CA2075910A1 - High impact polyethylene terephthalate-polycarbonate blend compositions - Google Patents
High impact polyethylene terephthalate-polycarbonate blend compositionsInfo
- Publication number
- CA2075910A1 CA2075910A1 CA 2075910 CA2075910A CA2075910A1 CA 2075910 A1 CA2075910 A1 CA 2075910A1 CA 2075910 CA2075910 CA 2075910 CA 2075910 A CA2075910 A CA 2075910A CA 2075910 A1 CA2075910 A1 CA 2075910A1
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- CA
- Canada
- Prior art keywords
- polycarbonate
- terpolymer
- poly
- formula
- polyester
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
-
- 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
- C08L69/005—Polyester-carbonates
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Compounds (AREA)
Abstract
Polymeric compositions comprising poly(ethylene terephthalate), polycarbonate and a terpolymer constituent featuring improved impact properties, particularly subsequent to heat aging are disclosed.
Description
W0 91/155q5 ~ 75~ P~ rtVS9~ 347 ~ i r 'HIGH IMPACT POLYETHYLENE ~E~EPHTHALATE-POLYCAR~ONATE
~L~ND COMPOSI~IONS
BACKG~Q~D
Ls~l-Fi~l~ of ~h~ Inven~,ion:
The present invention relates to par~icular polyester molding compositions which are characterized by e~ceptional toughness subsequent to ann~aling. More particularly, the pr~sent invention is direct~d towards a composition which comprises a polyester and . polycarbonate or a polyarylate whlch further includes 3 reactive impact modifier.
~L~ND COMPOSI~IONS
BACKG~Q~D
Ls~l-Fi~l~ of ~h~ Inven~,ion:
The present invention relates to par~icular polyester molding compositions which are characterized by e~ceptional toughness subsequent to ann~aling. More particularly, the pr~sent invention is direct~d towards a composition which comprises a polyester and . polycarbonate or a polyarylate whlch further includes 3 reactive impact modifier.
2. Des~ip~ hQ_~LL~
Engineered plastics enjoy widespread popularity for the production of articles through the use of molding or casting processes. The ma~erials typically comprise one or more polymeric materials which e~hibit specific properties, i.e., toughne~s, rigidity, chemical resistanc~, long-~erm hygrothermal ~imensio~al stability, dielectric stren~th, and the like.
Frequently, ma~erials which e~hibit particular features such as thos~ listed are utilized as constitutents in the formation of so call~d ~blended polymers~ which comprise two or mor~ constituen~ materials, such as a two or,more polym2rs, or a polym~r with a non-polyme~ic 25 material,- which eoalstitut~nts will ideally form a material which ~hibits the beneficial feature~ of ~he con titu~nts, wikh f@w if any dekximental quali~ies.
Unfortunat~ly, a~ is well known to the art, the formation o~ blended polymeric ma~eri~ls ar~ rarely 30 atta ned whioh offer the d~irabl~ ch~ract2ristics of the constituerlts, without simultan~ously suf~ering f r~lm some d~trimen~al quality.
One polymer which is widE31y used in the formulation of en~ineer~d plastics is a polymer of ~n 35 arosn~tic carbona'ce. Such carbonate polyrn~rs, also generi~:ally term~d in the art as ~PC's", may rsadily be W~ 9!/155q5 ~ ?~ b ; ~ ; P~/US91/~3~7 759~ 2~
prepared by reacting a dlhydri~ phenol, ~uch as 2,2-bis-(4-hydro~yphenyl)propane with a carbonate precursor, such as a phosgene, in the presence o~ an acid binding agent. Generally, aromatic polycarbonate plastics may be easily molded, hal~e a hiyh tensile and impa~t strength, and e~hibit an e~cellent d~gree o~
dimensional stability in most articl~s formed there~rom. However, in particular applications, aromatic poly~arbonates are unsuitable as they ar~ also known to e~hibit se~ere environmental str~ss crazing and cracking, i.e., a type of failure which is ~nhanced by the presence of organic solvents such as basic solvents su~h as many hydrocarbons, alcohol~, ketone~, etc which are the constituents of may common automobile fluids, ~asoline, paints, and th~ like. Most significantly, the loss of impact str~ngth a~d an increase in brittle type failures in standard testing procedures has been obser~ed. C~rtain formulations of polycarbonates have been devised which increase the resistan~e of poly~arbonates to envlronmental stress cracking including the a~dition of a minor amount of a polyalkylene terephthalate ~uch as poly(ethylene terephth~late) and polySbutylene t~rephthalate).
~ -~How~Yer, arti~les formed from a blend of a -polycarbon~te a~d a minor amoun~ of a polyalkylene terephkh~l~te haYe been observed t~ h~ve a lower impact r~ tan~e to that of the polycarbonate itself. This ha~ l~d to the suggestion of using additional co~titu~t~ in a poly~arbonate and poly~lkyle~e ~ereph h~ bl~nd in order ~o im~rove th~ impact r~ tanc~ o~ ~uch ~aterials.
Polyalkylene t~rephthalates including poly(ethylen~ tereph~halate), al~o k~own to the art by its at:ronym "P~T~, and poly~butylene t~r~phthalate), 35 similarly referred to as "P~T" are aromatic polye3~rs which ~njoy Fr~que~t us~ either as tlh~ sole materials or as consti tuent~ in plastic produc~ wh~re rigidi ty, WO 9 1 / 1 5~45 . r ~; PCT/ US91/0l347 ~ ~3~ 2~ 5~
impact resistance, and,,,~rasion resistance, are required. This is kno~n to the art to be due ~o the relatively high degree ~ crystal1inity which polyalkyle~e terephthalates, particularly P~T, ezhibit subseguent to cooling fromthe melt, a~d thus encourages ~their use in many molding op~rations, particularly ~njection molding processes. Ho~ever, these ma~erials most particularly PET, are known to e~hibit poor impact resistance properties subsequent to anneali~g or h~at aging. In contrast to PBT, injec~ion molding of PET
results in a slow rate of crystallization and non-uni~orm or low crystallinity in molded articles.
Subsequent annealing or h~at e~posure of PET molded articl~s caus~s further crystalliza~ion resulti~g in larger, non-uniform crystalline structures. Howsver, as is well known to the art, polymers which e~hibit large, non-uni~orm crys~alline struc~ur~s also e~hibit low impact re~i~tance, a quality which is frequently unde~irable in mold~d article~. Thu~, unfilled PET is not normally preferr~d a~ injection molding resins due to its low~r impact re~istanc~ as compared to P~T, after crystallization.
Further ~uggestQd improveme~t~ in the processing and khe phy~ical propertie~ of p:la~tic ma~erials comprising a bl~nd or mi~tur~ o a polycarbona~e and an poly(alkyl~ne t2r~ph halate) h~v~ iM~luded the addi~ion of furth~r constitu~nts to the~e two polymer~, or ~he u~ o ~p~cific molding proce~ es Eor ~he production o ar~icl~ form~d from polycarbona~ and poly~al~ylene t~r~phth~l~te) bl~d3. So~ ~ample~ iaclude U.S.
Pat~nt 4,522,979 to Chung ~t.al. or nMolding Compo~ition~ Having An E~hanc~d R~ t~nce to Gasoline"
which disclo~e~ PE and PC bl~nded ~i~h rubbery impact modified ~d a blocked polyi~ocy~nate prepolym~r, U.5.
P~tent 4,769~556 to ~u~b~rg et.al. ~or WT~rmoplastic Moldinq ~terial~ of Polye$t~r and Polycar~onate~
- - disclo~ing a th~rmopl~ti~ mold.ing m~t~r~al ~ompri~ing ~ q _ polyalkylono torephthalat9~, polycarbonat~ and a rubb~r toughon~r and rubb~ry ethylene copolym~r~, U.S.
Pat~nt 4,~97,44a for "polye~ter/polycarbonate Blends~
to Romanc~ for PE/PC ble~d~ ~hich include core shell S rubb~s as impac~ modifiersi U.S. Patent 4,737,5~5 to Liu et.al. for "Ternary Polycarbonat~ ~lend~
disclosing compo~ition~ having a major amount of an aromatic carbonatc polymer, and a minor amount o~ an aromatic carbonate polym~r impact modifying composition co~pri~ing a ~teleblock~ copolym~r o~-a vinyl aromatic compound and an ol~finic ela~tom~r, and an ol~in alkylacrylate. Furth~r ar~ U.S. Patent 4,S29,76Q to ~iu ot.al. for ~Compo~i~ion o~ Polycarbonat~, Polyc~ter, Acrylat~ Ela~tom~ric Copolym~r and a Pheno~y 15 Re~in~ di~cus~e~ a polymer compo~1tion which comyrises a PC, polyalkylene terephthalat0 and an ela~tomeric acrylat~ co~olym~r, and of particular not~ is U.S.
Pat~nt 4,753,980 to D~yru~ for ~Toughsned Thermoplastic PO1YQ~ter Compo~ition~ wh~r~ Deyrup d~3cribe~
compo~ition~ which includ~ a poly~t~r re~ln, which may - b~ a poly(alkylene ter~pbth~lat~ polym~r, ~uch a~ PET
or poly(butyl*n~ t~rephthalat~, which i3 commonly known as ~P~T~ ~ith~r a~ a homopolym~ or a copolymer, or mi~t~ of PET and P~T, and an 0thyl~n~ te~polymer such a~ ~thyl~n~Jm~th~c~ylat~/glycid~l m~thacrylat~.
Purth~r, Europ~n A~ atlon 0 180 648 to Toray - Indu~t~o~0 Inc. fot a "Poly~t~r Compo~itio~ and ~ol~ng~ Th~r~of~ di3010~ a polyme~ compo~ition com~ g ~ aromatic poly~st~r, an aro~atic polyc~bon~t~ ha~ing a numb~r av~rag~ rnol~cular weight o~ lo,ooo to ao,ooo and a oopolym~r consi3ting e~ ti~lly of an al~ha~ol~i~ and th~ gly~dyl es~er o an alpha,b~t~-ehylenlcally u~a~ura~d car~o~ylic acid.
T~ r~
.~
Additionally~ European Application 0 ~06 267 to BASF AG describes impact modi~ied polyester-polycarbonate composition~ containing polyethyl~ne tereph~halate, an aromatic polycarbonate, and ~
ethylene/n-butyl acrylate/glycidyl methacrylatQ
terpolymer.
While some of these technique~ have provided co~positions yielding articles havlng satisfactory properti2~, their diversity and number a r~
~i 7~
WO91/1~4~ Pcr/us9l/ol347 ~ 5 indi~ate that the n~ed fo~ novel compositions which e~hibit further i~proYem~nts in properties, and processability e:~i s~s .
In accordance with the instant in~ention there is provided an impact modified polyester-polycarbonate composition comprising:
a polyester, a polycarbonate represented by re~urring structural units o~ ~h~ formula:
-[-A-O-C-O-3-where A is a divalent aromatic radical de~ived from a dihydric aromatic compound, and a reac~ive terpolymer constituent (hereina~ter interchan~0~bly referred to as ~graft terpolymer~) which comprises a compound having the formula:
[Formula l] E/A/~
where W~ is.repr~entative of an alpha-olefin, or in the altern~tive, an alkadiene, ~A~ i~ r~presenta~ive of a mat~rial ha~ing the formula, [Formula 3] C~2 ~ C
z where ~Y~ is -H or an alkyl substituent~ ~Z~ is -COOR, -CN, -OCOR, or ~Ar, wh~rein "R~ may be a me~hyl, e~hyl, butyl or other alkyl group, and ~r~ may b~ a phenyl or q ~ 5 ~O91/15~45 ~ i ~ - P~T/US~1/01~7 substitued phenyl, and "X~ repr~sent~ a comono~er e~hibiting th~ structure [Formula 4] CH2 _ C
, -which contains a r~aotive functionality ~P" which is selected from epo~ide, isocya~ate, 1,3-o~azoline, or acyllactam ~unctio~alities, where the ~erpolymer forms graft linked bonds with other polymerie materials in a composition, particularly with polycarbonates an~ the poly(ethylene terephthalates).
Molded articles comprising the .inventive composition are also provided.
It ha~ al50 been unespectedly discoY~red that a polymer composition having impro~ed properties may be produced wherein the inv~ntive polymer composition comprises a polycarbonate and a poly(ethylene terephthalate) and an actiYe yraft terpolymer ac~ording to the afor~m~ntioned formula ~E/A/X~ which graft terpolymer eshibit~ th~ reactiv~ ability of forming graft-type bond~ wi~h poly~arbonat~s and with the terminal group~ of poly(ethyl~ne tersphthalate) exhibits impro~d properties, especially retention of high impact r~is~ance properties 3ubs~qu~nt ~ h~at a~in~.
A~cording to th~ pr~ent in~ntion, the polycarbona~es 30 whi~h ~y be u~ed ar2 the carbvnat~ pol~rs of dihydric ph~nols. Such poly~arbona~2s m~y be prepared by r~acting a dihyd~ic phenol with a 02rbonat~
precur~or such a~ a pho~gene, a halo form~t~, or a carbon~t~ ~t~r. In g~neral, the r~ulting WO91/15545 ~ 2 ~ ~S 9~ O Pc~/us9l/ol~7 polycarbonate may be represented by recurring structural uni~s of the formula:
.
