CA2066085C - Elastomeric thermoplastic copolyether-esters endowed with improved thermal and hydrolitic stabilities - Google Patents
Elastomeric thermoplastic copolyether-esters endowed with improved thermal and hydrolitic stabilities Download PDFInfo
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- CA2066085C CA2066085C CA002066085A CA2066085A CA2066085C CA 2066085 C CA2066085 C CA 2066085C CA 002066085 A CA002066085 A CA 002066085A CA 2066085 A CA2066085 A CA 2066085A CA 2066085 C CA2066085 C CA 2066085C
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- ester
- copolyether
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
Abstract
The thermal and hydrolytic stabilities of the elastomeric thermo-plastic copolyether-esters are remarkably improved by the addition of a synergistic mixture consisting of an tri (hydroxybenzyl) benzene and of a bis (alkyl-phenyl) pentaerythritol diphosphite.
The copolyether-esters thus compounded find use in the extrusion, blow and injection molding technologies.
The copolyether-esters thus compounded find use in the extrusion, blow and injection molding technologies.
Description
ELASTOMERIC THERMOPLASTIC COPOLYETHER-ESTERS ENDOWED
WITH IMPROVED THERMAL AND HYDROLYTIC STABILITIES
The present invention relates to elastomeric thermoplastic Copolye~ther-esters endowed with improved thermal and hydrolytic stabilities.
More particu:~Larly, the present invention relates to elastomeric thermoplastic copolyether-esters endowed with high rheologic~a.l and mechanical properties and improved resistance to the the:rmo-oxidation and to hydrolysis, particularly suitable for being transformed into shaped articles both by blow-molding extrusion and injection molding.
The elastomeric thermoplastic copolyether-esters are materials distinguishing in the: rubber field by their high physical and mechanical properties, such as toughness, fatigue resistance, impact resistance, abrasion resistance, and the like, as well as by their oil and gasoline resistances. In spite of these properties which are meaning fully higher than those of the copolyesters, the elastomeric thermoplastic copolyether-esters exhibit a poor resistances to thermo-oxidation and to the hydrolysis.
WITH IMPROVED THERMAL AND HYDROLYTIC STABILITIES
The present invention relates to elastomeric thermoplastic Copolye~ther-esters endowed with improved thermal and hydrolytic stabilities.
More particu:~Larly, the present invention relates to elastomeric thermoplastic copolyether-esters endowed with high rheologic~a.l and mechanical properties and improved resistance to the the:rmo-oxidation and to hydrolysis, particularly suitable for being transformed into shaped articles both by blow-molding extrusion and injection molding.
The elastomeric thermoplastic copolyether-esters are materials distinguishing in the: rubber field by their high physical and mechanical properties, such as toughness, fatigue resistance, impact resistance, abrasion resistance, and the like, as well as by their oil and gasoline resistances. In spite of these properties which are meaning fully higher than those of the copolyesters, the elastomeric thermoplastic copolyether-esters exhibit a poor resistances to thermo-oxidation and to the hydrolysis.
It is known; in fact, that the elastomeric copolyether-esters tend to degrade when subjected to an extended exposure at temperature higher than 150°C.
~l 1\ (r ~ i L. . , n i ~ a f 11 - _ ~ r, t -This drawback drastically reduces the fields wherein the copo=
lyethex-estexs may be used.
Moreover, the copolyether-esters undergo a hydrolysis of the ester gx°oups when they are dipped in water for an eacten=..
ded period of time.
In order to overcome- this drawback, it is Down tecni=
que to add to the copolyether-esters a stabilizing ~oduct.
Many stabilizing products have been propose ~t~r this end, but none of them allowed to solve the problem uetivelp and without undesired effects.
Thus, for example, it is Down from U.S. patent Nos. 3, 7.93, 522 and 3, 1g3, 524 to add polycarbodiimides for improvza~g the resistanaea to the thermo-oxidation, tn;the hydrol~ps~.s and to the light of polyesters.
The efferativeness of these compounds, ha~ever, is some=
what limited, since the low molecular weight polycarbodiimides are readily extraated by solvents or minerral oils, they have a tendency to migrate to the surface and result ineffective at high temperatures because they have a tendency to undergo po7~=
merization, thereby destroying the rea~tcivity o~ the carbodi=
imide group and thus the stabilization aotion of the taomposi=
tion.
Other carbodiimi.des s~xerh as, for e~pl:ep thoa~e contai=
ring other functional. groups such as hydro~rl groupy have b~e~
pcroposed as stabilizing agentss ho~eever' also th~ssH caomp~a m tend to react with themselves ands often a loss of the acti=
vity occurs following the storability.
To overcome all the above-drawbacks~ it has been ~opo=
s ed the ~as e, as stabiliz ers for polyest ers ~ of pol~y~xbodiim7.des having a molecular weight of at least 500 and havir3g at least. 3' caxbodiimide groups in the molecazl.e . ( see LTS-A- 3 p 1g3 y 5~ ) .
U.S. Patent No. 3, 896 078 proposes to improve the re=
sistance to thermo-oRidation of the copol~rether-esters by in.-.-corpor sting into the polymer an effective amount of amide lin=
kegs containing material, wich on h~Ydxolysis yields pry amino groups and carboxylia~groups~ together with an antioxip -~.
dent of arylamine or hindered phenol type. A typical examples of amide linkage containing compound is l, 6-bis ~3 .- (3'5 -di - tart. butyl - 4 - hydroxyphenyl) propiox~amide hexane k_r~own on the mar~tet by the trade-mark IRGA1Q0~ Z(~$ $ .
The elastomeric thermoplastic: copolyether~~te;rs stabi=
lied by the above compounds exxhibit~ however, a poor stability toward thermo-oxidation with the time. In fact, they tend to colour yeFllow after some days of treatment ir~ oven at 150aC in air. ~urther~morer, the stability to hydrolysis of thesew stabili=
red elastomsriQ aopolyether-esters is not pletel~y sati~fac-tort' for v~el1 deate~mir~e~d applications veher~in such a property is require~
Tt lass been new found that the res~.stanae toward the~o-oxidative degradation ax~c3, the re~3.stance °tto the hyd'colys-~.$. ~~
the elastomeric thermoplastic copolyether-estersmay be greatly enhanced by incorporating into such polymers an effective amount of a synergistic mixture consisting of a tris (hydroxy-benzyl) benzene and a bis (alkyl-phenyl) pentaerythritol di-phosphite.
The amount of the synergistic stabilizing mixture to be added is generally comprised between 0,01 and 10% by weight with respect to the elastomeric copolyester, and preferably between 0,2 and 5% by weight.
The weight ratio between the bis (alkyl phenyl) pentaerythritol diphosphite and the tris (hydroxy-benzyl) benzene in the synergistic mixture of the present invention can be varied within a wide range even if ratios comprised between 3 . 1 and 1 . 3 are preferred; particularly a bis (alkyl-phenyl) pentaerythritol diphosphite tris (hydroxy-benzyl) benzene weight ratio of about 2 . 1 has been found particularly advantageous.
The tris (hydroxy-benzyl) benzene used in the stabilizing mixture of the present invention has general formula:
~Rl~ U
~l 1\ (r ~ i L. . , n i ~ a f 11 - _ ~ r, t -This drawback drastically reduces the fields wherein the copo=
lyethex-estexs may be used.
Moreover, the copolyether-esters undergo a hydrolysis of the ester gx°oups when they are dipped in water for an eacten=..
ded period of time.
In order to overcome- this drawback, it is Down tecni=
que to add to the copolyether-esters a stabilizing ~oduct.
Many stabilizing products have been propose ~t~r this end, but none of them allowed to solve the problem uetivelp and without undesired effects.
Thus, for example, it is Down from U.S. patent Nos. 3, 7.93, 522 and 3, 1g3, 524 to add polycarbodiimides for improvza~g the resistanaea to the thermo-oxidation, tn;the hydrol~ps~.s and to the light of polyesters.
The efferativeness of these compounds, ha~ever, is some=
what limited, since the low molecular weight polycarbodiimides are readily extraated by solvents or minerral oils, they have a tendency to migrate to the surface and result ineffective at high temperatures because they have a tendency to undergo po7~=
merization, thereby destroying the rea~tcivity o~ the carbodi=
imide group and thus the stabilization aotion of the taomposi=
tion.
Other carbodiimi.des s~xerh as, for e~pl:ep thoa~e contai=
ring other functional. groups such as hydro~rl groupy have b~e~
pcroposed as stabilizing agentss ho~eever' also th~ssH caomp~a m tend to react with themselves ands often a loss of the acti=
vity occurs following the storability.
To overcome all the above-drawbacks~ it has been ~opo=
s ed the ~as e, as stabiliz ers for polyest ers ~ of pol~y~xbodiim7.des having a molecular weight of at least 500 and havir3g at least. 3' caxbodiimide groups in the molecazl.e . ( see LTS-A- 3 p 1g3 y 5~ ) .
U.S. Patent No. 3, 896 078 proposes to improve the re=
sistance to thermo-oRidation of the copol~rether-esters by in.-.-corpor sting into the polymer an effective amount of amide lin=
kegs containing material, wich on h~Ydxolysis yields pry amino groups and carboxylia~groups~ together with an antioxip -~.
dent of arylamine or hindered phenol type. A typical examples of amide linkage containing compound is l, 6-bis ~3 .- (3'5 -di - tart. butyl - 4 - hydroxyphenyl) propiox~amide hexane k_r~own on the mar~tet by the trade-mark IRGA1Q0~ Z(~$ $ .
The elastomeric thermoplastic: copolyether~~te;rs stabi=
lied by the above compounds exxhibit~ however, a poor stability toward thermo-oxidation with the time. In fact, they tend to colour yeFllow after some days of treatment ir~ oven at 150aC in air. ~urther~morer, the stability to hydrolysis of thesew stabili=
red elastomsriQ aopolyether-esters is not pletel~y sati~fac-tort' for v~el1 deate~mir~e~d applications veher~in such a property is require~
Tt lass been new found that the res~.stanae toward the~o-oxidative degradation ax~c3, the re~3.stance °tto the hyd'colys-~.$. ~~
the elastomeric thermoplastic copolyether-estersmay be greatly enhanced by incorporating into such polymers an effective amount of a synergistic mixture consisting of a tris (hydroxy-benzyl) benzene and a bis (alkyl-phenyl) pentaerythritol di-phosphite.
The amount of the synergistic stabilizing mixture to be added is generally comprised between 0,01 and 10% by weight with respect to the elastomeric copolyester, and preferably between 0,2 and 5% by weight.
