New Industrial Polymers

3 A New Thermoplastic Syndiotactic 1,2-Poylbutadiene. II. Applications

Downloaded by CORNELL UNIV on October 13, 2016 | http://pubs.acs.org Publication Date: June 1, 1974 | doi: 10.1021/bk-1974-0004.ch003

YASUMASA TAKEUCHI, AKIRA SEKIMOTO and MITSUO ABE* Butadiene Resin Development Dept., Japan Synthetic Rubber Co., Ltd., No. 1, 1-chome, Kyobashi, Chuo-ku, Tokyo, Japan

INTRODUCTION A new thermoplastic s y n d i o t a c t i c 1, 2-polybutadiene (1, 2PBD) have been developed by Japan S y n t h e t i c Rubber Co., L t d . (JSR). The 1, 2-PBD is a low c r y s t a l l i n e polymer (15-25% c r y s t a l linity) and a unique thermoplastic having property between p l a s t i c and rubber. On the other hand, the 1, 2-PBD is regarded as a novel f u n c t i o n a l polymer, namely, as a r e a c t i v e t h e r m o p l a s t i c . The c h a r a c t e r i s t i c p o i n t s o f 1, 2-PBD are summarized as f o l l o w s ; (1) S a f e t y f o r food (2) high r e a c t i v i t y (3) good transparent (4) pliability and flexibility (5) photodegradability. Its p o s s i b l e a p p l i c a t i o n s are very wide from above described characteristics. I t may fairly be s a i d that its a p p l i c a t i o n s cover all the polymer's field l i k e Figure I which are shown s c h e m a t i c a l l y some o f it's p o s s i b l e a p p l i c a t i o n s . Thermoplastics * Thermosetting

Resin

N

JSR 1, 2-PBD

CoatingRubber Figure 1.

Application fields of JSR 1,2-polybutadiene

The 1, 2-PBD can be a p p l i e d t o f i l m s and tubes in thermoplastics field. In rubber f i e l d , c r o s s - l i n k i n g foam l i k e EVA is a p o s i b i l i t y . I n c o a t i n g s , photo-curing p a i n t i s a p o s s i b i l i t y .

* Research Laboratory o f JSR No. 100, Kawajiri-cho, Y o k k a i c h i - s h i , Mie-ken

26

Deanin; New Industrial Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1974.

3.

TAKEUCHI

ET AL.

1,2-Polybutadiene

Applications

27

In the adhesion f i e l d , hot-melt type adhesive i s a p o s s i b i l i t y . In the f i b e r f i e l d , graphite f i b e r i s a p o s s i b i l i t y . In other f i e l d s , p h o t o - s e n s i t i v e polymer i s a p o s s i b i l i t y . We w i l l describe the f o l l o w i n g some o f p o s s i b l e a p p l i c a t i o n s o f the 1, 2-PBD that a r e u s e f u l from an i n d u s t r i a l view p o i n t . APPLICATION EXAMPLES IN THERMOPLASTIC FIELD


We developed the s t r e t c h f i l m o f the 1, 2-PBD as a represent a t i v e example i n thermoplastics f i e l d (photograph I , I I ) . The general p h y s i c a l p r o p e r t i e s o f 1, 2-PBD f i l m are shown i n Table 1 compared with f i l m p r o p e r t i e s o f other s o f t p l a s t i c s commercially a v a i l a b l e . The datas show that 1, 2-PBD f i l m i s comparable to LDPE, EVA and p l a s t i s i z e d PVC i n some p h y s i c a l strength. The c h a r a c t e r i s t i c p o i n t s o f 1, 2-PBD f i l m may be summarized as f o l l o w s : 1) 2) 3) k) 5) 6) 7)

Good transparency High gas p e r m e a b i l i t y Good elongation and s t r e t c h High tear r e s i s t a h c e (Elemendorf) High c o e f f i c i e n t o f f r i c t i o n P l i a b i l i t y and f l e x i b i l i t y Lower h e a t - s e a l i n g temperature and high welding efficiency

The gas p e r m e a b i l i t y o f 1, 2-PBD depends on the f i l m t h i c k ness, as shown i n F i g . 2 . When the f i l m thickness i s increased to s e v e r a l few m i l l i m e t e r s , the gas permeability o f 1, 2-PBD i s reduced and approaches that o f LDPE. In t h i s f i l m the gas permea b i l i t y o f 1, 2-PBD i s high, which i s assumed t o be a t t r i b u t a b l e to the good s o l u b i l i t y o f CO2, O2 and ethylene oxide gas i n the 1, 2-PBD f i l m surface, i n view o f the small gas d i f f u s i o n c o e f f i c i e n t o f 1, 2-PBD measured by J.D. F e r r y e t a l ( 2 ) . From these fundamental p h y s i c a l p r o p e r t i e s and nontoxic i n respect t o food hydiene described previous paper ^ , the 1, 2-PBD w i l l be s u i t a b l e f o r food packaging m a t e r i a l s . Because o f i t s good gas p e r m e a b i l i t y i n t h i s f i l m , 1, 2-PBD i s used, as the most s u p e r i o r a p p l i c a t i o n example, f o r s t r e t c h e d f i l m as a wrapping f o r f r e s h vegetables, f r u i t s and o t h e r s .