[Formula 2] 0 ..
-[-A-O-C-O-]-where A is a diYalent aromatic radical derived f rom a dihydric aro~atic compou~d, preferably ~isphenol A.
These dihydro~y aromatic compounds are defined as 4,4~-dihydro~ydi(mononucl~ar aryl)A compounds ~h~e th~
mononuclear aryl may be ph~nyl, tolyl, ~ylyl, ethylphenyl, isopropylphenyl~ etc., and the con~ecting A groups may be -CH2-, -C2H~ C3H6, -C H8-, -52-' -S-, -O-~ C3F
Typical dihydric phenols are 2,2-bis(4-hydro~yphenyl)propane 2,2-bis(4 hydro~yphenyl~ h~af luoropropane;
2,2-bis(4-hydro~yphenyl~pe~tane;
2,4'-(dihydro~ydiphenyl~m~thane;
bis-(4-hydro~yph~nyl3methane;
bi~-(2-hydro~yphenyl)m~thane;
hydroquino~e; .
Resorcinol;~
2S bis-(4-hydro~y-5-nltrophenyl)methane;
1,1-bis~4-hydro~yph~nyl~e~hane;
Engineered plastics enjoy widespread popularity for the production of articles through the use of molding or casting processes. The ma~erials typically comprise one or more polymeric materials which e~hibit specific properties, i.e., toughne~s, rigidity, chemical resistanc~, long-~erm hygrothermal ~imensio~al stability, dielectric stren~th, and the like.
Frequently, ma~erials which e~hibit particular features such as thos~ listed are utilized as constitutents in the formation of so call~d ~blended polymers~ which comprise two or mor~ constituen~ materials, such as a two or,more polym2rs, or a polym~r with a non-polyme~ic 25 material,- which eoalstitut~nts will ideally form a material which ~hibits the beneficial feature~ of ~he con titu~nts, wikh f@w if any dekximental quali~ies.
Unfortunat~ly, a~ is well known to the art, the formation o~ blended polymeric ma~eri~ls ar~ rarely 30 atta ned whioh offer the d~irabl~ ch~ract2ristics of the constituerlts, without simultan~ously suf~ering f r~lm some d~trimen~al quality.
One polymer which is widE31y used in the formulation of en~ineer~d plastics is a polymer of ~n 35 arosn~tic carbona'ce. Such carbonate polyrn~rs, also generi~:ally term~d in the art as ~PC's", may rsadily be W~ 9!/155q5 ~ ?~ b ; ~ ; P~/US91/~3~7 759~ 2~
prepared by reacting a dlhydri~ phenol, ~uch as 2,2-bis-(4-hydro~yphenyl)propane with a carbonate precursor, such as a phosgene, in the presence o~ an acid binding agent. Generally, aromatic polycarbonate plastics may be easily molded, hal~e a hiyh tensile and impa~t strength, and e~hibit an e~cellent d~gree o~
dimensional stability in most articl~s formed there~rom. However, in particular applications, aromatic poly~arbonates are unsuitable as they ar~ also known to e~hibit se~ere environmental str~ss crazing and cracking, i.e., a type of failure which is ~nhanced by the presence of organic solvents such as basic solvents su~h as many hydrocarbons, alcohol~, ketone~, etc which are the constituents of may common automobile fluids, ~asoline, paints, and th~ like. Most significantly, the loss of impact str~ngth a~d an increase in brittle type failures in standard testing procedures has been obser~ed. C~rtain formulations of polycarbonates have been devised which increase the resistan~e of poly~arbonates to envlronmental stress cracking including the a~dition of a minor amount of a polyalkylene terephthalate ~uch as poly(ethylene terephth~late) and polySbutylene t~rephthalate).
~ -~How~Yer, arti~les formed from a blend of a -polycarbon~te a~d a minor amoun~ of a polyalkylene terephkh~l~te haYe been observed t~ h~ve a lower impact r~ tan~e to that of the polycarbonate itself. This ha~ l~d to the suggestion of using additional co~titu~t~ in a poly~arbonate and poly~lkyle~e ~ereph h~ bl~nd in order ~o im~rove th~ impact r~ tanc~ o~ ~uch ~aterials.
Polyalkylene t~rephthalates including poly(ethylen~ tereph~halate), al~o k~own to the art by its at:ronym "P~T~, and poly~butylene t~r~phthalate), 35 similarly referred to as "P~T" are aromatic polye3~rs which ~njoy Fr~que~t us~ either as tlh~ sole materials or as consti tuent~ in plastic produc~ wh~re rigidi ty, WO 9 1 / 1 5~45 . r ~; PCT/ US91/0l347 ~ ~3~ 2~ 5~
impact resistance, and,,,~rasion resistance, are required. This is kno~n to the art to be due ~o the relatively high degree ~ crystal1inity which polyalkyle~e terephthalates, particularly P~T, ezhibit subseguent to cooling fromthe melt, a~d thus encourages ~their use in many molding op~rations, particularly ~njection molding processes. Ho~ever, these ma~erials most particularly PET, are known to e~hibit poor impact resistance properties subsequent to anneali~g or h~at aging. In contrast to PBT, injec~ion molding of PET
results in a slow rate of crystallization and non-uni~orm or low crystallinity in molded articles.
Subsequent annealing or h~at e~posure of PET molded articl~s caus~s further crystalliza~ion resulti~g in larger, non-uniform crystalline structures. Howsver, as is well known to the art, polymers which e~hibit large, non-uni~orm crys~alline struc~ur~s also e~hibit low impact re~i~tance, a quality which is frequently unde~irable in mold~d article~. Thu~, unfilled PET is not normally preferr~d a~ injection molding resins due to its low~r impact re~istanc~ as compared to P~T, after crystallization.
Further ~uggestQd improveme~t~ in the processing and khe phy~ical propertie~ of p:la~tic ma~erials comprising a bl~nd or mi~tur~ o a polycarbona~e and an poly(alkyl~ne t2r~ph halate) h~v~ iM~luded the addi~ion of furth~r constitu~nts to the~e two polymer~, or ~he u~ o ~p~cific molding proce~ es Eor ~he production o ar~icl~ form~d from polycarbona~ and poly~al~ylene t~r~phth~l~te) bl~d3. So~ ~ample~ iaclude U.S.
Pat~nt 4,522,979 to Chung ~t.al. or nMolding Compo~ition~ Having An E~hanc~d R~ t~nce to Gasoline"
which disclo~e~ PE and PC bl~nded ~i~h rubbery impact modified ~d a blocked polyi~ocy~nate prepolym~r, U.5.
P~tent 4,769~556 to ~u~b~rg et.al. ~or WT~rmoplastic Moldinq ~terial~ of Polye$t~r and Polycar~onate~
- - disclo~ing a th~rmopl~ti~ mold.ing m~t~r~al ~ompri~ing ~ q _ polyalkylono torephthalat9~, polycarbonat~ and a rubb~r toughon~r and rubb~ry ethylene copolym~r~, U.S.
Pat~nt 4,~97,44a for "polye~ter/polycarbonate Blends~
to Romanc~ for PE/PC ble~d~ ~hich include core shell S rubb~s as impac~ modifiersi U.S. Patent 4,737,5~5 to Liu et.al. for "Ternary Polycarbonat~ ~lend~
disclosing compo~ition~ having a major amount of an aromatic carbonatc polymer, and a minor amount o~ an aromatic carbonate polym~r impact modifying composition co~pri~ing a ~teleblock~ copolym~r o~-a vinyl aromatic compound and an ol~finic ela~tom~r, and an ol~in alkylacrylate. Furth~r ar~ U.S. Patent 4,S29,76Q to ~iu ot.al. for ~Compo~i~ion o~ Polycarbonat~, Polyc~ter, Acrylat~ Ela~tom~ric Copolym~r and a Pheno~y 15 Re~in~ di~cus~e~ a polymer compo~1tion which comyrises a PC, polyalkylene terephthalat0 and an ela~tomeric acrylat~ co~olym~r, and of particular not~ is U.S.
Pat~nt 4,753,980 to D~yru~ for ~Toughsned Thermoplastic PO1YQ~ter Compo~ition~ wh~r~ Deyrup d~3cribe~
compo~ition~ which includ~ a poly~t~r re~ln, which may - b~ a poly(alkylene ter~pbth~lat~ polym~r, ~uch a~ PET
or poly(butyl*n~ t~rephthalat~, which i3 commonly known as ~P~T~ ~ith~r a~ a homopolym~ or a copolymer, or mi~t~ of PET and P~T, and an 0thyl~n~ te~polymer such a~ ~thyl~n~Jm~th~c~ylat~/glycid~l m~thacrylat~.
Purth~r, Europ~n A~ atlon 0 180 648 to Toray - Indu~t~o~0 Inc. fot a "Poly~t~r Compo~itio~ and ~ol~ng~ Th~r~of~ di3010~ a polyme~ compo~ition com~ g ~ aromatic poly~st~r, an aro~atic polyc~bon~t~ ha~ing a numb~r av~rag~ rnol~cular weight o~ lo,ooo to ao,ooo and a oopolym~r consi3ting e~ ti~lly of an al~ha~ol~i~ and th~ gly~dyl es~er o an alpha,b~t~-ehylenlcally u~a~ura~d car~o~ylic acid.
T~ r~
.~
Additionally~ European Application 0 ~06 267 to BASF AG describes impact modi~ied polyester-polycarbonate composition~ containing polyethyl~ne tereph~halate, an aromatic polycarbonate, and ~
ethylene/n-butyl acrylate/glycidyl methacrylatQ
terpolymer.
While some of these technique~ have provided co~positions yielding articles havlng satisfactory properti2~, their diversity and number a r~
~i 7~
WO91/1~4~ Pcr/us9l/ol347 ~ 5 indi~ate that the n~ed fo~ novel compositions which e~hibit further i~proYem~nts in properties, and processability e:~i s~s .
In accordance with the instant in~ention there is provided an impact modified polyester-polycarbonate composition comprising:
a polyester, a polycarbonate represented by re~urring structural units o~ ~h~ formula:
-[-A-O-C-O-3-where A is a divalent aromatic radical de~ived from a dihydric aromatic compound, and a reac~ive terpolymer constituent (hereina~ter interchan~0~bly referred to as ~graft terpolymer~) which comprises a compound having the formula:
[Formula l] E/A/~
where W~ is.repr~entative of an alpha-olefin, or in the altern~tive, an alkadiene, ~A~ i~ r~presenta~ive of a mat~rial ha~ing the formula, [Formula 3] C~2 ~ C
z where ~Y~ is -H or an alkyl substituent~ ~Z~ is -COOR, -CN, -OCOR, or ~Ar, wh~rein "R~ may be a me~hyl, e~hyl, butyl or other alkyl group, and ~r~ may b~ a phenyl or q ~ 5 ~O91/15~45 ~ i ~ - P~T/US~1/01~7 substitued phenyl, and "X~ repr~sent~ a comono~er e~hibiting th~ structure [Formula 4] CH2 _ C
, -which contains a r~aotive functionality ~P" which is selected from epo~ide, isocya~ate, 1,3-o~azoline, or acyllactam ~unctio~alities, where the ~erpolymer forms graft linked bonds with other polymerie materials in a composition, particularly with polycarbonates an~ the poly(ethylene terephthalates).
Molded articles comprising the .inventive composition are also provided.
It ha~ al50 been unespectedly discoY~red that a polymer composition having impro~ed properties may be produced wherein the inv~ntive polymer composition comprises a polycarbonate and a poly(ethylene terephthalate) and an actiYe yraft terpolymer ac~ording to the afor~m~ntioned formula ~E/A/X~ which graft terpolymer eshibit~ th~ reactiv~ ability of forming graft-type bond~ wi~h poly~arbonat~s and with the terminal group~ of poly(ethyl~ne tersphthalate) exhibits impro~d properties, especially retention of high impact r~is~ance properties 3ubs~qu~nt ~ h~at a~in~.
A~cording to th~ pr~ent in~ntion, the polycarbona~es 30 whi~h ~y be u~ed ar2 the carbvnat~ pol~rs of dihydric ph~nols. Such poly~arbona~2s m~y be prepared by r~acting a dihyd~ic phenol with a 02rbonat~
precur~or such a~ a pho~gene, a halo form~t~, or a carbon~t~ ~t~r. In g~neral, the r~ulting WO91/15545 ~ 2 ~ ~S 9~ O Pc~/us9l/ol~7 polycarbonate may be represented by recurring structural uni~s of the formula:
.
[Formula 2] 0 ..
-[-A-O-C-O-]-where A is a diYalent aromatic radical derived f rom a dihydric aro~atic compou~d, preferably ~isphenol A.
These dihydro~y aromatic compounds are defined as 4,4~-dihydro~ydi(mononucl~ar aryl)A compounds ~h~e th~
mononuclear aryl may be ph~nyl, tolyl, ~ylyl, ethylphenyl, isopropylphenyl~ etc., and the con~ecting A groups may be -CH2-, -C2H~ C3H6, -C H8-, -52-' -S-, -O-~ C3F
Typical dihydric phenols are 2,2-bis(4-hydro~yphenyl)propane 2,2-bis(4 hydro~yphenyl~ h~af luoropropane;
2,2-bis(4-hydro~yphenyl~pe~tane;
2,4'-(dihydro~ydiphenyl~m~thane;
bis-(4-hydro~yph~nyl3methane;
bi~-(2-hydro~yphenyl)m~thane;
hydroquino~e; .
