Characterization of Crystalline Poly(trioxane) and Poly(tetraoxane

Sep 24, 1979 - 1 Current address: Department of Chemistry, Ibaraki University, Mito, Japan. Plasma Polymerization. Chapter 16, pp 263–274. Chapter D...
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16 Characterization of Crystalline Poly(trioxane) and Poly(tetraoxane) Obtained through Plasma-Initiated Polymerization AKIRA ODAJIMA Department of Applied Physics, Hokkaido University, Sapporo, Japan

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YOSHIAKI NAKASE Japan Atomic Energy Research Institute, Takasaki, Japan 1

YOSHIHITO OSADA , ALEXIS T. BELL, and MITCHEL SHEN Department of Chemical Engineering, University of California, Berkeley, CA, 94720 C r y s t a l s of t r i o x a n e (TOX) and tetraoxane (TEOX) have been polymerized i n the s o l i d s t a t e by high energy i r r a d i a t i o n followed by post-polymerization, α-ray (1), γ-ray (2,3) as w e l l as x-ray (4) were u t i l i z e d i n i n i t i a t i n g the p o l y m e r i z a t i o n . Recently, i t has been demonstrated that c r y s t a l l i n e polyoxymethylene (POM) can a l s o be obtained through plasma i n i t i a t e d p o l y m e r i z a t i o n i n the s o l i d state (5). Preliminary c h a r a c t e r i z a t i o n studies i n d i c a t e that s t r u c t u r e s of p o l y t r i o x a n e (PTOX) and polytetraoxane (PTEOX) polymerized by both techniques are s i m i l a r . In t h i s work, f u r t h e r f i n e s t r u c t u r a l i n v e s t i g a t i o n s were c a r r i e d out using s m a l l angle x-ray s c a t t e r i n g (SAXS), wide angle x-ray s c a t t e r i n g (WAXS) and d i f f e r e n t i a l scanning c a l o r i m e t r y (DSC). Experimental S i n g l e c r y s t a l s of TOX and TEOX of the approximate dimensions of 1 mm x 10 mm were prepared by sublimation under reduced p r e s ­ sure. R a d i a t i o n - i n i t i a t e d polymerizations of these c r y s t a l s were c a r r i e d out by γ-ray p r e - i r r a d i a t i o n (1 MR) a t room temperature i n air. They were subsequently post-polymerized a t 55°C f o r TOX, and at 62, 81 and 105°C f o r TEOX (6). Plasma i n i t i a t e d polymerizations were conducted bv^ s e a l i n g the c r y s t a l s i n a g l a s s ampule a f t e r degassing a t 10 - 10 t o r r . A glow discharge was i n i t i a t e d i n the gaseous space i n the ampule by i n s e r t i n g the ampule between p a r a l l e l e l e c t r o d e s . E x c i t a t i o n was provided by an I n t e r n a t i o n a l Plasma Corporation Model 3001 Radiofrequency Generator. A power of 40 watts a t 13.56 MHz was used. Post-polymerizations were permitted to proceed a t 45°C FOR TOX AND 110°C FOR TEOX. D e t a i l s of the p o l y m e r i z a t i o n c o n d i t i o n s f o r both techniques were summa­ r i z e d i n Table 1. X-ray measurements were c a r r i e d out on a Rigaku Denki RU-100PL Rotating Anode X-ray U n i t . N i c k e l - f i l t e r e d copper u

1

Current address: Department of Chemistry, Mito, Japan.

Ibaraki University,

0-8412-0510-8/79/47-108-263$05.00/0 © 1979 American Chemical Society

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Table I. S o l i d State Polymerizations of Trioxane and Tetraoxane by γ-Ray or Plasma I n i t i a t i o n

Sample

Post-Polymerization Temperature (°C)

Post-Polymerization Duration (hrs)

Yield M.P. (wt %) (°C)

RADIATION INITIATION PTOX-80 55 PTE0X-12 62 PTE0X-25 81 PTEOX-40 105 PTEOX-80 105

20 25 25 6 6

80 12 25 40 80

187 173 181 179 174

PLASMA INITIATION PTOX-20-1P PTOX-20-2P PTOX-40P PTE0X-4P PTE0X-5P PTE0X-83P

18 46 66 24 24 3

20 20 40 4 5 83

189 185 186 183

45 45 45 110 110 110

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15.

