Instructions for use
Title Polymerization of normal butene with mixed acid catalysts (I)
Author(s) Ohtsuka, Hiroshi; Morita, Takashi
Citation Memoirs of the Faculty of Engineering, Hokkaido University = 北海道大學工學部紀要, 9(1): 112-124
Issue Date 1952-03-31
Doc URL http://hdl.handle.net/2115/37770
Type bulletin (article)
File Information 9(1)_112-124.pdf
Hokkaido University Collection of Scholarly and Academic Papers : HUSCAP
Popgyggserfizattfiowa ijfi NerKxAal gewatease wfith
MExed AcEdi Caealysts (E)・
Hiroshi OHTsvi<A
Tal<ashi MoRiTA
(Received Oct, 1, 1951)
Xn'troduc'tion,
(1) In the previous paper,a study was reported of polymerization of butenes with
sulfufic acid catalyst to obtain mainly octenes, Low reaction teinperature and
short time of contact favored the production .of low molecular polyrners and sulfuric
acid'o'f oyer 87% concentration caused appreciable polymerization of butenes, In
the presence of su]furic acid, reaction temperatures higher than 1000C were quite
inadequate to obtain liquid polymer from butenes. Isobutene gave liquid polymer in
good yield with sulfuric acid catalyst. While, normal butene showed poor polymer
yield, probably its sulfuric acid ester being stable, and, in this case, the activity
of sulfuric acid decreased very rapidly. 'e In the present paper, po!ymerization of normal butene in the presence of mixed
acid catalyst is reported. The mixed acid catalyst consisted of 87% sulfuric acid
and phosphoric acid (ortho-- Qr pyro-phosphoric acid). With this catalyst, normal
butene was converted into liquid polymer in good yielcl. Dimers, trimers and tetra-
mers of butene were tbe main components of the liquid polymer.
In this se'ries of experiments, the polyrnerization conditions were so controled
as to produce chiefly trimers and tetramers of butene. These long chain olefins
have recently been used for various purposes in organic synthesis.
' ' rmxpetizl}entaX,
k, ,thppaTatus and xerocedure.
The polymerization apparatus was a three-necked round bottom flask of300cc
capactw equipped with an agitator. Norrnal butene gas was bubbled into the cata-
lyst acid contained in the flask under agitation. The temperature of the contents
'{1) H. Ohtsul<a et al,, ]>([emoirs of.the Faculty of Engineering, Hol<kaido Univer$ity, (ll), No 3 I)art I.
,
Hiroshi OH'fs'rJ<A Tal<ashi MoRrt'A 113
Was regulated by imrnersing the flask in a water bath or in an oil bath.
The conducted butene gas was partly polymeri4ed to liquid in the presence of
the acid catalyst and the unreacted gas left the flask through a reflux condenser.
The !iquid polymer thus produced was separated from the acid after cooling and
then washed, dried and fractionated into the following four fractions:
1)Upto1500C Butenedimers(Octenes) 2)150-2100C Butenetrimers(Dodecenes) 3)210-274QC Butenetetramers(Cetenes)
4)Over2740C Heavypolymers. 'About 20 litres of normal butene was used for each experiment and gas flow rate
was ca. 12 litres per hour, The normal butene was prepared by the dehydratjon
of fertnentation butyl alcohol with bentonite as a dehydration catalyst. Normal
butene thus prepared contained only trace of isobutene according to the analysis.
The amount of the mixed acid used for each run was 50 g.
In a series of experiments the tetramer fraction of butene was added to the
catalyst acid for the purpose of retarding heavy polymer production, The amount of
addition was 15g for each experiment.
fa.mexpeyimentaXmeesuXts, ・ ・・・ (1) Polymerization of Normal Butene with the Mixed Acid olr 87% Sulfuric
・ Acidand90%OrthophosphoricAcid. ' (Without the Addition of Butene Tetramer.) ' - ' The results of this serieS of experiments are summarized in Tables 1 to 4,
andillustratedinFigs.lto4, ' , ' ' Table 1. Polynlerization of Normal Butene with the Mixed
A.ictoff87%SulfuricAcid so%
anmarm..mm 2 l90%Phosi,::lhoricAcid so% N React. temp.
Conducted butene
Reacted butene
Conversion rate
Polymer yield
Polymer component
Dimer frac.
Trimer trac,
Tetramer frac.