Resorcinol;~
2S bis-(4-hydro~y-5-nltrophenyl)methane;
1,1-bis~4-hydro~yph~nyl~e~hane;
3,3-bi~(4 hydrs~yphenyl)pentane;
2,2~dihydro~ydiph2ayl;
2,6 dihydro~y~a~thalen¢;.
~bis-(4-h~dro~ydiph~nyl3sulfo~e;
bis-(3,5-diethyl~4-hydro~yphenyl~sulfon~;
2,2-bis (3,$-dim~ hyl-4-hydrosyphenyl~propane;
2,4~-dihydro~ydiph~nyl ~ul~one;
5'-chlvro-Z,4'-dihydro~ydiph~nyl sulfone, bi3~ hydro~yph~yl~diph~yl sulfone;
2,2~dihydro~ydiph2ayl;
2,6 dihydro~y~a~thalen¢;.
~bis-(4-h~dro~ydiph~nyl3sulfo~e;
bis-(3,5-diethyl~4-hydro~yphenyl~sulfon~;
2,2-bis (3,$-dim~ hyl-4-hydrosyphenyl~propane;
2,4~-dihydro~ydiph~nyl ~ul~one;
5'-chlvro-Z,4'-dihydro~ydiph~nyl sulfone, bi3~ hydro~yph~yl~diph~yl sulfone;
4,4~dihydro~ydiph~1 e~her;
4,4'-dihydro~y-3,3'-dichlorodiphenrl ~theri W~91/lS~S.; ,~ P~ 91/013~7 ~7 5 ~
~,4'-dihydroxy-2,5'-dihydro~ydiphenyl ether, and the like.
Other suitable dihydric phenols are disclosed in U.S. Pa~ents 4,126,602, 2,999,835, 3,02B,365, 3,~34,154, and 4,131,575. It is also possible to employ two or:mor~ different dihydric phenols for the preparation of the polycarbonate.
These aromatic polycarbonates can be manu~acture by known processes, such as noted above, by reacting a dihydric phenol wîth a carbonate pr~cursor, such as a phosgene with the methods set forth, and disclosed in U.S. Patent 4,018,750, or by transesterification processes disclo~d in U.S. Patent 3,153,008, as ~ell as other process~s well kno~n to the ar~.
Further, as noted above, two or more differ2nt dihydric phenols may be utilized, as well as a copolym~r of a dihydric phenol with a glycol or with a hydro~y or arid-t~rmina~ed polyester or with a diba~ic acid in the eve~t a carbonate copolym2r rather than a homopolymer is desire fox u~ in the preparation of ~he polycarbonat~. ~ranched polycarbonates are also useful, such as tho~ described in U.S. Pat nt 4,001,184. Furth~r, blend~ of a linear polycarbonate and a branch~d polycarbonate m~y al~o be u~ed:
Moreover, bl~nd~ of any of the above materials may be employed in the pr~etio~ of this in~ntion to pro~ide th~ arom~tic polycarbonate. In any ~ent, th2 pr~f~rr~d aromatic polycarbo~ate~ are those select2d from th~ group con~is~i~g o:
30 poly(2,2-bi~(4-hydro~ypehyl)alkane3 carbonates. The mos~ pre~err~d O~. ~he~e polycarbona~es is a polycarbonate deriv~d from 2,2-bis(4-hydro~yph~nyl3propane.
PolycDrbon~t~s utilizabl~ with th~ invention ~ho~ld h~ve a ~umb~r-aY~rage ~olecular ~eig~t of 10,000 to 80,000. Pr~ra~ly, th2 ranqe of the ~umber-av~rage molecular ~ight is in the range of 15,000 to 40,000.
W~91/15~5 2~ PCT/VS9~/~33q7 _9_ Whil~ the specific number-av~rage molecular weigh~ of the polycarbonate is recognized not to be detrim~ntal to the operation of the novel graft terpol~n~r which provides i~proved properties in polymer compositions within which it is utilized, it has be~n obser~ed that when the number-average molecular weight of the polycarbonate is less than about 10,000 or more than about 80,000, the resultant product polymer composition has been observed to be inferior in molding and processability, or deficient in mechanical prop~rties, particularly tensile strength subsequent to heat agi~g.
. The polycarbonates should preferably e~hibit an intrin~ic or inherent viscosity of about 0.2 to 1~2 dl/g, (deciliters/~ram) more preferably of about 0.~ to 0.9 dl/g in dichlor~methane by standard Ubbehlohde viscometry a~ room temperature, Although not essential, the polycarbonates should preferably contain hydro~yl end groups.
Suitable polye~ters include polym~rs which e~hibit an inherent visc03ity of 0.3 dl/g or greater and which generally are the linear saturat~d condensation products o gly~ols and dicarbo~ylic acids, or reactive derivate~ th~r~of. Pre~rably, ~hey will compri~e cond~n~tion products of aromatic dicarbo2ylic acid~ h~ing a to 14 carbon atoms and at least one glycol ~ cted rom the group consistin~ of cycloh~ne dim~thanol, neop~ntyl glycol, and alipha~ic glycols of the formula HO(CH2)nOH where th2 letter ~n~ m~y b~ ~ny i~t~ger of 2 to l0. Up to 5V mole p~rc~At o the aroma~ic dicarbo~ylic acids can be r~pl~c~d by at lea~t one diff~rent aromatic dicarbosyli~ acad having from 8 to l9 carbon atoms, and~or up to 20 mol~ p~rc~nt can be r~placed by an aliphatic dicarbo~rlic acid haYing from 2 to 12 car~on atoms.
In accorda~ with th~ pre~nt in~2ntion, suitable poly~s~er~ include:
W091/15~45 `~ 5 9~ 1 o- PCrtUS93/013~
poly(ethylene terephthalate);
polytl,4-butylene)terephthalate;
1,4-cyclohe~ylene dimethylene terephthalate/isophthalate copolymer and other linear S homopolymer esters derived from aromatic dicarbo~ylic acids, including but not limited to isophthalic, ~ , bibenzoic, naphthalene-dicarbo~ylic including 1,5-naphthalenedicarbo~ylic acid;
: 2,6-naphthalenedicarbo~ylic acid;
2,7-naphthalenedicarbo~ylic acid;
-~ 4,4'-diphenylenedicarbo~ylic acid;
bis(p-carboxyphenyl)methane;
1,4-tetramethylene bis(p-02ybenzoic~ acid;
ethylen~ bis~p-o~ybenzoic) acid;
ethylene bis-p-benzoic acid;
1,3-trimethylene bis(p-o~ybenzoid)acid; and 1,4-tetramethylene bis~p-o~ybenzoic) acid;
and glycols sele~ted from but not limited to 2,2-dim~thyl-1,3-propan~ diol;
20 neopeDtyl glycol;
cyclohe~ane dimethanol and aliphatic glycols of the general formula HO~CH2)nO~
where ~ may be an int~yer from to 10, and thereby, for e~ample and not by~-limitation, may be one of the - 25 following:
ethylene gly~ol;
1,3-trim~thyl~ne glycol;
1,4~te~ram~thylen~ glycol;
1,6-h~ htyl~n~ glycol;
1,8-o6ta~th~1ene ylycol;
l,10-d~cam~thylene glycol;
1,3-propyl~e glycol; and 1,4-butylene gly~ol. Vp to 20 mole percent~ as indicated abo~e, or one or more aliphatic a~id may be included. For e~mple, suitable alipha~ic acids include adipic, ~b~ic, azzelaic, dod~andioic and 1,4 eycloh~n~dic~rbo3ylic.
W0 91/15545 ~ , YC'I/lJS91/013q7 Prefereably, the polyester is one or morE~ o~ the poly(alkylene terephthalates), either as a ho~opolymer or as a copolymer of two or more poly(alkylene terephthalates). The acronym "PAT~ will b~
S - interchangeably used as a designator for poly(alkylene terephthalates) as a labelling convention herein. I
The pr2ferred compositions include PET
homopolymers, or PET copolymers ~ontaining minor ~ amounts of comonomers, as distinct from-PBT
-homopolymers as as is well known to the art, these two materials e3hibit different morphologies due to the differences in their crystallization behavior. This difference, viz. the lower crystallization rate and th~
tend~n~y to form large, non-uniform crystalline structures in the case of PET as compared to PBT, in finished arti~les is known to the art to account for the different impact stren~ths of these materials subsequent to an ann2aling operation, or subsequent to any e~tended e~posure to heat . PET' s relatively rigid non-uniform crystalline morphology is known to cause more brittlene~s, and is thus le~ de~irable as a material or use in forming articles, particularly in the absence of ~ rs and reinEorcing agents.
~ The;polyester should preferably have an intrinsic vi cosity of about 0.2 dl/g to about 1.2 dl/9; mor~ preferably the viscosity ~hould be in the range of b~tween about 0.4 ~o about 0.95 dl~g. ~h~s~
vi~osi~y values are determined wi~h the use of a 3tandard Ubbehlohd~ com~ter in a 30 ph~nol-t~trachloroethane ( 6a/40 v/v) solution in a cor~c~ntr~tion of O . 5~ at room temp~rature . The poly~t~r~ ~hould preerably have active chain ~nd groups viz., carbo:cylic acid and~or hydro:cyl snd qroups in a conc~ntration of at least 0.01 m~q/~. The end 35 groups are determin~d by s~c~nclard til:rametric met31ods or carbo~yl or hydro~yl determinat.ion.
4,4'-dihydro~y-3,3'-dichlorodiphenrl ~theri W~91/lS~S.; ,~ P~ 91/013~7 ~7 5 ~
~,4'-dihydroxy-2,5'-dihydro~ydiphenyl ether, and the like.
Other suitable dihydric phenols are disclosed in U.S. Pa~ents 4,126,602, 2,999,835, 3,02B,365, 3,~34,154, and 4,131,575. It is also possible to employ two or:mor~ different dihydric phenols for the preparation of the polycarbonate.
These aromatic polycarbonates can be manu~acture by known processes, such as noted above, by reacting a dihydric phenol wîth a carbonate pr~cursor, such as a phosgene with the methods set forth, and disclosed in U.S. Patent 4,018,750, or by transesterification processes disclo~d in U.S. Patent 3,153,008, as ~ell as other process~s well kno~n to the ar~.
Further, as noted above, two or more differ2nt dihydric phenols may be utilized, as well as a copolym~r of a dihydric phenol with a glycol or with a hydro~y or arid-t~rmina~ed polyester or with a diba~ic acid in the eve~t a carbonate copolym2r rather than a homopolymer is desire fox u~ in the preparation of ~he polycarbonat~. ~ranched polycarbonates are also useful, such as tho~ described in U.S. Pat nt 4,001,184. Furth~r, blend~ of a linear polycarbonate and a branch~d polycarbonate m~y al~o be u~ed:
Moreover, bl~nd~ of any of the above materials may be employed in the pr~etio~ of this in~ntion to pro~ide th~ arom~tic polycarbonate. In any ~ent, th2 pr~f~rr~d aromatic polycarbo~ate~ are those select2d from th~ group con~is~i~g o:
30 poly(2,2-bi~(4-hydro~ypehyl)alkane3 carbonates. The mos~ pre~err~d O~. ~he~e polycarbona~es is a polycarbonate deriv~d from 2,2-bis(4-hydro~yph~nyl3propane.
PolycDrbon~t~s utilizabl~ with th~ invention ~ho~ld h~ve a ~umb~r-aY~rage ~olecular ~eig~t of 10,000 to 80,000. Pr~ra~ly, th2 ranqe of the ~umber-av~rage molecular ~ight is in the range of 15,000 to 40,000.
W~91/15~5 2~ PCT/VS9~/~33q7 _9_ Whil~ the specific number-av~rage molecular weigh~ of the polycarbonate is recognized not to be detrim~ntal to the operation of the novel graft terpol~n~r which provides i~proved properties in polymer compositions within which it is utilized, it has be~n obser~ed that when the number-average molecular weight of the polycarbonate is less than about 10,000 or more than about 80,000, the resultant product polymer composition has been observed to be inferior in molding and processability, or deficient in mechanical prop~rties, particularly tensile strength subsequent to heat agi~g.
. The polycarbonates should preferably e~hibit an intrin~ic or inherent viscosity of about 0.2 to 1~2 dl/g, (deciliters/~ram) more preferably of about 0.~ to 0.9 dl/g in dichlor~methane by standard Ubbehlohde viscometry a~ room temperature, Although not essential, the polycarbonates should preferably contain hydro~yl end groups.
