes. The data suggests that optimum solvent resistance is obtained when the thermoplastic polyurethane is present in about 25 weight percent based on combined weights of (a) and (b) in the polyblend.
Comparative Examples B, C and D are polyblends prepared from thermoplastic polyether polyol-based polyurethanes. As can be seen from the table, the polyblends of this invention offer better modulus, DTUL
and ESCR performance.
37,913-F -24--:, ~. . ;
. , .
~' ,
Claims (12)
1. A thermoplastic composition comprising a polyblend of a thermoplastic aromatic polycarbonate polymer and a thermoplastic polyurethane characterized in that said polyblend consists essentially of (a) from 65 to 95 weight percent based on the combined weights of (a) and (b) of a thermoplastic aromatic polycarbonate polymer; and (b) from 5 to 35 weight percent based on the combined weights of (a) and (b) of a thermoplastic aromatic polycarbonate polymer; and polyester polyol-based polyurethane having a Shore Hardness from 70A to 70D.
2. A composition as claimed in Claim 1, wherein said polyblend exhibits an environmental crack stress resistance of at least 15 MPa (2150 psi) and a flexural modulus of at least 1.5 GPa (2.20 x 105 psi).
3. A composition as claimed in Claim 1 or Claim 2, wherein the thermoplastic polyester polyol-based polyurethane is present in from 15 to 35 weight percent based on the combined weights of (a) and (b).
4. A composition as claimed in any one of the preceding claims, wherein the thermoplastic polyurethane has a Shore Hardness of from 70A to 100A.
5. A composition as claimed in any one of Claims 1 to 3, wherein the thermoplastic polyurethane has a Shore Hardness of from 40D to 70D.
6. A composition as claimed in any one of the preceding claims which additionally comprises an impact modifying agent in an amount of from 0.1 to 10 weight 37,913-F -25-percent based on the combined weights of (a) and (b), and/or a filler in an amount of from 2.0 to 25 weight percent based on the combined weights of (a) and (b).
7. A composition as claimed in any one of the preceding claims, wherein the thermoplastic aromatic polycarbonate polymer has a melt-flow rate of at least
8 g/10 minutes at 300°C/1.2 kg.
8. A composition as claimed in any one of the preceding claims, wherein the composition contains no or less than 3 weight percent based on the combined weights of (a) and (b) of acrylic polymer.
8. A composition as claimed in any one of the preceding claims, wherein the composition contains no or less than 3 weight percent based on the combined weights of (a) and (b) of acrylic polymer.
9. A composition as claimed in any one of the preceding claims, wherein the thermoplastic aromatic polycarbonate polymer is derived from bisphenol.
10. A composition as claimed in any one of the preceding claims, wherein the thermoplastic polyurethane is derived from a polyalkylene adipate ester polyol, a methylene bis(phenylisocyanate), and a diol extender selected from 1,4-butanediol, neopentyl glycol, 1,4-cyclohexane dimethanol, ethylene glycol, diethylene glycol and mixtures thereof.
11. A process for preparing a thermoplastic composition by melt blending a thermoplastic aromatic polycarbonate polymer and a thermoplastic polyurethane characterized in that (a) from 65 to 95 weight percent based on the combined weights of (a) and (b) of a thermoplastic aromatic polycarbonate polymer; and 37,913-F -26-(b) from 5 to 35 weight percent based on the combined weights of (a) and (b) of a thermoplastic polyester polyol-based polyurethane having a Shore Hardness from 70A to 70D, are melt blended in the absence of, or in the presence of less than 5 weight percent based on the combined weights of (a) and (b) of, an acrylic polymer processing aid.