The weight ratio between the bis (alkyl phenyl) pentaerythritol diphosphite and the tris (hydroxy-benzyl) benzene in the synergistic mixture of the present invention can be varied within a wide range even if ratios comprised between 3 . 1 and 1 . 3 are preferred; particularly a bis (alkyl-phenyl) pentaerythritol diphosphite tris (hydroxy-benzyl) benzene weight ratio of about 2 . 1 has been found particularly advantageous.
The tris (hydroxy-benzyl) benzene used in the stabilizing mixture of the present invention has general formula:
~Rl~ U
wherein: R1, R2 and R3, which may be equal to or different from each other, represent an alkyl group, preferably containing from ~ '.~ i1 1v b 1 to 8 carbon atoms ~-3nd n i.s an integ~ac comprised between 1 and 3.
It is preferred that at. least one of R~ and Rs radi=
Gals, and preferably both the radicals, are al~y3s contairLlng from 3 to 8 carbon atoms and are branched on the carbon atoms in alpha-position.
The pr ef err ed c ompounds of f orm~u7.a ( I ) ar a thw symme=
trical hexasubstit~zted benzenes. These compounds axe the' l, 8:, 5-tr ialkyl-~ , ~., 6~tr is ( 3 , 5-d.ialkyl-4-Y~ydro~r-benzyl ) berg yes having the formula:
g2 (II) CHI
R2 ~ R3 OFi wherein Rl R2 and R3 have th.e significances set forth above.
Typical ea~amples of compoutlds which may be used as co-stabilizers in the synergistic: nnixture of the present invention are:
1, 3, 5 -tri-methyl-2, 4, 6 -tri(3,5 -d.i-tert~ butyl- ~. -hydr os~yb enzyl ) bent en~e;
l, 3, 5 -tri-etk~,yl- 2, ø~ 6~ -tri(8, 5 -di-tart. b~xtyl- ~ --hydroxybenzyl~ benzene;
- 7 .
1,3,5-tri-methyl-2,4,6-tri(3,5-di-isopropyl-4-hydroxybenzyl) benzene;
1,3,5-tri-octyl-2,4,6-tri(3,5-di-tert. butyl-4-hydroxybenzyl) benzene;
1,3,5,-tri-ethyl-2,4,6-tri(3,5-di-tert. amyl-4-hydroxybenzyl) benzene;
1,3,5-tri-butyl-2,4,6-tri(3-isopropyl-5-tert. amyl-4-hydroxy-benzyl)benzene;
1,3,5-tri-propyl-2,4,6-tri (3,5-di-tert. octyl-4-hydroxy-benzyl)benzene.
Among these, the particularly preferred compounds are those having three 3,5-di-tert. butyl-4-hydroxybenzyl radicals.
These compounds and their preparation processes are known in the literature and disclosed in U.S. Patent Nos. 3,026,264; 4,340,767 and 4,754,07'7.
Particularly, the 1,3,5-tri-methyl-2,4,6-tri(3,5-di-tert. butyl-4-hydroxybenzyl)benzene is known on the market by the trade name ETHANOX 330~ of the ETHYL
Corporation Society.
The bis(alkyl-phenyl)-pentae:rythritol diphosphite that may be used in the synergistic mixture of the present invention, may be of the general formula:
R4 ~O-CH2 ~ H2 ~ R4 P 'C
" (III) o l Q--CH2 CH2_..0 g5 wherein R4 and R5, which can be either equal or different from each other, alkyl radicals containing from 1 to 10 carbon atoms.
_ 8 _ All the above compounds and their preparation are well known in the literature and disclosed in U.S. Patent Nos. 3,281,381; 3,310,609; 3,192,243 and 3,205;269, the content thereof is integral part of the present description as a reference.
The invention as claimed is however restricted to the use of the bis-(alkyl-phenyl)-pentaerythritol diphosphites of the formula:
C ( CH3 ) 3 0-CH2 ,CH2-O C ( CH3 ) 3 -P~ 'C (IV) e_,~v ~
wherein R5 is an alkyl radical cont=aining form 1 to 6 carbon atoms.
A particularly preferred compound is bis-(2,4-di-tert. butyl-phenyl)-pentaerythritol diphosphite know in the market with the trade name ULTRANOX~626 produced and sold by BORG WARNER Chemicals.
Fd ~~ ~ ~ l i '~f ~ i _ ~ -An<y e:Lastomer is thermoplastic copol.yether-ester cony taining ester bonds i1 - ~ _ o and ether bonds - C - 0 - C -may be stabilized by the syn.ergistic mixture of the present irwention, provided that said polyether-esters exhibit a sof=
teeing or melting temperature lower than ~50pC, which ais the temperature at which the stabilizing system usually is no mo=
re effective.
The elastomeric thermoplastic copolyether-esters ha=
ving a segmented strwcture are pexticzz7.arly preferred. These elastomeric thermoplastic copolyether-esters cons~.st of a mu1=
tiplicity of repeating long-chain ester urs.ts anal of repeating short-chain ester units connected t~ each other in head-to-tail fashion through linkages of the ester type. Said Kong-chain a st er unit s ax a r epr es e~.t ed by general formula s -0-G-0.-G-~t-aC-and said short-chain ester units arm represented by general f ormula ~ D~ ) whet ein:
G is a divalent group rsma~.n.ing aftex° the re~o~ra3. of the ;_ ..~ J ~, ~ '..' c.' 1~ -terminal ;~Ydro~r groups from a poly-(al~lene oacide) gly=
col having an molecular weight of from about 250 to 5'000 and a carbo~/o~ygen ratio of about 1.8 to 4.3;
R is a divalent gioup remaining after the removal of the carbolic group from a dicarboxylic acid having a moleau=
lar weight lower than about 300; and D is a divalent radical remaining after the removal of the hydroxylie groups from a diol having a ~nol.ecular weight lo=
wer than about 250.
In said copolyether-esters the short-chain ester units of general formula (VI) are present in an amount of about 15 to 9~~ by weight, preferably 33 to 86~ by weight, with: respect to the weight of the copolyester; the remainis~ past being com=
pos ed of long-chain eat es° unit s of general f ormnla (V ) .' Said ~lastomeric copolyether-esters are well known in the literature and described', for example, yn D.S. Patent Nos.
3,023, 19~ and 3:, 651, 015; Italian, Patent i~os.~ 947589; 963304 and 973059 and published Ita7:~.an Patent Application No. X12 filed on ,19880 The repression "long--chain ester un:i.ts" refs to the reaction product of a poly(alk,~rlene o~.de) glyv~ith a diear=
boxylic acid, resulting in ester un3.ts represa~ate~3: by the a'bave?
f oryuula (V ) .
As pol~r(all~rlen~-oxide) gl;~cwla there mar ldo~ rxa~d thoe~
which contain from 2 to 10 carbon atoms in the al~lenaPgroupp w f~ tt r3 i, '. .' such as poly-X1,2- and lf~-propylene-oxide)-glycal; poly-(te=
trametbylene--oxide)--glycol; poly-{pentamethylene-oxide)-glycol;
poly-{hexamet2~ylene-oxide)-glycol; poly-(heptamethylene-oxide)-glycol; poly-(octamethylene-oxide)-glycol; po:l,,~-(nonametl~len~
oxide)-glycol; poly-(decamethylen~-.oxides)-gly~l; and poly-( 1' 2 -but y1 ene--oxid a ) -glycol ; OH t erminat ed poly~t ~e-1-poky=
butadiene; random copolymers or block copolymers of ethylen~-oxide and 1,2-propylene-oxide; and the lake.
In the present inventions parti~alarly p~refe~r~di i,s poly-(tetramethylene-oxide)~gly~l having a very narraw ave=
rage distribution of the maleuular weights' such as' for exam=
plc, a ~dw/%n ratio lower than 2 ~ which generally re~u1ts in an improved resistance= to fluids such as oi:E..s, gasoline, water, fats etc.
the session "short-chain ester units" relates to the reaction product of a diol having a loev molecular weight (lower than about 250) with a dicarbo~yliG acid in order to f orm es t er uni.t a r epr es ent ed by t he ab vv a f ox~mnzla (~ T. ) .
Among the diols having a low molecular weight Ahieh by reaction produce the short-chin ester units' non-cey~.ia' alicyclic an3 aromatic di-hydroxy compounds are includ~sd.
Diols of from 2 to 15' carbon atoms such as eathyhene-glycol propylene-glyaol~ :Lscbutylen~-glycol' tetx~methylen~-gl~~l.i pentamethylene~glycol! 2 s2-dimethyl trim~hylen~gly~l.~ h~
xamethylene-glycol and decamethyhene°-gl~rcol.' di by~x~PCy~lo-~. p y , hexane! cyclohexane-dimethanol, resorcinol, htydroc~uinone;~ 1,~-di-~h~~Tdroxy-~phthalene, etcg are prefex°red.
3?articular 1y preferred are aliphatic diols conta~.ning from 2 to 8 carbon atoms.
Ales of di-hydroxy aTOmatic compounds which may be used are bisphenols, such as bis-(p~hydroxy)-diphe~rl' bi.a-(p-hydroxyphenyl)-methane, and bis-(Ps°2~yd~'ox~gher~,yl)"PQ'opane, et a .
The term "lose-molecular-weight diols" as used herein should hence be understood as also including all of' the egu,i=
valent derivatives suitable for formir~ estera~ although the molecular weight requirem~.t refers exc3.usively to they basic' diol, and not to the derivatives thereof.
However, 1,4-butane-diol is. pa,rticul.arl~ ~xref'a~ed, for the purpose of the present in~rention.
Dicarboxylic acids which are reacted with thg abov~
poly(alkylene oxide) glycpls and: with the low molecular weight diols to yield the copolyether-esters of the present invention are aliphatic, cycloaliphatic~ and/or aromatie da.carba~rl.ia;
acids having a low molecular weight, i.e., ha~oirag a ~aol.ecul.ax weight of preferabl~r less than about 3~a.
The term "dicarboxylic acids" also includes equi:~ralent derivatives of dicarbox~lic aids which show a beh,aeLowe s~,mis lar to that of dicarht~x3rl:~c aai.de~: in the reaat3.on ~r~.th gl~anl~
and dials to for~a copolyether-eatez° pol~ers.e Theses ~q.uivel.ea~
'~ ~ ~"~ ;6 w c' i..~ f3 ;; ,,v -r - lV~ -compounds include esters arid ester-forming derivatives such as, e.g. acid halides and ann"vdrides. The moles weight requirement, however= relates exclusively to the acids and not to its corresponding estexs or other ester-forming dsri.=
vat iv es .
