Effect of oxazoline graft€d polyethylene on the structule and plopelties

hdust,alChcmEty Rcfa(r rnshbt.
uL.
Rydysror
em.il
3, 01-793
Wavawi
rcsina [email protected] pl
Effect of oxazoline graft€d polyethylene on the structule and plopelties
01 poly(butylene terephthalate)/polyamide 6 bl€nds
RAPID COMMUNICATIONS
sunnary_ stucfunlPhascs
and blelds
Plop.łies of Poly(butyhnc hrc.
blends were studied in a ch.ńjcrlmodiiication iF
Phthaliic)/polyamide
volvi']8 rcaĆtive ctusion q'ith ł riĆindl2 Óta2olńc mdhrlmaleate (Ro]VD
ó
lralbd polyetlrylel.' The inhrfa.ial r4di.n bcŃc.n bl.nd conpon.nh
w*.*ldied by djfcrcnhalKannin8 GlonnrcĘ (Dsc) and s.ańijns elc.
Eon ńiqosoPy {sEM) Thc*ah.lcNil. and flcxural ProPcrties antl impad
rcsisiincc rcsPonsc of thc bl.nds were l.s€d' ArtoldinE to Dsć d .' thc
mactivc PrmcŚin8 resulh h formaiiÓn of l.t.rogeious blcnds. PhasP stuc
6!eel PE3 RoIv'' Poly(butyldn! krePhthalab) Jnd polyamideó Óniai']in8
8bups lvele erledivo in d'Ć .onpahb Ełion o1blends invcsli
Ph35c
ńdPhologv ol ihc bl.nds NŹ5 o( i]tcĘenetaiinB Polyńd n.t
Ełed.
wolk (lPN) t-vFc a(oIdń8 to sEM rcsuLts Which was in a(oldanc. Wth
hrnr ings lrcnr DTA sP(ba FI']R' Dsc and DTA inveŚhsahons 5u gg?$ cvl
dc!.c iol lhc .hcmi.il readion. The 8nlt Polymł fÓrned dunn8 thc rcactivc
cxtrusion rault in an łlloy with 8ood interlaĆial adhcsion and hi8h inPad
co tea.tive
I<€y uoldś: PBT/PA 6 blcńds,.o
rorv d.nsi N po Lycthvlcnc, .ircl-2.oxizolinc mdhvlmareatr,
sjon,moPholog' m{h ri.i] ProPcńics
PoniŃ licld oair
duskńl ł|d scicnhńc idlvrtics. Thc modifi. ioI of
dcE io prcdu.. n.N
mate ilsisanimxpeBiveandrapid waytoobbinn.w
.omncrciallv ralrable polym.B. T
readion has a grrat Pofontial Lr ńakin8 nclv Pod!.b
wiih lrighł .ońńerĆial valuc fn,fr gcnEal PlrPosc
pÓlyńd5 FundjoD'lizłion oipolyohńns (Po) by m.]t
graftins of unsatolard Forar sloups onro rh. poLymer
cro\id6 rs lrcc radi
.al inińłols h's rmciycd conJddible attlnhon re.ent]y
n 3l For imr.nc, narci. ryd
sly.idyl mcthacrylaie hivc been Erarbd otrro polyole
IiN sPc.ially i'] ordł to improve lhe' .onPatibility
ł'ith polar lhemoplxli.s k.3 Polyanidos and Polycs
teF) łnd tj Pfuńot thdt adh$l
polyner ompositls. A15., polydhyleDcsraircd wth vi
nylsjlane5can bcoosljnkcd i]rthcP.csĆn.cof moisfurc
!i' hydrol]'9s łnd luńhd .ondcnsation lal. As i rcsult,
j6 c.cP,
rca.hv. cxru
ablłsio\hełtdefohatiotr and Ćheni.a] r$n
FundioMlizĆd PolyńcĄ a.c Widc
.ompatibilireĘ ln Polyncr blends l5_9l Bciusconly
PÓlyńc6.Ic misciblP, an efled
n rtqUircd io rcduc! ih€ int€rfł.ial
a few
ilc
.omPa
tibilize
Thc ovenll obiEdjvc ol thn vork w
elfeclivenesŚ of !!clnol 2'oxJzoljnc mcthylmilcŃc
(RoM) gialtud poly.rhylcnc (PE-s.Ro\t on rhc mor
p]rolĘ' phasc b.hiviol ind PoPotics ol Poly(buivlcnc
ó ble|ds'
'.l.ph'halate)/pojvamide
Poly€ihylene lPE) Uscd in rhis sfudy v6 lol d.Ąity
polyelhyl.ne (Polish Pctolcunr concc.r orlen sA, ]ł]
net now rate (MIR) or 2.1 g/10 nin
IPN_EN Iso n$;2002 (U), 190 'c' 2']ó kgl. PE was
died ar 30 r ror 2 h b.Ior. LsinB
Fln.tiońaliŻed pÓlye&ylene was Prcparcd by nck
slaftins of ncinol,2-oxazoline neihylmleatu onb PE
homoPolymer o{FR = 1.73110 min).