OSADA E T A L .

Liquid

Vinyl

Monomers

265

r a d i a t i o n was generated a t 40 kV and 80 mA. WAXS p r o f i l e s of the (009) and (0018) r e f l e c t i o n s were measured by a step scanning method with a f i x e d time of 80 or 400 sec i n a symmetrical t r a n s m i s s i o n arrangement. For the l i n e broadening a n a l y s i s of PTOX, instrument broadening was c o r r e c t e d by using a TOX s i n g l e c r y s t a l of comparable dimensions as a r e f e r e n c e sample. The x-ray r o t a t i o n diagram of PTOX was obtained p h o t o g r a p h i c a l l y with the f i b e r a x i s as the r o t a t i o n a x i s . To o b t a i n the volume f r a c t i o n of subc r y s t a l s i n the polymer, i n t e g r a l i n t e n s i t i e s were measured by a microdensitometer f o r two (100) r e f l e c t i o n s , i . e . , one produced only by twin o r i e n t a t i o n and the other on the equator with c o n t r i butions from both o r i e n t a t i o n s . Thermal analyses of the polymer samples were conducted on a Perkin-Elmer DSC-1B D i f f e r e n t i a l Scanning Calorimeter. Approximately 1 mg of sample was used i n each determination. The heating r a t e employed was 16°C/min. The instrument was c a l i b r a t e d using indium as a standard. Scanning e l e c t r o n micrographs were taken on an ISI Mini-SEM. Samples f o r observation were coated with an evaporated 60% gold and 40% platinum a l l o y to a thickness of approximately 200A. Results and D i s c u s s i o n The scanning e l e c t r o n micrograph of plasma samples of PTOX i s shown i n F i g u r e 1. The c r y s t a l s a r e seen to c o n s i s t of r o d l i k e f i b r i l s w e l l a l i g n e d with respect to each other. The appearance of these c r y s t a l s i s s i m i l a r to that of the monomer as w e l l as r a d i a t i o n samples of PTOX (7). The PTEOX c r y s t a l (Figure 2 ) , on the other hand, c o n s i s t s of coarse f i b e r s with rather i r r e g u l a r s i z e s and shapes and no p r e f e r e n t i a l o r i e n t a t i o n . There i s a l s o considerable branching i n PTEOX, whereas i n PTOX no branching i s evident* Recent s t u d i e s i n the f i n e s t r u c t u r e s of r a d i a t i o n polymerized PTOX show that they are d i s o r d e r e d c r y s t a l s i n which m a i n - c r y s t a l l i t e s and s u b - c r y s t a l l i t e s a r e arranged i n s e r i e s (7). The f i n e s t r u c t u r e s of PTEOX are even more d i s o r d e r e d and complex than those of PTOX, and are b e l i e v e d to possess an o r i e n t e d l a m e l l a r morphology. However, when the p o s t - p o l y m e r i z a t i o n i s c a r r i e d out at temperatures above 90°C, the s u b - c r y s t a l l i t e s disappear. WAXS studies i n d i c a t e that the (009) and (0018) r e f l e c t i o n s of PTEOX have an asymmetrical p r o f i l e , suggesting the existence of two d i f f e r e n t l a t t i c e spacings along the f i b e r a x i s . Odajima, e t a l . (8) suggested that there may be two kinds of c r y s t a l l i t e s present, namely those with the extended f i b r i l l a r and the f o l d e d l a m e l l a r morphologies. SAXS p a t t e r n of r a d i a t i o n - p o l y m e r i z e d PTOX i n F i g u r e 3A shows only a sharp e q u a t o r i a l s c a t t e r i n g , but no m e r i d i o n a l s c a t t e r i n g . Those f o r PTOX obtained by plasma i n i t i a t e d p o l y m e r i z a t i o n (samples PT0X-20-1P and PTOX-40P shown i n F i g u r e s 3B and 3C) a r e similar. In the case of PTEOX, those polymerized through r a d i a t i o n i n i t i a t i o n but post-polymerized below 80°C (sample PTE0X-12)

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PLASMA

Figure

Figure

1.

2.

Scanning electron micrograph of polytrioxane (Sample obtained by phsma-initiated polymerization

Scanning electron micrograph of polytetraoxane (Sample obtained by phsma-initiated polymerization

POLYMERIZATION

PTOX-40P)

PTEOX-4P)

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16.