Heavy polymer
Gas & loss
coc)' 60
・1u,N.T.P.) i
(t,Nmp・) l
(%) lf (g) I{ c%)
(%)
c%)
(%} , (%)
(%)
65
19,O
3.i
16.3
1.0
12.9
Hetmth"nd'
19.0
4e2
22.1
1.6
15.2
70
l9.0
5,7
30.2
2.4
i6.8
75
ptmnt,pmmmvt
, 7.8 62.4
2g.8
19.1
6.2 32,4
2.7 17.Gm-w-f'-]
nmtsttutunb
ll4 Polymerizatino of Normal Butene with Mixed
Table 2. Polymerization of Nurmal Butene Acid oi { ?g%% S.¥,'.f,";,l.f.,"i,C'X.id'
Acid
with
60%40%
Catalysts (I ),
the Mixed
meMt・ptww-dza.muystpaVUmnsu t-tnytumormopmumptmuarmiwwSmuflrm'''
React. temp. (oc) 60 65 .tt...tt.t.-.t.T...-.tt.....t.tt. t...t .. . ' (l,N.T.P" Conducted butene l9.0 19.1 l9.0
Reactedbutene Cl,N.T.P.)・ 10.4 7.7 6.5
Conversionrate (%)' 34.2 40.5 54・6 f(g) 3,4 5,5 IO.5 Polymer yield l(%) 2o,g 2s.6 40.4 ' Polymer component ・ ' Diruerfrac, (%) -- 7e6
Trimerfrac. (%) '- - 56eO
Tetramerfrac. <%) ・;-- -・'2B.6 ' Heavypolymer (%} . 3e8 'ank.s an&tmi maoss th.mathtm(wn%)ueth/ im-rmmaptdithmotm4.o
70 75 80 85 mo
Table 3. Polymerizablon
Acid of { g8o7;
ptwwoppttump・ pmmuuama
of Normal Butene with
SulfuricAcid 70%PhotsphoricAcid 30%
l8,9 18.0 18.014.5' 14.7 14.276.7 82,O 79eO
18e5 '24el 22e5
51・O 65・5 63e5
6.5 3,3 2.2
52.5 46,5 45;8 47.1 45.631.9
5,4 4.6. 4.9
3.7 ' tttupLimolm-Nxveanm=pt=uaattmmu
the Mixed '
React. temp. <e C) 60
Conducted butene
Reacted butene
Conversion rate
Polymer yield
Polymer・ component
Dimer frac.
Trimer frac.
Tetramer frac.
Heavy polymer
Gas&loss '
(teNT・P.)
(l,N.T.P.>
(%>
{ (g) (%)
[Zl
[;]
1 (%)
19.0
14.5
76.5
l510
41,4'
5.3
44.6
40.0
5.3
4.8
65maanelltmmuevumrmmu,・opnn 70 75
19,1
16.0
84.0
21.3
53.3
4.S
42.2
44.6
5..6
2.8
I'
'
19.0
16.4
86.5
26.2
64.0
5.4
40e1
47.8
4.6
2il
pmanmutm'nym=rmmtvamummutmuorm4murpmrmumtrm' Table 4. Polymerization of Normal Butene with the '. Acidof{ij67%%.Sp"hi.f,"prAC.,".,CiAd.id 620o;
Mixed
18e9 '15s6 '
82.5
25g4
65eO
ELe3
37,4
48.1
7,1
3,1
anma:DNrmuua
rmT'sunvE!llmutomonntthi=Jen-nrmMg";;.bhEIfi.!wnma]ICttsS-!SinMVIMMrmT]:ruarmErmatuti[X=tMumffppE"-ptM-tmVn . React,temp.("C) l55 60 65 70,..75 ttttttttttttttt tttttttttttttttttttttttttttttttttl tttttttttttttttttttttttt ttttttt tttttttttttttttt tttttttConductedbutene (l,N.T.P.) 18.5l 19,OReactedbutene (l,N.T.P,) 16.8i' l8.3Conversionrate C%) 91.0i96.5 L 28.6i 32.6 {f-;j 6s.ol・ 7i.2Polymer yield
iPolymer component I Dimerfrac. (%) 5.3I3.1 Trinaerfrac. (%) 29.7I33.2 Tetramerfrac. {%) 59・5I58.0 /g.egvg?g,ig-er lS] .g:,5, 2:g ' umVmawuNrm.rm-tuMLzanmtm
i
18.9
17e8
94.5
28.6
64.2
2.5
31.'4
59.2
4.9
2.0
19.0
l6.8
88.5
25.6
61.0
2.3
30.5ss,b
6.3
2.9
lF
18 9'15I3
SO.8
22.4
58.6
1.8
28.1
58.5
8.1
3.5
mu
}Iiroshi OH'iBui<A Takashi・ Moiu'rA I15
RusN
q.9.