Therefore, the term "dicarbo~ylia: acid" includes: also an ester of a dicarba~lic acid which ester has a molecular weight higher than 300' or az~y other dicarbo~lic: act3..d deri=
vat iv a having a molecular w eight gr eat er than 3 00' proga.d;ezl that the corresponding acid has a molecular weight below about 300. The dicarbo~ylic acids may contain any substituent~groups or arty combination of substiiment. groups which do not: signi~fi=
cantly interfere with the formation of the copolysste~ polymer and with the use thereof in the end products accarding. to the present invention.
Within the context of thc~ present: inventiozay by "ali=
phatic~ dicarbo~lic acids" those carbolic acids are-meant which contain two carboaQrlic groups, each attached ~bo a satur rated carbon atom. If the carbon atom to which the carbox3rlic group is attached is a saturated one and is~ psrt of a ring, the acid is cycloaliphatic:. Generally aliphatic:acid.a or cy=
cloaliphatic acids: containing a conjugated unsaturation carp not be used' in that they are liable to hrnnopol~erizee. Hove=
very some unsaturated aside sash as' e.g., malefic awaid and the dimer or trimer of: oleic said can be used.
D i_ ~
_ 1~
fihe term "aromatic dicarboa~vlic acids" s.:~ used herein refers to dica.~rbo~ylic acids having two carbo~ylicy-z~ou~, each carbo~rlic group being attached to a carbon atom in an isolated or fused benzene ring. It is not necessary that both carboxylic groups be attached to the same aroma.ti~ ring, amri, where more than one ring is present, said rings may be linked through divalent aliphatic or aromatic radicals or through divalent radicals such as, e.g., -Q- or -S~~-, or eve~a by a carbon-carbon single bond.
Examples of aliphatic and eycloaliphatia dicarboxiylie acids which can be used for preparing the aopolyether-esters of the present invention are sebacia: acid, 1,3-cyclohexane.-dicarbox3rlic acids 1,4-cyclohe~cane-dicarboa~ylic acid, adipic acid, glutaric acid, succinic acid, oxalic acid, azelaic acid, diethyl-malonic acid, allyl. malox~.c aaad, 4-cyclohexane-1,2-dicarboxylic acid' 2-ethyl.suberic~ acid, 2'2,3,3-tetramethyl-succinic acid, ayc3opentan~-dicarboxylic said, decahydro-1,5-naphthalene-dicarbo~rlic acid, 4,4°-dicyclohexyl-dicarbox3rlic acid, decahydro-2,6-naphthalene-dicarboxylic acids 4~,4'-~methy=
lene-bis-(cyclohexyl)-carbox~rlit~ said, 3'4-.ran-dicarboxylic acid, 1,1-cyalobutane--d~.carboxylic acid., etc.
Cyclohexane-dicar'boa~lic said and adipie acid are pre=
farted dicarbox~lic acids.
Ales of aromatic dicarboxyli.t~ acids which can be used comprise phthalic aaid9 isophtha3:3.c said, te~~phtbalia~
~ k i ; ' ~ ~ ; a v ~a '.
acid, dibenzoic acid, dicarbo_~lic compoiuzds substituted with two benzene rings, such as, e.g., bis(para-carboxy-phenyl)-methane, pare-oxy-(pare-carboxy-phen'yl)-benzoic acid, ethylene-bis-(pare-o~ybenzoic acid), l,5-naphths.lene-dicarbo~lic acid, 2,6-naphthalene-dicarboxylic acid, ~,7-naphthalene-dicarboxy=
lic acid, phenanthrene-dicarbox<ylic acid, anthralenea-dicarbo=
xylic acid, 4,4'-sulfor~yl- diben~oic acids thiofurra~ane-3:'4°-dicarboxylic acid, as well as their Cl-C~-aryl esters and derivatives resulting from substitution on thw ring=' such as, e.g., halo, alkoxys and aryl derivatives.
Aromatiw acids containr~ a Y~ydroxg groups such asp e.g., pare-1~...hydrox<y-ethoxy)benzoic acids may also be usedy gravided that an aromatic dicarbo~ylic ard.d is also presexxtr.
The aromatic dicarbo~ylic acids constitute a preferred class for preparing the copolyethex°-ester polymers of they com=
positions of the present' invexition.
Among the aromatic aaids~ those with from ~ to 16 carbon atoms are preferred; particularly preferred are phe~lena-dicer=
boxylic acids= i.e., phtha.lic: acid, isophthalic acid and ~terephh~
thalic acid. In particular, either terephtha~aa:aaid alone or a mi~cture of terephthali~ said and isophthaliQ acid are preferxced.
At least about 746 by mfll of the dicarboaylic said inalu%-ded in the polymer are preferably cc~nnposed~ of t~xephthah~.ee said' i.e.g about 70y~ of the "R" groups in formn.~lae (V) and (~~) abo~
ve are preferably 1,4-phlene radicalss . ;, ,.
L '.: 'i ~: , ..
1E, -The carboxylic acids or their derivatives and the po=
lymeric ghycols ar'e included in the final praducts in the: same moles proportions in which they are contained in the reaction mixtures. The actually inc?uded amount of low-molecular weight diol corresponds to the difference between the mole of diacid and the cools of polymeric glycol evntained in the reaction mlXtLl2' a a The mast preferx°ed copolyether-est~°s of thee present invention are those prepared form terephthalie acid (SPA), 1'ø-butanediol (HD), and polytetramethyleneglycol (~G) ha=
ving an average mo~_ecular weight of from about X50 to about ø500 and, optionally isophthalic acid (IPA) in an amount not higher than about 5~ by weight with respect to the total amo=
unt of the two acids.
The polymers of the apmpositions of the present ir~ven.=
tion may suitably b~ prepared by means of a normal traasestar~i=
fication reaction, A preferred process comprises heatingsi at 154 - 230~C' the ester of the~~ dicarbo~ylic~ acid (for e~ple the dimethyl ester of texe~phtrhalic; acid) with the pol.,p(all~rle=
ne vide) glyQ~ol and. a molar e~sa~ss of a diol~ in the pareaena~
of a catalyst. T!he amount of the diol is at le~.st 1.1 molee of diol per each mole of acid.
The heating is continued ~atil °~he rc~aa~al of methanol is eaeentially complete.
~
.. t~ ~.1 t~ i The resulting prepolymer is then carried to high no=
lecular weight by distillation under vacuum of the s of the low molecular weight diol (polycondesation). During tln~.s distiilation~ additional transesterification occurs, which leads to an increase-in molecular weight and to a random ar=
rangement of the various copolyester units in the molecule.
In order to avoid an excessively long hold time of the polymer at high temperatures with possible irrevers~.ble thermal degradation, catalysts for the: ester-interchange reac=
tion are advantageously employed.. While a wide variety of ca=
talysts can be employed, organic titanates~ such asp e.g,, tetrabutyl titanate~ either alone or in combination with ma=
gnesium or calcaum acetates are' preferred. Cample~ titanates derived from alkali or alkaline-earth metal alkoxid~es and ea=
ters of titanic: acid are: also very effective. Inorganic: tita--nates, such as lanthanium titanate~ mixtures of aalc3.um ace=
tote and antimony dioxide' and lithium and magnesium alkoxi=
des are further examples of catalysts: which can be used.
The ester-interchange polymerizations are generally carried out in the molten states but inert solvents can also be used to :facilitate thw removal of volatile companerata: from the mass by operating at lo9ver temperatures~s-During the- preparation of the, el.as-t~omeri~ thexmop3.a:
stir: copolye~ther-ester it is common practiee~ tro add a stabd=
liter in order to prevent an oxZdat~,v~ and hydrolyt~.~ d~a=
dations of the reagents and of the polymer during its formation. The known phenolic stabilizers can be used for this purpose.
The synergistic mixture of tris(hydroxy-benzyl) benzene (I) and bis(alkyl-phenyl) pentaerythritol phosphate (III) may be added to the copolyether-ester either during the poly-condensation reaction, at the end, of this reaction when the polymer is again in the molten state, or after this reaction in a separate step by re-melting the copolyether-ester in an extruder.
The synergistic mixture may be added in the form of a solid, a liquid in the molten state or in solution or dispersion in one or more of the reagents. It is generally suitable to add the synergistic mixture in the solid form to the finished copolyether-ester by melt blending.
In this last case, it is possible to prepare a master batch of the stabilizer, for example having a concentration of synergistic mixture of 20 - 40~ by weight, and then to dilute this master batch with the pure copolyether-ester. This blending is preferably carried out in an extruder at a temperature of from 150 to 280°C, depending on the particular type of copolyether-ester; the extruder may be of the single-screw or double-screw type, preferably equipped with venting, or a Banbury mixer.
The copolyether-esters stabilized with the synergistic mixture employed in the present invention exhibit a high resistance to the thermo-oxidation and to the hydrolysis.
~~ -7 ~~ ;-. ,.
N l.? ',~ ~~ ~;
- 1a Chuing to these peculiar properties, the stabilized copolyethe_r-ester compositions of the present :invention find use in the production of hydraulic pipes, coatings for cables, elastic supports far bumpers, beLla~s far cove~°ing joints or couplings, composite gaskets orr generally, shaped articles to be used at high operating temperatures, generally higher than 120~C.
The characteristics of the copolyether-esters of the present invention may be further modified by the incorpora=
tion of various conventional inorganic fillers, such as, e.g., carbon blacks silica gel, alumina, clays fiberglass, etc. In general, the effect of these additives is to increase the no=
dulus of the material, although at the expense of elongation, tear strength and abrasion resistance.
Besides the above, the product may be rendered, flame-proof (UL 94 Class: V2, V0, etc.) by the addition of various flarue-proofing systems containing aromatic halides, aliphatic halides or not containing halogen atoms, in amounts ranging from 5 to q~5~ by weight based on the final product.
As conventional flame=proofing systems therw may be used decabromo-bisphenol A with Sb~O~ in the ratio of 1.511, or flame.-prooi'inga eubstax~oces such as melamine, hydrobronaide (see published Italian patent application No. 2-0548 A/$5) com'~ined with Sb203 in the rati~ of 3;:1, ors final7ly, oyner~
gistic systs haloge3n-free, such as aca.d pip~.zine~ pyropho~~
> > , -)J t' a~ ~.! 1.' '.. ..
phate combined Evith melamine phosphate in the ratio ranging from 3:1 to 1:l see published Italian patent applicatiozx Ido. 21,149 Af83).
In order to make the present invention stz.l.l. better understood, some examples are reported below which are of a merely illustrative characters and. no way are limitative' of the invention.
All parts' proportions and parameters given in the following are by weight, unless othe~r~.se spenified.
~PL~S 1 t o q.