ODAJIMA ET AL.

Poly(trioxane)

and

Poly(tetraoxane)

267

a l s o show no m e r i d i o n a l s c a t t e r i n g i n t h e i r SAXS patterns. How­ ever, f o r those polymerized above 80°C (sample PTEOX-40) both e q u a t o r i a l and m e r i d i o n a l s c a t t e r i n g a r e present (Figure 4A). (This photograph was taken by using a point f o c u s s i n g camera with a mirror-and-monochrometer o p t i c a l system, hence the sharper e q u a t o r i a l s c a t t e r i n g . ) The s p o t - l i k e s c a t t e r i n g s beyond the m e r i d i o n a l s c a t t e r i n g s a r e i n d i c a t i v e of a long spacing of about 100 X a s s o c i a t e d w i t h stackings of the f o l d e d chain l a m e l l a o r i e n t e d p a r a l l e l to the f i b e r a x i s (9). The e q u a t o r i a l s c a t t e r ­ ing i s a t t r i b u t e d to the existence of n e e d l e - l i k e v o i d s between PTEOX f i b e r s oriented i n the d i r e c t i o n of the f i b e r a x i s . The SAXS p a t t e r n f o r PTEOX-5P i s s i m i l a r (Figure 4B), although the s p o t - l i k e s c a t t e r i n g i s very f a i n t . We note that the PTEOX-5P p a t t e r n i s more s i m i l a r to the annealed sample of r a d i a t i o n poly­ merized PTEOX (10). I t i s not c l e a r why the SAXS data f o r PTE0X-83P e x h i b i t only weak m e r i d i o n a l s c a t t e r i n g , even though the post-polymerization was c a r r i e d out a t the same temperature (110°C). Figures 5A and 5B show the WAXS patterns f o r PTOX obtained through r a d i a t i o n i n i t i a t i o n (sample PTOX-80) and plasma i n i t i a ­ t i o n (sample PTOX-40P). Both show the h i g h l y o r i e n t e d f i b e r diagrams. The (100) r e f l e c t i o n s c l e a r l y i n d i c a t e the twin spots i n a d d i t i o n to spots on the equator. The amorphous halo i s very weak i n both samples. For PTEOX, F i g u r e 6A shows that the r a d i a ­ t i o n polymerized sample (PTEOX-80) a l s o possesses h i g h l y o r i e n t e d f i b e r diagrams. I t appears to have no twin spots, but samples PTE0X-12 and 25 do. In the case of plasma samples, the (100) twin spots a r e present i n PTE0X-5P, though very f a i n t (Figure 6B). Sample PTE0X-83P, on the other hand, shows a r i n g - l i k e WAXS p a t t e r n (Figure 6C). The reason f o r the absence of d i s c r e t e s c a t t e r i n g may p o s s i b l y be a t t r i b u t e d to the i s o t r o p i c s t r u c t u r e of l a m e l l a s t a c k i n g . The amorphous halos i n a l l of the PTEOX samples may be due to the amorphous regions between the lamellae of f o l d e d chain c r y s t a l s . S u b - c r y s t a l f r a c t i o n s i n PTOX from both r a d i a t i o n and plasma i n i t i a t e d polymerizations were determined from the (100) r e f l e c ­ t i o n s and summarized i n T a b l e 2. T h e i r values a r e somewhat, but not s u b s t a n t i a l l y , lower f o r the plasma samples than f o r the r a d i a t i o n samples. However, s i n c e the amount of s u b c r y s t a l f r a c t i o n depends on both the temperature and the y i e l d , meaningful comparisons between these two types of samples a r e d i f f i c u l t on the b a s i s of these r a t h e r l i m i t e d data. In t h e i r recent p u b l i c a t i o n , Odajima and h i s coworkers (11) have shown that the r a t h e r broad and asymmetric (009) and (0018) WAXS p r o f i l e s of PTEOX polymerized above 80°C by r a d i a t i o n i n i t i a ­ t i o n may be r e s o l v e d i n t o two curves. One can be a t t r i b u t e d to the extended chain c r y s t a l s (the only kind present i n sample PTE0X-12), and the other i s the l a m e l l a r type c r y s t a l s with t h i c k ­ nesses of about 100 X. F i g u r e 7 shows that the l i n e shape of the (009) p r o f i l e of the plasma sample PTEOX-5P i s r a t h e r sharp and s i m i l a r to that of the r a d i a t i o n sample PTEOX-25. The h a l f width (Δ2θ)ι = 1.72° or 0.012 S" ) o f the (0018) p r o f i l e i s narrower than those*of PTEOX-25 (2.50° or 0.017 A ) and PTEOX-80 (2.25° o r 1

1

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268

PLASMA POLYMERIZATION

Figure 3. Small-angle x-ray scattering patterns of polytrioxane. (A) Sample PTOX-80 by radiation initiation; (B) Sample PTOX-20-1P by plasma initiation; and (C) Sample PTOX-40P by plasma initiation.

