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