Suitable polye~ters include polym~rs which e~hibit an inherent visc03ity of 0.3 dl/g or greater and which generally are the linear saturat~d condensation products o gly~ols and dicarbo~ylic acids, or reactive derivate~ th~r~of. Pre~rably, ~hey will compri~e cond~n~tion products of aromatic dicarbo2ylic acid~ h~ing a to 14 carbon atoms and at least one glycol ~ cted rom the group consistin~ of cycloh~ne dim~thanol, neop~ntyl glycol, and alipha~ic glycols of the formula HO(CH2)nOH where th2 letter ~n~ m~y b~ ~ny i~t~ger of 2 to l0. Up to 5V mole p~rc~At o the aroma~ic dicarbo~ylic acids can be r~pl~c~d by at lea~t one diff~rent aromatic dicarbosyli~ acad having from 8 to l9 carbon atoms, and~or up to 20 mol~ p~rc~nt can be r~placed by an aliphatic dicarbo~rlic acid haYing from 2 to 12 car~on atoms.
In accorda~ with th~ pre~nt in~2ntion, suitable poly~s~er~ include:
W091/15~45 `~ 5 9~ 1 o- PCrtUS93/013~
poly(ethylene terephthalate);
polytl,4-butylene)terephthalate;
1,4-cyclohe~ylene dimethylene terephthalate/isophthalate copolymer and other linear S homopolymer esters derived from aromatic dicarbo~ylic acids, including but not limited to isophthalic, ~ , bibenzoic, naphthalene-dicarbo~ylic including 1,5-naphthalenedicarbo~ylic acid;
: 2,6-naphthalenedicarbo~ylic acid;
2,7-naphthalenedicarbo~ylic acid;
-~ 4,4'-diphenylenedicarbo~ylic acid;
bis(p-carboxyphenyl)methane;
1,4-tetramethylene bis(p-02ybenzoic~ acid;
ethylen~ bis~p-o~ybenzoic) acid;
ethylene bis-p-benzoic acid;
1,3-trimethylene bis(p-o~ybenzoid)acid; and 1,4-tetramethylene bis~p-o~ybenzoic) acid;
and glycols sele~ted from but not limited to 2,2-dim~thyl-1,3-propan~ diol;
20 neopeDtyl glycol;
cyclohe~ane dimethanol and aliphatic glycols of the general formula HO~CH2)nO~
where ~ may be an int~yer from to 10, and thereby, for e~ample and not by~-limitation, may be one of the - 25 following:
ethylene gly~ol;
1,3-trim~thyl~ne glycol;
1,4~te~ram~thylen~ glycol;
1,6-h~ htyl~n~ glycol;
1,8-o6ta~th~1ene ylycol;
l,10-d~cam~thylene glycol;
1,3-propyl~e glycol; and 1,4-butylene gly~ol. Vp to 20 mole percent~ as indicated abo~e, or one or more aliphatic a~id may be included. For e~mple, suitable alipha~ic acids include adipic, ~b~ic, azzelaic, dod~andioic and 1,4 eycloh~n~dic~rbo3ylic.
W0 91/15545 ~ , YC'I/lJS91/013q7 Prefereably, the polyester is one or morE~ o~ the poly(alkylene terephthalates), either as a ho~opolymer or as a copolymer of two or more poly(alkylene terephthalates). The acronym "PAT~ will b~
S - interchangeably used as a designator for poly(alkylene terephthalates) as a labelling convention herein. I
The pr2ferred compositions include PET
homopolymers, or PET copolymers ~ontaining minor ~ amounts of comonomers, as distinct from-PBT
-homopolymers as as is well known to the art, these two materials e3hibit different morphologies due to the differences in their crystallization behavior. This difference, viz. the lower crystallization rate and th~
tend~n~y to form large, non-uniform crystalline structures in the case of PET as compared to PBT, in finished arti~les is known to the art to account for the different impact stren~ths of these materials subsequent to an ann2aling operation, or subsequent to any e~tended e~posure to heat . PET' s relatively rigid non-uniform crystalline morphology is known to cause more brittlene~s, and is thus le~ de~irable as a material or use in forming articles, particularly in the absence of ~ rs and reinEorcing agents.
~ The;polyester should preferably have an intrinsic vi cosity of about 0.2 dl/g to about 1.2 dl/9; mor~ preferably the viscosity ~hould be in the range of b~tween about 0.4 ~o about 0.95 dl~g. ~h~s~
vi~osi~y values are determined wi~h the use of a 3tandard Ubbehlohd~ com~ter in a 30 ph~nol-t~trachloroethane ( 6a/40 v/v) solution in a cor~c~ntr~tion of O . 5~ at room temp~rature . The poly~t~r~ ~hould preerably have active chain ~nd groups viz., carbo:cylic acid and~or hydro:cyl snd qroups in a conc~ntration of at least 0.01 m~q/~. The end 35 groups are determin~d by s~c~nclard til:rametric met31ods or carbo~yl or hydro~yl determinat.ion.
5~5~ ' -` ` PCr/~S9~/01347 2~ 12- ' The compositions in accordance with the present invention, based on the total weight percentage of the compo~ition, includes relative weight ratios of the polycarbonate in the range of about 30 to about 60 percent; the polye~ter in the range of about 30 to about 60 percent; and the graft terpolym~r more fully discussed below in a range of weight ratios of between about 2 and about 30 percent. ~ore preferably the polyester should comprise about 40 percent of th~
10 composition, with the polycarbonate and the graft terpolymer comprising the remaining amount of the composition, as it has been observed that favorable impact properti~s sub~equent to heat aging haYe has not been realized where the polyester is present in less than such a proportion.
According to the inve~tion, the compositio~s will further include a terpolymer constituen~, or as interchangeably ref~ren~ed above, a ~graft terpolymer"
comprising a compound having the formula:
~Formula 1] E/~/X
where ~E~ is r0pre~entative of an alpha-olefin, or in the alternative, an alkadiene, WA~ is representative of a material having the ormula, [~ormula 3~ C~12 ~ C /
wh~re ~yl is -H or an alkyl substitu~nt, ~ZA is -COOR, ~CM, -OCOR, or -Ar, of which "Rn may bP a methyl, ethyl, butyl or other alkyl group, and ~Ar~ may be a WO 9l/155qS ., ? ~ ; PC'r/US9~ 1,3~17 3-- ¦
phenyl or substitued phenyl, and r'XA represents a comonomer e~hibiting the structure S [Formula 4] - CH2 , C
,. ~ p which contains a reactive function P" which is selected from epo~ide, isocy~,nate, 1,3-o~azoline, or acyllactam funetionalities. Typically, nxn has a moiety derived from acrylic and methacrylic acid or allyl alcohol, e.g., glycidyl acrylates, glycidyl methacrylates, or glycidyl allyl eth~r. ~he terpolymer ~orms graft type bn~ds with other polymeric materials in a composition, particularly with polycarbonates and the poly(~thyle~e t~rephthalates).
In accordanc~ with the in~ention, the constitu~nts of ~ are epo~ide, isocyana~e, acyllactam or o~azoline. Accordingly, ~ having epo~ide functio~aIities may be derived from glycidyl acryla~e, glycidyl methcrylate, gly~idyl allyl ether, asld other glycidyl contal~ing compounds. W~ere ~ is ~o have an isocyan~te unctionality, ~ may be~derived from 2-isocyanoto~thylmethacrylat~, p-isoprop~nyl alpha,alpha-dimethyl benzrl iso~yana~e, m-isoprop~nyl alpha,alpha-di~thyl benzyl i~ocyanat~) and ths like.
Wher~ ozazoline functionalities are d~sir2d, 2 may ~e d~riv~d from 2-i~oprop~nyl~1~3~o~azoline, 2-(p-~inyl phenyl)-1,3-o~azoline, and the lik0. Wh~re acyllac~a~
function~ligy i~ de~ired, ~ may ~'i2 deri~ed rom metha~ryloyl c~,prolactam, m~thacryloyllaurolactam, compounds of th~ g~neral form~la:
[Formula 51 ~2 ~ C ~
\ CO~ - CO
~ (C}12 )) WO9l/15545 ' . G r .~ ~ PCr/ ~S9 1 /~ 13 where "~ may have a value of ~ to 10, and ~y~ may b~
-H or -CH3~
The grafted terpolymer may be synthesiz~d by copolymerization o~ E, A or X in bulk or solution phase, catalyzed by free radical initia~ors or other types of i~itiators. The relative weight ratios of the constituents comprising the graft terpolymer may be .present in p.roportions which, relativ~ to the total ~,~weight of the terpolymer of between about 98.9 and 45 weight. percent E, hetween about 1 and 40 weight percen~
A, and between about 0.1 and about 15 wcight percent X. It is to ~e noted that the relative proportions of the co~stituents relative to the total weight are subject to a gr~at deal of variation and are dependent upon the w~ight of the individual constituents.
Further, their relative proportions may be adjus~ed ~o suit the reactivity of a particular composition.
All of these functional groups of the terpolymer disclosed in this inYention are found to eshibit 2n graft~ng with the PET and the PC due ~o ~heir high r~activity; E/A/~ ~ompositions where X e~hibits an epo~ide or oxazoline functionality were found to be highly ad~antageous.
. An.ad~antag~ouq feature of-the t~rpolyrner is that the "X~ ~un~tion~lities also act as ~water scaveng~rs~ within the pol~mer~ and during the production o th~ polymer may act to remove free wa~er molecule~ from the polym~r melt. Such a feature eliminate~ th~ ~c~sity of dryi~g the poly~ethylene ter~phthalate) before it is melt~d during processing, which.is a f~ture e~p~cially advantageous when recycled PET i~ u~d as a ~eedstock. This is beneficial in forming polymer compositions which have lower w~ter contents, and hence, require less or no 35 ~ryin9 It should ba ~vident to those s~illed in -thP art that minor amounts of organic modiFier~, gen2rally to WO91/15545 ~ ~ ~59~ cr/us~l/0]3~7 comprise no mor~ than about 10% of a composition, may be added to the composition according to the invention. E~amples of such typical modifiers include heat stabilizers, flame retardants, pigm~nts and ; coloring agents, nuclea~ors, lubricants and ~low modifiers, especially ethylen~ copolymèrs which are frequently used additives for improving the melt flowcharaotsristics of many polymer ~aterials. Also, the use of in-organic materials as in-organic modifiers, such as fillers, and reinforcing agents (including qlass fibers, talc carbon fibers, and th~
like~ may be includ~d in any suitablP amount, which is preferably in a range typically used in the art, between about 40 and 50%.
The compositions in ~he E~amples were generally prepared by one of two methods. In the first method, where there is ~o preblending of the components, the melt blend is pr~p~r~d by first dry blending the constituents in their appropriate weight percen~ages by tumble blending or in a rotary drum, then feeding in the blended constituents into the hopper o~ a single screw e~truder which was heated so to form a melt of the-co~stituents and th~n e~truding it through a die to form strands; The e~trudate was rapidly pa~sed through a water bath in ord~r to quenoh and cool tAe strands.
TA~ stra~d~ wsr~ th~n pas~ed through a pell~izing m~chine and the p~llets w~r~ collectsd and dried.
- In the 3~cond method ~Jh~re an additional pr~ ndi~g 3tep i~ includ~d in th~ ~ormation process, th~ polyc~rbon~t~ utilized and th~ terpolymer are firs~
prebleQd~d beore combinlng th2m with the PET of any d~sired compo~ition. Thi~ s~cond method is the pre~rr~d on~ as the pr~bl~nding allo~s for a mo.re homogen~ou~ pha~ distribution of th~ t~rpoly~er and ~he polycarbon~te~ ~hich b~ing pr2bl~nded, impro~es t~2 distribution of the terpolymer within th2 poly~arbonat~
and PET, incr@~ing the amount of grafting in ~he ~inal W091/15545~ 16- P~r/us91Jol~7 composltion and thereby enhancing the improYed properties of the final composition. Accor~ing to ~his second method, the polycarbonate and the t2rmpolymer are first preblended via a melt e~trusion before blending with the PET by another melt extrusion operation, thus essentially constituting a 2~step single screw extrusion process. Alternatively, the melt blend may be prepared by use of a 2-stage, single pass e~rusion process. In such a process, a dry blend o the polycarbonate and the terpolymer in their appropriate weight percentages is introduced into a first hopper of a single screw e~truder. The appropriate amount of PET is introduce into a second hopper of the estruder at location downstream approximately midway between the first hopp~r and the die at the e~it of the e~truder. Similarly, the e~trudate was rapidly passed through a water bath in order to quench and cool the strands which were then pelletized, and collected, and when nec~ssary, dried.
The pellet~ were utilized to mold te~t specimens which were 1/8 inch test bars which are a standardized sample size well known to the art by use of an injection molding machine. ~oth tensile bars and Izod impact bars wer~ prepar~d utilizing this process.
. ,.. ~ .... , -, . . .
Subseguently, a quantity of the test bars wele annealed in an ann~aling oven at a t~mp~ratur~ of about 150 deg.C wher~ they were retained for periods of either 16 hours or 72 hours in accordance with testing parameters well k~own to the art.
~e3ting of ~he te~t bars was ~ccomplished in accordance with the standardized testing procedur~s pre~alent in the art; the tensile strength was test~d in accordanre with ASTM D-3029 sta~dards using a falling w2ight impact tester, and th~ imp~ct str~ng~h was de ermined under th~ ~esting condition~ o~ D-256 using a notshed Izod p~dulum impact appara'eus ~or measuremerlt.