Figure 4. PTEOX-40

Small-angle x-ray scattering patterns of polytetraoxane. (A) Sample by radiation initiation; (B) Sample PTEOX-5P by plasma initiation; and (C) Sample PTEOX-83P by phsma initiation.

Shen and Bell; Plasma Polymerization ACS Symposium Series; American Chemical Society: Washington, DC, 1979.

Shen and Bell; Plasma Polymerization ACS Symposium Series; American Chemical Society: Washington, DC, 1979.

Figure

5.

Wide

angle x-ray scattering patterns of polytrioxane. (A) Sample PTOX-80 tion initiation; and (B) Sample PTOX-40P by plasma initiation.

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by

radia­

to

Ci

ο

ο

ο

Ο

>

Η

> w

ο ο >

PLASMA

POLYMERIZATION

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270

Figure 6. Wide-angle x-ray scattering patterns of polytetraoxane. (A) Sample PTEOX-80 by radiation initiation; (B) Sample PTEOX-5P by plasma initiation; and (C) Sample PTEOX-83P by plasma initiation.

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16.

ODAjiMA E T A L .

Table I I .

and

271

Poly(tetraoxane)

S u b c r y s t a l F r a c t i o n s i n Polytetoxane

Yield (wt %)

Sample

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Poly(trioxane)

Sub-crystal Fraction (Vol %)

Post P o l y m e r i z a t i o n Temperature (°C)

RADIATION INITIATION PTOX-80 PTOX-2 PT0X-19 PTOX-50

80 2 19 50

55 50 50 50

36 - 39 ^45 ^40 V30

PLASMA INITIATION PTOX-20-1P PTOX-40P

20 40

45 45

^40 27 - 31

44

Figure

7.

45

46

47 48 2 θ (degrees)

49

50

X-ray diffraction profiles of the (009) and (0018) reflections obtained by plasma initiation (s = 2sin ®/A)

of

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PTEOX

272

PLASMA POLYMERIZATION

J

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o . o i s r ). On the b a s i s of these f i n d i n g s , one might conclude that PTE0X-5P contains l e s s f o l d e d chain c r y s t a l s and i t s cspacings i n the extended chain c r y s t a l s are longer than those i n the r a d i a t i o n samples. T h i s c o n c l u s i o n , however, must be q u a l i ­ f i e d by the p o s s i b i l i t y that the higher p o s t - p o l y m e r i z a t i o n tem­ perature used i n the plasma i n i t i a t i o n method may have annealed out some of the l o n g i t u d i n a l compression during the post-polymer­ i z a t i o n period. On the b a s i s of the p a r a c r y s t a l l i n e theory, the Cauchy-plot method can be employed i n line-broadening a n a l y s i s (12). In t h i s method, the i n t e g r a l breadth of the f i r s t order r e f l e c t i o n i s approximated by ASx