ee
ge
g
o
e
1OO
sA-"=t....-lt / tak'Ss
6:4
60
50
40
30 !5:5
le
ndmutu-.de;th!4nvku. imt 55 60 65,70 75 80 85 React, temp. (oc)
Fig. 1 Conversion Rate
Note:(8:2) xneans the mixed acid of
87% Sulfurie acid 80% { 90% Orthophosphoric acid 20%
Geo,'
90
80
70Rw 60N.se
>, 50
8a 4oxpto'gi` 3o
20
10
,
t) -
si・2ptXX 7,3
of
ima..E.-.lts
..ppt 5:5
6・4
55 60
React.
r,ig. 2
65 70 75
temp. c"c)
Polymer Yield
se' 85
'
RVJ
o88gQ
1OO
90
80
70
60 '
5Q'
40・
30
20
10
'---"""N..
ON-i.ve.Qt-.. '
,,, . rox.7,3 cry.-"---"""O-----uOhhkhb
8:2
"S=m-rrn
6:4
55 60 65 70 75 80 85 React. temp. C"C)
Fig. 3 Dodeeene % in Polyrner
ge
L-V
y,.se
pt
osucof')
ovoA
leo
90
tie
70
60
50
40
30
20'
10
e
eor'"N
*.tptg;.:J tk.-- ¢:2af50ny4zaNo6.,
su 8:2
=ue4kutmatamsmbnfema'-angmtaE"de1un
;.
'
I55 60 65 70 75 80 React. temp, ("c)
Fig. 4 Dodecene Yield
85
l16
and
Polymerization o±,Normali Butene witla Mixed Aeid Catalysts(I ).
(2) Polymeyization of Normal Butene with the Mixed Acid of
Acid and 90% Orthophosphoric acid.
(With the Addition of Butene Tetramer.)
The results of this series of experiments are summarized in
illustratedinFigs.5to8. ' Table 5, Polymerization of Normal Butene with the Mixed A,id.f{g8o7;iuhl.f,u,rAc.,ft..ciiil.id goO%%
uaE9tnm!Vrm-E-UgeE ' wnumltrrmvamu ' nmsum." ,.utstt ''lma' ' "MZllnm・''
87%
Tables
'det'
Sulfuric
5to 8,
React. temp. (o C) ll
60 l 65
Conducted butene
Reacted butene
Conversion rate
Polymer yield
Polymer component
Dimer frac.
Trimer frac.
Tetramer frac.
Heavy polymer
Gas & loss
annvmpto m
{
(l,NT.?.>
(l,N.T.P"
(%)
Cg)
c%)
(%) -
c%)
(%)
(%)
(%)
ig,o I ' ' ,gJ,
I'5i7I 7,1 I30.0l 37,51.61 3.6 1・1,],,3 j 20.3 l- l- I
-I h- I・ ,
hl- - I
H l- hl "- i
'- i - "-mteavtme==tww
70
]8.9
8.7
46.0
7.4
34.0
16.3
83.7
75
l
18.9
10.0
52.8
11.0
44.0
18A74.5
+7,1
80
l8,O
9.1
50,O
9.6
42g3
1],5
67.7
14e6
3.0
3.2
Table 6. Polymerization of Normal Butene
Acid of j 87% Sulfuric Acid
i 90% Phosphoric Acidop-1
with
60%
40%
the Mixed
fiETR-
React. temp. CiC)6o 'il,-MrmIi'masmmeff1:ww-
70・m75 80 85
mh
6onducted butene
Reacted butene
Conversion rate
'Polymer yield
Polymer component
Dimer frac.
Trimer frac.
Tetramer frac.
Heavy polymer
Gas & loss
rm wwI
{
(l,N,T,P.) '<l, N.T.P .)
(%)
cg)
(%)
(%)
(%)
(%)
(%)
<%)
19'.O
IO.6
55,7
4・.9.