WO 91/15545 2~ 5~ ~ . PCT/US91/01~7 ~';,l - 1 7 -EXA~oeh~5_gF TH~ vE~IQ~ i Th~ following examples show par~icular embodiments of the pr2sent invention, and illustra~e the e~traordinary touyhness properties of specific S compositions of PET and polycarbonates by the incl~sio~
of a reactive terpolymer disclosed herein. It is ~o be understood that the following e~amples of the invention are for illustration only and the scope of the t invention is bounded only by the accompanyi~g clai~s.
Unless otherwise indicated, the use of percentages within any E~ample are to be understood as the weight percentages of the indi~idual constitut~s relative to the total weight of ~he constituents.
~am~
E~ample l is a melt blend composition consisting essentially o~ 90~ PET, 40% of a polycarbonate and 20%
of an ethylene/~thyl acrylate/glycidyl methacrylate terpolymer. The PET used w~s a bottle grad~ resin with 0.67 I.V. ( as determined in phenol/TCE) and typically containing between about 0.035-0.04 me~/g of carbo~yl chain ends. The polycarbonate used was commercially available from the undcr the trade name ~Le~an", a name used for a family of polycarbonate materials. The . ~ particular polycarbo~ate us~d was ~Le~an lOl". The ethylene/ethyl acryl2t~glycidyl ~erpolymer was de~crib~d a~ h~ing a relati~e weight ra~io of 75 ethylene, 17~ ethyl acrylate and a~ glycidyl func~io~ali~y.
The melt bl~d was prepared by first dry bl~ndinq all of the constitu~nts toge~her and subs~quently, the dry blended co~stituents were then fed i~to the hopp~r of a ~illion l inch single scr~w e~trud~r with a L/D ratio of 30~l using a f2ed scre~
equipped wlth a M~ddo~ mi~.ing head. The ~truder barrel temperatur~ for each zone were kept at ~he followi~g appro~imate ~empera~ur~s of: Zone l, 205 deg.C; Zo~e 2, 250 deg.C; Zvne 3, 27~ d0g.C; ~one 4, WO91/15545 ~ ~ `'` -18- P~T/US91/0~3~7 250 deg.C. The te~perature of the flange waS kept at appro~imately 250 deg.C and th~ temp~rature of the dies was kept at approsimately 210 deg.C. The e~trude~
screw rotational sp~ed was maintained at about 60 rp~
The e~trudate was rapidly passed through a water bath in order to quench and cool the strands. The cooled strands were then passed through a pelletizinq maohine and the pellets formed wer@ collected and dried.
Thereafter, the pellets were molded into test specimens by injection molding using an injection molding machine. The barrel temperature o~ the machine during the injection process was maintained ~ithin a temperature range o about 280 - 287 deg.C and the mold was kept at a temperature of about 50 deg.C. During the molding operation, the cycle time was appro~imately 10 seconds during the injection step, and appro~imately 20 second during cooling. The pressure of the operation was approzimately 300 psi, with a pre~sure hold of 500 psi. Standardized tensile bars and Izod 20 impact bars were pr~pared. A quantity of the test bars were annealed, or heat aged in a circulating hot air oven at about 150 deg.C for periods of either 16 hours or 72 hours.
~ ~ T~ting of the samples included impact testin~, tensile elongation, tensile modulus and yield stress according to known t~sting proc~dures. ~he physical propertie~ mea~ured indicate e~tr~ordinary toughness o~
th~ material sub~equent to annealing. Resul~s of the ke~ts are summ~rized under the heading ~E~ on Ta~les 1 and 2 b~low.
The comparati~e e~amples A, ~, C, D and E are composikioAs ~omprising P~T, PC and various impact modifi~rs. Ea~h of these e~ample~ was prepared in the same manner as kh~ cvmposition of ~zample 1, and consi~t~d e~ ~ntially of 40~ PET, 40~ of a polycarbo~ate and 20% of one of the various impact modifiers.
~ ~a/15545 ;~ ~7~ 3 PCr/VS91/0~3~7 Comparativ~ E~ample A used an m~thYl methacrylate butadiene-styrene, (which is frequently catergorized in the ~rt as a~ "interpolymer") or ~MBS~
core shell rubber as its impact modifier. This rubber ~njoys significant usage in the art as an impact modifier as this material e~hibits good elasticity and provides good impact absorption.
The impact modifier used in the composition of Comparative E~ample ~ was an acrylonitrile-butadiene-styrene, or "A~S~ rubbe~ which similarly to M~S e~hibits good elasticity and good impact absorption. The formulation B was comm~rcially obtained from Mobay Chemical Co. under the trade designation "Makroblend UT1018n.
The impact modifier used in comparative e~ample C is an all-acrylate core shell rubber, which is marketed under the trademark ~Paraloid KM 3~0" by Rohm ~ Haas, and consists of a cross linked polybutylacrylate cor~ and polymethylmethacrylate shell.
In the formulation of Comparati~e E:~ample D, an ethyl/ethyl acetate copolymer ~as used as the irnpact modif ier ~
Compa~atiYe Esample ~ utilizes an ethyl/glycidyl me~hacryla~e copolymer as the impact modifi~r. The particular copolymer is comm~rcial1y mar~eted under the trad~name ~ondfast 2C~ and is aYailable rom the Sumitomo Chemical Co. The relative weight ratios o~
the ethyl to th~ glycidyl m~thacrylate in the copolymer is 94/60 The compositions of e~amples ~, B, C, D and E
were all produced, mold0d and subs2qu~ntly tested in the manner utiliz~d in the productiorl of e3ample 1, so to more cl~arly illustrat~ th~ distinct adYantage o compositions made in accordance with the inYention~
Likewise, the testin~ o~ the samples included i.mp~ct testing, t~nsile elongation, tensil2 modulus ~nd yield 2~7~9 ~
W091/155~5 ~ ? ~ 20- pcr/vs9l/ol3 stress according-to the same testing proc~dur~s utilized in testing the composition of Esample 1. The physical properties measured for these ComparatiYe ~xamples indicate the marked reduction in the toughness S of the material subsequent to annealing, or heat aging at 150 deg.C. R~sults o~ the tests are also summarized under the appropriate headings and listed on Tables 1 :. and 2 below.
1 0 ~,~ ,, _____________________________________ Example 1 A B C D
_________________________._____________ Notched Izod, ft.lb/in: 14.9 12.4 12.5 13.3 13.1 -aged 16 hrs.:12.6 10 o O 10.1 9.2 2.5 -aged 72 hrs.:11.5 5.6 5.3 3.7 ---Drop Weight Impact ft.lb: 97 ~ 156 --- ----aged 72 hrs.:~6 ---- 1.6 --- ---- :- Te~s~
Elongation, ~: llS 128 113 95 97 -~ged 16 h~s.:85 40 30 18 33 -aged 72 hrs.:
T~n~
Modulu~, p~200,000 29~,000 270,000 ---~
-aged lS hrs.: 215,000270,000 29~,000 -~
Yield Stre~s, psi: 5,400 6,160 6,~65 S,~20 2~2~0 -ag~d 16 hr~O 6,430 7,400 8,325 6,1~0 4,450 -aged 72 hr~.: 6,240 6,5lO 0,230 6,300 ~
W~91/1~545 , -21- PCT~US~]~3~7 TA~L~_~
__________.__________________________ E~a~ple: 1 E
______________ ___________ .
Notched Izod, ft.lb/in: 14.9 1q.5 -aged 16 hrs.: 12.6 13.2 lO -aged 72 hrs.: 11.5 3.
Drop Weight Impact ft.lb: 97 ----l; -aged 72 hrs.: 86 ----Tensile Elongation, s: 115 210 -ayed 16 hrs.: 85 125 20 -aged 72 hrs. : 67 7 The resultant physical test data particularly illustrates that the compo~itions of the present .ai invention, namely, the ~omposit:ions which include a re3ctive graft-terpolymer show the une~pected ad~antages of improved toughness subsequ~nt to annealing and superior impact strength retention. This is attributed to the functionality of the terpolymer in lts ability to form a graft copol~mer throuyh reaction with th~ terminal end groups, carbo~yl and hydro~yl, o~
PET and PC. Further, the e~cellent elasticity of the terpolymer imparts good impact energy absorp~ion qu~lities to the molded composition, and which is furth~r b~ ed to act as a compatibilizing ayent for the PET and PC u~d.
~a~
E~amples 2,3,4,5 and 6 are further embodim~ts of the invention which utilized the constitu~nts as WO91/1~545 PCT/~S91/0134~., ;
2~ ~ 3 ~ - 22-used to formulate E~ample l, but varies the relativ~
proportions of the PET, PC and the reactive terpolYme{
used in E~a~ple 1. The range of variation for ~he respective components based on the total weight o~ the S composition ~as: 30% t~ 80% PET, 0~ to 50~ PC, and a constant Z0% of the terpolymer. The speci~ic proportions are outlined in Table 3.
I~LE ~ 1, _______________________________________________________ I
E~amples: Z 3 4 5 5 ____________.__________________________________________ Constituent, weight %
~.~~ ~D
PET: 80 60 50 40 30 PC: -- 20 30 40 50 E/EA/GMA
terpolymer: 20 20 20 20 20 The compositions of E~amples 2-6 were produced in the same manner as that used ~or the production of E~ample 1.
. The physlcal charact~ristics-of the materlals produced from the compositions outlined in Table ~ are summarized in Table 4.
WO 91/l5545 . 2 ~ 59~ ~ P~/US~1/111347 ~, , ,. ., .-, , , TAELLE ~
______________.______ ___________________ E~cample: 2 3 4 5 :, ------------ ------------------ ---- -- ---- -------- -- :
. .
No t c:hed I æ od, ft~.lb/in: 7.4 16.6 16.4 14.9 14.5 -aged 16 hrs .: 3 . 2 3 .1 5 . 7 lZ . 6 19 . l lO -aged 72 hrs .: 3 . 2 --- 9 . 0 11 . 5 ---Tens i le Elongation, %: 2~g 165 127 115 72 -aged 16 hr~.: 23 29 41 85 100 15 -aged 72 hrs.: ~1 --- 25 67 ---Tens i 1 e ModulLIs, psi.: 5,400 5,400 5,523 5,980 6,380 -aged 16 hrs.
20 at 150 d~g.C: 6,390 6,000 6,400 6,640 6,770 -aged 72 hrs.
at 150 deg.C: 6,400 ~ 5,68~ 6,100 -----T~nsi le 25 Modulus, p~ 18~, 000 183, 000 195, 000 200, 000 2~5, 000 -aged 16 hr~. :235,000 221,000 221,000 21~000 216, 0~
A~ ~118y b~ d~t~rmined rom Tabl~s3 and 4, the compo~i~ion ~f ~:~a~Dpl~ 5 ~shibi~d par~icula~ly good r~en~ion o impac~ properties and elorlgation tr~ngSh.
E:ac~m~lo~ 7-12 e3~mplify th~ ~ec:o~d, alt~rnati~e tn~thod o pr~paring the composition3. Accordin~ ~o thi~ 3~::0nd m~'chod, an additional ~tep, apr~b1~ndirlq~
:
WO 91/1554S ~ . A'~ PCT/US9l/~1347 , ,, !, , ,,,`, ~,.' ';;
~75~?~ -2~
of the polycarbonate and the reactive terpolymer This preblending may be ~c~omplished by methods known to the art, including a two-step process, or a two-stage, single pass e~trusion process. This latter process was used for the formation of the compositions of E2ampl~s 7-12.
Table 5 indicates the various ratios of constituents utilized in the compositions of E~amples 7-12 which were produced using a preblending step. The percentages shown are percent by weight of the composition of each E~ample.
T~L~ S
_______________________________________________._______ E~amples: 7 8 9 lO ll 12 _________________________________________________~_____ Constituent, weight ~
PET: 40 40 45 50 50 60 PC: 40 45 35 30 33.3 2g E/EA/GMA
terpolymer: 20 lS 20 20 16.7 16 Th~ corre~ponding physieal proper~ies observed during th~ t~sting of thes~ materials is summarized on Table 6.
WO 91/15~4S ~Cr/VS9~/nl3~7 -2S_ ~ S~
____________.. __________________~_________ ____________ Ea~:ample: 7 8 9 10 11 12 __________________________________________ ~____ ______ 5 Notched Izod -molded: lS . 816 . 816 . 518 . 717 . 518 . 8 -annealed, 16 hrs. a~
150 deg.C:14.~ 13.7 12.9 15.0 7.3 4.3 Ultimate Elongation, ~6: 110 105 119 159 190 165 - anne a 1 ed , 16 hrs. at lS 150 deg.C: ~0 80 78 85 ~5 30 Ultimate Tensi 1~
St rength, psi: 5600 6~30 56~0 6060 6125 5880 -annealed, 16 hrs. at . lS0. deg.C:64107445 613S 6580 6715 6100 - . ~ .. ii~, ,... ;, .. . .. . .
