(298) Gypsum & Lime No. 204 (1986)

*(,*)

Adsorption and Polymerization of Vinyl Monomers with Natural Zeolites

Fumio ISO and Zenjiro OSAWA*

(Kennan Industrial Research Institute of Tochigi Prefecture,* Faculty of Engineering, Gunma University)

The adsorption characteristics of some vinyl monomers on several natural zeolites including

clinoptilolite and mordenite type, and also catalytic activities of these zeolites in the polymeriza-

tion of a-methylstyrene were examined in connection with preheating of the clays in the range

of 100`900.

The results obtained were as follows :

1) The adsorption capacity of some vinyl monomers such as metylmethacrylate, vinyl acetate and

acrylonitrile to the clinoptilolite and mordenite was remarkably affected by preheating tem-

perature, and the maximum adsorption of these monomers was observed in the zeolites pre-

heated around 600.

2) Clinoptilolite heat-treated at 600 reveals the maximum expansion in (020) spacing due to

adsorption of methyl methacrylate.

3) The natural zeolites were found to polymerize -methystyrene effectively, and the higher the

42

Gypsum & Lime No. 204 (1986) (299>

preheating temperature of the clays, the higher the conversion was observed.

4) The weight average molecular wight (Mw) and the number average molecular weight (Mn)

of thus obtaied poly-a-methylstyrene were around 1500`3100 and around 800`1900, respec-

tively. The Q-values (Mw/Mn : around 1.6` 2. 1) indicated that the molecular weight distribu-

tion of the polymers was narrow.

(Received May 22, 1986)

Key words : Natural zeolite, Vinyl monomers, Adsorption, -Methylstyrene, Polymerization

1

,

(SiO2)Al

,,(Ai,Si)04

3

,,

, ,

1),2), , 2

1)

3),

,

100900

, ,

,,

,(Mw)240011000, ,Q(Mw/Mn)

2 ,Mn

,

3)7), ,

,

, ,

2

21

: 4( 2

, 2), 1,

16 (

),100 mesh

,4 ,

,

, 1 , 2 , : -,2

,4-, ,

Table 1 Occurrence place and producing factory of the raw materials and their components.

Table 2 Chemical analysis of natural zeolites (%) .

43

(300) Gypsum & Lime No. 204 (1986)

, ( 1,

())n- , , ,

, ( 1, ()),

22

(), ( TG-

DTA) , (TG)

(DTA)

23

KBr , (),IR215

24

-2.5g 50ml

, ,30

(),pH M-7

25

50ml (

, , )20m1

,

( Clino.(1) (2) ),

( Morde.(1)(2)

)59 ,

24 , ,n-

, ,

, ,

Clino.(1)Morde.

(1)1g

,45 , ,

(), 063

26

Clino.(1)

Ciino.(1) (), 2012 ,020

, Cu,Ni ,

40kV, 25mA, 1/4/min, 2cm/min

27

271

, - (5ml)18

mm , 0.5g

, ,20 30 ,

40m1 2

, (300ml) ,

(1G-4)

, (30m1) ,

(1G-4) ,

(300ml) ,

, ,

,- 5m1

5ml , ,-10

,600 Morde.(1)

0.59 ,

272

2- 4-

,100900 0.5

g ,2030 ,

271

28

(THF) ,

(), TSK-HPLC-801

TSK-HPLC-PC8 ,

5mg/ml .300

1, :G4000H6+2000H8, : ,

:1.2m1/min,:45kg/cm2, :RI, :10mm/min

3

31

TG-DTA ciino.(1)

Mordo.(1)1,2 Clino.(1)

(1)146,Clino.(2)148 ,

,100400

,

600

,Clino.(1)495807,Clino.(2) 489 771

Fig. 1 TG-DTA curves of clinoptilolite (1) .