= 1/5

w

+

cOrgSj

2

where Dw i s the weight average c r y s t a l l i t e s i z e along the c - a x i s , c i s the averaged c-spacing, g i s the p a r a c r y s t a l l i n e d i s t o r t i o n parameter and S = 2 s i n θ/λ. From the slope and i n t e r s e c t i o n of a Si v s . S i p l o t , values of g and Dw can be r e a d i l y obtained. For the plasma sample PTOX-40P, D = 650 X and G = 1.25%. By c o n t r a s t , the comparable r a d i a t i o n samples have values of 550 S and 0.7%, r e s p e c t i v e l y . The l o n g i t u d i n a l dimensions f o r both samples are c o n s i d e r a b l y s h o r t e r than the extended length of the m i c r o f i b r i l , which i s of the order of 10* X. The most l i k e l y i n t e r p r e t a t i o n f o r t h i s observation i s that the type of d e f e c t s suggested by the k i n k model (7) must e x i s t i n the c h a i n d i r e c t i o n . DSC thermograms f o r plasma samples of PTOX and PTEOX are shown i n Figure 8. The endothermic p r o f i l e s of PTOX e x h i b i t no superheating phenomenon, resembling those of the r a d i a t i o n samples post-polymerized below 50°C a t high y i e l d or above 50°C a t low yield. I t has been observed that a double endothermic peak appears i n the heating curve of r a d i a t i o n polymerized PTOX a t 55°C with a y i e l d of over 20% (13). Superheating i n these polymers was a t t r i b u t e d to a new type of POM texture produced a t the l a t e r stage of s o l i d s t a t e p o l y m e r i z a t i o n . A l s o shown i n Figure 8 are the thermograms f o r PTE0X-4P and PTE0X-83P. They are very s i m i l a r d e s p i t e the d i f f e r e n c e s i n y i e l d and morphologies. Neither sample shows superheating e f f e c t , a l ­ though both have r e l a t i v e l y long t a i l s e c t i o n s i n the low tempera­ ture range. For the sake of comparison, we show i n F i g u r e 9 the endothermic p r o f i l e s of r a d i a t i o n polymerized PTEOX. The p r o f i l e of PTE0X-12 i s extremely sharp, with a r e l a t i v e l y low peak tempera­ ture (170°C). Samples PTEOX-25 and PTEOX-80, on the other hand, have much broader heating curves, i n d i c a t i n g the presence of s u p e r p o s i t i o n of two endothermic curves r e s o l v e d by the dotted lines. I t i s b e l i e v e d that these p r o f i l e s c o n s i s t of two c r y s t a l ­ l i n e forms, namely the lower m e l t i n g f o l d e d chain c r y s t a l l i t e s and the higher melting extended chain c r y s t a l l i t e s (6, _9, 14). It i s of i n t e r e s t to note that only one melting peak i s present i n the plasma samples, even though they were post-polymerized a t e l e v a t e d temperatures. In c o n c l u s i o n , we can s t a t e that PTOX obtained through e i t h e r x

2

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16.

ODAjiMA E T A L .

Poly(trioxane)

and

273

Poly(tetraoxane)

I73°C J 120

I

I

I

140

160

180

I— 200

TEMPERATURE ( ° C ) Figure 8. Differential scanning calorimetry polytetraoxane obtained by phsma-initiated

-I 140

I 160

thermograms polymerization

of polytrioxane in the solid

1

1

1—

180

200

220

and state

TEMPERATURE ( C) e

Figure 9. Differential scanning calorimetry thermograms of polytetraoxanes ob­ tained by γ-ray-initiated polymerizations in the solid state. Dotted curves indi­ cate the decomposed endothermic profiles caused by the extended chain crystals and folded chain crystals.

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P L A S M A POLYMERIZATION

274

plasma or γ-ray i n i t i a t e d polymerizations have r a t h e r s i m i l a r f i n e s t r u c t u r e s . However, there are some d i f f e r e n c e s i n the r a d i a t i o n samples and plasma samples of PTEOX. These d i f f e r e n c e s can not yet be d e f i n i t i v e l y e s t a b l i s h e d , s i n c e the f i n e s t r u c t u r e s are known to depend i n t i m a t e l y on the polymerization c o n d i t i o n s (tem­ perature, y i e l d , e t c . ) which are not e x a c t l y the same i n the two polymerization techniques.

Downloaded by UNIV OF ARIZONA on June 7, 2017 | http://pubs.acs.org Publication Date: September 24, 1979 | doi: 10.1021/bk-1979-0108.ch016

Abstract Crystals of trioxane and tetraoxane can be polymerized in the solid state by plasma initiation followed by post-polymerization. Scanning electron micrographs indicate that PTOX consists of well aligned fibrils, while PTEOX have irregular coarse fibers with considerable branching. Small and wide angle x-ray scattering patterns indicate that PTOX crystals obtained through plasma initiation resemble those by γ-ray initiation. However, plasma samples of PTEOX appear to consist of one rather than two crys­ talline forms, as shown by both x-ray and differential scanning calorimetric data. Literature Cited 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14.

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Received March 29, 1979.

Shen and Bell; Plasma Polymerization ACS Symposium Series; American Chemical Society: Washington, DC, 1979.