Dimethyl-terephthalatey optionalJ;y isophtha7.ic aoid, 1'4-butane-diol and poly(tetramethylene oxide) glya~ol (PEG) having diff er~ent average moleaulax weights were charged, in the amounts listed in Table I' into an autoclave equipped with distillation column, variable~speed st:~rr~ing means and temperature control system.
The temperature was graduall~r increased to 110 - 150°G
over about 1 hour and 150 ppm of Ti(0Pu)4' pr~ious7.,~r disaol=
ved in a few ml of butane.-diol (about 10 - 20 m1.), we~r~ added.
After a short. induction period,. the= transeetex°ifiaation reac=
tion startedy this reaction was evidenced by an incise of the temperature in they dis~.llation column overhto about 65°Cs which ~..dicatretl the re~noveGl. of methanol. ~hee t~pe~a~
re of the r3.on mass was: gradl~.~.7,g i~acre~; up ~0 205°t~
( over° 2 hours ) and was kept constant: at; trhisv va.~.~a,e un°~3~.1~ ~ht~
:~~':~.. ': ..
metn~nol eti.~-~i~y..~.tion ~,~,rzr cottm~ etc.
l50 ppm off' catal~rst (~~;clrabutyl titanate) and about 4,000 p:rn o~ =? rneno~ is stabi liter (Trg-anox ~ 1010, produced.
:a.nd ~~o7d by CIBA C~IGY) '.~r ere e.dc~ed anal v~.cu~zr~: w~.s gradually ~.n~lied. until a resid~:a.l nressu~°e of about 0,05 mm HJ eras re~.c'~.ed (vritr~in ab'~ut 30 mim.ztes) and ?~eatzn~; vr~.s continued unta.l e.n intern<al t~m~nerature of about 250~C ~~ra.s r cached.
'lJhen the m°oduct had reached the desa.s-ec~ melt index, about 200 - 600 F~.. sec a.t 232°C, aor:respondir~ to a melt index bet~,veen 15 a 30 ,/10 min., the polder ~F~Tas discharged by extrusion onto a water-cooled conveyor belt, :~.nd ~~ras chop=
ped int o small cubic ~r~.nt~l.es .
The properties of the obtained conolyesters are 1i=
st ed in Table I .
~.t'_~U;r;.,;
i A E I
B
L
(EXAMPLES I I ( 'I I
( 1 2 3 d (Monomers tt:od ,TNITS-I Me I I
i I I I I I I I
Dimethyltere=
(phthalate I I 455 498 I 644 613 I
I I I
I I i I
Ispphthalic lacid I 23 I
I I I ! l ( I !
1,4 - butene-Idiol I 212 244, 353 224 I
I 6 ( !
PTMG having a I I I
mol.weight 263 250' I PTMG-having a I
Imol.weight I 117 I
IPTMG havingwa I
Imol.weight I I 7 296 - I
i I 530 47 ~ I
~ , ~
IPROPGRTIES ~L I ~
I
i I I i I I I
(Melting 2117 'C I82 191 I 209 I 160,51 point ID I I I
(Glass transi=DxhT 'C ~60 -50 I -12 I -41 Ition temperate 'i r e (Melt Index at I
I
I 230C and y)1238 g/10 20 2I I 18 I 23 2.1~ I ~
I
I
2 ;~
'i s ~ j ': 1:
iJ l! ~~ . , ..
~- ~3 8X._Aa'4'PL~ 5 The elastomeria thermoplastic copolyester of examplff 2 was mixed at 1g0 - 195~C; in a double~'scre~r extruder ARTS 1~3~'S
type, with 20;o by weight of a stabilizer listed in ~.rableII.
The thus obtained mast er was added t~ the respectiv~r pure ao=
polymer so as to obtain compounds oontaining 0~~~~ by we2ght of stabilizer. The thus stab~.lized products was injeet~.on mol=
ded at about 200pC and the p~psical-mecharxical arul~ teelano7~og~r=
cal properties were measured.
The obtained values arer listed an ~bllo~ving Table TI.
6Z :'y ~-~ ~~ ~~
~,r ',J '-~ ,,' ..
t .D N
:0 r-1 N O l0 Cn 47 M s M 10 N O r-1 r-! O N O
x et N 6f7 N N O N ~
ox aH
ow x o N ~~ o o ~ 6n 0 0 60 0 os o M d' N I' N ri I!7 ri CO
M t0 1f1 d°
W
x O r M a u~
6D tO N O ri N t0 !~ O
N d' N C11 N e-W 1 '-i C~
H ~O 1C N 6t9 a H ~ O
1.~ O ~ M O .-1 1!1 O 1fl O
w O ~~W' N O N e-1 I~ r-1 M
O +~ ~ e,-t of a ~ b -. _ w ~1 O
H
Z
N ~' M M M CO t0 00 OD
p N 1!D 10 N M M M M
O N r1 t~ tp 1p 1D
W ~
oa» W A O A C1 4 r~7 Ca La w , o ~ ~~ ~ a cxo o w .c s~'. ~ ,~ t°'.
.c s°'. ° a ~ '° iWno '°
W ~ .o N 3 ~ ~ O
H
~ .~ .a~ z c. z s~
W d> 615 lsf H -1~ 'L." H ~ '~.,"
t, m O m O
m O N U O ~ U N --4 .
H m O .1~ G td) d ..1 >ap ~ CO
~' x ~ ~ o ea ~ a' m c .~% co H d~ .-, H ~ N . ..
a~6 ~ ~ v W ~' ~ ,~ j N W
x r ~ W ~ cv ~ ~ ~ s>~ . o y ,...~.a;,. ,:
c;ili'.; ,,~~.
a i'.~ It ~.: t.' <:
N
r~
VJ U? C>
N
O
t0 N
M
C1 N tf) 'O
x N 00 ox ca o w a ~
~
~ o D o o W
G
U +~
x a, o cc Q
O 01 O O ~ O
M ri O
~
C'1 l~ ~ E
H t~ ~ c0 W H ?C
C. Cn v N
~ N
~
x 3 ~t O d~ O
~ o0 j WD ~-i O
N N t~ O
o E w .-~ v a ~o a H X c0 H v X f, v v +~
W ~ .C v 4, G +~ .C cU
a c~ +.~
c oo ~s w +~ ~ O a op v o o ~, a +~
a. a E
H +~ .~ a c, 2s .~ .o .~ v .o 3 'o +~
cu s v , c. a v +~ v m '~
rt 0 3 H
~ ~
H ~S N 'O C
z ~ a~ o E ~ +~
t~ E ~1 v G~ b v G7 v + X
M M
O 'O v O
'O I
~ ~ ~ 3 ~ t W .
a 3 v w c, x a' .-I +~
~' c 0 0 o o '~ ~
t~ c .. a~
~
o ~ v -~ v w ~ fi o cx + n v .~ .
~
H H ~ ~ +~ W
U1 * N SO +~
W O * t, +~ Ui W 'O
I H * +~ ~ m M m Lx -- m O r4 ~0 i.v f-W U1 W .~ fQ v x' W U ?. v +> v E.a v Ta H ~-tz O r1 of f.~ .C O
W H ~ r-a.a b~ v H 4.a ?~ C~ H H m C N .C
a W iYa2 C O x H A
O t3. H to v r-aH
H ~' 1~
O f~ W ?4 !t ~
r0 0 .I~ O . . v v v --~ 5 1 1-~ 9 ~
al ,l.' ,u' ~~~ 1,~ '.,~ ~.~
- 2b --By operating according the process conditions of example 5, stabilized com=
positions with the copolyesters of examples 1,2 and 3 were prepared.
The properties of the thus obtained stabilized compositions are listed in following Table III.
.i' '.) ( ~ i; ~. ..
t c~ oN h o Cl~r1 h N ~I 01 e~iO
O ~ O
' d fi +~ O O .-1 N O i0 O
~ ,-Itn N .-aO r~ 119 C
O O N OG
O
h~
h v t! O O 01 O O O
M tI1 N 00 M 'd' N
U~ h d' M
Il c0 d' O 00 d' O o0 O
~C M O H N In N O
OO h ~ h hri ri O 1~ h CO O O h O a1 O
(l)~-1N N r-iIl1 ~ O~
pp tD h II
ro H (U
-i-~CT O O c'1O h O
O '~ O N <i 00 '-iO
O
O e-1 h W .1~
a x~
'a td O ft1 !a F tn dP dP ~ dp F ~ ~ ~
H
z a M M M M M M M
t0 N ~! 10 10 ~D
F
~
w G7 O G1 CJ D Ca G3 a a x *
W .-.
w ~ p W ~ ~, ~ OD H Cd a 3 O
X11 aD N to N t6 ~ ~ H ~
v N H ~ .i ~
f-, m O uI O
m ~ z ~ ~ " 4i ~
H v- .
~
OG .-i(f1 H t0 f0 H
' O 4ZafA ~ ~ H ~ .-1 H N .
.--1 ~ v W H W ~ f~ W
O ~ ~
U L4 F W ~ G:
~~: ~ ' l .
v i~
r~r O
't' w y ..
m M O --+~ c~
3 ,["
V
~i' O
M
M
~;
I -I
b (d ~ O
C~
tn N N U
- r1 a 3 x H
rv W
r~ <i v O
fl) e-1 O
O
ni ~
r I X
I
'O O
N
d O H
O ~ N a ~f'a i~ .ri 4-, .
1~ O H H
H
U __ - H 'r-1 H
U O[1 '-' ~ N N
N
((! -ri r-1 r1 e--I
~ ~
~
~
H H ~ U1 ( U
H H .~ E-<
H
E.
s; 4-~
W U 4-t 4.~
O O
O
U
a sue..~ x x a M c~ ~ +~
+~
+~
x em o x ~ a E
H E~ ~ ~ .-1 W W E U N
U
.C
.G
.~
' f1. U +
.i +~
+~
W ,.,i .~
.,a .,..( ! CD 'CS
O ,'~ t0 v O O
p Ix W ~ to U U
U
W x +~ L1 W c4 id cE
~
fH * ~ d~ ~ ~O
rt7 W O * a> (C W
I E-~ * C.
t~ --~ .1~ G ~ ..d ..~
..a ~ O
x W U Z -i ~. fe . F~
f, E~ H ~ O N +~ a7 N
~
W H <C H ~ (tb -N
+~
+?
fx E-r H -.-1 M U
O tz.H A ~ O
~.LO U7 F-1 N r-I ~ 4C
' O t~ W ?C E-i C=1a-~ ~.
~6 it U C4 PC O ri k '1E
a a S ~ v N
v °2g_.
It is preferred that at. least one of R~ and Rs radi=
Gals, and preferably both the radicals, are al~y3s contairLlng from 3 to 8 carbon atoms and are branched on the carbon atoms in alpha-position.