25 T~nsile ~o~ulus, ~1000'~) p i.: 2D0 257 190 230 210 250 -ann~ d~
16 hrs. aé
lS0 d~g.C:2~0 2R0 210 ~60 2~0 ~67 ~r~ 05Jln~O~a~rDr~/l lYII ~9~ C~ V/~V!~r8~/ll Y~lmO O~IJ~ ~I OV~ 0 113~1~D 51/ ~ ~l iD Cl ~11il 31 Q ~!III Q ~0 Q ~ D
As may be di3cerned rolT lth~ rssults shown on Table 6, th~ co~positions show~d good retsntion of 35 impac:t str~ngth throus~hout, esp~cially ~or ;@~amples 7-10. It m~y ~urth~r b~ obs~rYed tha~ th~ ~cond m~thod of forming c:ompositions, wh~re th~3r~ is WC) 91/155415 ` PCr/VS()~/()13'17 J~
~ 2fi~ ~, preblending may be ad~antageous to the f irst method without preblending of the constitutents by a comparison of the physical test data o Tabl~s Z and 3 with Tables 5 and 6 which contrasts similar compositions produced by processes including no preblending with processes including preblending.
Particularly, the following paired compositions having th~ same ratio of constituents, arld their r~sultant physical properties may be cumpared: E~ample 5 and E~ample 7, E~ample 4 and 10. Particularly, the impact test values (notched Izod) indi~ate improved toughness~ Such results are believed to be attributable to improved graftin~ of the reActive graft terpolymer and the polycarbonate prior to the lS introduction of the poly(ethylen~ terephthalate.) E~amDle 13, CQmp~rativ~ ~am~
Th~ composition of E~ample 13 was a composition consisting essentiall~ of 90~ PET, 40~ PC and 20 ethylene/ethyl acrylate/glycidyl methacrylate terpolymer was produced. Comparativ~ Example E was a composition of PET, PC and an acrylonitrile-butadiene-styrene terpol~ner, which is marked u~der the tradename nMakroblendn wa~ ~ested wi th th~ composition of ~zample 11. ~oth compositions were subjec~ed to drop weight imp~ct testing at low temperatur~s (-40 d~.C) prior to, and subsequent to heat agin~, and the results of thes~ tes~s is listed on Table 7.
W(~ 91/155~1~ P~r/lJS~1iO~3~7 -27~ 5~, ~
X~,~ .. . ... . ..
E~ample: 13 E
_____________________________ _________________________ S ~rop weight irnpact st rength a t -40 deg.C.
(ft. lbs) prior to heat aging: 9~ . 7S 123 . 75 af ter heat aging at 150 deg.C, for 72 hrs .119 . 64 3 . 24 _________ ____________________________._________________ The composition o E~cample 13 was no~ed to be completely ductile b~fore h~at-aging, and the composition of Comparati~e E~ample E was noted to be 20 completely brittl~ ater heat aging, and showed poor strength reterltionO
Thr2e e~e~nplary composition~ comprising the terpolym~r of the pre~nt in~ention by m~lt blendlllg 25 the constitu37lts in accordan~e with the me~hod describ~d ~or ~E;3ample 1, with ~he f~llowing particular compo~ition~ outlined on Table 8.
3~
WO 91/~15545 ~ t ~ PCT/US91/01347 r --2 El ~
_____________________________________________.____ ..._____ E~amples: 19 15 16 __ ___________.________________________~________________ Constituent, weight %
ID W 1 11~ 8 31 IID il D ~111 --PET: 40 40 40 PC: 40 40 qo E/EA/GMA
terpolymer: 16 12 10 lS E/EA 4 8 10 copolymer The following phy~ical prop~rti~ outlined o~
Table 8~ were obser~ed.
WO 91/355~5 . ,, PCr/US91~0~3~i7 -29- ~ J;~
______________________________..._______________________ E:~ampl~: 14 15 16 __~______ Notched Izod -molded:16.2 16.2 15.8 - a nnea 1 ed , 16 hrs. at 150 deg.C: 16.6 15.9 19.3 Ul t imate Elongation, %: 1~5 145 133 -annea led, lS 16 hrs. at 150 deg . C:125 125 113 Ultimate Tens i le 20 Stren~th, psi: 6Z~ 65~5 62~0 -annea1ed, 16 hrs. at 150 deg.C 7900 7400 698q Tensile Pqo~ulu~, ~ 100~
p~ 21~ ~18 ---3 -aQn~ d, 16 hr~. at lS0 d~9~C: 245 250 ---Th~ r~$ult~t l:~tirlg data re~reals thi3 t the 35 compo3itios~ on~ining an amolln~ of an ~hylene copolymer, such ~ ~/~ not~d abo~?~, but not to b limit~d G~ol~ly to E~EA, m~y b2 in::lu:led in WO91/1~45 ~ P~/IJS91~U13~7 compositions, generally in amounts of up to about 10%
so to replace up to about half of the reactive terpolymer may be used without detracting from the beneficial qualities of the present invention.
While these e~emplary embodiments have described various aspects of the invention, it is to be understood that the scope of the invention is to be limited only by the following claims.
10 composition, with the polycarbonate and the graft terpolymer comprising the remaining amount of the composition, as it has been observed that favorable impact properti~s sub~equent to heat aging haYe has not been realized where the polyester is present in less than such a proportion.
According to the inve~tion, the compositio~s will further include a terpolymer constituen~, or as interchangeably ref~ren~ed above, a ~graft terpolymer"
comprising a compound having the formula:
~Formula 1] E/~/X
where ~E~ is r0pre~entative of an alpha-olefin, or in the alternative, an alkadiene, WA~ is representative of a material having the ormula, [~ormula 3~ C~12 ~ C /
wh~re ~yl is -H or an alkyl substitu~nt, ~ZA is -COOR, ~CM, -OCOR, or -Ar, of which "Rn may bP a methyl, ethyl, butyl or other alkyl group, and ~Ar~ may be a WO 9l/155qS ., ? ~ ; PC'r/US9~ 1,3~17 3-- ¦
phenyl or substitued phenyl, and r'XA represents a comonomer e~hibiting the structure S [Formula 4] - CH2 , C
,. ~ p which contains a reactive function P" which is selected from epo~ide, isocy~,nate, 1,3-o~azoline, or acyllactam funetionalities. Typically, nxn has a moiety derived from acrylic and methacrylic acid or allyl alcohol, e.g., glycidyl acrylates, glycidyl methacrylates, or glycidyl allyl eth~r. ~he terpolymer ~orms graft type bn~ds with other polymeric materials in a composition, particularly with polycarbonates and the poly(~thyle~e t~rephthalates).
In accordanc~ with the in~ention, the constitu~nts of ~ are epo~ide, isocyana~e, acyllactam or o~azoline. Accordingly, ~ having epo~ide functio~aIities may be derived from glycidyl acryla~e, glycidyl methcrylate, gly~idyl allyl ether, asld other glycidyl contal~ing compounds. W~ere ~ is ~o have an isocyan~te unctionality, ~ may be~derived from 2-isocyanoto~thylmethacrylat~, p-isoprop~nyl alpha,alpha-dimethyl benzrl iso~yana~e, m-isoprop~nyl alpha,alpha-di~thyl benzyl i~ocyanat~) and ths like.
Wher~ ozazoline functionalities are d~sir2d, 2 may ~e d~riv~d from 2-i~oprop~nyl~1~3~o~azoline, 2-(p-~inyl phenyl)-1,3-o~azoline, and the lik0. Wh~re acyllac~a~
function~ligy i~ de~ired, ~ may ~'i2 deri~ed rom metha~ryloyl c~,prolactam, m~thacryloyllaurolactam, compounds of th~ g~neral form~la:
[Formula 51 ~2 ~ C ~
\ CO~ - CO
~ (C}12 )) WO9l/15545 ' . G r .~ ~ PCr/ ~S9 1 /~ 13 where "~ may have a value of ~ to 10, and ~y~ may b~
-H or -CH3~
The grafted terpolymer may be synthesiz~d by copolymerization o~ E, A or X in bulk or solution phase, catalyzed by free radical initia~ors or other types of i~itiators. The relative weight ratios of the constituents comprising the graft terpolymer may be .present in p.roportions which, relativ~ to the total ~,~weight of the terpolymer of between about 98.9 and 45 weight. percent E, hetween about 1 and 40 weight percen~
A, and between about 0.1 and about 15 wcight percent X. It is to ~e noted that the relative proportions of the co~stituents relative to the total weight are subject to a gr~at deal of variation and are dependent upon the w~ight of the individual constituents.
Further, their relative proportions may be adjus~ed ~o suit the reactivity of a particular composition.
All of these functional groups of the terpolymer disclosed in this inYention are found to eshibit 2n graft~ng with the PET and the PC due ~o ~heir high r~activity; E/A/~ ~ompositions where X e~hibits an epo~ide or oxazoline functionality were found to be highly ad~antageous.
. An.ad~antag~ouq feature of-the t~rpolyrner is that the "X~ ~un~tion~lities also act as ~water scaveng~rs~ within the pol~mer~ and during the production o th~ polymer may act to remove free wa~er molecule~ from the polym~r melt. Such a feature eliminate~ th~ ~c~sity of dryi~g the poly~ethylene ter~phthalate) before it is melt~d during processing, which.is a f~ture e~p~cially advantageous when recycled PET i~ u~d as a ~eedstock. This is beneficial in forming polymer compositions which have lower w~ter contents, and hence, require less or no 35 ~ryin9 It should ba ~vident to those s~illed in -thP art that minor amounts of organic modiFier~, gen2rally to WO91/15545 ~ ~ ~59~ cr/us~l/0]3~7 comprise no mor~ than about 10% of a composition, may be added to the composition according to the invention. E~amples of such typical modifiers include heat stabilizers, flame retardants, pigm~nts and ; coloring agents, nuclea~ors, lubricants and ~low modifiers, especially ethylen~ copolymèrs which are frequently used additives for improving the melt flowcharaotsristics of many polymer ~aterials. Also, the use of in-organic materials as in-organic modifiers, such as fillers, and reinforcing agents (including qlass fibers, talc carbon fibers, and th~
like~ may be includ~d in any suitablP amount, which is preferably in a range typically used in the art, between about 40 and 50%.
The compositions in ~he E~amples were generally prepared by one of two methods. In the first method, where there is ~o preblending of the components, the melt blend is pr~p~r~d by first dry blending the constituents in their appropriate weight percen~ages by tumble blending or in a rotary drum, then feeding in the blended constituents into the hopper o~ a single screw e~truder which was heated so to form a melt of the-co~stituents and th~n e~truding it through a die to form strands; The e~trudate was rapidly pa~sed through a water bath in ord~r to quenoh and cool tAe strands.
TA~ stra~d~ wsr~ th~n pas~ed through a pell~izing m~chine and the p~llets w~r~ collectsd and dried.
- In the 3~cond method ~Jh~re an additional pr~ ndi~g 3tep i~ includ~d in th~ ~ormation process, th~ polyc~rbon~t~ utilized and th~ terpolymer are firs~
prebleQd~d beore combinlng th2m with the PET of any d~sired compo~ition. Thi~ s~cond method is the pre~rr~d on~ as the pr~bl~nding allo~s for a mo.re homogen~ou~ pha~ distribution of th~ t~rpoly~er and ~he polycarbon~te~ ~hich b~ing pr2bl~nded, impro~es t~2 distribution of the terpolymer within th2 poly~arbonat~
and PET, incr@~ing the amount of grafting in ~he ~inal W091/15545~ 16- P~r/us91Jol~7 composltion and thereby enhancing the improYed properties of the final composition. Accor~ing to ~his second method, the polycarbonate and the t2rmpolymer are first preblended via a melt e~trusion before blending with the PET by another melt extrusion operation, thus essentially constituting a 2~step single screw extrusion process. Alternatively, the melt blend may be prepared by use of a 2-stage, single pass e~rusion process. In such a process, a dry blend o the polycarbonate and the terpolymer in their appropriate weight percentages is introduced into a first hopper of a single screw e~truder. The appropriate amount of PET is introduce into a second hopper of the estruder at location downstream approximately midway between the first hopp~r and the die at the e~it of the e~truder. Similarly, the e~trudate was rapidly passed through a water bath in order to quench and cool the strands which were then pelletized, and collected, and when nec~ssary, dried.
The pellet~ were utilized to mold te~t specimens which were 1/8 inch test bars which are a standardized sample size well known to the art by use of an injection molding machine. ~oth tensile bars and Izod impact bars wer~ prepar~d utilizing this process.
. ,.. ~ .... , -, . . .
Subseguently, a quantity of the test bars wele annealed in an ann~aling oven at a t~mp~ratur~ of about 150 deg.C wher~ they were retained for periods of either 16 hours or 72 hours in accordance with testing parameters well k~own to the art.
~e3ting of ~he te~t bars was ~ccomplished in accordance with the standardized testing procedur~s pre~alent in the art; the tensile strength was test~d in accordanre with ASTM D-3029 sta~dards using a falling w2ight impact tester, and th~ imp~ct str~ng~h was de ermined under th~ ~esting condition~ o~ D-256 using a notshed Izod p~dulum impact appara'eus ~or measuremerlt.