I8.5
'mu"E
l
iit:ii:
EI
I
19,O
l'1.3
59.5
6o8
24.I
19eO
8].O
19.0
12.4
65.2
]'2.5
40.4
16.0
76.0
6.4
1.6
"
i
I
19.0
13.6
71.7
i7.0
50.0
l5g3
70.0
13.5
1.2
18.2
]5.6
EO.5
24.2
62.0
6,2
55.4
28,l
10.3
Table 7. Polymerization
Acid of I l):%%
' uEtm=thwwww#mmznms .React. temp. ("c)
ttttttttttttttttttttttttttttttttttt
of Normal ButeneSulfuric Acid
Phosphoric Acid
with
70%
30%
the Mixed
l8.0
13.9
77,3 20,O
57.5 '
8,5
53.0
27.0
11,5
in・i -- tt
1'"'c' ollduct5d' butene
Reacted butene
l:
(l,NT.P.)
U.N.T,P.)
EIII
60
ig,6
14.1[i
65
19,O,
l6.0・
E
E
momuzwa=ILmu#ruH"=m-mumu"mu
7e 1 7s tttttttttt tt
19.l
17n2
[l
19.0
l6.2
HiroShi
Conversion rate (%)
Polymeryield ([;}]
Polymer component
Dimerfrac. (%) Trimerfrac. (%> Tetramerfrac. C%) Heavypolymer <%) Gas&loss <%)mu-Ytm'tu-- ttdiedidiw'u!-ws[u-or'wuAtiv
eHTsvic・,t Takashi
i 74.sl
l l.4:3
I 4o.6
I- ,I
i 8e4i.・ 67,O
19.6
2.1 . 2.9
-hEtt
MOIcl.・liA
84a2
21.1
52.8
7.6
65.4
24.0
L9
Ll ・muza ntt
90.0
24.1
56o2
5.8
62e8
26.6
2.5
2.3
85.5
22.3
55.0
5.4
59e7
29,6
3.6
1.7
ntINmuNX=-!;W
117
ua
Table 8, Polymerization
Acid of I g8o7%%
of Norfnal Butene
Sulfuric Acid
Phosphoric Acid
with the Mixed
80%
20%
React temp. (ec)
Conducted butene
Reacted butene
Conversion rate
Polymer yield
Polymer component
Dimer frac.
Trimer frac. '
Tetramer trac.
Heavy polyrner
Gas&loss /
`
{
(I,N.T.P.)
<l,N.T.P,)
(%)
(g)
(%)
(%)
(%)
(%)
(%)
(%)
55 60
m
18.5 19.0 16.8 18.2 91.0 96.0
24.8 29.6
59,O 65.0
9.3 4.4
44,4 4-5.0
43.6 44,.3
2,7 2,7mmwaH
{-"ua--m.mumn 3'6
65 E 70annminNrmca"mtuuaTthmue
75
'R-"'
vwo
"
q.9
9.o
g
o
{oo
90
80
g 70
N. 60
.・>H, 50
b !l, qo
acta
30
20
10
18.919.0
17.617.8
93.0'94,O
25.628.3
58.363.5
3.1 3,9
39.141.8
51,248.2
3.9 3.5
2,7 2.6
-taMorfima-Mlz4""veti.,
19.0
17.1
90.2
22.9 53.5
2.6 38.0 50.7
5.3
3.4 7
lt]o
so
so
7'e
60
50
40
30
20
10
55
Fig.
60 65 70 7S 80React. temp. eC)
5 Conversion Rate
85
'rfO-o-...f Xx・u '82 , 7,>X ":),
"er'/!
6:4
ss 6""o='"-"t"gl,r==zarm`I;7,xx;"'=eim, ,im,muM"uasiMs -
React. temp. ("c)
Fig. 6 Polyiner Yield
118
100
90
80
70"w-S
60
tsi 50
'vo
QO 40
30
20
10
Polymerization of Normal Butene with Mixed Acid Catalysts CI).
sa
sNN
tt
oeL--.-. 5:5 .O-X .----07',3
sh---・q 6r4
o--m'li
gv---n s:2
animtuwk-=ww"TtTdefissm=i
gii'
L..
ndv
-put
tw
89eOcL,
8
55 60 65 70 75''8'O '85 React. temp. (oc)
Fig. 7 .Dodecene % in Polymer
(3) Polymerization of Normal Butene Acid and Pyrophosphoric Acid. (Without the Addition of Butene In this series of experiments
the mixed acid in place of orthophosphoric
by heating orthophosphoric acid at ca. 2150C.
acid was continued until one drop of the acid
addition of ammonium molybdate solution.