The pr ef err ed c ompounds of f orm~u7.a ( I ) ar a thw symme=
trical hexasubstit~zted benzenes. These compounds axe the' l, 8:, 5-tr ialkyl-~ , ~., 6~tr is ( 3 , 5-d.ialkyl-4-Y~ydro~r-benzyl ) berg yes having the formula:
g2 (II) CHI
R2 ~ R3 OFi wherein Rl R2 and R3 have th.e significances set forth above.
Typical ea~amples of compoutlds which may be used as co-stabilizers in the synergistic: nnixture of the present invention are:
1, 3, 5 -tri-methyl-2, 4, 6 -tri(3,5 -d.i-tert~ butyl- ~. -hydr os~yb enzyl ) bent en~e;
l, 3, 5 -tri-etk~,yl- 2, ø~ 6~ -tri(8, 5 -di-tart. b~xtyl- ~ --hydroxybenzyl~ benzene;
- 7 .
1,3,5-tri-methyl-2,4,6-tri(3,5-di-isopropyl-4-hydroxybenzyl) benzene;
1,3,5-tri-octyl-2,4,6-tri(3,5-di-tert. butyl-4-hydroxybenzyl) benzene;
1,3,5,-tri-ethyl-2,4,6-tri(3,5-di-tert. amyl-4-hydroxybenzyl) benzene;
1,3,5-tri-butyl-2,4,6-tri(3-isopropyl-5-tert. amyl-4-hydroxy-benzyl)benzene;
1,3,5-tri-propyl-2,4,6-tri (3,5-di-tert. octyl-4-hydroxy-benzyl)benzene.
Among these, the particularly preferred compounds are those having three 3,5-di-tert. butyl-4-hydroxybenzyl radicals.
These compounds and their preparation processes are known in the literature and disclosed in U.S. Patent Nos. 3,026,264; 4,340,767 and 4,754,07'7.
Particularly, the 1,3,5-tri-methyl-2,4,6-tri(3,5-di-tert. butyl-4-hydroxybenzyl)benzene is known on the market by the trade name ETHANOX 330~ of the ETHYL
Corporation Society.
The bis(alkyl-phenyl)-pentae:rythritol diphosphite that may be used in the synergistic mixture of the present invention, may be of the general formula:
R4 ~O-CH2 ~ H2 ~ R4 P 'C
" (III) o l Q--CH2 CH2_..0 g5 wherein R4 and R5, which can be either equal or different from each other, alkyl radicals containing from 1 to 10 carbon atoms.
_ 8 _ All the above compounds and their preparation are well known in the literature and disclosed in U.S. Patent Nos. 3,281,381; 3,310,609; 3,192,243 and 3,205;269, the content thereof is integral part of the present description as a reference.
The invention as claimed is however restricted to the use of the bis-(alkyl-phenyl)-pentaerythritol diphosphites of the formula:
C ( CH3 ) 3 0-CH2 ,CH2-O C ( CH3 ) 3 -P~ 'C (IV) e_,~v ~
wherein R5 is an alkyl radical cont=aining form 1 to 6 carbon atoms.
A particularly preferred compound is bis-(2,4-di-tert. butyl-phenyl)-pentaerythritol diphosphite know in the market with the trade name ULTRANOX~626 produced and sold by BORG WARNER Chemicals.
Fd ~~ ~ ~ l i '~f ~ i _ ~ -An<y e:Lastomer is thermoplastic copol.yether-ester cony taining ester bonds i1 - ~ _ o and ether bonds - C - 0 - C -may be stabilized by the syn.ergistic mixture of the present irwention, provided that said polyether-esters exhibit a sof=
teeing or melting temperature lower than ~50pC, which ais the temperature at which the stabilizing system usually is no mo=
re effective.
The elastomeric thermoplastic copolyether-esters ha=
ving a segmented strwcture are pexticzz7.arly preferred. These elastomeric thermoplastic copolyether-esters cons~.st of a mu1=
tiplicity of repeating long-chain ester urs.ts anal of repeating short-chain ester units connected t~ each other in head-to-tail fashion through linkages of the ester type. Said Kong-chain a st er unit s ax a r epr es e~.t ed by general formula s -0-G-0.-G-~t-aC-and said short-chain ester units arm represented by general f ormula ~ D~ ) whet ein:
G is a divalent group rsma~.n.ing aftex° the re~o~ra3. of the ;_ ..~ J ~, ~ '..' c.' 1~ -terminal ;~Ydro~r groups from a poly-(al~lene oacide) gly=
col having an molecular weight of from about 250 to 5'000 and a carbo~/o~ygen ratio of about 1.8 to 4.3;
R is a divalent gioup remaining after the removal of the carbolic group from a dicarboxylic acid having a moleau=
lar weight lower than about 300; and D is a divalent radical remaining after the removal of the hydroxylie groups from a diol having a ~nol.ecular weight lo=
wer than about 250.
In said copolyether-esters the short-chain ester units of general formula (VI) are present in an amount of about 15 to 9~~ by weight, preferably 33 to 86~ by weight, with: respect to the weight of the copolyester; the remainis~ past being com=
pos ed of long-chain eat es° unit s of general f ormnla (V ) .' Said ~lastomeric copolyether-esters are well known in the literature and described', for example, yn D.S. Patent Nos.
3,023, 19~ and 3:, 651, 015; Italian, Patent i~os.~ 947589; 963304 and 973059 and published Ita7:~.an Patent Application No. X12 filed on ,19880 The repression "long--chain ester un:i.ts" refs to the reaction product of a poly(alk,~rlene o~.de) glyv~ith a diear=
boxylic acid, resulting in ester un3.ts represa~ate~3: by the a'bave?
f oryuula (V ) .
As pol~r(all~rlen~-oxide) gl;~cwla there mar ldo~ rxa~d thoe~
which contain from 2 to 10 carbon atoms in the al~lenaPgroupp w f~ tt r3 i, '. .' such as poly-X1,2- and lf~-propylene-oxide)-glycal; poly-(te=
trametbylene--oxide)--glycol; poly-{pentamethylene-oxide)-glycol;
poly-{hexamet2~ylene-oxide)-glycol; poly-(heptamethylene-oxide)-glycol; poly-(octamethylene-oxide)-glycol; po:l,,~-(nonametl~len~
oxide)-glycol; poly-(decamethylen~-.oxides)-gly~l; and poly-( 1' 2 -but y1 ene--oxid a ) -glycol ; OH t erminat ed poly~t ~e-1-poky=
butadiene; random copolymers or block copolymers of ethylen~-oxide and 1,2-propylene-oxide; and the lake.
In the present inventions parti~alarly p~refe~r~di i,s poly-(tetramethylene-oxide)~gly~l having a very narraw ave=
rage distribution of the maleuular weights' such as' for exam=
plc, a ~dw/%n ratio lower than 2 ~ which generally re~u1ts in an improved resistance= to fluids such as oi:E..s, gasoline, water, fats etc.
the session "short-chain ester units" relates to the reaction product of a diol having a loev molecular weight (lower than about 250) with a dicarbo~yliG acid in order to f orm es t er uni.t a r epr es ent ed by t he ab vv a f ox~mnzla (~ T. ) .
Among the diols having a low molecular weight Ahieh by reaction produce the short-chin ester units' non-cey~.ia' alicyclic an3 aromatic di-hydroxy compounds are includ~sd.
Diols of from 2 to 15' carbon atoms such as eathyhene-glycol propylene-glyaol~ :Lscbutylen~-glycol' tetx~methylen~-gl~~l.i pentamethylene~glycol! 2 s2-dimethyl trim~hylen~gly~l.~ h~
xamethylene-glycol and decamethyhene°-gl~rcol.' di by~x~PCy~lo-~. p y , hexane! cyclohexane-dimethanol, resorcinol, htydroc~uinone;~ 1,~-di-~h~~Tdroxy-~phthalene, etcg are prefex°red.
3?articular 1y preferred are aliphatic diols conta~.ning from 2 to 8 carbon atoms.
Ales of di-hydroxy aTOmatic compounds which may be used are bisphenols, such as bis-(p~hydroxy)-diphe~rl' bi.a-(p-hydroxyphenyl)-methane, and bis-(Ps°2~yd~'ox~gher~,yl)"PQ'opane, et a .
The term "lose-molecular-weight diols" as used herein should hence be understood as also including all of' the egu,i=
valent derivatives suitable for formir~ estera~ although the molecular weight requirem~.t refers exc3.usively to they basic' diol, and not to the derivatives thereof.
However, 1,4-butane-diol is. pa,rticul.arl~ ~xref'a~ed, for the purpose of the present in~rention.
Dicarboxylic acids which are reacted with thg abov~
poly(alkylene oxide) glycpls and: with the low molecular weight diols to yield the copolyether-esters of the present invention are aliphatic, cycloaliphatic~ and/or aromatie da.carba~rl.ia;
acids having a low molecular weight, i.e., ha~oirag a ~aol.ecul.ax weight of preferabl~r less than about 3~a.
The term "dicarboxylic acids" also includes equi:~ralent derivatives of dicarbox~lic aids which show a beh,aeLowe s~,mis lar to that of dicarht~x3rl:~c aai.de~: in the reaat3.on ~r~.th gl~anl~
and dials to for~a copolyether-eatez° pol~ers.e Theses ~q.uivel.ea~
'~ ~ ~"~ ;6 w c' i..~ f3 ;; ,,v -r - lV~ -compounds include esters arid ester-forming derivatives such as, e.g. acid halides and ann"vdrides. The moles weight requirement, however= relates exclusively to the acids and not to its corresponding estexs or other ester-forming dsri.=
vat iv es .
Therefore, the term "dicarbo~ylia: acid" includes: also an ester of a dicarba~lic acid which ester has a molecular weight higher than 300' or az~y other dicarbo~lic: act3..d deri=
vat iv a having a molecular w eight gr eat er than 3 00' proga.d;ezl that the corresponding acid has a molecular weight below about 300. The dicarbo~ylic acids may contain any substituent~groups or arty combination of substiiment. groups which do not: signi~fi=
cantly interfere with the formation of the copolysste~ polymer and with the use thereof in the end products accarding. to the present invention.
Within the context of thc~ present: inventiozay by "ali=
phatic~ dicarbo~lic acids" those carbolic acids are-meant which contain two carboaQrlic groups, each attached ~bo a satur rated carbon atom. If the carbon atom to which the carbox3rlic group is attached is a saturated one and is~ psrt of a ring, the acid is cycloaliphatic:. Generally aliphatic:acid.a or cy=
cloaliphatic acids: containing a conjugated unsaturation carp not be used' in that they are liable to hrnnopol~erizee. Hove=
very some unsaturated aside sash as' e.g., malefic awaid and the dimer or trimer of: oleic said can be used.