WO 91/15545 2~ 5~ ~ . PCT/US91/01~7 ~';,l - 1 7 -EXA~oeh~5_gF TH~ vE~IQ~ i Th~ following examples show par~icular embodiments of the pr2sent invention, and illustra~e the e~traordinary touyhness properties of specific S compositions of PET and polycarbonates by the incl~sio~
of a reactive terpolymer disclosed herein. It is ~o be understood that the following e~amples of the invention are for illustration only and the scope of the t invention is bounded only by the accompanyi~g clai~s.
Unless otherwise indicated, the use of percentages within any E~ample are to be understood as the weight percentages of the indi~idual constitut~s relative to the total weight of ~he constituents.
~am~
E~ample l is a melt blend composition consisting essentially o~ 90~ PET, 40% of a polycarbonate and 20%
of an ethylene/~thyl acrylate/glycidyl methacrylate terpolymer. The PET used w~s a bottle grad~ resin with 0.67 I.V. ( as determined in phenol/TCE) and typically containing between about 0.035-0.04 me~/g of carbo~yl chain ends. The polycarbonate used was commercially available from the undcr the trade name ~Le~an", a name used for a family of polycarbonate materials. The . ~ particular polycarbo~ate us~d was ~Le~an lOl". The ethylene/ethyl acryl2t~glycidyl ~erpolymer was de~crib~d a~ h~ing a relati~e weight ra~io of 75 ethylene, 17~ ethyl acrylate and a~ glycidyl func~io~ali~y.
The melt bl~d was prepared by first dry bl~ndinq all of the constitu~nts toge~her and subs~quently, the dry blended co~stituents were then fed i~to the hopp~r of a ~illion l inch single scr~w e~trud~r with a L/D ratio of 30~l using a f2ed scre~
equipped wlth a M~ddo~ mi~.ing head. The ~truder barrel temperatur~ for each zone were kept at ~he followi~g appro~imate ~empera~ur~s of: Zone l, 205 deg.C; Zo~e 2, 250 deg.C; Zvne 3, 27~ d0g.C; ~one 4, WO91/15545 ~ ~ `'` -18- P~T/US91/0~3~7 250 deg.C. The te~perature of the flange waS kept at appro~imately 250 deg.C and th~ temp~rature of the dies was kept at approsimately 210 deg.C. The e~trude~
screw rotational sp~ed was maintained at about 60 rp~
The e~trudate was rapidly passed through a water bath in order to quench and cool the strands. The cooled strands were then passed through a pelletizinq maohine and the pellets formed wer@ collected and dried.
Thereafter, the pellets were molded into test specimens by injection molding using an injection molding machine. The barrel temperature o~ the machine during the injection process was maintained ~ithin a temperature range o about 280 - 287 deg.C and the mold was kept at a temperature of about 50 deg.C. During the molding operation, the cycle time was appro~imately 10 seconds during the injection step, and appro~imately 20 second during cooling. The pressure of the operation was approzimately 300 psi, with a pre~sure hold of 500 psi. Standardized tensile bars and Izod 20 impact bars were pr~pared. A quantity of the test bars were annealed, or heat aged in a circulating hot air oven at about 150 deg.C for periods of either 16 hours or 72 hours.
~ ~ T~ting of the samples included impact testin~, tensile elongation, tensile modulus and yield stress according to known t~sting proc~dures. ~he physical propertie~ mea~ured indicate e~tr~ordinary toughness o~
th~ material sub~equent to annealing. Resul~s of the ke~ts are summ~rized under the heading ~E~ on Ta~les 1 and 2 b~low.
The comparati~e e~amples A, ~, C, D and E are composikioAs ~omprising P~T, PC and various impact modifi~rs. Ea~h of these e~ample~ was prepared in the same manner as kh~ cvmposition of ~zample 1, and consi~t~d e~ ~ntially of 40~ PET, 40~ of a polycarbo~ate and 20% of one of the various impact modifiers.
~ ~a/15545 ;~ ~7~ 3 PCr/VS91/0~3~7 Comparativ~ E~ample A used an m~thYl methacrylate butadiene-styrene, (which is frequently catergorized in the ~rt as a~ "interpolymer") or ~MBS~
core shell rubber as its impact modifier. This rubber ~njoys significant usage in the art as an impact modifier as this material e~hibits good elasticity and provides good impact absorption.
The impact modifier used in the composition of Comparative E~ample ~ was an acrylonitrile-butadiene-styrene, or "A~S~ rubbe~ which similarly to M~S e~hibits good elasticity and good impact absorption. The formulation B was comm~rcially obtained from Mobay Chemical Co. under the trade designation "Makroblend UT1018n.
The impact modifier used in comparative e~ample C is an all-acrylate core shell rubber, which is marketed under the trademark ~Paraloid KM 3~0" by Rohm ~ Haas, and consists of a cross linked polybutylacrylate cor~ and polymethylmethacrylate shell.
In the formulation of Comparati~e E:~ample D, an ethyl/ethyl acetate copolymer ~as used as the irnpact modif ier ~
Compa~atiYe Esample ~ utilizes an ethyl/glycidyl me~hacryla~e copolymer as the impact modifi~r. The particular copolymer is comm~rcial1y mar~eted under the trad~name ~ondfast 2C~ and is aYailable rom the Sumitomo Chemical Co. The relative weight ratios o~
the ethyl to th~ glycidyl m~thacrylate in the copolymer is 94/60 The compositions of e~amples ~, B, C, D and E
were all produced, mold0d and subs2qu~ntly tested in the manner utiliz~d in the productiorl of e3ample 1, so to more cl~arly illustrat~ th~ distinct adYantage o compositions made in accordance with the inYention~
Likewise, the testin~ o~ the samples included i.mp~ct testing, t~nsile elongation, tensil2 modulus ~nd yield 2~7~9 ~
W091/155~5 ~ ? ~ 20- pcr/vs9l/ol3 stress according-to the same testing proc~dur~s utilized in testing the composition of Esample 1. The physical properties measured for these ComparatiYe ~xamples indicate the marked reduction in the toughness S of the material subsequent to annealing, or heat aging at 150 deg.C. R~sults o~ the tests are also summarized under the appropriate headings and listed on Tables 1 :. and 2 below.
1 0 ~,~ ,, _____________________________________ Example 1 A B C D
_________________________._____________ Notched Izod, ft.lb/in: 14.9 12.4 12.5 13.3 13.1 -aged 16 hrs.:12.6 10 o O 10.1 9.2 2.5 -aged 72 hrs.:11.5 5.6 5.3 3.7 ---Drop Weight Impact ft.lb: 97 ~ 156 --- ----aged 72 hrs.:~6 ---- 1.6 --- ---- :- Te~s~
Elongation, ~: llS 128 113 95 97 -~ged 16 h~s.:85 40 30 18 33 -aged 72 hrs.:
T~n~
Modulu~, p~200,000 29~,000 270,000 ---~
-aged lS hrs.: 215,000270,000 29~,000 -~
Yield Stre~s, psi: 5,400 6,160 6,~65 S,~20 2~2~0 -ag~d 16 hr~O 6,430 7,400 8,325 6,1~0 4,450 -aged 72 hr~.: 6,240 6,5lO 0,230 6,300 ~
W~91/1~545 , -21- PCT~US~]~3~7 TA~L~_~
__________.__________________________ E~a~ple: 1 E
______________ ___________ .
Notched Izod, ft.lb/in: 14.9 1q.5 -aged 16 hrs.: 12.6 13.2 lO -aged 72 hrs.: 11.5 3.
Drop Weight Impact ft.lb: 97 ----l; -aged 72 hrs.: 86 ----Tensile Elongation, s: 115 210 -ayed 16 hrs.: 85 125 20 -aged 72 hrs. : 67 7 The resultant physical test data particularly illustrates that the compo~itions of the present .ai invention, namely, the ~omposit:ions which include a re3ctive graft-terpolymer show the une~pected ad~antages of improved toughness subsequ~nt to annealing and superior impact strength retention. This is attributed to the functionality of the terpolymer in lts ability to form a graft copol~mer throuyh reaction with th~ terminal end groups, carbo~yl and hydro~yl, o~
PET and PC. Further, the e~cellent elasticity of the terpolymer imparts good impact energy absorp~ion qu~lities to the molded composition, and which is furth~r b~ ed to act as a compatibilizing ayent for the PET and PC u~d.
~a~
E~amples 2,3,4,5 and 6 are further embodim~ts of the invention which utilized the constitu~nts as WO91/1~545 PCT/~S91/0134~., ;
2~ ~ 3 ~ - 22-used to formulate E~ample l, but varies the relativ~
proportions of the PET, PC and the reactive terpolYme{
used in E~a~ple 1. The range of variation for ~he respective components based on the total weight o~ the S composition ~as: 30% t~ 80% PET, 0~ to 50~ PC, and a constant Z0% of the terpolymer. The speci~ic proportions are outlined in Table 3.
I~LE ~ 1, _______________________________________________________ I
E~amples: Z 3 4 5 5 ____________.__________________________________________ Constituent, weight %
~.~~ ~D
PET: 80 60 50 40 30 PC: -- 20 30 40 50 E/EA/GMA
terpolymer: 20 20 20 20 20 The compositions of E~amples 2-6 were produced in the same manner as that used ~or the production of E~ample 1.
. The physlcal charact~ristics-of the materlals produced from the compositions outlined in Table ~ are summarized in Table 4.
WO 91/l5545 . 2 ~ 59~ ~ P~/US~1/111347 ~, , ,. ., .-, , , TAELLE ~
______________.______ ___________________ E~cample: 2 3 4 5 :, ------------ ------------------ ---- -- ---- -------- -- :
. .
No t c:hed I æ od, ft~.lb/in: 7.4 16.6 16.4 14.9 14.5 -aged 16 hrs .: 3 . 2 3 .1 5 . 7 lZ . 6 19 . l lO -aged 72 hrs .: 3 . 2 --- 9 . 0 11 . 5 ---Tens i le Elongation, %: 2~g 165 127 115 72 -aged 16 hr~.: 23 29 41 85 100 15 -aged 72 hrs.: ~1 --- 25 67 ---Tens i 1 e ModulLIs, psi.: 5,400 5,400 5,523 5,980 6,380 -aged 16 hrs.
20 at 150 d~g.C: 6,390 6,000 6,400 6,640 6,770 -aged 72 hrs.
at 150 deg.C: 6,400 ~ 5,68~ 6,100 -----T~nsi le 25 Modulus, p~ 18~, 000 183, 000 195, 000 200, 000 2~5, 000 -aged 16 hr~. :235,000 221,000 221,000 21~000 216, 0~
A~ ~118y b~ d~t~rmined rom Tabl~s3 and 4, the compo~i~ion ~f ~:~a~Dpl~ 5 ~shibi~d par~icula~ly good r~en~ion o impac~ properties and elorlgation tr~ngSh.
E:ac~m~lo~ 7-12 e3~mplify th~ ~ec:o~d, alt~rnati~e tn~thod o pr~paring the composition3. Accordin~ ~o thi~ 3~::0nd m~'chod, an additional ~tep, apr~b1~ndirlq~
:
WO 91/1554S ~ . A'~ PCT/US9l/~1347 , ,, !, , ,,,`, ~,.' ';;
~75~?~ -2~
of the polycarbonate and the reactive terpolymer This preblending may be ~c~omplished by methods known to the art, including a two-step process, or a two-stage, single pass e~trusion process. This latter process was used for the formation of the compositions of E2ampl~s 7-12.
Table 5 indicates the various ratios of constituents utilized in the compositions of E~amples 7-12 which were produced using a preblending step. The percentages shown are percent by weight of the composition of each E~ample.
T~L~ S
_______________________________________________._______ E~amples: 7 8 9 lO ll 12 _________________________________________________~_____ Constituent, weight ~
PET: 40 40 45 50 50 60 PC: 40 45 35 30 33.3 2g E/EA/GMA
terpolymer: 20 lS 20 20 16.7 16 Th~ corre~ponding physieal proper~ies observed during th~ t~sting of thes~ materials is summarized on Table 6.
WO 91/15~4S ~Cr/VS9~/nl3~7 -2S_ ~ S~
____________.. __________________~_________ ____________ Ea~:ample: 7 8 9 10 11 12 __________________________________________ ~____ ______ 5 Notched Izod -molded: lS . 816 . 816 . 518 . 717 . 518 . 8 -annealed, 16 hrs. a~
150 deg.C:14.~ 13.7 12.9 15.0 7.3 4.3 Ultimate Elongation, ~6: 110 105 119 159 190 165 - anne a 1 ed , 16 hrs. at lS 150 deg.C: ~0 80 78 85 ~5 30 Ultimate Tensi 1~
St rength, psi: 5600 6~30 56~0 6060 6125 5880 -annealed, 16 hrs. at . lS0. deg.C:64107445 613S 6580 6715 6100 - . ~ .. ii~, ,... ;, .. . .. . .