The pyrophosphoric acid thus
acid.
The results of this series of experimentsillustrated in-Figs. 9 to 12.
Table 9. Acid of [
pnE・trww ' '' ' muV
1OO
sio
80
70
60
50
40
30
20
ld
.cr---
/,"P!l`(('gllll)7,k,,....--.I'lil,)Oss
lt ,
mts--mtiimop, m
6:4
55 60 65 70 React. temp.
Fig, 8 Dodecene
the Mixed Acid of
75 80(oC)
Yield
87%
-85
with Sulfuric Tetramer.)pyrophosphoric acid was used as a component of
acid. Pyrophosphoric acid was prepared
The heat treatment of orthophosphoric
gave no more yellow precipitate by
prepared contained only a trace of metaphosphoric
are summarized in Tables 9 to 12, and
Polymerization of Normal Butene
87% Sulfuric Acid
Pyrophosporic Acid
with the Mixed
50%
50%II
"-
React. temp. (oc) 6o 1 6s 70 mp 75=・
Conducted btitene
Reactecl butene
Conversion rate
Polymer yield
Polymer component
Dimer frac.
Trirner frac.
Tetramer frac:
Ueavy polymer Gas & losspm' '''uaungxonrc
l
(l,N.T.P.)
(le N・T.P ・)
(%) (g){ (%)
[zl
E.%)
(%)
19.0
18.4
97.0
32.0
69.5
2.5
22.5
71.3
l.9
1.8
19.0
18.3
96.5
33,5
73.3
2.7
29.5
64.0
1.8
2.0
18.8
18.0
95.7
33.2
73.7
2.7
34,1
58.5
2.4
2.3
19,O
18.0
95,O
33.1
73.5
2.4 36.6
56,1
2,4 2,5・pm
so
18.{
16,8
89,O
29.8
71.0
3,2
37.0
50.4
7.1
2.3
85
vaum
19.0,
15.S
83.3
26.0
65.8
3.8
37.3
4S.9
8.0
2.0
ww"ww
Table
Hiroshi OHTsui<A 'I`al<ashi Moiu'rA
10, Polymerization of Normal Butene with the
Acidof{:Z%,.,S,tg,fX,rtC,Stid,,, 2gZ
ifi[fi[aiiftmdi=Fitttu-sew=..-ww-
Mixed
l19
nvwwu.=idisurumReact. temp. (. C) 60
mxww-----+L==--.s==tan--thww"
'L-Conducted btitene
Reacted butene
Conversion rate
Polymer yield
Polymer component
Dimer frac.
Trimer frac.
Tetramerfrac. ・ Heavy polymer
Gas & loss
ptnvmaImmtrmmnnepm
L
{
(l,N.T.P.)
(l,N.T.P.)
<%)
cg) (.ofe)
(%)
<%) c%)
(%)
(%) -
19.0
18.2
96eO
33.0
72.5
2.1
23.9
70.7
1.5
1.8
65 70 l1
19,O
18.4
97.0
34.0
73.6
2.3
28e2
66.0
1.5
2.0
nm=
'
1
l
IIl
19.0 '
18.5
97.5
33.8
73.2
3.6
32.0 60.4
2e3
L7.ptmuarm"nrmmx'h
t-- .ur-tttH-.ti
75 .
19.0
17.5
92.3
31.2
71.4
3,8
33.4
58.4
2.6
L8
Table 11. Polymerizatien
Acid of
mpmim・ ・-・nmmut.
of Normal Butene with 87% Sulfuric Acid( Pyrophosphoric Acid
the Mixed70%30%
React. temp. (.C)rm"muenrmlt'-ttmutmx
60 ・i 65l
-'Conducted butene
Reacted butene
Copversion rate
Polymer yield
Polymer component Dlmer frac.
Trimer frac.
Tetramer frac.
Heavy polymer
Gas & loss
Table
l
ll
' {Z,NeT・P・)I 18・9
(l,1>l.T.P.)l 18.0 (%> 1 95.3{E.g= ?sig i
(%) I 2.s l (%) 23.7 (%> l 68.3 (%) 3.2 (%) 2.3 MITme .