D i_ ~
_ 1~
fihe term "aromatic dicarboa~vlic acids" s.:~ used herein refers to dica.~rbo~ylic acids having two carbo~ylicy-z~ou~, each carbo~rlic group being attached to a carbon atom in an isolated or fused benzene ring. It is not necessary that both carboxylic groups be attached to the same aroma.ti~ ring, amri, where more than one ring is present, said rings may be linked through divalent aliphatic or aromatic radicals or through divalent radicals such as, e.g., -Q- or -S~~-, or eve~a by a carbon-carbon single bond.
Examples of aliphatic and eycloaliphatia dicarboxiylie acids which can be used for preparing the aopolyether-esters of the present invention are sebacia: acid, 1,3-cyclohexane.-dicarbox3rlic acids 1,4-cyclohe~cane-dicarboa~ylic acid, adipic acid, glutaric acid, succinic acid, oxalic acid, azelaic acid, diethyl-malonic acid, allyl. malox~.c aaad, 4-cyclohexane-1,2-dicarboxylic acid' 2-ethyl.suberic~ acid, 2'2,3,3-tetramethyl-succinic acid, ayc3opentan~-dicarboxylic said, decahydro-1,5-naphthalene-dicarbo~rlic acid, 4,4°-dicyclohexyl-dicarbox3rlic acid, decahydro-2,6-naphthalene-dicarboxylic acids 4~,4'-~methy=
lene-bis-(cyclohexyl)-carbox~rlit~ said, 3'4-.ran-dicarboxylic acid, 1,1-cyalobutane--d~.carboxylic acid., etc.
Cyclohexane-dicar'boa~lic said and adipie acid are pre=
farted dicarbox~lic acids.
Ales of aromatic dicarboxyli.t~ acids which can be used comprise phthalic aaid9 isophtha3:3.c said, te~~phtbalia~
~ k i ; ' ~ ~ ; a v ~a '.
acid, dibenzoic acid, dicarbo_~lic compoiuzds substituted with two benzene rings, such as, e.g., bis(para-carboxy-phenyl)-methane, pare-oxy-(pare-carboxy-phen'yl)-benzoic acid, ethylene-bis-(pare-o~ybenzoic acid), l,5-naphths.lene-dicarbo~lic acid, 2,6-naphthalene-dicarboxylic acid, ~,7-naphthalene-dicarboxy=
lic acid, phenanthrene-dicarbox<ylic acid, anthralenea-dicarbo=
xylic acid, 4,4'-sulfor~yl- diben~oic acids thiofurra~ane-3:'4°-dicarboxylic acid, as well as their Cl-C~-aryl esters and derivatives resulting from substitution on thw ring=' such as, e.g., halo, alkoxys and aryl derivatives.
Aromatiw acids containr~ a Y~ydroxg groups such asp e.g., pare-1~...hydrox<y-ethoxy)benzoic acids may also be usedy gravided that an aromatic dicarbo~ylic ard.d is also presexxtr.
The aromatic dicarbo~ylic acids constitute a preferred class for preparing the copolyethex°-ester polymers of they com=
positions of the present' invexition.
Among the aromatic aaids~ those with from ~ to 16 carbon atoms are preferred; particularly preferred are phe~lena-dicer=
boxylic acids= i.e., phtha.lic: acid, isophthalic acid and ~terephh~
thalic acid. In particular, either terephtha~aa:aaid alone or a mi~cture of terephthali~ said and isophthaliQ acid are preferxced.
At least about 746 by mfll of the dicarboaylic said inalu%-ded in the polymer are preferably cc~nnposed~ of t~xephthah~.ee said' i.e.g about 70y~ of the "R" groups in formn.~lae (V) and (~~) abo~
ve are preferably 1,4-phlene radicalss . ;, ,.
L '.: 'i ~: , ..
1E, -The carboxylic acids or their derivatives and the po=
lymeric ghycols ar'e included in the final praducts in the: same moles proportions in which they are contained in the reaction mixtures. The actually inc?uded amount of low-molecular weight diol corresponds to the difference between the mole of diacid and the cools of polymeric glycol evntained in the reaction mlXtLl2' a a The mast preferx°ed copolyether-est~°s of thee present invention are those prepared form terephthalie acid (SPA), 1'ø-butanediol (HD), and polytetramethyleneglycol (~G) ha=
ving an average mo~_ecular weight of from about X50 to about ø500 and, optionally isophthalic acid (IPA) in an amount not higher than about 5~ by weight with respect to the total amo=
unt of the two acids.
The polymers of the apmpositions of the present ir~ven.=
tion may suitably b~ prepared by means of a normal traasestar~i=
fication reaction, A preferred process comprises heatingsi at 154 - 230~C' the ester of the~~ dicarbo~ylic~ acid (for e~ple the dimethyl ester of texe~phtrhalic; acid) with the pol.,p(all~rle=
ne vide) glyQ~ol and. a molar e~sa~ss of a diol~ in the pareaena~
of a catalyst. T!he amount of the diol is at le~.st 1.1 molee of diol per each mole of acid.
The heating is continued ~atil °~he rc~aa~al of methanol is eaeentially complete.
~
.. t~ ~.1 t~ i The resulting prepolymer is then carried to high no=
lecular weight by distillation under vacuum of the s of the low molecular weight diol (polycondesation). During tln~.s distiilation~ additional transesterification occurs, which leads to an increase-in molecular weight and to a random ar=
rangement of the various copolyester units in the molecule.
In order to avoid an excessively long hold time of the polymer at high temperatures with possible irrevers~.ble thermal degradation, catalysts for the: ester-interchange reac=
tion are advantageously employed.. While a wide variety of ca=
talysts can be employed, organic titanates~ such asp e.g,, tetrabutyl titanate~ either alone or in combination with ma=
gnesium or calcaum acetates are' preferred. Cample~ titanates derived from alkali or alkaline-earth metal alkoxid~es and ea=
ters of titanic: acid are: also very effective. Inorganic: tita--nates, such as lanthanium titanate~ mixtures of aalc3.um ace=
tote and antimony dioxide' and lithium and magnesium alkoxi=
des are further examples of catalysts: which can be used.
The ester-interchange polymerizations are generally carried out in the molten states but inert solvents can also be used to :facilitate thw removal of volatile companerata: from the mass by operating at lo9ver temperatures~s-During the- preparation of the, el.as-t~omeri~ thexmop3.a:
stir: copolye~ther-ester it is common practiee~ tro add a stabd=
liter in order to prevent an oxZdat~,v~ and hydrolyt~.~ d~a=
dations of the reagents and of the polymer during its formation. The known phenolic stabilizers can be used for this purpose.
The synergistic mixture of tris(hydroxy-benzyl) benzene (I) and bis(alkyl-phenyl) pentaerythritol phosphate (III) may be added to the copolyether-ester either during the poly-condensation reaction, at the end, of this reaction when the polymer is again in the molten state, or after this reaction in a separate step by re-melting the copolyether-ester in an extruder.
The synergistic mixture may be added in the form of a solid, a liquid in the molten state or in solution or dispersion in one or more of the reagents. It is generally suitable to add the synergistic mixture in the solid form to the finished copolyether-ester by melt blending.
In this last case, it is possible to prepare a master batch of the stabilizer, for example having a concentration of synergistic mixture of 20 - 40~ by weight, and then to dilute this master batch with the pure copolyether-ester. This blending is preferably carried out in an extruder at a temperature of from 150 to 280°C, depending on the particular type of copolyether-ester; the extruder may be of the single-screw or double-screw type, preferably equipped with venting, or a Banbury mixer.
The copolyether-esters stabilized with the synergistic mixture employed in the present invention exhibit a high resistance to the thermo-oxidation and to the hydrolysis.
~~ -7 ~~ ;-. ,.
N l.? ',~ ~~ ~;
- 1a Chuing to these peculiar properties, the stabilized copolyethe_r-ester compositions of the present :invention find use in the production of hydraulic pipes, coatings for cables, elastic supports far bumpers, beLla~s far cove~°ing joints or couplings, composite gaskets orr generally, shaped articles to be used at high operating temperatures, generally higher than 120~C.
The characteristics of the copolyether-esters of the present invention may be further modified by the incorpora=
tion of various conventional inorganic fillers, such as, e.g., carbon blacks silica gel, alumina, clays fiberglass, etc. In general, the effect of these additives is to increase the no=
dulus of the material, although at the expense of elongation, tear strength and abrasion resistance.
Besides the above, the product may be rendered, flame-proof (UL 94 Class: V2, V0, etc.) by the addition of various flarue-proofing systems containing aromatic halides, aliphatic halides or not containing halogen atoms, in amounts ranging from 5 to q~5~ by weight based on the final product.
As conventional flame=proofing systems therw may be used decabromo-bisphenol A with Sb~O~ in the ratio of 1.511, or flame.-prooi'inga eubstax~oces such as melamine, hydrobronaide (see published Italian patent application No. 2-0548 A/$5) com'~ined with Sb203 in the rati~ of 3;:1, ors final7ly, oyner~
gistic systs haloge3n-free, such as aca.d pip~.zine~ pyropho~~
> > , -)J t' a~ ~.! 1.' '.. ..
phate combined Evith melamine phosphate in the ratio ranging from 3:1 to 1:l see published Italian patent applicatiozx Ido. 21,149 Af83).
In order to make the present invention stz.l.l. better understood, some examples are reported below which are of a merely illustrative characters and. no way are limitative' of the invention.
All parts' proportions and parameters given in the following are by weight, unless othe~r~.se spenified.
~PL~S 1 t o q.
Dimethyl-terephthalatey optionalJ;y isophtha7.ic aoid, 1'4-butane-diol and poly(tetramethylene oxide) glya~ol (PEG) having diff er~ent average moleaulax weights were charged, in the amounts listed in Table I' into an autoclave equipped with distillation column, variable~speed st:~rr~ing means and temperature control system.
The temperature was graduall~r increased to 110 - 150°G
over about 1 hour and 150 ppm of Ti(0Pu)4' pr~ious7.,~r disaol=
ved in a few ml of butane.-diol (about 10 - 20 m1.), we~r~ added.
After a short. induction period,. the= transeetex°ifiaation reac=
tion startedy this reaction was evidenced by an incise of the temperature in they dis~.llation column overhto about 65°Cs which ~..dicatretl the re~noveGl. of methanol. ~hee t~pe~a~
re of the r3.on mass was: gradl~.~.7,g i~acre~; up ~0 205°t~
( over° 2 hours ) and was kept constant: at; trhisv va.~.~a,e un°~3~.1~ ~ht~
:~~':~.. ': ..
metn~nol eti.~-~i~y..~.tion ~,~,rzr cottm~ etc.
l50 ppm off' catal~rst (~~;clrabutyl titanate) and about 4,000 p:rn o~ =? rneno~ is stabi liter (Trg-anox ~ 1010, produced.