Poly(butyl.ne kiePhihalaie) (PBT) wis obtóined
fion Jehrre sA, loland lMfn * 5 'l g/] 0 ńin
'(o.ding
to PN EN rSO 33:2002 ((t,270 !C, r.2 ks. dic
rl. PBT
0c
was dried at n0
fo 4 h lnd vr.uum
Polyanidc 6 (PA 6) w.s supplied by Nilmg€n Works
Tarnów sA, Polłn,l IMIR = 2'ó c/
PN EN Iso 113]:2002 ru)' 230 t, 0'32 kgl' PA ó wm
land) showin8
and dried undcr
was
PrÓdld
u.uum
ar
7s't
fo
chłrad.ri2ed lsińg FTiR ŚPc.tosoPy
Prepalalion olpoly(bt9l€ne t.lePhdElit.'
Pdly.nide6blends by meónś Óf PE's'RoM
Poly(buiylene rrcphthalarc)/polyimidc 6 brerds
(PBTIPA ó) welc PĆPard using ihc same Beniorff ex
kuder Lsed ror ihc gEItinB pro
.ouPled ios.th.r with PET and FA
rea.t for3nilat210 230 it |.q!atiÓn (2)] Thn my
Ploduccd IBT/PEJ RoM/PA ó blends oI dlffcrcnt
Ricinol-2-oxazoline neihylnaleah tFormula (r)l
Goxamid \/!F 331t was obbine
r
IT
, _r.,-rr1
-)
As P.rÓxide initiab. di td-bu!'l
Riedel de Hacn, Gcm.ny) was sel€d€d'
P.mxide (DTBP
ol
Men 8ia'li!E of ń.i.ol_ż-ox.zolin
.
Melt 8rahiń8 of RoM onb PE LD lcquaiion (I)l was
ri€d ÓLl ar 130 200 oc in a Pi]ol Planl6vjHde('
cołolatiĘ eftudg Bssblff zE_2'-3D
= 25 nm,
L/D = 33, reedinc lare 3! LClh, 30 rpm ), a(ordinB ro
rhe proced!rc publishcd ckcwhep 110 131.
(D
. li
!!r'
*' -.-c* ( ( o.',o.r,
"",,"
) \
ll
PD
(i)
In a iyPi.al 8raItjĘ Pr@$, lh. Pcroxidc iniliłtor
was mjxed with RoM in the ńbbon ńircl and iń€ nix.
turc was added ro sorid PE Thc w
f.d iŃo i]r. neńtioned above Mn-Yrcw .}mtaiing ex
tud.r and allorcd b rict lor 3 min. The r6crion po
dud (PE'ś'RoM) was cool€d in waler, Penetjżed ald
dncd for 4 h in a vadum oven ar 30 0c.
For purificadon, PE,T ROM was
in3 ioru.ne.r iylen. at a con
(wt./vol.). The soluhon was prc.ip
Uns
Óf
ńethanol and thc Prc'luct
dislv.d
in renux-
{
,!*
IY
I
.'
o
rBL
.ońPosiiioB Gee Tabh r) vsc thcn 8rcund to snmll
Pcllcb lor iliedion ńoldinE lnjcdion molding Prmes\
was pdromed with ihe injedion molder (Arb!rs) ai
tump.ratorc 3-5 iic highor than melrins
dcrcr
min.d ar Rociius
apFntoi
Fo,nt
slro.fur.rnd Physko.teniral n€thÓdŚ
Thinfilms (s0sminthi.Lncs)of thcpu ticdEmfied
polycthylen. was comprcsion molded at 210 't undft
a Presure o{ ] 3 3 MPa fol 1 min' FT_IR sPe.ta Óf rhesc
thn'
rihŚ
klc
rmrded
Ę sptfu
The morpholosrcs oI thc hicturc trraces or ihe
spc.inens wde stodicd by yinnin8 el.dron ni.ro
]sł' 6rL\r, Jcol' s.mplśwer
quid nibÓgen aftd 3 min ald i]r.tr
scope
Di11.rcntiłI s.annin8 .alorińety (Dsc) vas
pcr
{Ómed with P€rłin Elnet (Dsc 2) aPPa!'fus Thc pro'
ccss was caiii€d olt in a tip]c.vclc hcihnt<ool_
ń8-hcatin8 in the teńPgaforc lanEcs fmm _r00,'c lo
300
lvii]r t]ie raie or heahĘ or coolin8 ]0 L'c/min.
t
claŚ EaEitjon
tcmperature (7*) !v
lh€ tenPerature dia3rans as ttle igmperatlr. corc
spondins ro thc uppPi innrrion p
Ćuflc Meliin! poini (ł' ańd
'h.
peratue (T.) vere dtuined a3 onsponding io ihe
n inh oI tie mdońemic we and the ńiniĄf
tuti@i. ĆNq r6Fdively.
DyMnlc nehani6l ln@al aMlysjs @MTĄ was
preforned wiih nD9IlRhŃńeń6 a'parafus wiu n
t€mp€rafue
ńnfe Lm 0 oc b 3o0 t at r H2 with
hdhnE !óle ] oc/nin' Th€ com!]o mo'lulu! (c)' dymm'c usGlry h ):nd lN bnAent ltA6) w€.€ dekF
ot the
solubiliy
soxnr€i
bh
oI thg
apPmfus in
enPl6 reĘ Ćaried out
35 wt' %
fomic acid.
wiih
Bdual steĘth .nd modulu re ndśu!€d a.
.ording ro PN rN Iso 1731993, .nd the bb wae car
rjed t at ]shon 4505 aPp.ratus łt mm lmPaafurc'
The te*ś concerning tecil€
Pcrabre
EiĘ
lŃfun
4605
data (a.ĆÓrdin8 to
teBile
chaĘy inPad nokhed and uńnoth.d 16L Mt
perldmed amding ro PN-EN rSO 179.r:2002 (U).
Ddlecbon tenp@fur€ wE ne6utd a.rńin8 b
Ha]dnc$
v.s BlińaEd ac.dding
l'o
PN EN Iso
Met now rate LĄ4R) w6 examined usi$ Plasbńe.
ter rype rI RT a@rding b PN-EN Iso 1r$:20o2 (U)
RoM*raled IE showed
.laBcbistiĆ fm uuoljre rĘ,
dE Eia{ting pE.Ś Ms su@sful nł
FT IR sre.ba oi purfied
pak
onfirnIn8
a
new
at ]6'44
that
6l
131.
Blend!
onPon
nt3
ńiśc|bllity
Th. effed oI PE{'RoM in conpatibilizing or
PBT/PA 6 blent'. wó fiEi obsaed in sEM ima36 (Fia'
1)' The niĆrglapns o1rhe fracbEd surla.es of the
blen& *ńPlc Pffintd iń Fi8. 1
Palible hehrcPhasic óaracb of inleĘ.reEating poly'
nł ngfuolk (IPN) tyPe, łhich was iń a(rdane with
le&niĘs ft'on DMIA spefu GĘ 2). Th]śiśdue L the
very 8ood adi6ion and conńms the fomation of bloc*
rP.lynffi located in ihe interfa.e.
PIEsg shchre śfudi6 śhowed that ińteifa.ial Ęaś
rioN b€treen funchonalizgd PE3'RoM, PBT and PA 6
Ćonbining Gr€adive 8rcuF aE e'fehve in the @ń_
patibiliż.tion of inBĘad blen ls' llle 8I'It oPoly_ IiE.1' sEM bie phśr|
RaMIP 6 bLrtds: a) 3al2a5a,
ngg fom.d dfting Edive pmmsjng.be.auśe of lnt6
Ćhain dĆhange rscrlN, p]ay a r.le ol cońPaiibjlizm'
f n
b)
aJ PETIPE 3 RaMtPA 6 Bat2also)
Pluse tansitions orth. blends
Ac.ordins to DSC drb ot PRT/PE{-RoM/PA 6
p!6c.tcd jn Tablc ] ind ln FiEures 3 łnd 4' lhe
fucśa€c prcreŚ IGUlh in hetmoPhmk bhnds widr
fuo matked melting Peakś (ł, and h'o ayslalliżation
r+ions (ą) .dle.PondiĘ b thc blcnds .onPoncnb
MeltiĘ pÓint of PE fradion i5 fouńd the ińc as lh of
thĆ nlat PE 0 _ 3!c),whjlethc cnihalPy is gmwjn8
uP \'; !ńi o l .uwcs Prcscn ling th c cfic.ś of endoihel
ńic or cEzoihcni. Proress obsened ilr m.lling and
cv{allizaiion rcgions łI. ihe lesulb of an ovellapPin8
bleńds
oI ih?
thm%nphs of blend .omponenh (PBT
TlbI.l'DŚcrcin!dBTfDenoMtrIóH!nd!.]
and
FiŚ 3. Dsc ,lt ns nr aJ PBT|PE Ś RaMlPA 6 blddŚ,
ń a| blć1d r panńs dł 0 Ż5a'
PA 6) dle lo theil .1G. attibde o! ńi.loPhasc dispĆr
Thi6,togdho wiih ihe aisappe łnc.of8lastansi
les.sociłlPd with
.aks, indtecrl), rhat intc ..ial rcrc
b€Ń.en thc ÓXazolirc€buPs in P
gioups in PBT ind PA6 Phaśdnrins reaclive *tu.
tiÓn bmpEafo
I
ir!!,
,
,E
Fzs6 sdl'biliłdllr
Dłia o1ine Ęsulh.g blends 8ohbillhcs nr a formic
a.id.an b.lsd for qu iiarive evaluation oI rhe liMl
polyner .onpositions solubil y o1 the product ob
biled by naclive proBin8 of polyesbr/pÓlyamid! ó
blcn,js in th. preŚĆne Óf ÓiażÓlinĆ 1undnjnalfty dc
dcases siBni1iGntly, whiĆh onfnms rhe fonatbn 01
8rait copolynds and bcfr.! chcńi
be seen fiom Table 2 the solubiljly .hanEes ńrh blend
ompBilion' ]}e rslltin8 Polynd sy*eńs Ćan bc cÓn
sider€d a PBT/PE
RoM/PA6b
'q
in .omPa son with PBT and PA 6, respedively' ThiŚ
pnenomenon may bc duc to ńcnti
with pa i.ipation ol tun.tio.al grcups oI three .onp&
nenl! ol a blcnd Tne impmvemeni in inpact shength
cnhaned slightly wi& imssinB
€
Ps;;;T,
rr)ntrjr
L .lelli a ll
F$ a Dsc
5
M6
thżhnryn 6 q PBTIPE3RaNPA6 b]ends
n1 r twhlliżalbn ftii'1j Śirnd
rnd 4 bknd ąnlpańdłs
oih.r ng.hani.al PePeltićs
sone .onhnś of stalting homoPolyńers' It should be
noted ih ihed a of ih€ soIubiliry t6b do noi Povide
ilE pNibility to .alculai€ exaclly lhe polyneI Ómposi.
iion o1fi. r€sulting pmdld
ljie invBiigal€d bl€nds retain pioP€rties
ing pol)mec. As .lidenr lrom Ta
of
eĘin€eŁ
śPĘlhand nodllN
oń onc hand
tion ar trield pomt on the other However, the blends
łow highł leBil. st€n8in' don8ation at btea( and
dcnc.tion lenP.rafoĘ in omParis
rhe blends dramrically dseased
subsbnri.l amounh ol interla.ial re
PBT/PA 6 blcnds rcre inrestiSated nainly in order
dNelop new en8inPe ng Polynas showin8 hĘh in_
pad ste$rh. nP rEulb proved th
a.njev€d' Table 3 stows lhe df€d
PE on rhe inpad sderyri ol d,e invetigated br.nds.
io
)t has bP€n showń thar $e interfa
tueen polydhyl.ne, @dilcry tu
oxazoline giolp, and PBT and PA 6
tiv.8rouPs arc €'ielive in lhe compaljbilizaiion ol ihe
polync! blends nE grart rpolymer rdned during d,e
loy with grÓd ińtr
facial adhesion T]t. PresenEd ńerh
sion by fuÓ{bEt Plrcss lbvidś a PGjbiljty to PG
duc. a vari.b' or ncw hish-inpJcr and sood chcmi.il
resislanĆe (bekl than PA 6) Polymeric matcnak by
varyins thc on.enbation of PE-s-RoM d initial poly.
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