19.0
18.0
95.0
32.6
72.5
1 l 3.4 2`le5
66,O
3.7
2.4 'rmmmmusu.1ual
mtsdipmmm#nvl-fan-
70 75...
1:
IE
12. Polymerization of Normal Acid of l .87,%,.,S,tg,`,",1".C,,".
Butenecid
Acid
with80%20%
18e9
17n`1
92.0
29.6
68.0
4.0
29.4
60.2
4el
2'M3.
the Mixed
18,9
16.9
89o3
26,4
62e5
2・ .3
26e1
63e7
53 ' 2.G
mam 21:tilllr,t.rm:gt II:m .pm(・'ZYc)-Jrmnm Iwttmsorm imm'ss
' ' ' 1 18.5(l,N.T.P.)
(t,N.T,P,) 18.1
(%) 97.6 (g) 26.0 (%) 57.7
(%) - <%) 13.1 (%) 67.3 (%) 14.4 (%) 5.2 . -StMwtrmIWmu'#.mu=tpmrm
,
L60
2mmrmasnwmmrmm
Conducted butene
Reacted butene
Conversion rate
Polymer yield
Polymer cgmponent
Dimer frac.
Trimer frac.
Tetramer frac.
Heavy polymer
Gas & loss
"nt-- ・ptme"pmua
(1
18.0
17.6
97.6
30.0
68.4
1.4
23.3
60.0
11.3
4.0
65 70 75
lg,o lsL9 18.9 19.0'18.0 17.1 16.5 15.1 90.5 87.5 79.794.6
26e2 21・O 17e728.0
61.2 50.8 47.062.3 I E
2.9 3,1 b'.3 3.419.6 20.2 22.4 18.171.1I 68.4 63.8. 65.0 . I, 4n3 5・3 6・7 9・O 2.].ll 3eO 3・8 `1,5 E rmdiTpmpmJ.TTMwnnvpmW.FwnMMnv
l20 Polymerization of Norma! Butene with・
.-"s
t・nv.t
v -o Lv4-
`o'
a h 'el
fu
Mixed
1eo
'90
80
70
60
50
40
30
20
IO
Acid
Rwo-cukpt
,9
e.o
go
Catalysts (I ).
.foo
90
so
70
6e
,v
50
40
30
20
IO
,/ ., os-m-O'tXscptif-'tta.-x:.i .6'...
x<i・u '61-
55
ilil
.JoGooowom
leo
90
80
70
6Q N50
40
30
2e
to
]Mts-mhva-mp-tsMt-T"aSmbrurpdnMptum" 50 55 G(, G5 7(i 75 80 85 React, temp.("c)
Fig. 9 Conversion Rate
Note : (8:1') means the mixed acid of
(87% Sulfuric acid 80% IPyrophosphoric acid 20%
s5
tt ' /nxtL:-1ffix'O"].6・hl S.f:fiNlxbs:s
x
---t,8:L,
'
----kLajntatu-rmth---imdm--bo-50 5P 6t,
React,
Fig. 10
6F 7fi 7S 80
temp. ("c)
?olymer Yield.
gs
Iou
uo
60
ge 70L".rV-. 60.9.
os
o SOqoUo 40voQ 30
20
l{J f-.
i
erti'k)'.//,rs
tX---O+---"SNSV8・`
,
React, temp. (ec)
Fig. 11 Dodecene % in Polymer
n
rm50 55 Gb React.
Fig. I2
6g 7f,J 7q Be 85
temp. (" c)
Dodecene Yield
.
Hiroshi OH'rsui<A Tal<ashi MoRiTA 121
(4) Polymerization of Normal Butene with Mixed Acid of 87% Sulfuric Acid
'andPyrophosphoricAcid. ' ' (With the Addition of Butene Tetramer.) , The results of this series of experiments are summarized in Tables 13to 16,
and illustrated in Figs.13to16. ' ' ' Table 13, Polymerization of Normal Butene with the Mixed. ..
, ・ - c87%SulfuricAcid 50% .. ..matmtmnm. A"id Of .1('Pyrophosphoric 5.cid.ua '50% .. .av
React. temp. (. C)
Conducted butene
Reacted butene
Conversion rate
Polymer yield
Polymer component
Dimer frac.
Trimer frac.
Tetramer frac.
Heavy polymer
Gas & loss
EF
[
tI
F
F:
i
jt
(l', N.T.P,)
(l,N.T.P.)