:a.nd ~~o7d by CIBA C~IGY) '.~r ere e.dc~ed anal v~.cu~zr~: w~.s gradually ~.n~lied. until a resid~:a.l nressu~°e of about 0,05 mm HJ eras re~.c'~.ed (vritr~in ab'~ut 30 mim.ztes) and ?~eatzn~; vr~.s continued unta.l e.n intern<al t~m~nerature of about 250~C ~~ra.s r cached.
'lJhen the m°oduct had reached the desa.s-ec~ melt index, about 200 - 600 F~.. sec a.t 232°C, aor:respondir~ to a melt index bet~,veen 15 a 30 ,/10 min., the polder ~F~Tas discharged by extrusion onto a water-cooled conveyor belt, :~.nd ~~ras chop=
ped int o small cubic ~r~.nt~l.es .
The properties of the obtained conolyesters are 1i=
st ed in Table I .
~.t'_~U;r;.,;
i A E I
B
L
(EXAMPLES I I ( 'I I
( 1 2 3 d (Monomers tt:od ,TNITS-I Me I I
i I I I I I I I
Dimethyltere=
(phthalate I I 455 498 I 644 613 I
I I I
I I i I
Ispphthalic lacid I 23 I
I I I ! l ( I !
1,4 - butene-Idiol I 212 244, 353 224 I
I 6 ( !
PTMG having a I I I
mol.weight 263 250' I PTMG-having a I
Imol.weight I 117 I
IPTMG havingwa I
Imol.weight I I 7 296 - I
i I 530 47 ~ I
~ , ~
IPROPGRTIES ~L I ~
I
i I I i I I I
(Melting 2117 'C I82 191 I 209 I 160,51 point ID I I I
(Glass transi=DxhT 'C ~60 -50 I -12 I -41 Ition temperate 'i r e (Melt Index at I
I
I 230C and y)1238 g/10 20 2I I 18 I 23 2.1~ I ~
I
I
2 ;~
'i s ~ j ': 1:
iJ l! ~~ . , ..
~- ~3 8X._Aa'4'PL~ 5 The elastomeria thermoplastic copolyester of examplff 2 was mixed at 1g0 - 195~C; in a double~'scre~r extruder ARTS 1~3~'S
type, with 20;o by weight of a stabilizer listed in ~.rableII.
The thus obtained mast er was added t~ the respectiv~r pure ao=
polymer so as to obtain compounds oontaining 0~~~~ by we2ght of stabilizer. The thus stab~.lized products was injeet~.on mol=
ded at about 200pC and the p~psical-mecharxical arul~ teelano7~og~r=
cal properties were measured.
The obtained values arer listed an ~bllo~ving Table TI.
6Z :'y ~-~ ~~ ~~
~,r ',J '-~ ,,' ..
t .D N
:0 r-1 N O l0 Cn 47 M s M 10 N O r-1 r-! O N O
x et N 6f7 N N O N ~
ox aH
ow x o N ~~ o o ~ 6n 0 0 60 0 os o M d' N I' N ri I!7 ri CO
M t0 1f1 d°
W
x O r M a u~
6D tO N O ri N t0 !~ O
N d' N C11 N e-W 1 '-i C~
H ~O 1C N 6t9 a H ~ O
1.~ O ~ M O .-1 1!1 O 1fl O
w O ~~W' N O N e-1 I~ r-1 M
O +~ ~ e,-t of a ~ b -. _ w ~1 O
H
Z
N ~' M M M CO t0 00 OD
p N 1!D 10 N M M M M
O N r1 t~ tp 1p 1D
W ~
oa» W A O A C1 4 r~7 Ca La w , o ~ ~~ ~ a cxo o w .c s~'. ~ ,~ t°'.
.c s°'. ° a ~ '° iWno '°
W ~ .o N 3 ~ ~ O
H
~ .~ .a~ z c. z s~
W d> 615 lsf H -1~ 'L." H ~ '~.,"
t, m O m O
m O N U O ~ U N --4 .
H m O .1~ G td) d ..1 >ap ~ CO
~' x ~ ~ o ea ~ a' m c .~% co H d~ .-, H ~ N . ..
a~6 ~ ~ v W ~' ~ ,~ j N W
x r ~ W ~ cv ~ ~ ~ s>~ . o y ,...~.a;,. ,:
c;ili'.; ,,~~.
a i'.~ It ~.: t.' <:
N
r~
VJ U? C>
N
O
t0 N
M
C1 N tf) 'O
x N 00 ox ca o w a ~
~
~ o D o o W
G
U +~
x a, o cc Q
O 01 O O ~ O
M ri O
~
C'1 l~ ~ E
H t~ ~ c0 W H ?C
C. Cn v N
~ N
~
x 3 ~t O d~ O
~ o0 j WD ~-i O
N N t~ O
o E w .-~ v a ~o a H X c0 H v X f, v v +~
W ~ .C v 4, G +~ .C cU
a c~ +.~
c oo ~s w +~ ~ O a op v o o ~, a +~
a. a E
H +~ .~ a c, 2s .~ .o .~ v .o 3 'o +~
cu s v , c. a v +~ v m '~
rt 0 3 H
~ ~
H ~S N 'O C
z ~ a~ o E ~ +~
t~ E ~1 v G~ b v G7 v + X
M M
O 'O v O
'O I
~ ~ ~ 3 ~ t W .
a 3 v w c, x a' .-I +~
~' c 0 0 o o '~ ~
t~ c .. a~
~
o ~ v -~ v w ~ fi o cx + n v .~ .
~
H H ~ ~ +~ W
U1 * N SO +~
W O * t, +~ Ui W 'O
I H * +~ ~ m M m Lx -- m O r4 ~0 i.v f-W U1 W .~ fQ v x' W U ?. v +> v E.a v Ta H ~-tz O r1 of f.~ .C O
W H ~ r-a.a b~ v H 4.a ?~ C~ H H m C N .C
a W iYa2 C O x H A
O t3. H to v r-aH
H ~' 1~
O f~ W ?4 !t ~
r0 0 .I~ O . . v v v --~ 5 1 1-~ 9 ~
al ,l.' ,u' ~~~ 1,~ '.,~ ~.~
- 2b --By operating according the process conditions of example 5, stabilized com=
positions with the copolyesters of examples 1,2 and 3 were prepared.
The properties of the thus obtained stabilized compositions are listed in following Table III.
.i' '.) ( ~ i; ~. ..
t c~ oN h o Cl~r1 h N ~I 01 e~iO
O ~ O
' d fi +~ O O .-1 N O i0 O
~ ,-Itn N .-aO r~ 119 C
O O N OG
O
h~
h v t! O O 01 O O O
M tI1 N 00 M 'd' N
U~ h d' M
Il c0 d' O 00 d' O o0 O
~C M O H N In N O
OO h ~ h hri ri O 1~ h CO O O h O a1 O
(l)~-1N N r-iIl1 ~ O~
pp tD h II
ro H (U
-i-~CT O O c'1O h O
O '~ O N <i 00 '-iO
O
O e-1 h W .1~
a x~
'a td O ft1 !a F tn dP dP ~ dp F ~ ~ ~
H
z a M M M M M M M
t0 N ~! 10 10 ~D
F
~
w G7 O G1 CJ D Ca G3 a a x *
W .-.
w ~ p W ~ ~, ~ OD H Cd a 3 O
X11 aD N to N t6 ~ ~ H ~
v N H ~ .i ~
f-, m O uI O
m ~ z ~ ~ " 4i ~
H v- .
~
OG .-i(f1 H t0 f0 H
' O 4ZafA ~ ~ H ~ .-1 H N .
.--1 ~ v W H W ~ f~ W
O ~ ~
U L4 F W ~ G:
~~: ~ ' l .
v i~
r~r O
't' w y ..
m M O --+~ c~
3 ,["
V
~i' O
M
M
~;
I -I
b (d ~ O
C~
tn N N U
- r1 a 3 x H
rv W
r~ <i v O
fl) e-1 O
O
ni ~
r I X
I
'O O
N
d O H
O ~ N a ~f'a i~ .ri 4-, .
1~ O H H
H
U __ - H 'r-1 H
U O[1 '-' ~ N N
N
((! -ri r-1 r1 e--I
~ ~
~
~
H H ~ U1 ( U
H H .~ E-<
H
E.
s; 4-~
W U 4-t 4.~
O O
O
U
a sue..~ x x a M c~ ~ +~
+~
+~
x em o x ~ a E
H E~ ~ ~ .-1 W W E U N
U
.C
.G
.~
' f1. U +
.i +~
+~
W ,.,i .~
.,a .,..( ! CD 'CS
O ,'~ t0 v O O
p Ix W ~ to U U
U
W x +~ L1 W c4 id cE
~
fH * ~ d~ ~ ~O
rt7 W O * a> (C W
I E-~ * C.
t~ --~ .1~ G ~ ..d ..~
..a ~ O
x W U Z -i ~. fe . F~
f, E~ H ~ O N +~ a7 N
~
W H <C H ~ (tb -N
+~
+?
fx E-r H -.-1 M U
O tz.H A ~ O
~.LO U7 F-1 N r-I ~ 4C
' O t~ W ?C E-i C=1a-~ ~.
~6 it U C4 PC O ri k '1E
a a S ~ v N
v °2g_.
Claims (19)
1. An elastomeric thermoplastic copolyether-ester having an improved resistance to thermo-oxidation and to hydrolysis, wherein said copolyether-ester has incorporated therein an effective amount of synergistic mixture consisting of a tris(hydroxy-benzyl) benzene and a bis(alkyl-phenyl) pentaerythritol diphosphite of the general formula:
wherein R5 is an alkyl radical containing from 1 to 6 carbon atoms.
wherein R5 is an alkyl radical containing from 1 to 6 carbon atoms.
2. The elastomeric thermoplastic copolyether-ester according to claim 1, wherein the tris(hydroxy-benzyl) benzene is of the general formula wherein: R1, R2 and R3, which are identical or different from each other, represent a C1-C8 alkyl group and n is an integer ranging from 1 to 3.
3. The elastomeric thermoplastic copolyether-ester according to claim 2, wherein at least one of the radicals R2 and R3 is an alkyl radical containing from 3 to 8 carbon atoms and is branched on the carbon atom in alpha position.