25 T~nsile ~o~ulus, ~1000'~) p i.: 2D0 257 190 230 210 250 -ann~ d~
16 hrs. aé
lS0 d~g.C:2~0 2R0 210 ~60 2~0 ~67 ~r~ 05Jln~O~a~rDr~/l lYII ~9~ C~ V/~V!~r8~/ll Y~lmO O~IJ~ ~I OV~ 0 113~1~D 51/ ~ ~l iD Cl ~11il 31 Q ~!III Q ~0 Q ~ D
As may be di3cerned rolT lth~ rssults shown on Table 6, th~ co~positions show~d good retsntion of 35 impac:t str~ngth throus~hout, esp~cially ~or ;@~amples 7-10. It m~y ~urth~r b~ obs~rYed tha~ th~ ~cond m~thod of forming c:ompositions, wh~re th~3r~ is WC) 91/155415 ` PCr/VS()~/()13'17 J~
~ 2fi~ ~, preblending may be ad~antageous to the f irst method without preblending of the constitutents by a comparison of the physical test data o Tabl~s Z and 3 with Tables 5 and 6 which contrasts similar compositions produced by processes including no preblending with processes including preblending.
Particularly, the following paired compositions having th~ same ratio of constituents, arld their r~sultant physical properties may be cumpared: E~ample 5 and E~ample 7, E~ample 4 and 10. Particularly, the impact test values (notched Izod) indi~ate improved toughness~ Such results are believed to be attributable to improved graftin~ of the reActive graft terpolymer and the polycarbonate prior to the lS introduction of the poly(ethylen~ terephthalate.) E~amDle 13, CQmp~rativ~ ~am~
Th~ composition of E~ample 13 was a composition consisting essentiall~ of 90~ PET, 40~ PC and 20 ethylene/ethyl acrylate/glycidyl methacrylate terpolymer was produced. Comparativ~ Example E was a composition of PET, PC and an acrylonitrile-butadiene-styrene terpol~ner, which is marked u~der the tradename nMakroblendn wa~ ~ested wi th th~ composition of ~zample 11. ~oth compositions were subjec~ed to drop weight imp~ct testing at low temperatur~s (-40 d~.C) prior to, and subsequent to heat agin~, and the results of thes~ tes~s is listed on Table 7.
W(~ 91/155~1~ P~r/lJS~1iO~3~7 -27~ 5~, ~
X~,~ .. . ... . ..
E~ample: 13 E
_____________________________ _________________________ S ~rop weight irnpact st rength a t -40 deg.C.
(ft. lbs) prior to heat aging: 9~ . 7S 123 . 75 af ter heat aging at 150 deg.C, for 72 hrs .119 . 64 3 . 24 _________ ____________________________._________________ The composition o E~cample 13 was no~ed to be completely ductile b~fore h~at-aging, and the composition of Comparati~e E~ample E was noted to be 20 completely brittl~ ater heat aging, and showed poor strength reterltionO
Thr2e e~e~nplary composition~ comprising the terpolym~r of the pre~nt in~ention by m~lt blendlllg 25 the constitu37lts in accordan~e with the me~hod describ~d ~or ~E;3ample 1, with ~he f~llowing particular compo~ition~ outlined on Table 8.
3~
WO 91/~15545 ~ t ~ PCT/US91/01347 r --2 El ~
_____________________________________________.____ ..._____ E~amples: 19 15 16 __ ___________.________________________~________________ Constituent, weight %
ID W 1 11~ 8 31 IID il D ~111 --PET: 40 40 40 PC: 40 40 qo E/EA/GMA
terpolymer: 16 12 10 lS E/EA 4 8 10 copolymer The following phy~ical prop~rti~ outlined o~
Table 8~ were obser~ed.
WO 91/355~5 . ,, PCr/US91~0~3~i7 -29- ~ J;~
______________________________..._______________________ E:~ampl~: 14 15 16 __~______ Notched Izod -molded:16.2 16.2 15.8 - a nnea 1 ed , 16 hrs. at 150 deg.C: 16.6 15.9 19.3 Ul t imate Elongation, %: 1~5 145 133 -annea led, lS 16 hrs. at 150 deg . C:125 125 113 Ultimate Tens i le 20 Stren~th, psi: 6Z~ 65~5 62~0 -annea1ed, 16 hrs. at 150 deg.C 7900 7400 698q Tensile Pqo~ulu~, ~ 100~
p~ 21~ ~18 ---3 -aQn~ d, 16 hr~. at lS0 d~9~C: 245 250 ---Th~ r~$ult~t l:~tirlg data re~reals thi3 t the 35 compo3itios~ on~ining an amolln~ of an ~hylene copolymer, such ~ ~/~ not~d abo~?~, but not to b limit~d G~ol~ly to E~EA, m~y b2 in::lu:led in WO91/1~45 ~ P~/IJS91~U13~7 compositions, generally in amounts of up to about 10%
so to replace up to about half of the reactive terpolymer may be used without detracting from the beneficial qualities of the present invention.
While these e~emplary embodiments have described various aspects of the invention, it is to be understood that the scope of the invention is to be limited only by the following claims.
Claims (11)
1. An impact modified polyester-polycarbonate composition which includes at least one polyester, at least one polycarbonate represented by recurring structural units of the formula:
where "A" is a divalent aromatic radical derived from a dihydric aromatic compound, c h a r a c t e r i z e d by:
further including a terpolymer constituent having the formula:
E/A/X
where "E" is representative of an alpha-olefin, or in the alternative, an alkadiene, "A" is ethyl acrylate or methyl acrylate, and "X" is glycidyl methacrylate.
where "A" is a divalent aromatic radical derived from a dihydric aromatic compound, c h a r a c t e r i z e d by:
further including a terpolymer constituent having the formula:
E/A/X
where "E" is representative of an alpha-olefin, or in the alternative, an alkadiene, "A" is ethyl acrylate or methyl acrylate, and "X" is glycidyl methacrylate.
2. The impact modified polyester-polycarbonate composition of claim 1 wherein the at least one polyester is selected from the group which includes:
linear condensation products of saturated glycols;
linear condensation products of a saturated dicarboxylic acid;
poly(alkylene terephthalte)s;
poly(ethylene terephthalate);
poly(butylene terephthalate);
condensation products of an aromatic dicarboxylic acid having 8 - 14 carbon atoms and at least one glycol selected from among cyclohexane dimethanol, neopentyl glycol, aliphatic glycols of the formula HO(CH2)nOH
where the letter "n" represents an integer of 2 - 10.
linear condensation products of saturated glycols;
linear condensation products of a saturated dicarboxylic acid;
poly(alkylene terephthalte)s;
poly(ethylene terephthalate);
poly(butylene terephthalate);
condensation products of an aromatic dicarboxylic acid having 8 - 14 carbon atoms and at least one glycol selected from among cyclohexane dimethanol, neopentyl glycol, aliphatic glycols of the formula HO(CH2)nOH
where the letter "n" represents an integer of 2 - 10.
3. The impact modified polyester-polycarbonate composition of claim 1 wherein the at least one polycarbonate is selected from the group which includes:
4,4'-dihydroxydi(mononuclear aryl)A compounds where the mononuclear aryl may be phenyl, tolyl, xylyl, ethylphenyl, isopropylphenyl, and where the connecting "A" groups may be -CH2-, -C2H4-, -C3H6-, -C4H8-, -SO2-, -O-, -S-, or -C3F6;
polycarbonates derived from a dihydric phenol and a dibasic acid;
poly(2,2-bis(4-hydroxyphenyl)alkane)carbonates;
poly(2,2-bis(4-hydroxyphenyl)propane).
4,4'-dihydroxydi(mononuclear aryl)A compounds where the mononuclear aryl may be phenyl, tolyl, xylyl, ethylphenyl, isopropylphenyl, and where the connecting "A" groups may be -CH2-, -C2H4-, -C3H6-, -C4H8-, -SO2-, -O-, -S-, or -C3F6;
polycarbonates derived from a dihydric phenol and a dibasic acid;
poly(2,2-bis(4-hydroxyphenyl)alkane)carbonates;
poly(2,2-bis(4-hydroxyphenyl)propane).
4. The composition according to claim 1 wherein the relative weight ratios of the constituents comprising the graft terpolymer are of the following relative weight percentages: 45-98% of "E", 1-40% of "A", 1-15%
of "X".
of "X".
5. The composition according to any preceeding claim further c h a r a c t e r i z e d by:
further including an ethylene copolymer.
further including an ethylene copolymer.
6. The composition according to any preceeding claim further c h a r a c t e r i z e d by:
including at least one modifier selected from among the group which includes; organic modifiers, inorganic modifiers.
including at least one modifier selected from among the group which includes; organic modifiers, inorganic modifiers.
7. The composition according to any preceeding claim further c h a r a c t e r i z e d by:
the relative weight ratios of the constituents of the impact modified polyester-polycarbonate composition consists of at least 40% polyester, 40% polycarbonate, and 10% of the terpolymer constituent having the formula:
E/A/X.
the relative weight ratios of the constituents of the impact modified polyester-polycarbonate composition consists of at least 40% polyester, 40% polycarbonate, and 10% of the terpolymer constituent having the formula:
E/A/X.
8. A molded article c h a r a c t e r i z e d by:
comprising the impact modified polyester-polycarbonate composition according to any preceeding claim.
comprising the impact modified polyester-polycarbonate composition according to any preceeding claim.
9. An impact modified polyester-polycarbonate composition which includes at least one polyester, at least one polycarbonate represented by recurring structural units of the formula:
where "A" is a divalent aromatic radical derived from a dihydric aromatic compound, c h a r a c t e r i z e d by:
further including a terpolymer constituent having the formula:
E/A/X
which is selected from the group which includes:
terpolymer constituents which have an isocyanate functionality derived from a material selected from the group consisting of; 2-isocyanoethylmethacrylate, p-isopropenyl-alpha,alpha-dimethyl benzyl isocyanate, n-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate;
terpolymer constituents which have an acyllactam functionality derived from a material selected from the group consisting of; methacroyl caprolactam, methacryloyllaurolactam, compounds of the general formula where "x" may have a value of 3 to 10, and "Y" is -H or an alkyl constituent.
where "A" is a divalent aromatic radical derived from a dihydric aromatic compound, c h a r a c t e r i z e d by:
further including a terpolymer constituent having the formula:
E/A/X
which is selected from the group which includes:
terpolymer constituents which have an isocyanate functionality derived from a material selected from the group consisting of; 2-isocyanoethylmethacrylate, p-isopropenyl-alpha,alpha-dimethyl benzyl isocyanate, n-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate;
terpolymer constituents which have an acyllactam functionality derived from a material selected from the group consisting of; methacroyl caprolactam, methacryloyllaurolactam, compounds of the general formula where "x" may have a value of 3 to 10, and "Y" is -H or an alkyl constituent.
10. The composition according to claim 9 wherein the relative weight ratios of the constituents comprising the graft terpolymer are of the following relative weight percentages: 45-98% of "E", 1-40% of "A", 1-15%
of "X".
of "X".
11. The composition according to any preceeding claim further c h a r a c t e r i z e d by:
further including an ethylene copolymer.
further including an ethylene copolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US504,456 | 1983-06-15 | ||
| US50445690A | 1990-04-04 | 1990-04-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2075910A1 true CA2075910A1 (en) | 1991-10-05 |
Family
ID=24006347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2075910 Abandoned CA2075910A1 (en) | 1990-04-04 | 1991-02-26 | High impact polyethylene terephthalate-polycarbonate blend compositions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0523087A1 (en) |
| JP (1) | JPH05501128A (en) |
| BR (1) | BR9106113A (en) |
| CA (1) | CA2075910A1 (en) |
| WO (1) | WO1991015545A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0528462A1 (en) * | 1991-07-31 | 1993-02-24 | ENICHEM S.p.A. | Solvent-resistant polycarbonate-polyester blends with improved impact properties |
| US5814712A (en) * | 1996-04-25 | 1998-09-29 | General Electric Company | Impact-modified thermoplastics resin molding compositions and articles molded therefrom |
| DE19739686A1 (en) * | 1997-09-10 | 1999-03-11 | Basf Ag | Thermoplastic molding compounds based on polyesters and polycarbonate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3585935D1 (en) * | 1984-02-24 | 1992-06-04 | Du Pont | REINFORCED THERMOPLASTIC POLYESTER COMPOSITIONS. |
| JPS60231757A (en) * | 1984-05-01 | 1985-11-18 | Toray Ind Inc | Polyester composition |
| DE3521956A1 (en) * | 1985-06-20 | 1987-01-02 | Basf Ag | REFRIGERANT IMPACT THERMOPLASTIC MOLDS FROM POLYESTER AND POLYCARBONATE |
| DE3601422A1 (en) * | 1986-01-20 | 1987-07-23 | Basf Ag | THERMOPLASTIC MOLDS BASED ON POLYCARBONATES AND POLYESTERS |
-
1991
- 1991-02-26 EP EP19910906621 patent/EP0523087A1/en not_active Withdrawn
- 1991-02-26 WO PCT/US1991/001347 patent/WO1991015545A1/en not_active Application Discontinuation
- 1991-02-26 BR BR919106113A patent/BR9106113A/en not_active Application Discontinuation
- 1991-02-26 CA CA 2075910 patent/CA2075910A1/en not_active Abandoned
- 1991-02-26 JP JP3507147A patent/JPH05501128A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05501128A (en) | 1993-03-04 |
| BR9106113A (en) | 1993-02-24 |
| WO1991015545A1 (en) | 1991-10-17 |
| EP0523087A1 (en) | 1993-01-20 |
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