(%) ・ (g)
(%)
(%)
(%)
(%)
(%)
(%)
55'
18.5'
18.1
98.0
32,6
72.0
27.9
66.5
2.3
3.3
wh
60
l8.9
l8.8
99.6
36.9
78.5
3.0
37.4
57.5
2.1
65
18.9
l8.8
99.7
37.0
76.7
3.2
39.5
55.1
2.2
70
19.0
18.8
99.0
35.0
74.5
3.4
40.9
53.2
O.9
1.6
75
:
l
i
l
19.0
18.8
,99.0
34.2
72.7
4ol
40.0
52.6
1.2
2el
mu
Table l.4. Polymerization of Normal Butene with the
AcidofIX%,.,S,Lg,fXiLC,,2trg,, 28"%.
tunwh" 't't ''"t'x-tt' 't''''ta t't' '- "'T .tva-' tL
Mixed
React, temp. (. C) 55 ・60 65 '70--pt・ unnmmu
Conducted butene
Reacted butene
ConVersion rate
Polymer yield・
Polymer component
Dimer frac,
Trimer frac.
Tetramer frac.
Heavy polymer
Gas & loss
t'
{
(l,N.T.P,)
(i・ ¥ILTI ・P')・
(g) 1 (%)
lz・i
[%%]
18,5
17.9
97.0
32.7
73.0
1.2
24.8
6S.5
3.l
2,4 i
l9.0
18.8
99.0
tt5.4
75e5
5.7
33.4
58.5
2.4
19.0
18,8
99.0
34.0
72.5
5.3
42.7
48.6
1,2
2.2
19.0
18o8
99.0
33.2
70.6
5:4
37e4
54.0
L2 2eO
75
Vws.
Table ]5. 9olymerization of Normal Butene
Acicl of l ec%..,S,".ilgi`.C,,SCAI,,
・utmnvunm
with
70%
30%
the Mixed
19eO
18.7
98.7
30.9
66.0
4.2
34.7
57.4
1.6
2.1
.
React. temp, (oc) 55 60 65av
Conducted bu'tene
Reacted butene
g (l,N.T.P.)
(l, N.T, P .)
il
70 75
l
18.6
18.2
18o9
18.81
19.1
l9.0
l8.4
17.5 l
18.4
17.0
.
e
122 Polymerization of
Coriversion rate
'Polymer yield
Polymer component
Dimerfraa ' Trirner ・frac.
Tetramer frac.
Heavy Polymer Gas・ & loss
・ (%){ E.gl
(%)
(%)
(%)
(%)
(%)
Normal Butene
98,O
30.6
67.e
・l・.9・
.21.2
68.7
6,1
2.1
with Mixed
99.5 '
32,,O,
68.0
3.7 '36.9
55.7
・ 1.9 ・
, 1.8
・Acid
{- .
Catalysts
99.・5
30.9
65.0
7.1
48,6
40.5
2.6
1.2
'
Table 16. Polymenization of Normal'Butene
Acid of J 87% Sulfuric Acid
t Pyrophosphoric Acid
with the
80%
20%
(l ).
95,O 92.3 26'.2 22.6 tt 60,O 53.3 '
6.9 ・' '3.6 43o2. ,,32e3
44.7 57.1 3.8 4.4 1.4 2.6 anN ,Mixed
React. temp, (a C)
Conducted btitene
Reacted butene
Conversion rate
Polymer yield
Polymer component
Dimer frac.
Trimer frac.
Tetramer frac.
Heavy polymer
Gas & loss
(l, N.T,P .)
(l, N.T,? .)
(%)
cg){ (%)
[z),
(%)
(%)
(%)
55 ' 60
i・
18.5
18..3
99.0
25.7
56.2
3.1
14.4
74.7
5e5
2.3
i9rO
18,8
99.3
28.0
59.7
2.5
16.4
75.4
2.9
2.8
65
19.0
17,9
94.5
24.2
54.0
5,O
33.4
55.0
3.3
3,3
70
19,O
17,4
91.7
20.9・
' 48,O
4.3
30.6,
58.0
3.8
3.3
75
lou
ge
80
70
'r"' 60J・
N so:o'S 40"o
zo :30o zo
i6
5:5 // tt
18.9
1,5.7
83.0
16.7
42.5
4.8
24,5
59.B
6,6
4.8
ptiiiiiitwiEptEiipaiiiifiis
'
t,
6:4,
7・:3
8:・2
,
55 6o' 65 7e 75React. temp. (oc)
13 Conversion Rate
l60
90
80
70
.ts'-R"
" 60
℃r"-(
・Y 50h1-
e 4o
htr-AO, 30
20
]e
,・ ・,11/1..,Cgi ;'%9:rsg"-`g.s:s'
er"ptx.. tuN ',di"-w
Nl>, 1×・{ l. :'
-××6 '
,8'e2
"55 60 65 70 75-
React, temp. '(oC):
Fig. J4 Polymer Yield .,
,.. 1/t.. . // /
:
Fig.