12. An article prepared by melt extrusion or moulding of a composition as claimed in any one of Claims 1 to 10.
37,913-F -27-
37,913-F -27-
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/346,506 US4912177A (en) | 1989-05-02 | 1989-05-02 | Thermoplastic polyblends of aromatic polycarbonates and thermoplastic polyurethanes |
| US346,506 | 1989-05-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2012761A1 true CA2012761A1 (en) | 1990-11-02 |
Family
ID=23359725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002012761A Abandoned CA2012761A1 (en) | 1989-05-02 | 1990-03-22 | Thermoplastic polyblends of aromatic polycarbonates and thermoplastic polyurethanes |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4912177A (en) |
| EP (1) | EP0396245A3 (en) |
| JP (1) | JPH02308851A (en) |
| KR (1) | KR900018269A (en) |
| CA (1) | CA2012761A1 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2012763A1 (en) * | 1989-05-02 | 1990-11-02 | Richard E. Skochdopole | Thermoplastic polyblends of aromatic polycarbonates and thermoplastic polyurethanes |
| US5162461A (en) * | 1989-05-02 | 1992-11-10 | The Dow Chemical Company | Thermoplastic polyblends of aromatic polycarbonates and thermoplastic polyurethanes |
| US5258445A (en) * | 1990-03-08 | 1993-11-02 | The B. F. Goodrich Company | Fiber-reinforced thermoplastic molding compositions using a copolyester |
| EP0488617B1 (en) * | 1990-11-26 | 1997-09-17 | Showa Highpolymer Co., Ltd. | A method for producing saturated polyester |
| US5219933A (en) * | 1991-03-25 | 1993-06-15 | The Dow Chemical Company | Blends of polycarbonate and thermoplastic polyurethane resins containing an impact modifier |
| US5334647A (en) * | 1991-09-16 | 1994-08-02 | The B. F. Goodrich Company | Fiber-reinforced thermoplastic molding compositions |
| US5519094A (en) * | 1992-03-06 | 1996-05-21 | B. F. Goodrich Company | Fiber-reinforced thermoplastic molding compositions using a modified thermoplastic polyurethane |
| DE4305637A1 (en) * | 1993-02-24 | 1994-08-25 | Basf Ag | Thermoplastic molding compounds based on polycarbonates, thermoplastic polyurethanes and styrene copolymers |
| US6284839B1 (en) | 1995-12-29 | 2001-09-04 | The B.F. Goodrich Company | Blends of thermoplastic polymers, electrostatic dissipative polymers and electrostatic dissipative enhancers |
| KR20030097413A (en) * | 2002-06-21 | 2003-12-31 | 제일모직주식회사 | Composition of Polycarbonate Resin with high thin-wall crack resistance and transparency |
| US20050158561A1 (en) * | 2004-01-16 | 2005-07-21 | General Electric Company | Weatherable multilayer articles and method for their preparation |
| KR20090117013A (en) * | 2008-05-08 | 2009-11-12 | 삼성전자주식회사 | Exterior material for electrode machine including elastomer-resin alloy |
| KR100955482B1 (en) * | 2008-05-08 | 2010-04-30 | 삼성전자주식회사 | Novel elastomer-resin alloy composition and the preparation method thereof |
| CN103547629B (en) | 2011-04-21 | 2016-09-07 | 路博润高级材料公司 | Electrostatically dissipative polycarbonate compositions |
| CN102604357B (en) * | 2012-03-19 | 2014-11-26 | 深圳市科聚新材料有限公司 | High-fluidness PC/TPU (polycarbonate/thermoplastic urethane) alloy material and preparation method thereof |
| HUE049812T2 (en) * | 2014-12-12 | 2020-10-28 | Lubrizol Advanced Mat Inc | Halogen-free flame-retardant composition |
| CN105504648A (en) * | 2015-12-28 | 2016-04-20 | 江苏金发科技新材料有限公司 | High-fluidity, scratch-resistant and low-temperature-folding-resistant ABS (acrylonitrile butadiene styrene)/TPU (thermoplastic polyurethane) alloy material and preparation method and application thereof |
| JP7060013B2 (en) * | 2017-04-07 | 2022-04-26 | ソニーグループ株式会社 | Resin composition and method for producing the resin composition |
| CN108017894B (en) * | 2017-11-29 | 2020-04-17 | 合肥圆融新材料有限公司 | High-low temperature resistant hydrolysis-resistant PC alloy and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE634842A (en) * | 1962-07-11 | |||
| US4034016A (en) * | 1976-07-15 | 1977-07-05 | Mobay Chemical Corporation | Ternary polyblends prepared from polybutylene terephthalates, polyurethanes and aromatic polycarbonates |
| US4179479A (en) * | 1978-04-20 | 1979-12-18 | Mobay Chemical Corporation | Thermoplastic polyurethane blends containing a processing aid |
| US4350799A (en) * | 1981-09-16 | 1982-09-21 | Mobay Chemical Corporation | Thermoplastic ternary molding composition of polyurethane polyphosphonates and polycarbonate resins |
| NL8203542A (en) * | 1982-09-11 | 1984-04-02 | Stamicarbon | POLYMER COMPOSITION. |
| NL8301738A (en) * | 1983-05-17 | 1984-12-17 | Stamicarbon | IMPACT RESISTANT THERMOPLASTIC MOLD. |
| US4743650A (en) * | 1986-10-31 | 1988-05-10 | General Electric Company | Thermoplastic molding blends of polycarbonates and polyurethanes |
| CA2012763A1 (en) * | 1989-05-02 | 1990-11-02 | Richard E. Skochdopole | Thermoplastic polyblends of aromatic polycarbonates and thermoplastic polyurethanes |
-
1989
- 1989-05-02 US US07/346,506 patent/US4912177A/en not_active Expired - Fee Related
-
1990
- 1990-03-22 JP JP2069878A patent/JPH02308851A/en active Pending
- 1990-03-22 CA CA002012761A patent/CA2012761A1/en not_active Abandoned
- 1990-03-22 EP EP19900303082 patent/EP0396245A3/en not_active Withdrawn
- 1990-03-30 KR KR1019900004295A patent/KR900018269A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| KR900018269A (en) | 1990-12-21 |
| US4912177A (en) | 1990-03-27 |
| EP0396245A3 (en) | 1992-03-18 |
| JPH02308851A (en) | 1990-12-21 |
| EP0396245A2 (en) | 1990-11-07 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |