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The synthesis and properties of filled polyvinyl chloride
1414
S. A, KunrA e / e l .
7. N. A. ADROVA, A. I. ARTYLIKHOV, Yu.G. B/~KI,AGINA, T. I. BORISOVA, M. M. KOTON, N. V. MIKHAILOVA, V. N. NIKITIN and A. V. SLDOROVICH, Vysokomul. soyed. AI6: 16.~8, t~'74 (Translufed in Polymer Sci. U.S S.R. 16: 7, Iq21, 1974) N. V. MIX HAJI£)VA, V. N. NIKIT[N, A. V. SIDOROVICH, N. A. AJDROVA, Yu. G. BAKLAGINA, A.M. DUBNOVAandN. V. YEFANOVA, Vysok~,mol soyed. AI9: 1030, Iq77(Translaled in Polymer Sea I.I.SS R. tO: ~, IINS, Iq77) 9. A. V. SIDOROVICH, N. V. MIKHAI]..,OVA, Yu. G. BAK.L,AGINA, L. K. PROKHOROVA and M. M. KOTON, Vv,~ukclmol ,,,wed A22: 12~9, IqSO ('Tran,,lafed ir= Polyrriel SOL LI S S.R. 22' h I '~'~8, 1980) It) A. I. KOL"rsov, N. G. BEL'NIKE'VICH, V. M. DENISOV, L. N. KORZHAVIN, N. V. MIK_HAJLOVA and V. N. NIKITI~, Vysokorntfl. :,eyed AI6: 2'~00, Iq-)'74 (Tran,,laled in Polymel S~.'L LI.S.S R. 16: I I, 2~12, Iq74) I I Yu. G. BAKLAGINA, I. S. MJLEVSKAYA, N. V. YEFANOVA, A. V. SIDOROVICH and V. A. ZLJBKOV, V'vsuk~m~l. suycd. At8: 12t'~, ll-Y7~('T'ransluled in Polvrrler Sci. U.SS.R. 18: O, 1417, 19'76) 12 M. M. KOTON, Vys~k~mul..,,,~y,.=d. AI3: 1t48, 1~-~'71(Trunslalcd m Polym*:r S,:i. LJ S.S R. 13: O, I.~73, 1971)
Piplymer.'JcieueeLIS S R Vol 27. No. h, pp 1414-1422,ll'~H'l PHnlc'drrJ Poland
ool:p, lq~,ojg,P $1000 .I- (X)
Pergamlm Journal,,L.tt.'L
THE SYNTHESIS AND PROPERTIES OF FULLED POLYVINYL CHLORII~E* S. A. KUR'TA, A. A. CmJ=KO, N. V. KHABER and L. A. NOV=)KSHONCWA "Khlorviml" Indusfrlal Asset=alien, Kalu.shko ( Reccwcd t0 ¢)¢'t,ber ll-)8l)
Polymerlzalion or vinyl chloride, m Ihe presence of melhylvmyl Aerosd has been invest=galed. II =s shown Ihat Ihe filler ha,, a sigmficanl influence ~m the kinelics or Ihe princess, on propetlies o1' Ihe resulhng lalex and on those, uf Ih¢ hlled PVC puwder. IN recent years investigat(~rs have been showing ever increasing interest in fillers used ror reiuforcement of rubbers and plastics. A m o n g fillers o r l h l s type is Aerosd I l l However the specific sud'ace or Aerosd is high, m a k i n g it impracticable to increase the a m o u n t it~ a polymer matrix abuve the level or 5-3()iIi~ without Impairing the processing properties or mixes. This makes I~w dilSculties in blending highly dispersed Aerosils, and a c c o u n t s for n o n u n d ' o r m i t y in their distribulion as well as ror greatly increased viscosity a n d I'or deterioration in some other properties or the materials [2] In the present instance it was desired thai the effect or Aerosfl on the kmelics el' vinyl chloride polymerizahLm and o n * Vysokomol. soyed A27: No O, 12¢~2-12h8, 198'L
Synthesis and properties of filled PVC
141'~
properties of Ihe filled PV(.' should be investigated. 'To do so a study was made o r features or the polymerization filling procedures [3]. "l"h,s paper relales I~ nut study ol Ihe emulst¢'~n polymertzalJnn of VC' m presence ul'rnclhvl. vinyl A e r ~ s t l ( M V A ) p r e v = o u s l y d=.spersed =n Ih¢ VC, and havtrig chemically bnund - S t t C H = C'H,,)
(CH ~)CI Woup;~ on =Is ,surl'ace. MVA had ;J bulk weq~,hl ~d' b(I ~.,,,'1, spec,hc surface S,,p 2,.10 rn"/V, pH ~4, hulntdtly I)'1%, annealing, loss ~I','., vinyl gl'(~lJp eori~.'enlrall~n t~H-CH~ =(I ~' mm~fl'-',~f~ AS an iriili~ll~r of free radi~.'al polymerizalinr= we Io~k ammunium persulphale (NH,D,,S,,()~, and, as an emulsifier, E: ~11alkvln-ionosulphemale, Ihe averaf,c' ~.'haln length being (.."~,, T'he kinehe,, ¢~l Ih¢ pulymerizali~m proce~,~ were trlvc'sltp,aled IILrnugh IIle r,:rri~wal el samples from IIie aul~.'lave rea~.h~r alice vuric~us mlervals ¢~1 lime These were Ihen analyz~.'d fur PVC ~.',~nlenl ha~ed ~n dclerrninali~l V(.' p~dyfrlertzulH~ri ~,as ioveShL.,,aled irl I[le lemperalure Inlerval 5,..[-h8", Ihe illlllUh~r ¢,mcenlrall~m bemf,, ()()1-1) I",i, and Ihe cmulmher ¢~ricerllrall,~rl I 2",-,-I 7'~",', The waler m,~duhJs H.,(.) V(. = I-2 I
OI I~)'~,~et, dullrH-~, ~.'ah.'inall~rl
()n the basts of experimental results kineltc curves nf VC polymerizatton were plotled for different mtlial amounts of M V A (Fig. I) Fnr comparison we took the initial porlion of the kmehc curve or ordmary emulsion polymerization of VC (curve I) [41. It ts seen from curves 2-4 in Fig. I Ihul the mtroductlon or 5, I(.)and I'~".', M V A increases Ihe polymerizalion rate (see 'Table). Acceleration of VC pnlymerization m presence of M V A is apparently due h) Aerosd parlrcles (d = () ()1 -() 02 ltm) [I ] d=slrlbuted in druplels ~1" m~momers, rnlcelles (din =().()~-O. II)pro) [4]: Ihe resulting macroradicals are made fast to the Aerosd surface by grarting. 'The same eft'eel Js observed when particles (d= () ()2-1). l() pro) of seed latex are introduced into Ihe medltim during VC polymerization and increase Ihe rate of the polymerizahon reaction [4]. 'T'his agrees wilh the data .n [~], m wluch reference Is made to the catalytic ml-luence of the hard sud'aee ~.d' morgamc subslnnces in the pnlymerlzalion of monomers. A further increase m the MVA concentruti4m Io 20, 30 and b()',l~ not only fails to increase the rate of the reaclion, bnt even reduces it shghlly (see Table; F'ig. I, curves 5 - 7 ) . 'This could well be due h) Ihe filler passing intn the dispersion medmm (water) ultimately leading to reductions =n the initiator and emuls=fier concentrations =n the medium owing to their adsorption by the Aerosd and lu a col~espondmg reduction tn the rate of initiation. 'The 1"able gwes the orders of the reaction wtth respect to monomer calculated by the C)slwa[d meth~ld It is known that intens~ficattnn of adsorptwm interaction at phase Inlerl'~ces [6] leads t(~ reducltLms in the ~.wder of the reaclton ranging:.,, I'rnm fractions ~1' unity t~.~ zern (for emulsion p~.dymerization of VC without a filler, it:.':, I), which is m keeping with ~ur data (see 'Table) where the urder varies f r o m , = 0.4 ( 5- I 5 ".., concenlralion of MVA) t~.)n =() (3()-60"., MVA concentration). The p¢flymerlzahon rate constants calculated by Ihe I'nrmula i, = k'[C]~'[M ]" [,-I] are given in the Table. 'Temperature dependences of the rate Ld' VC polymerization m presence of MVA are described by the Arrhemus equat~m. Morenver the introducl~on of MVA is accnmpamed by a shght reduich~)n in the acltvulirm enerl::y ~1" the process, :~nd by a rise in K (see 'ruble). To determine l e c h n o h ~ c a l properties nf the filled PVC lalex a viscometnc study was made of Ifie kinematic viscosity of the lat=ces relative to the filler concentration (Fig. 2, curves I, 2) 'The method of polymer~zat=on filhnL~ of PVC makes ~t possible to
S. A. KUr'l'A
1416
el al.
K.INKIqC FEA'rLIRES OF V C POLYMERIZAT'ION IN 'THE,, PR['$ENCB OF M V A
Ordc'r or rea¢llon in respool Io monomer n
MVA CorlceB-
ffalion, 0 / ,, 0
0
Polymcrizalion role conslanl I or VC, I/mole. min ~7"
~,4"
0 hX
I
04 O~ 0~ 04 OI
I0 20 ~0 hi.)
f,'2"
()'0
I'(I 0 '7 0 60 0 h9 0 72 (.) hh
0I 72 08 12 09
I t 0 91
0 i.lh 0 9t 0 '~8
1.2 I
0 87
I 02
Aclivallon energy,
l l(.) 8,, ['vq'
IP.~4,,
(a, =i4")
k J/mole
2 l)~ 20I
I 0
I I0
I 98
I. 12 I.'21
I f12 1 8h
1"79 I'lq III
I iX)
1 89 1.9'7 I fl'7
0 1'19 0 '7H
6H" 1.12
1 12 1 42 I 21
I I
i
8'7 I00 102 I IX)
i n t r o d u c e up to 50-0()'.!,~, filler, whereas .n the ca',;*: o r a m~.c,ba.,cal mixture o r PVC latex and M V A the same viscosity is obtained already when the M V A concenlratnon n,~ 2()i,',',. This el-Toot is apparently due to the I'act Ihat m the rormer case M V A ut a c o n c e n t r a t i o n o f up In 20'}1", goes mainly i n l n PVC globules (d,~ I or vc
p o l y m e r i z a t i o n [3].
Accordin~.,lyM V A 2 3
.7"5
¢: ¢J,
/,m), which
arc I'ormed m Ihe ,:nurse
below a c e r t a i , concentration ( .-.,20 ',;{,)
*l, c~t
~
,i0.~
50
'd
25
J
6 T/me, hp PiG.I
9
20
~0
60 HVA,%
F,.~ 2
Fro. I. Kiac"ti¢ curves ol" VC polymeriz.ation in presc,nc¢ or various amounls of MVA (l]ller), Ib¢ ,.,,, '~4". pH R. MVA ¢onc©ntrahorm, %' E-30 conccntralion being 3'8 and (NH4),S~Oo = 0 ' 03 of ,.. I - 0 , 2 - % . 1 - 1 0 , 4 - 1 ' ~ , 5 - 2 0 , 6 - . 1 0 , 7-bO. P'io. 2. KJUemati¢ vis*.'osily of PVC (I, 2) and Fickentcber con.staBts for PVC (3-6) vs. MVA con¢¢utxation. I - Mechamcal miP.lurc or 3 0 ~ PVC lalex and MVA; 2 - l a l c x obtaiaad during VC polymeri~inon ia pr©sc,nca or MVA; 3-6 - F.ckenl,.:ber coQstanl K ror PVC ¢xlracled in dicbloroethane and obtained at 54 (.f)..~7 (4"), 62 (.'0 and 68" (5).
Synlhes~'~ and PrOlL')~rlies of filled PVC'
1417
has but a negljguble effect on properties el" the latex. However, m the latt,:r ca.se, already when the same amounts of MVA are introduced, the filler part~cles are located at Ih~: phase interface and interact vta adsorption wtlh ingredients of tbe latex (emuls=fier, PVC, water), which leads t,) a marked tbtckening destab~fizatt(.m arid c(.)agulahon ()r Ihe PVC latex, whtle the amount or MVA being inlrod,wed i,; apprectablv smaller F'=gure 2 shows the Ftcketltcher c(.)n.~tant,~ I'()r PVC vs tfic am(runt (.)f MVA intr() dLiced ul the polymer,zatl()n stage, S)O, being extracted [)y fi,/dr()l]uortc acid rr(.)in Ifi.: re,~ullin~2 PVC samples A visc()mctric, melh()d was used h)(Jetermtile the F'icl~ent~'fier c(.)nstanl. It wa;~ rotin(l that the filler ha.~ n(.) ,',tl..,mficunt tnfluen(.'~. ()n the F'icl
()r the r~-~,ultmg, PVC. In the range ()r filh..r c(.)ncentratt()ns exanHned Jt ~s r~:duced on avera!~,,¢ by I() LInI[S, wlilch is a(..'c()u=llt.~d r()r l')y a higher rale (_)flermtnati(m. "r() reduce the znfluencc (.)I"the added filler ()n tl)e w'.,c()!,zty (.)r the PVC late.,, .') ~,tud,, was made ()fchange'., tn th(: c()ncentrati()n ()I' El 30 (.'omme)ctal emulsrfier (.)n the vz,wL),,~lv ()1' the filled PVC' lalex (Ft[.,. '~) A 2=?, fold tncrea'~e tn Lhe ~'n|ul~,lfier c(mcerltratt(m l=ll-]UellCt.'s llle ~,l,,;co'.)ily ()I' the latex only I=I lhe case (.)f fiiL.)fide!:,ree,, ~)I"filling, rt.'dt.tct=LT,
It by practically ())le=half. "rfiis i~ further evidence fuv()uring an a:,,~ti)npli()n that wtlfi all MVA c()nce))hati()n above ~)()i',)the filler l_)a,>,,,~.':;from dispersed l:)ILa'~e(V(.') t(.) di~,l)e),,)o~t medium (water), and st_) lfie addih()nal tntr()du(.'h()n ~)I' a '.,urfactant (emul,,)ficr F. I()) d()cs It) .,,()me extenl olTsef the (ht(.'kctHri!., acti(m ()I" filler that ha,,; l')a,,,,:~cd mr() the water 'The t)ic()rp()r,',l~)=| ol'a :,,tr()ng ad~.;()r'beitl, MVA, inh.) PV(." lea(J,~ t,) a marked )ncrea,)e II) lfie am()unl ()I" l-)la~lrcizer ((..]iL)ctyI l')Iithalah.' (E)t.)P)) C()ll,',;Llllll'd [~]. A sLIJdy wa% [fiere l'~)re made of l:)la~,tlClZCr capacity w)tfi resp~'ct t~) DOP for tlir,.'c dlfl~renl PVC samples (F')g. 4, (.'urw's I-.)'). "rhe low pla.'.,Iic=zer c()nsumpti()i) .,.,ub,,tantlate,~ lhe l'ea!,il:)dltV ()I" IJsrn,3, tht: polymerlzallo)) filling method to till p()lymer c(,.)Irl[.')()Sltl(.)nN C()l'lLall'I=tlt~, a lar~.:,c am()unt oi" plashc=zer. Moreover these conip()SillOnS call l()r' a lower c orv,,urnptr(.)n el" DOP thnn do (.)rd=nary PVC c(.')mp()sttt()ns. It ts kn<.)wn that the pac'l,ung d~'nstly (.)I" polymer macr=')molecules near the filler surface, i.e m the ad,,,,orption laye), )s h.)w~r titan at p()mts far away from )t [7]. 'I'fie tfi=cknes:~ (.)f tbe PVC layc.r ad,~orb~'d ()n the inmal A 17';, Aero~,tl when the latter )s )ntr'oducv, d =nt=) plasttctzed PVC =n the ~:t)ur,,,e ur mechanical processing amounts It.) It) ltm [~[. In additt(.)n, the average dens=ty of the polymer portion is in tiffs case I 21 g/cm ), while the volume I'raction of Aerosd tn PVC is (.).12 ,~I .';,._,.,.,.'v'~,),,,, by weight). For comparison we determined (tie average density or the polymer portion of Ihe filled PVC obtained by adding Aerosil at the stage of VC polymerizat=on in relation to the MVA concenlra(ion in volume I'racl=ons (Fig. 5). 'To find the thick)tess or the adsorbed PVC layer we used Ih¢ tk~rmula [8l: / ) - q)i l')r ,(,,,=~,
I - f~j
D.=d
,~I
~'e/~f,
D- d 2
a=--
where p,, is the avera~ density of the polymer portion of the filled IAtC; P is the density of the ti|led sample dL-termined by p y ~ o m e ~ , Pr is the liller density; ~f is the volume
1418
K uR'rA et al.
S.A.
Fraction oF filler; D is the diameter o1" the filler particles plus the adsorbed layer o1" polymer; d - is the diameter of MVA particles (0.02 pro); J is the thickness of the polymer layer adsorbed on Aerosil; ~Pa= I. By calculation we obtained D = 33.6 pro; d = 6"8 pro.
r~,c3t
V, ml
I
250
2
3
")
qO
20 -'
i
I ?.
1 3
0 °
I50
I # E'30,%
50
25
50 Filler, %
75
Fla. 4
Fro. 3
Fie. 3. K.inemalic v,scosily or PVC lalex vs. concentrahon of E-30 emulsifier wilh MVA conceuU'ations 5 (I), 10 (2), 15 (3), 20 (4), .10 (5) and 60~ (6). Fl('~. 4. Plasticizer capacily wilh respect to DOP k~r Ihe PVC-filler syslem vs. coucenU'ation of various fillers: I - mechanical mixlure of PVC and MVA; 2 - mechonieal mixlu.rc o1" PVC aud MVA modified wilh 20~ of grarled PVC; 3 - compositions oblained through VC polymerizalion in presence of MVA. V - amouut el" mJ DOP per 100 g PVC. In line with the cited calculations we may say that a s i ~ i f c a n t reduction in the adsorbed PVC layer thickness occurring in the case of polymerization filling is due to a change in the way the filler is packed when its volume Fraction in the filled PVC is increased. T o allow comparison o f the packing modes we computed the theoretical n r and the experimental ne amounts o1" M V A particles that may be Found in the volume o1" a PVC globule (devc= I pro) [3J. Calculations were based on the Formulas
"T =
Vt~vc V" • ~,,
"B =
' v;vc
V: ~,vc
I V l' v c =
n(devc)
v,'l.c =-~I ~ (D) ~ '
Here V~,vc is the volume of the PVC globule, It-' is the volume o f a n Aerosil particle, and V'lvv c is the volume of an Acrosil particle having an adsorbed layer of polymer.
Synlhesis and properties o f filled P V C
1419
The calculations show that for mechamcally filled PVC nr amounts to 1360 particles, while ror Ihe polymerized PVC nr amounts Io 2380 particles. At the same ome the number or part.des calculated on the basns of the experimental data in [8] amounted to 142() for the mecbanncally filled PVC, compared wnlh 2380 for the polymerizaUon filled PVC. 'Thus nn the case of polymerization filling of PVC the mode or packing or filler part=des conncided ndeully wnth that wlinch was theoretically reasnble; this substantiates Ihe assumption Ihat Aerosil particles are m the case under cons~deratmn located wnthnn PVC' globule.s. Thin being so, Ihe whole of the polymer gues into tlie adsorptnon laver m which li~.sentng of the polymer take,; place as ~s evident rrom the I'~ct that the mean density or tlie polymer portion us reduced It.) I.(.)0 g,/cmL Reductmn nn the thickness o f the PVC layer on the filler surface, down to a level or 6.8 itm lakes place on accmJnt ~)1 :in increase nn the w.~lume I'ract,'m or MVA m the p~flvmenzaliun filled PVC, wlinch amounts to I).21 (,)r t~) 30--40 wt i','~), ~.e. pracUcallv twnce that in Ihe mechamcally filled PVC, =n which Aerosd is =n extra structural segments or p v c macrJ~m~lecules located between PVC globules. q
t
/:~c: g/crnJ
f g ~'~ ,'1 II
~.~. EI
,,
c,j.,__=~..=..~
I
~
0,1 F'Jq; '~
I
I
173
~pf
,IS/' I
32
~z j~t
I
I
30
i
I
Z8 18
I
I
/6"
I
i
14 ,,
I
I?
v,/(7"'j ,.,"o"i
FIO h
F0; '~ AveraF?,e den,my ~1' polymer I'racl.m of filled PVC" u b l a m e d by polymcrnz, ahon filhnL.', v~s. M V A tor,.'enlralJun nn w~lume I'racl,ms ~/,~. ,4 - pq~ml al whnch PV(? I:,,ue~ uver h.~ ,,I;:lle ¢~1'adsorbed laver during mechanical hlhnp, 18], B - dl(Io, in Ihe ~:a';,e of p.lymernz, alnon filhng. Fur; 6 IR ,,per'Ira of~,urface or M V A healed under I O ~ I . r r vacuum / - M V A healed al 2'~O" v, flhoul (NH~),,S~(.),, J - M V A and () I ',','i uf (N H,;).,S~(.)a ul 2()", t, 4 - dHIo, afler healnn~..,, al t~() (2) and 80" (4).
For the obtained filled PVC samples it was also desired to determine the degree or PVC grarting to the filler surt'ace. 'To do so products were extracted ror48 br in a Soxhlet apparatus wnth hot dichloroethane. 'This was accompanied by the extraction of PVC bomopolymer, and the amount or grafted PVC was ascertained by determination or
'1420
S . A . KunlA et al.
weight losses during calcination. It was found that from I0 Io 30 % of the PVC remains on In the filler surface. Apparenlly this takes place by graft polymer,zation or v c with sud;ace unsaturaled M V A ~.~oups. The reacl=vily of vinyl groups entering rain interact=on w=th VC was invest=gated by inl'rared spectroscopy 0.1 '!;, (NH4).,S,.Os was depos=ted from aqueous solut=on on M V A powder. After drying the samples were press moulded in the I\~rm of disks and the. spectra were recorded (UR-20 speclrophotomeler, standard prcn.'edure [91) after the samples had been heated at varmus temperatures under vacuum. It was Ik~und (Fig. 6, curves 3 and 4) that I'rom 60" the IR spectrum of M V A fealures reduced intensity of bands at 3070 and 161() cm" ~ relating, to C - H bond stretch, and to stretching ol'C = (.7 of the MVA vinyl group, which suggests bond opening during dlssociahon ol'ammonium peroxodisulphale to tree radicals.
t I
I
I
I
?R
I
I
I7
I
I
/,=/
i
~,,-LI
~"--
I
13
7,5
f]
h"5 y,lO 2 crn'l ,!
'
F'JO. 7. Change in IR spct'tra of the compos=te conlaming 20 ,~,',PVC, grafled on MVA, during healing under at IO" ~ torr vacuum. Spectra recorded at 110 (I), 160 (2), 190 (3) and 220" (4), I' - 4peclrum of (he initial MVA
It was further des=red to investigate the heat resistance or PVC grafted to the filler surface and to compare this w=lh that of ordinary PVC, given as 87.1-127" in II01. To do so an M V A d=sk containing gral'Led PVC extracted I'rom homopolymer was placed ,n a quartz c¢11, which was heated under a 10- "~ tort vacuum In 130--220, whilst changes =n the IR spectrum were recorded. The spectrum of the sample containing 20% grafted PVC (F=g. 7, spectrum /) has no bands at 1610 and 3070 cm relating to C - - C and C - H bond stretch in MVA (Fig. 7, spectrum I), which substantiates the
Synthesm and properlie,i *~1 filled PVC
1421
proposed opening o1" double bonds nf the surface cnmpound of MVA as a result of Iheir cupolymerlzation with VC. A rise in temperature brings the onset of decomp**s~t~on of PVC accompanied by hberat~on ,~1" HCI and by the format=on of conlugated polyene compounds, vtz. dehydrochlorination products of PVC These are ~denlifiable hv bands appear,ng ~n Ihe IR spectrum at 161(] and t()2'~ cm" ~ relating to slretchmg
3 Z qcb t: 1'23
I
t
I
I
I
ZR
It/
l
t'h
I
I
I
I
I.L,
hr
t/
? ~,, i ,1[1 ~ C/'TI
I
F'l¢.; 8 Change m the IR sp,eclra of PVC (film from solutinn in dlt:hloroelharle) durmlz healmL.,,in a IO ~ Iorr vacuum. Spectra recorded at IO0 (/), 111)(2), ItpO(i') and 191)"(4). Of C = C and C - H=n these compounds. It ~s seen I'rom spectra 3 and 4 in F'~g. 7 that decompos,tion of the grafted PVC starts at IqO", whereas for the ordinary PVC homo polymer with no filler the onset of det.~adatlon appears already at lf~()"(Fig. 8, spectrum 3). Monitoring of the prot.,',;ress o1" degradat!on may also be based on reduct,ons in the mlensity of bands at 1450 and ~81.) e r a - ' corresponding In deformation vibrations of C - H groups of CH., and CCI respectively (Figs. 7 and 8). 'Thus =t appears that siliceous matrix has .'= slabihzing effect on PVC grafted to its surface and increases its heat resistance. Tran~'latedbv R. J A HEsv,Rv REFERENCES I J . E . MORELAND and D. V. MBLEVSK]], In' Napolnileh dlva pol,mernvkh komp~z,l.~mnn~ kh malertalov (Filler,~ for Polymeric Composiles). p 1'7'2, Kh=rr~iva, Mnsc¢~w, 1~81 2. V. V. GtlZEYEV, Pal Di~serlal,m al Chem Doclorale Exam, p. ,4h, Karp, w Phvsic.u~'hem Re.~ear~h Insl , Moscow, 1979 1. N. S. YENTKOLOPOV, S. A. KtlRTA, A. A. CHUg(O, N. V. KHABER, M. I. K H O M A , R. V. SI.ISH]KO, S. S. A.LEKSAPOL'SKII, V. P. LAVRENTOVICH and A. I. KLrRTA, LI.S S R. Pal. 90/0OR, publ. an Bvull. Izob., N¢~. '7, I10, 1982 4 Ye. N. ZI]UBERMAN, Poluchente i swfislva pohvmilkhlorida (Svnlhe~i;, and ProperHc,, *,1 PVC).pp 8b, 101,273, Khtmiya, Mn,,cnw, 1968 M. G. BRYK, Pohmertz.al,~lya na Iverdoi plwcrkhnosl, neorganichesktkh veshche;,Iv (Polymerit.aLton on Solid SurFace nf Innrganic SubMunces) p. '28'7, 'Nauk. dumka, K,t'v, 1981 h. K. V. ']rOPCH]]EVA and N. V. FEDOROVICH, In. Fizicheskava kh=m=ya v vopru;,akh = o l w lakh (Physical Cherrd~lr.v m Problems and Answers). p. 10, MGLI, Moscow, 1981
1422
A.
K.
BONEI'SKAYA
('t
ttl.
7. Yu. S. LIPATOV, Fizicheskaya khimiya napolnennvkh polimerov (Physical Chemislry of Filled Polvmer~0. p 17, KhlmJya, Moscow, 1977 8. M. N. RAFIKOV, V. V. GLIZEYEV and G. T. MALYSHEVA, Vvsokomol. soyed. Al?,: 2625, It)'7l (Translated in Polymer ScJ. LI.S.S.R. 13: I I, 2954, It~TI) t~ A.V. KISELEV and V. I. LYGIN, Inl'rakrasnve speklry poverkhnoslnvkh soyedinenu I ad.~of birovannykh ve!,hchestv (IR .~peclra of Surface Complmnds and Adsorbed Subslances) Nauka, Moscow, Iq'72 IO K. S. MINSKER and G. 'IF. F'EDOSEYEVA, Deslrukl,,iva i slabillzal:,lyu pohvinilkhlorlda (Degraduhon andSlabihzaflon el PVC) p. 15, Khlrmva, Moscow, It~'79
PolymeiStieuce LISS R Vol 27, N4~.~p,pp 1422-1427, IqSS
(l(.) 12 - )~)'H)/H'~ $ IO.Ot) "F .O4)
Pfinled In Poland
Per~,amtm Ioulnul,, thJ.
T H E K I N E T I C S A N D T H E H[EAT O F C Y C L O T R I M E R I Z A T I O N O F ARYL- A N D ALKYLISOCYA NATES* A. K. BONE'rsKAvA,M. A. KRAVCI-~.'NKO,TS M. FKE:NKE,L', V. A. PANe~ArOV, S. V. VINOGRADI.)VA and V. V. K(.)RSHAK Nesmeyanov Inslllule or Helero orgame Compounds, I.l S S R L orrilmosov Slafe I.In~vern,ly, Mo,,cq~w ( R e c e i v e d I N,n,embt,i
Academy of Sclence:~
1'~81)
Kinelic I'caluren have been mve~lq:,aled at)d rea¢lton heal.~ measured by a eulorimelric nielhod for Ihe cvth.)lrlmerizahon L~I' mono- and dilsoeyanale~J m d~l, lyme ~ohJIiOri and m bulk in Ihe pre:,ence el Irlefhylenedlamme, and using IIie calaiylic ny:~lem Irleltiylenedl a m i n e - p h e n y l g l y c i d y l e l h e r II wa~,foundlhalcurv¢~.~ of Ihe rea¢lio, rule v,~. time go Ihrou~.,,h a m a x i m u m E,rilhalpie,, el Ihe process for phenylisocyauale and ,4,4' dlphenylmelhane diP, o. cyanal¢ =n diglyme are -'~1.8 and - 0 1 2 k J/mole, while Ihe valuen for 1,6-hexam¢lhyl enedw~lcyanale in dil-.,,lyme and in bulk arc - I S O 2 and -I'~(~ 4 k J/mole respeclively
]N T'E:~',s'r on the part of authors mvestigatzng reactzous of cyclotrimerizat,on of aryland alkyhsocyanates is due to their aim of preparing, ,socyanurate-conta,mng polymers possessmg a number or g~)od properlies. 'These include heat stabil.ty, thermal-, chemical
resistance, hghl I'~slness and good mechanical properties [I, 21. However, to obta.n these properties Ihe polycyclolrimenzation reactions must be conducted =n a way that will resull in quanhlat=ve conversions of isocyanate groups, and take place under opt.real ' Vysokomol. soyed. A27. No. 6, 1269-12'71, 1985.
S. A, KunrA e / e l .
7. N. A. ADROVA, A. I. ARTYLIKHOV, Yu.G. B/~KI,AGINA, T. I. BORISOVA, M. M. KOTON, N. V. MIKHAILOVA, V. N. NIKITIN and A. V. SLDOROVICH, Vysokomul. soyed. AI6: 16.~8, t~'74 (Translufed in Polymer Sci. U.S S.R. 16: 7, Iq21, 1974) N. V. MIX HAJI£)VA, V. N. NIKIT[N, A. V. SIDOROVICH, N. A. AJDROVA, Yu. G. BAKLAGINA, A.M. DUBNOVAandN. V. YEFANOVA, Vysok~,mol soyed. AI9: 1030, Iq77(Translaled in Polymer Sea I.I.SS R. tO: ~, IINS, Iq77) 9. A. V. SIDOROVICH, N. V. MIKHAI]..,OVA, Yu. G. BAK.L,AGINA, L. K. PROKHOROVA and M. M. KOTON, Vv,~ukclmol ,,,wed A22: 12~9, IqSO ('Tran,,lafed ir= Polyrriel SOL LI S S.R. 22' h I '~'~8, 1980) It) A. I. KOL"rsov, N. G. BEL'NIKE'VICH, V. M. DENISOV, L. N. KORZHAVIN, N. V. MIK_HAJLOVA and V. N. NIKITI~, Vysokorntfl. :,eyed AI6: 2'~00, Iq-)'74 (Tran,,laled in Polymel S~.'L LI.S.S R. 16: I I, 2~12, Iq74) I I Yu. G. BAKLAGINA, I. S. MJLEVSKAYA, N. V. YEFANOVA, A. V. SIDOROVICH and V. A. ZLJBKOV, V'vsuk~m~l. suycd. At8: 12t'~, ll-Y7~('T'ransluled in Polvrrler Sci. U.SS.R. 18: O, 1417, 19'76) 12 M. M. KOTON, Vys~k~mul..,,,~y,.=d. AI3: 1t48, 1~-~'71(Trunslalcd m Polym*:r S,:i. LJ S.S R. 13: O, I.~73, 1971)
Piplymer.'JcieueeLIS S R Vol 27. No. h, pp 1414-1422,ll'~H'l PHnlc'drrJ Poland
ool:p, lq~,ojg,P $1000 .I- (X)
Pergamlm Journal,,L.tt.'L
THE SYNTHESIS AND PROPERTIES OF FULLED POLYVINYL CHLORII~E* S. A. KUR'TA, A. A. CmJ=KO, N. V. KHABER and L. A. NOV=)KSHONCWA "Khlorviml" Indusfrlal Asset=alien, Kalu.shko ( Reccwcd t0 ¢)¢'t,ber ll-)8l)
Polymerlzalion or vinyl chloride, m Ihe presence of melhylvmyl Aerosd has been invest=galed. II =s shown Ihat Ihe filler ha,, a sigmficanl influence ~m the kinelics or Ihe princess, on propetlies o1' Ihe resulhng lalex and on those, uf Ih¢ hlled PVC puwder. IN recent years investigat(~rs have been showing ever increasing interest in fillers used ror reiuforcement of rubbers and plastics. A m o n g fillers o r l h l s type is Aerosd I l l However the specific sud'ace or Aerosd is high, m a k i n g it impracticable to increase the a m o u n t it~ a polymer matrix abuve the level or 5-3()iIi~ without Impairing the processing properties or mixes. This makes I~w dilSculties in blending highly dispersed Aerosils, and a c c o u n t s for n o n u n d ' o r m i t y in their distribulion as well as ror greatly increased viscosity a n d I'or deterioration in some other properties or the materials [2] In the present instance it was desired thai the effect or Aerosfl on the kmelics el' vinyl chloride polymerizahLm and o n * Vysokomol. soyed A27: No O, 12¢~2-12h8, 198'L
Synthesis and properties of filled PVC
141'~
properties of Ihe filled PV(.' should be investigated. 'To do so a study was made o r features or the polymerization filling procedures [3]. "l"h,s paper relales I~ nut study ol Ihe emulst¢'~n polymertzalJnn of VC' m presence ul'rnclhvl. vinyl A e r ~ s t l ( M V A ) p r e v = o u s l y d=.spersed =n Ih¢ VC, and havtrig chemically bnund - S t t C H = C'H,,)
(CH ~)CI Woup;~ on =Is ,surl'ace. MVA had ;J bulk weq~,hl ~d' b(I ~.,,,'1, spec,hc surface S,,p 2,.10 rn"/V, pH ~4, hulntdtly I)'1%, annealing, loss ~I','., vinyl gl'(~lJp eori~.'enlrall~n t~H-CH~ =(I ~' mm~fl'-',~f~ AS an iriili~ll~r of free radi~.'al polymerizalinr= we Io~k ammunium persulphale (NH,D,,S,,()~, and, as an emulsifier, E: ~11alkvln-ionosulphemale, Ihe averaf,c' ~.'haln length being (.."~,, T'he kinehe,, ¢~l Ih¢ pulymerizali~m proce~,~ were trlvc'sltp,aled IILrnugh IIle r,:rri~wal el samples from IIie aul~.'lave rea~.h~r alice vuric~us mlervals ¢~1 lime These were Ihen analyz~.'d fur PVC ~.',~nlenl ha~ed ~n dclerrninali~l V(.' p~dyfrlertzulH~ri ~,as ioveShL.,,aled irl I[le lemperalure Inlerval 5,..[-h8", Ihe illlllUh~r ¢,mcenlrall~m bemf,, ()()1-1) I",i, and Ihe cmulmher ¢~ricerllrall,~rl I 2",-,-I 7'~",', The waler m,~duhJs H.,(.) V(. = I-2 I
OI I~)'~,~et, dullrH-~, ~.'ah.'inall~rl
()n the basts of experimental results kineltc curves nf VC polymerizatton were plotled for different mtlial amounts of M V A (Fig. I) Fnr comparison we took the initial porlion of the kmehc curve or ordmary emulsion polymerization of VC (curve I) [41. It ts seen from curves 2-4 in Fig. I Ihul the mtroductlon or 5, I(.)and I'~".', M V A increases Ihe polymerizalion rate (see 'Table). Acceleration of VC pnlymerization m presence of M V A is apparently due h) Aerosd parlrcles (d = () ()1 -() 02 ltm) [I ] d=slrlbuted in druplels ~1" m~momers, rnlcelles (din =().()~-O. II)pro) [4]: Ihe resulting macroradicals are made fast to the Aerosd surface by grarting. 'The same eft'eel Js observed when particles (d= () ()2-1). l() pro) of seed latex are introduced into Ihe medltim during VC polymerization and increase Ihe rate of the polymerizahon reaction [4]. 'T'his agrees wilh the data .n [~], m wluch reference Is made to the catalytic ml-luence of the hard sud'aee ~.d' morgamc subslnnces in the pnlymerlzalion of monomers. A further increase m the MVA concentruti4m Io 20, 30 and b()',l~ not only fails to increase the rate of the reaclion, bnt even reduces it shghlly (see Table; F'ig. I, curves 5 - 7 ) . 'This could well be due h) Ihe filler passing intn the dispersion medmm (water) ultimately leading to reductions =n the initiator and emuls=fier concentrations =n the medium owing to their adsorption by the Aerosd and lu a col~espondmg reduction tn the rate of initiation. 'The 1"able gwes the orders of the reaction wtth respect to monomer calculated by the C)slwa[d meth~ld It is known that intens~ficattnn of adsorptwm interaction at phase Inlerl'~ces [6] leads t(~ reducltLms in the ~.wder of the reaclton ranging:.,, I'rnm fractions ~1' unity t~.~ zern (for emulsion p~.dymerization of VC without a filler, it:.':, I), which is m keeping with ~ur data (see 'Table) where the urder varies f r o m , = 0.4 ( 5- I 5 ".., concenlralion of MVA) t~.)n =() (3()-60"., MVA concentration). The p¢flymerlzahon rate constants calculated by Ihe I'nrmula i, = k'[C]~'[M ]" [,-I] are given in the Table. 'Temperature dependences of the rate Ld' VC polymerization m presence of MVA are described by the Arrhemus equat~m. Morenver the introducl~on of MVA is accnmpamed by a shght reduich~)n in the acltvulirm enerl::y ~1" the process, :~nd by a rise in K (see 'ruble). To determine l e c h n o h ~ c a l properties nf the filled PVC lalex a viscometnc study was made of Ifie kinematic viscosity of the lat=ces relative to the filler concentration (Fig. 2, curves I, 2) 'The method of polymer~zat=on filhnL~ of PVC makes ~t possible to
S. A. KUr'l'A
1416
el al.
K.INKIqC FEA'rLIRES OF V C POLYMERIZAT'ION IN 'THE,, PR['$ENCB OF M V A
Ordc'r or rea¢llon in respool Io monomer n
MVA CorlceB-
ffalion, 0 / ,, 0
0
Polymcrizalion role conslanl I or VC, I/mole. min ~7"
~,4"
0 hX
I
04 O~ 0~ 04 OI
I0 20 ~0 hi.)
f,'2"
()'0
I'(I 0 '7 0 60 0 h9 0 72 (.) hh
0I 72 08 12 09
I t 0 91
0 i.lh 0 9t 0 '~8
1.2 I
0 87
I 02
Aclivallon energy,
l l(.) 8,, ['vq'
IP.~4,,
(a, =i4")
k J/mole
2 l)~ 20I
I 0
I I0
I 98
I. 12 I.'21
I f12 1 8h
1"79 I'lq III
I iX)
1 89 1.9'7 I fl'7
0 1'19 0 '7H
6H" 1.12
1 12 1 42 I 21
I I
i
8'7 I00 102 I IX)
i n t r o d u c e up to 50-0()'.!,~, filler, whereas .n the ca',;*: o r a m~.c,ba.,cal mixture o r PVC latex and M V A the same viscosity is obtained already when the M V A concenlratnon n,~ 2()i,',',. This el-Toot is apparently due to the I'act Ihat m the rormer case M V A ut a c o n c e n t r a t i o n o f up In 20'}1", goes mainly i n l n PVC globules (d,~ I or vc
p o l y m e r i z a t i o n [3].
Accordin~.,lyM V A 2 3
.7"5
¢: ¢J,
/,m), which
arc I'ormed m Ihe ,:nurse
below a c e r t a i , concentration ( .-.,20 ',;{,)
*l, c~t
~
,i0.~
50
'd
25
J
6 T/me, hp PiG.I
9
20
~0
60 HVA,%
F,.~ 2
Fro. I. Kiac"ti¢ curves ol" VC polymeriz.ation in presc,nc¢ or various amounls of MVA (l]ller), Ib¢ ,.,,, '~4". pH R. MVA ¢onc©ntrahorm, %' E-30 conccntralion being 3'8 and (NH4),S~Oo = 0 ' 03 of ,.. I - 0 , 2 - % . 1 - 1 0 , 4 - 1 ' ~ , 5 - 2 0 , 6 - . 1 0 , 7-bO. P'io. 2. KJUemati¢ vis*.'osily of PVC (I, 2) and Fickentcber con.staBts for PVC (3-6) vs. MVA con¢¢utxation. I - Mechamcal miP.lurc or 3 0 ~ PVC lalex and MVA; 2 - l a l c x obtaiaad during VC polymeri~inon ia pr©sc,nca or MVA; 3-6 - F.ckenl,.:ber coQstanl K ror PVC ¢xlracled in dicbloroethane and obtained at 54 (.f)..~7 (4"), 62 (.'0 and 68" (5).
Synlhes~'~ and PrOlL')~rlies of filled PVC'
1417
has but a negljguble effect on properties el" the latex. However, m the latt,:r ca.se, already when the same amounts of MVA are introduced, the filler part~cles are located at Ih~: phase interface and interact vta adsorption wtlh ingredients of tbe latex (emuls=fier, PVC, water), which leads t,) a marked tbtckening destab~fizatt(.m arid c(.)agulahon ()r Ihe PVC latex, whtle the amount or MVA being inlrod,wed i,; apprectablv smaller F'=gure 2 shows the Ftcketltcher c(.)n.~tant,~ I'()r PVC vs tfic am(runt (.)f MVA intr() dLiced ul the polymer,zatl()n stage, S)O, being extracted [)y fi,/dr()l]uortc acid rr(.)in Ifi.: re,~ullin~2 PVC samples A visc()mctric, melh()d was used h)(Jetermtile the F'icl~ent~'fier c(.)nstanl. It wa;~ rotin(l that the filler ha.~ n(.) ,',tl..,mficunt tnfluen(.'~. ()n the F'icl
()r the r~-~,ultmg, PVC. In the range ()r filh..r c(.)ncentratt()ns exanHned Jt ~s r~:duced on avera!~,,¢ by I() LInI[S, wlilch is a(..'c()u=llt.~d r()r l')y a higher rale (_)flermtnati(m. "r() reduce the znfluencc (.)I"the added filler ()n tl)e w'.,c()!,zty (.)r the PVC late.,, .') ~,tud,, was made ()fchange'., tn th(: c()ncentrati()n ()I' El 30 (.'omme)ctal emulsrfier (.)n the vz,wL),,~lv ()1' the filled PVC' lalex (Ft[.,. '~) A 2=?, fold tncrea'~e tn Lhe ~'n|ul~,lfier c(mcerltratt(m l=ll-]UellCt.'s llle ~,l,,;co'.)ily ()I' the latex only I=I lhe case (.)f fiiL.)fide!:,ree,, ~)I"filling, rt.'dt.tct=LT,
It by practically ())le=half. "rfiis i~ further evidence fuv()uring an a:,,~ti)npli()n that wtlfi all MVA c()nce))hati()n above ~)()i',)the filler l_)a,>,,,~.':;from dispersed l:)ILa'~e(V(.') t(.) di~,l)e),,)o~t medium (water), and st_) lfie addih()nal tntr()du(.'h()n ~)I' a '.,urfactant (emul,,)ficr F. I()) d()cs It) .,,()me extenl olTsef the (ht(.'kctHri!., acti(m ()I" filler that ha,,; l')a,,,,:~cd mr() the water 'The t)ic()rp()r,',l~)=| ol'a :,,tr()ng ad~.;()r'beitl, MVA, inh.) PV(." lea(J,~ t,) a marked )ncrea,)e II) lfie am()unl ()I" l-)la~lrcizer ((..]iL)ctyI l')Iithalah.' (E)t.)P)) C()ll,',;Llllll'd [~]. A sLIJdy wa% [fiere l'~)re made of l:)la~,tlClZCr capacity w)tfi resp~'ct t~) DOP for tlir,.'c dlfl~renl PVC samples (F')g. 4, (.'urw's I-.)'). "rhe low pla.'.,Iic=zer c()nsumpti()i) .,.,ub,,tantlate,~ lhe l'ea!,il:)dltV ()I" IJsrn,3, tht: polymerlzallo)) filling method to till p()lymer c(,.)Irl[.')()Sltl(.)nN C()l'lLall'I=tlt~, a lar~.:,c am()unt oi" plashc=zer. Moreover these conip()SillOnS call l()r' a lower c orv,,urnptr(.)n el" DOP thnn do (.)rd=nary PVC c(.')mp()sttt()ns. It ts kn<.)wn that the pac'l,ung d~'nstly (.)I" polymer macr=')molecules near the filler surface, i.e m the ad,,,,orption laye), )s h.)w~r titan at p()mts far away from )t [7]. 'I'fie tfi=cknes:~ (.)f tbe PVC layc.r ad,~orb~'d ()n the inmal A 17';, Aero~,tl when the latter )s )ntr'oducv, d =nt=) plasttctzed PVC =n the ~:t)ur,,,e ur mechanical processing amounts It.) It) ltm [~[. In additt(.)n, the average dens=ty of the polymer portion is in tiffs case I 21 g/cm ), while the volume I'raction of Aerosd tn PVC is (.).12 ,~I .';,._,.,.,.'v'~,),,,, by weight). For comparison we determined (tie average density or the polymer portion of Ihe filled PVC obtained by adding Aerosil at the stage of VC polymerizat=on in relation to the MVA concenlra(ion in volume I'racl=ons (Fig. 5). 'To find the thick)tess or the adsorbed PVC layer we used Ih¢ tk~rmula [8l: / ) - q)i l')r ,(,,,=~,
I - f~j
D.=d
,~I
~'e/~f,
D- d 2
a=--
where p,, is the avera~ density of the polymer portion of the filled IAtC; P is the density of the ti|led sample dL-termined by p y ~ o m e ~ , Pr is the liller density; ~f is the volume
1418
K uR'rA et al.
S.A.
Fraction oF filler; D is the diameter o1" the filler particles plus the adsorbed layer o1" polymer; d - is the diameter of MVA particles (0.02 pro); J is the thickness of the polymer layer adsorbed on Aerosil; ~Pa= I. By calculation we obtained D = 33.6 pro; d = 6"8 pro.
r~,c3t
V, ml
I
250
2
3
")
qO
20 -'
i
I ?.
1 3
0 °
I50
I # E'30,%
50
25
50 Filler, %
75
Fla. 4
Fro. 3
Fie. 3. K.inemalic v,scosily or PVC lalex vs. concentrahon of E-30 emulsifier wilh MVA conceuU'ations 5 (I), 10 (2), 15 (3), 20 (4), .10 (5) and 60~ (6). Fl('~. 4. Plasticizer capacily wilh respect to DOP k~r Ihe PVC-filler syslem vs. coucenU'ation of various fillers: I - mechanical mixlure of PVC and MVA; 2 - mechonieal mixlu.rc o1" PVC aud MVA modified wilh 20~ of grarled PVC; 3 - compositions oblained through VC polymerizalion in presence of MVA. V - amouut el" mJ DOP per 100 g PVC. In line with the cited calculations we may say that a s i ~ i f c a n t reduction in the adsorbed PVC layer thickness occurring in the case of polymerization filling is due to a change in the way the filler is packed when its volume Fraction in the filled PVC is increased. T o allow comparison o f the packing modes we computed the theoretical n r and the experimental ne amounts o1" M V A particles that may be Found in the volume o1" a PVC globule (devc= I pro) [3J. Calculations were based on the Formulas
"T =
Vt~vc V" • ~,,
"B =
' v;vc
V: ~,vc
I V l' v c =
n(devc)
v,'l.c =-~I ~ (D) ~ '
Here V~,vc is the volume of the PVC globule, It-' is the volume o f a n Aerosil particle, and V'lvv c is the volume of an Acrosil particle having an adsorbed layer of polymer.
Synlhesis and properties o f filled P V C
1419
The calculations show that for mechamcally filled PVC nr amounts to 1360 particles, while ror Ihe polymerized PVC nr amounts Io 2380 particles. At the same ome the number or part.des calculated on the basns of the experimental data in [8] amounted to 142() for the mecbanncally filled PVC, compared wnlh 2380 for the polymerizaUon filled PVC. 'Thus nn the case of polymerization filling of PVC the mode or packing or filler part=des conncided ndeully wnth that wlinch was theoretically reasnble; this substantiates Ihe assumption Ihat Aerosil particles are m the case under cons~deratmn located wnthnn PVC' globule.s. Thin being so, Ihe whole of the polymer gues into tlie adsorptnon laver m which li~.sentng of the polymer take,; place as ~s evident rrom the I'~ct that the mean density or tlie polymer portion us reduced It.) I.(.)0 g,/cmL Reductmn nn the thickness o f the PVC layer on the filler surface, down to a level or 6.8 itm lakes place on accmJnt ~)1 :in increase nn the w.~lume I'ract,'m or MVA m the p~flvmenzaliun filled PVC, wlinch amounts to I).21 (,)r t~) 30--40 wt i','~), ~.e. pracUcallv twnce that in Ihe mechamcally filled PVC, =n which Aerosd is =n extra structural segments or p v c macrJ~m~lecules located between PVC globules. q
t
/:~c: g/crnJ
f g ~'~ ,'1 II
~.~. EI
,,
c,j.,__=~..=..~
I
~
0,1 F'Jq; '~
I
I
173
~pf
,IS/' I
32
~z j~t
I
I
30
i
I
Z8 18
I
I
/6"
I
i
14 ,,
I
I?
v,/(7"'j ,.,"o"i
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F0; '~ AveraF?,e den,my ~1' polymer I'racl.m of filled PVC" u b l a m e d by polymcrnz, ahon filhnL.', v~s. M V A tor,.'enlralJun nn w~lume I'racl,ms ~/,~. ,4 - pq~ml al whnch PV(? I:,,ue~ uver h.~ ,,I;:lle ¢~1'adsorbed laver during mechanical hlhnp, 18], B - dl(Io, in Ihe ~:a';,e of p.lymernz, alnon filhng. Fur; 6 IR ,,per'Ira of~,urface or M V A healed under I O ~ I . r r vacuum / - M V A healed al 2'~O" v, flhoul (NH~),,S~(.),, J - M V A and () I ',','i uf (N H,;).,S~(.)a ul 2()", t, 4 - dHIo, afler healnn~..,, al t~() (2) and 80" (4).
For the obtained filled PVC samples it was also desired to determine the degree or PVC grarting to the filler surt'ace. 'To do so products were extracted ror48 br in a Soxhlet apparatus wnth hot dichloroethane. 'This was accompanied by the extraction of PVC bomopolymer, and the amount or grafted PVC was ascertained by determination or
'1420
S . A . KunlA et al.
weight losses during calcination. It was found that from I0 Io 30 % of the PVC remains on In the filler surface. Apparenlly this takes place by graft polymer,zation or v c with sud;ace unsaturaled M V A ~.~oups. The reacl=vily of vinyl groups entering rain interact=on w=th VC was invest=gated by inl'rared spectroscopy 0.1 '!;, (NH4).,S,.Os was depos=ted from aqueous solut=on on M V A powder. After drying the samples were press moulded in the I\~rm of disks and the. spectra were recorded (UR-20 speclrophotomeler, standard prcn.'edure [91) after the samples had been heated at varmus temperatures under vacuum. It was Ik~und (Fig. 6, curves 3 and 4) that I'rom 60" the IR spectrum of M V A fealures reduced intensity of bands at 3070 and 161() cm" ~ relating, to C - H bond stretch, and to stretching ol'C = (.7 of the MVA vinyl group, which suggests bond opening during dlssociahon ol'ammonium peroxodisulphale to tree radicals.
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It was further des=red to investigate the heat resistance or PVC grafted to the filler surface and to compare this w=lh that of ordinary PVC, given as 87.1-127" in II01. To do so an M V A d=sk containing gral'Led PVC extracted I'rom homopolymer was placed ,n a quartz c¢11, which was heated under a 10- "~ tort vacuum In 130--220, whilst changes =n the IR spectrum were recorded. The spectrum of the sample containing 20% grafted PVC (F=g. 7, spectrum /) has no bands at 1610 and 3070 cm relating to C - - C and C - H bond stretch in MVA (Fig. 7, spectrum I), which substantiates the
Synthesm and properlie,i *~1 filled PVC
1421
proposed opening o1" double bonds nf the surface cnmpound of MVA as a result of Iheir cupolymerlzation with VC. A rise in temperature brings the onset of decomp**s~t~on of PVC accompanied by hberat~on ,~1" HCI and by the format=on of conlugated polyene compounds, vtz. dehydrochlorination products of PVC These are ~denlifiable hv bands appear,ng ~n Ihe IR spectrum at 161(] and t()2'~ cm" ~ relating to slretchmg
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F'l¢.; 8 Change m the IR sp,eclra of PVC (film from solutinn in dlt:hloroelharle) durmlz healmL.,,in a IO ~ Iorr vacuum. Spectra recorded at IO0 (/), 111)(2), ItpO(i') and 191)"(4). Of C = C and C - H=n these compounds. It ~s seen I'rom spectra 3 and 4 in F'~g. 7 that decompos,tion of the grafted PVC starts at IqO", whereas for the ordinary PVC homo polymer with no filler the onset of det.~adatlon appears already at lf~()"(Fig. 8, spectrum 3). Monitoring of the prot.,',;ress o1" degradat!on may also be based on reduct,ons in the mlensity of bands at 1450 and ~81.) e r a - ' corresponding In deformation vibrations of C - H groups of CH., and CCI respectively (Figs. 7 and 8). 'Thus =t appears that siliceous matrix has .'= slabihzing effect on PVC grafted to its surface and increases its heat resistance. Tran~'latedbv R. J A HEsv,Rv REFERENCES I J . E . MORELAND and D. V. MBLEVSK]], In' Napolnileh dlva pol,mernvkh komp~z,l.~mnn~ kh malertalov (Filler,~ for Polymeric Composiles). p 1'7'2, Kh=rr~iva, Mnsc¢~w, 1~81 2. V. V. GtlZEYEV, Pal Di~serlal,m al Chem Doclorale Exam, p. ,4h, Karp, w Phvsic.u~'hem Re.~ear~h Insl , Moscow, 1979 1. N. S. YENTKOLOPOV, S. A. KtlRTA, A. A. CHUg(O, N. V. KHABER, M. I. K H O M A , R. V. SI.ISH]KO, S. S. A.LEKSAPOL'SKII, V. P. LAVRENTOVICH and A. I. KLrRTA, LI.S S R. Pal. 90/0OR, publ. an Bvull. Izob., N¢~. '7, I10, 1982 4 Ye. N. ZI]UBERMAN, Poluchente i swfislva pohvmilkhlorida (Svnlhe~i;, and ProperHc,, *,1 PVC).pp 8b, 101,273, Khtmiya, Mn,,cnw, 1968 M. G. BRYK, Pohmertz.al,~lya na Iverdoi plwcrkhnosl, neorganichesktkh veshche;,Iv (Polymerit.aLton on Solid SurFace nf Innrganic SubMunces) p. '28'7, 'Nauk. dumka, K,t'v, 1981 h. K. V. ']rOPCH]]EVA and N. V. FEDOROVICH, In. Fizicheskava kh=m=ya v vopru;,akh = o l w lakh (Physical Cherrd~lr.v m Problems and Answers). p. 10, MGLI, Moscow, 1981
1422
A.
K.
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7. Yu. S. LIPATOV, Fizicheskaya khimiya napolnennvkh polimerov (Physical Chemislry of Filled Polvmer~0. p 17, KhlmJya, Moscow, 1977 8. M. N. RAFIKOV, V. V. GLIZEYEV and G. T. MALYSHEVA, Vvsokomol. soyed. Al?,: 2625, It)'7l (Translated in Polymer ScJ. LI.S.S.R. 13: I I, 2954, It~TI) t~ A.V. KISELEV and V. I. LYGIN, Inl'rakrasnve speklry poverkhnoslnvkh soyedinenu I ad.~of birovannykh ve!,hchestv (IR .~peclra of Surface Complmnds and Adsorbed Subslances) Nauka, Moscow, Iq'72 IO K. S. MINSKER and G. 'IF. F'EDOSEYEVA, Deslrukl,,iva i slabillzal:,lyu pohvinilkhlorlda (Degraduhon andSlabihzaflon el PVC) p. 15, Khlrmva, Moscow, It~'79
PolymeiStieuce LISS R Vol 27, N4~.~p,pp 1422-1427, IqSS
(l(.) 12 - )~)'H)/H'~ $ IO.Ot) "F .O4)
Pfinled In Poland
Per~,amtm Ioulnul,, thJ.
T H E K I N E T I C S A N D T H E H[EAT O F C Y C L O T R I M E R I Z A T I O N O F ARYL- A N D ALKYLISOCYA NATES* A. K. BONE'rsKAvA,M. A. KRAVCI-~.'NKO,TS M. FKE:NKE,L', V. A. PANe~ArOV, S. V. VINOGRADI.)VA and V. V. K(.)RSHAK Nesmeyanov Inslllule or Helero orgame Compounds, I.l S S R L orrilmosov Slafe I.In~vern,ly, Mo,,cq~w ( R e c e i v e d I N,n,embt,i
Academy of Sclence:~
1'~81)
Kinelic I'caluren have been mve~lq:,aled at)d rea¢lton heal.~ measured by a eulorimelric nielhod for Ihe cvth.)lrlmerizahon L~I' mono- and dilsoeyanale~J m d~l, lyme ~ohJIiOri and m bulk in Ihe pre:,ence el Irlefhylenedlamme, and using IIie calaiylic ny:~lem Irleltiylenedl a m i n e - p h e n y l g l y c i d y l e l h e r II wa~,foundlhalcurv¢~.~ of Ihe rea¢lio, rule v,~. time go Ihrou~.,,h a m a x i m u m E,rilhalpie,, el Ihe process for phenylisocyauale and ,4,4' dlphenylmelhane diP, o. cyanal¢ =n diglyme are -'~1.8 and - 0 1 2 k J/mole, while Ihe valuen for 1,6-hexam¢lhyl enedw~lcyanale in dil-.,,lyme and in bulk arc - I S O 2 and -I'~(~ 4 k J/mole respeclively
]N T'E:~',s'r on the part of authors mvestigatzng reactzous of cyclotrimerizat,on of aryland alkyhsocyanates is due to their aim of preparing, ,socyanurate-conta,mng polymers possessmg a number or g~)od properlies. 'These include heat stabil.ty, thermal-, chemical
resistance, hghl I'~slness and good mechanical properties [I, 21. However, to obta.n these properties Ihe polycyclolrimenzation reactions must be conducted =n a way that will resull in quanhlat=ve conversions of isocyanate groups, and take place under opt.real ' Vysokomol. soyed. A27. No. 6, 1269-12'71, 1985.