t
'
Hiroshi OH'rsui<A Takashi
!oo
9Q
80
70 't" )R 60 v- t/, N o 50' 'N g 4d vu.
8 3o
20
Io
MORITA 123
,lOO'
,6
s9
70
vtsR 60
g so
8g ・4o
Q 3'o
20
IO
YYf#i9 ,:,
e
f.Xg・,i ,e
55 60 ・65 70 75 55 60 65 70 75 Reabt, temp, (OC) React. temp. ("C) Fig.'15'Dodecene%in Polymer Fig. 16 Dodecene Yield
Piseussionofthewaesuits,' '
tt(1) In the presence of the mixed acid consisting of 87% sulfuric acid and 90% ortho-
phosphoric acid, n-butene polymerized'readily into liquid polymer, which was chiefly
composed of trimers and tetramers of butene. In general, the trimer content of the
liquid polymer decreased with the increase of the reaction temperature and with
the increase of the amount of sulfuric acid in the mixed acid catalyst.
The polymer yield was 65 - 70% at maximum baSed on the n-butene absorbed.
The maximum yield of trimer was obtained with the mixed acid of 87% sult'uric
caid 60% - 90% orthophosphoric acid 40% and at the reaction temperature of 800C.
The yield was 30.5% with a tetramer ptoduction of 29.9%. The maximum, yield
of tetramer was 41,,3% with a trimer production of 23,6%, which was obtained
with the mixed acid of 87% sulfuric acid 80%-90% orthophosphoric acid 20%
and at the reaction temperature of 600C.
It was clearly observed that the addition of butene tetramer promoted the tri-
mer production by retarding the production of the tetramer and other higher
polymers. With the addition of butene tetramer, the maximum yield of trjmer was
elevated to 35% with a tetramer production of only 6.8% in the presence of the
mixed acid of 87% sulfuric acid 60%-90% orthoPhosphoric acid 40% and at the
reaction temperature of 750C. (See Tables 1to8 and Figs.1to8)
(2) When pyrophosphoric acid was used as a component of the mixed acid in
place of 90% orthophosphoric acid, the activity of the mixed acid became much
higher. Even the mixed acid of 87% sulfuric acid 50%-pyrophosphoric acid 50%
124 Polymerization of Normal Butene with Mixed Acid Catalysts(I),・
absorbed almost 100% of conducted n-butene at 60-850C and the absotbed butene
was converted into liquid polymer in the yjeld of over 70%. . The use of pyrophosphoric acid in place of orthophosphoric acid favored the
tetramer producti8n especially at low reaction temperatures. The maximum yield of
trimer, which was 26.8%, vias obtained with the mixed acid of 87% sulfuric acid
50%-pyrophosphoric acid 50% and at the reaction temperature of 750C, At the
same time, tetramer was produced in the yield of 41,2%. The maximum yield of
tetramer was 51.2% with the trimer production of 17.3%, which w.as obta'i ed with the
mixed acid of 87% sulfuric acid 60%-pyrophosphoric acid 40% and at the
reaction temperature of 60eC.
.With the addition of tetramer, the trimer yield was increased to over 30%
under optimum conditions. (See Tables 9to16, Figs. 9to16.)
(3) The mixed acid converted absorbed n-butene into liquid polymer in much
larger yield than did sulfuric acid. Accordingly, the catalyst life of the mixed acid
for n-butene polymerization was longer than that of sulfuric acid. But, even in
the case of the mixed acid, after treating 40 Iiters of n-butene, the catalytic
activity of the acid dropped to about one half of the value that was observed during
the treatment of the first 20 litres of'n-butene. Hence, elongation of the catalyst
life was a matter ot rr!oment in the rescarch. This prcblcm will be discussed in the