Sample weight : 197 mg

Heating rate : 10/min

44

Gypsum & Lime No. 204 (1986) (301)

Morde.(1)(2)134,Morde.(2)140

,100400

Morde.(1)

, 549 689

, 600

Morde.(2)DTA ,

8)

,Morde.(1)460 962

, ,Morde. (2)557887

DTA ,262

,732 851

,

, 600

,477

804

DTA ,147

,677,891 ,

, 800

,clino.(2) ,

8)

32 IR

OH,Si-O,Al-O ,

9)11)

Clino.(1)Morde.(1)IR

3 37003600cm-1 17001600

cm-i ,

9), OH

, 10)

, OH IR ,

11) 12)

, ,1150

900cm-i Si-O,Al-O,,1000cm-1

Si-0,Al-OH,Si-O-Al

33 pH

pH 4

, ,

, ,

(300 )

,

,pH ,

34

Clino.(1)Morde.(1) 3

( ,

)

5,6

Fig. 2 TG-DTA curves of mordenite (1) .

Sample weight : 151 mg

Heating rate : 10/min

Fig. 3 IR spectra of clinoptilolite (1) and mordenite (1) .

45

(302) Gypsum & Lime No. 204 (1986)

5 6,

,

, 600 ,Clino.(1)6%,Morde.(1)34%

,Clino.(1),

, 0.5%

e***

1.20 ,

,

5),13)

, ,

,X ,

14) , ,X

Clino.(1)

Clino.(1)020

3

Clino.(1),

Clino.(1) ,

,020

, 600

,900 ,

,020

, ,

3),5),13)

35

- ,20 30

7

Fig. 4 Effect of preheating temperature on the pH of clays.

Fig. 5 Effect of preheating temperature on adsorption capacity of clinoptilolite (1).

Fig. 6 Effect of preheating temserature on adsorption capacity of mordenite (1).

46

Gypsum & Lime No. 204 (1986) (303>

( H0:-3.0-

5.63)) , Morde.(2)(H0:

-3.0-5.63)) , (H0:-

5.6-8.28))Morde.(1) ,

,

,

900

3),

600 ,

X 5),13), 5),13)

,

- ,

900 ,

3)

, - (

e:-1.27***)

,600 Morde.(1)

,,-10 ,63

% -

,300

-,

(30%) ,

,(5%) ,

,

, T-,

,715),1

( )

-, -

, , (2,4-

),100900

,

e***

3),

, ,

() ,-,

, ,

*** e:- -1.27

-0.80 -1.77

2- -0.504- -0.20 +0.40

-0.22 +1.20

Table 3 Effect of preheating temperature on 020-spacing expansion in clinoptilolite (1) (A).

Fig. 7 Effect of preheating temperature of clays on the conversion of a-methyl-

styrene.

47

(304) Gypsum & Lime No. 204 (1986)

, , ( ,

,)e***

36

--

HPLC --HPLC 8 9 ,

,

,4 , (Mw)

15003100,(Mn)8001900,-

, ,Q1.6

2.1

, ,

, , 16)

Fig. 8 Chromatogram of poly--methylstyrenes

by high performance liquid chromato-

graphy.

Fig. 9 Chromatogram of poly--methylstyrenes

by high perfomance liqid chromato-

graphy.

Table 4 Molecular weight of poly-a-methylstyrenea).

48

Gypsum & Lime No. 204 (1986) (305)

, , -

3),

, ,

4

, -

,

(1) Clino.(1)Morde.(1)

( , , ) ,

600

(2) Clino.(1)

Clino.(1)020 ,

600

(3) ,-

,,

, -

(4) -

, ,

(5) --,Mw:

15003100,Mn:8001900,Q1.62.1

,X,

1) , ,"

", (1974)p.300.

2) , ,17,No.5,3 (1983).

3) , , ,1984,631

4) , , 46

,p.74(1972).

5) , , 47

,p.46(1973).

6) , , , ,11,8

(1976).

7) , , ,2

,85 (1984).

8) , , , ,

,1971,2012.

9) , , ,2,61 (1962).

10) , , ,3,211 (1963).

11) , ,

,134 (1967).

12) , , ,33,No.5,

137 (1984).

13) , , , ,

No.118,13 (1972).

14) , ,6,50 (1967)

15) , ,

(1970)p.230.

16) ," ",

(1975)p.4.

(1986.5.22)

4

1 027(),1028()

( 2-6-1Te1.0258-32-4500

102712:30

2000,3000(

)9

1 (

)

2 (

)

: 1027()18:0020:00

:

: 3000

949-54 1603-1

(Tel.0258-46-6000 5123,5301)

49