4. The elastomer thermoplastic copolyehter-ester according to claim 2, wherein both radicals R2 and R3 are alkyl radicals containing from 3 to 8 carbon atoms and are branched on the carbon atom in alpha position.
5. The elastomeric thermoplastic copolyether-ester according to any one of claim 1 to 4, wherein the tris(hydroxy-benzyl) benzene is a 1,3,5-trialkyl-2,4,6-tris (3,5-dialkyl-4-hydroxy-benzyl)benzene of formula (II):
wherein R1, R2 and R3 have the meanings set forth in claim 2.
wherein R1, R2 and R3 have the meanings set forth in claim 2.
6. The elastomeric thermoplasitc copolyether-ester according to any one of claims 1 to 4, wherein the tris(hydroxy-benzyl) benzene is 1,3,5-tri-methyl-2,4,6-tri(3,5-di-tert. butyl-4-hydroxybenzyl)benzene.
7. The elastomeric thermoplastic copolyether-esters according to any one of claims 1 to 6, wherein the bis(alkyl-phenyl) pentaerythritol diphosphite is bis (2,4-di-tert. butyl-phenyl) pentaerythritol diphosphite.
8. The elastomeric thermoplastic copolyether-ester according to any one of the claims 1 to 7, wherein the amount of the stabilizing system is between 0.01 and 10% by weight with respect to the elastomeric copolyether-ester.
9. The copolyether-ester according to claim 8, wherein the amount of the stabilizing mixture is between 0.2 and 5% by weight with respect to the elastomeric copolyether-ester.
10. The elastomeric thermoplastic copolyether-ester according to any one of claims 1 to 9, wherein the weight ratio between the bis(alkyl-phenyl) pentoerythritol diphosphite and the tris(hydroxy-benzyl) benzene is comprised between 3:1 and 1:3.
11. The elastomeric thermoplastic copolyether-esters according to claim 10, wherein the weight ratio between bis(alkyl-phenyl) pentaerythritol diphosphite and the tris(hydroxy-benzyl) benzene is 2:1.
12. The elastomeric thermoplastic copolyether-esters according to any one of claims 1 to 11, wherein said copolyether-ester consist of a multiplicity of repeating long-chain ester units and of short-chain ester units, joined to each other by head-to-tail connections through ester bonds; the long-chain ester units being represented by the formula:
and the short-chain units being represented by the formula:
wherein G is a divalent radical remaining after the removal of the end hydroxyl groups from a poly-(alkylene oxide)-glycol having a molecular weight comprised between approximately 250 and 6,000 and a carbon/oxygen ratio of approximately 1.8-4.3;
R is a divalent radical remaining after the removal of the carboxyl groups from a dicarboxy acid having a molecular weight lower than about 300; and D is a divalent radical remaining after the removal of hydroxyl groups form a diol having a molecular weight lower than about 250, and wherein the short chain ester corresponding to the above formula (VI) are in an amount of about 15-95% by weight with respect to the weight of the copolyester, the remaining part being constituted by long-chain ester units corresponding to the formula (V).
and the short-chain units being represented by the formula:
wherein G is a divalent radical remaining after the removal of the end hydroxyl groups from a poly-(alkylene oxide)-glycol having a molecular weight comprised between approximately 250 and 6,000 and a carbon/oxygen ratio of approximately 1.8-4.3;
R is a divalent radical remaining after the removal of the carboxyl groups from a dicarboxy acid having a molecular weight lower than about 300; and D is a divalent radical remaining after the removal of hydroxyl groups form a diol having a molecular weight lower than about 250, and wherein the short chain ester corresponding to the above formula (VI) are in an amount of about 15-95% by weight with respect to the weight of the copolyester, the remaining part being constituted by long-chain ester units corresponding to the formula (V).
13. The elastomeric thermoplastic copolyether-ester according to claim 12, wherein the short chain ester corresponding to the above formula (VI) are in an amount of about 15-95% by weight with respect to the weight of the copolyester.
14. The elastomeric thermoplastic copolyether-ester according to any one of claims 1 to 13, wherein said copolyeter-ester is prepared from terephthalic acid, 1,4-butanediol and polytetramethyleneglycol having an average molecular weight of from about 250 to about 4,500.
15. The elastomeric thermoplastic copolyether according to claim 14, wherein said copolyether ester also contains isophthalic acid in an amount not higher than about 5% by weight with respect to the total amount of the two acids.
16. The elastomeric thermoplastic copolyether-ester according to any one of claims 1 to 15, containing in addition from 5 to 45% by weight of flame-proofing agent selected from the aromatic halides, aliphatic halides and the synergistic flame-proof halogen-free systems.
17. The elastomeric thermoplastic copolyether-ester according to any one of claims 1 to 16, containing in addition a phenolic stabilizer to prevent oxidative and hydrolytic degradations of the reagents and the polymer during its preparation.
18. A molded article made from an elastomeric themoplastic copolyether-ester according to any one of claims 1 to 17.
19. The article of claim 18, what is made by extrusion, blow molding or injection moulding.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI911091A IT1247504B (en) | 1991-04-19 | 1991-04-19 | THERMOPLASTIC ELASTOMERIC COPOLETE-ESTERS WITH IMPROVED THERMAL AND HYDROLYTIC STABILITY |
| ITMI91A001091 | 1991-04-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2066085A1 CA2066085A1 (en) | 1992-10-20 |
| CA2066085C true CA2066085C (en) | 2002-12-10 |
Family
ID=11359702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002066085A Expired - Lifetime CA2066085C (en) | 1991-04-19 | 1992-04-15 | Elastomeric thermoplastic copolyether-esters endowed with improved thermal and hydrolitic stabilities |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5236979A (en) |
| EP (1) | EP0510545B1 (en) |
| JP (1) | JPH05125262A (en) |
| AT (1) | ATE143682T1 (en) |
| CA (1) | CA2066085C (en) |
| DE (1) | DE69214192T2 (en) |
| DK (1) | DK0510545T3 (en) |
| ES (1) | ES2092591T3 (en) |
| GR (1) | GR3021232T3 (en) |
| IT (1) | IT1247504B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5922828A (en) * | 1996-09-03 | 1999-07-13 | Hoechst Celanese Corp. | Process for producing polyethylene terephthalate using a specific catalyst stabilizer system |
| US5874517A (en) * | 1997-12-23 | 1999-02-23 | Hoechst Celanese Corporation | Method to reduce regenerated acetaldehyde in pet resin |
| US6300399B1 (en) * | 1999-08-27 | 2001-10-09 | General Electric Company | High specific gravity polyester blend |
| JP2006131711A (en) * | 2004-11-04 | 2006-05-25 | Nippon Ester Co Ltd | Readily alkali-soluble polyester resin |
| KR101198673B1 (en) * | 2009-11-26 | 2012-11-12 | 현대자동차주식회사 | Plastic-intercooler pipe of noising having multi-layer |
| WO2017063849A1 (en) | 2015-10-12 | 2017-04-20 | Sabic Global Technologies B.V. | Polyether ester block copolymers |
| WO2018159487A1 (en) * | 2017-02-28 | 2018-09-07 | 東洋紡株式会社 | Polybutylene terephthalate resin composition for molded body for welding polyester elastomer, and composite molded body |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3856749A (en) * | 1973-04-17 | 1974-12-24 | Du Pont | Stabilization of polymers containing poly(alkylene oxide) units |
| US4156702A (en) * | 1973-10-29 | 1979-05-29 | E. I. Du Pont De Nemours And Company | Adhesion promoted block copolyester composition with multi-functional carboxylic compound |
| JPS56152863A (en) * | 1980-04-28 | 1981-11-26 | Adeka Argus Chem Co Ltd | Synthetic resin composition |
| NL8403880A (en) * | 1984-12-21 | 1986-07-16 | Akzo Nv | Co-polyether-ester with short and long chain ester gps. - stabilised with hindered phenol or aryl:amine, and polyvinyl-pyrrolidone |
| IT1202611B (en) * | 1987-03-03 | 1989-02-09 | Enichem Sintesi | SOLID STABILIZING COMPOSITION FOR SYNTHETIC POLYMERS |
| EP0321126B1 (en) * | 1987-12-16 | 1994-03-16 | Ford Motor Company Limited | Stabilizer system for extrudable polyester blends |
| IT1226148B (en) * | 1988-07-04 | 1990-12-19 | Ausimont Spa | SEGMENTED THERMOPLASTIC COPOLYESTERS WITH ELASTOMERIC PROPERTIES. |
| JP2928266B2 (en) * | 1989-05-08 | 1999-08-03 | ポリプラスチックス株式会社 | Polyester resin composition and molded article |
| IT1237549B (en) * | 1989-12-29 | 1993-06-08 | Ausimont Spa | THERMOPLASTIC ELASTOMERIC COPOLETE-ESTERS WITH IMPROVED THERMO-OXIDATION RESISTANCE |
-
1991
- 1991-04-19 IT ITMI911091A patent/IT1247504B/en active IP Right Grant
-
1992
- 1992-04-14 US US07/868,136 patent/US5236979A/en not_active Expired - Lifetime
- 1992-04-15 CA CA002066085A patent/CA2066085C/en not_active Expired - Lifetime
- 1992-04-16 ES ES92106683T patent/ES2092591T3/en not_active Expired - Lifetime
- 1992-04-16 AT AT92106683T patent/ATE143682T1/en not_active IP Right Cessation
- 1992-04-16 DE DE69214192T patent/DE69214192T2/en not_active Expired - Lifetime
- 1992-04-16 EP EP92106683A patent/EP0510545B1/en not_active Expired - Lifetime
- 1992-04-16 DK DK92106683.3T patent/DK0510545T3/da active
- 1992-04-17 JP JP4096862A patent/JPH05125262A/en active Pending
-
1996
- 1996-10-03 GR GR960402412T patent/GR3021232T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0510545A1 (en) | 1992-10-28 |
| IT1247504B (en) | 1994-12-17 |
| JPH05125262A (en) | 1993-05-21 |
| DK0510545T3 (en) | 1997-03-03 |
| ES2092591T3 (en) | 1996-12-01 |
| US5236979A (en) | 1993-08-17 |
| ITMI911091A1 (en) | 1992-10-19 |
| ITMI911091A0 (en) | 1991-04-19 |
| GR3021232T3 (en) | 1997-01-31 |
| CA2066085A1 (en) | 1992-10-20 |
| ATE143682T1 (en) | 1996-10-15 |
| DE69214192D1 (en) | 1996-11-07 |
| EP0510545B1 (en) | 1996-10-02 |
| DE69214192T2 (en) | 1997-02-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed | ||
| MKEC | Expiry (correction) |
Effective date: 20121202 |