APPLICATION TO EVA SPONGE FIELD We have developed many kinds o f c e l l u l a r sponge i n s t e a d o f EVA sponge u t i l i z i n g i t s r u b b e r - l i k e p r o p e r t i e s and r e a c t i v i t y with chemical reagents. The 1, 2-PBD sponge i s superior to EVA i n the f o l l o w i n g p o i n t s .


NEW

INDUSTRIAL

POLYMERS


Photo I. Stretch film and pellets of syndiotactic 1 ^-polybutadiene

Photo II. Some packaged fresh foods with syndiotactic 1^-polybutadiene stretch film

Photo III. Various kinds of cellular sponge shoe soles made of syndiotactic 1 ^-polybutadiene



blow blow blow

2 sec)

C

2

ratio » 2.5 ratio = 2 . 5 , V A c . cont. , 12% ratio = 2 . 5 , plastitizer 50%

2

Optimum heat-sealing temperature (2 k g / c m ,

Water vapor permeability

°2 Ethylene oxide g- 0. 1mm/ m -24 hrs.

C C - 0. 1mm/ m - 24 h r s aim

Gas permeability co

JIS Z 0208

ASTM D 1434

ASTM D 1003

%

Haze

2

ASTM D 1003

%

JIS Z 1702

JIS Z 1702

JIS Z 1702

Testing methods

Light transmittance

2

kg/cm

T e a r resistance Machine direction T r a n s v e r s e direction

F r i c t i o n angle

%

Elongation Machine direction T r a n s v e r s e direction

2

Unit

kg/cm

/>

Tensile strength Machine direction T r a n s v e r s e direction

g/cc

Density

Test item

75 ^ 8 0

110

31,000 7, 100 320,000

1

91

>70

97 150

500 710

180 170

50

0.91

75 ~ 8 0

98

28,000 6,000

1

91

>70

78 76

500 570

200 200

50

0.91

JSR 1, 2 - P B D T-die " * extrusion inflation

100

25

7, 900 1, 500 20,900

14

80

10

13 33

290 410

170 140

53

0. 92

LDPE

80—85

45

11,400 1, 800

6

88

45

15 19

400 560

175 180

47

0. 93

EVA'"'

1,

85 —90

100

3,000 9, 300

1

91

>70

58 67

240 240

250 250

47

1. 26

Soft"** PVC

Comparison o f g e n e r a l p h y s i c a l p r o p e r t i e s o f s y n d i o t a c t i c 2-Polybutadiene ( c r y s t a l l i n i t y : 2%, [ ^ J = 1.3) f i l m s and f i l m s o f s o f t p l a s t i c s commercially a v a i l a b l e .

F i l m thickness

Table 1.


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NEW

1) 2) 3) k) 5) 6) 7)

INDUSTRIAL

POLYMERS

The process r e q u i r e s only one step cure Wide range adjustment o f the expansion r a t i o i s p o s s i b l e C e l l s i z e o f the sponge i s uniform High f i l l e r l o a d i n g i s p o s s i b l e Compression set i s smaller than EVA Adhesion i s easy Performance c o a t i n g with p a i n t i s good


In sponge production, 1, 2-PBD can be loaded with f i l l e r s and cured with s u l f u r , while EVA cannot be cured with s u l f u r , only with peroxide. F i g u r e 3 shows the cure curves obtained with a JSR Curelastometer using s u l f u r c u r i n g system. The cure r a t e o f 1, 2-PBD i s s i m i l a r to t h a t o f SBR. C o n s i d e r i n g t h a t the cure agent o f EVA i s r e s t r i c t e d only to peroxide, the 1, 2-PBD i s a l s o s u p e r i o r to EVA, as f a r as cure agent i s concerned. Table 2 shows the r e s u l t s o f the weathera b i l i t y t e s t q u a l i t a t i v e l y obtained with specimens prepared i n accordance with some f o r m u l a t i o n . The c r o s s - l i n k i n g products of the 1, 2-PBD show e x c e l l e n t w e a t h e r a b i l i t y and ozone r e s i s t a n c e l i k e that o f EPDM. T h i s i s s u r p r i s i n g , c o n s i d e r i n g i t s poor w e a t h e r a b i l i t y on non c r o s s - l i n k i n g products. Some Japanese companies have developed c e l l u l a r sponge i n t o many k i n d s o f shoe s o l e s , as shown photograph I I I . R e s u l t s from p r a c t i c a l use have confirmed that these sponges have the same d u r a b i l i t y as rubber sponges.

APPLICATIONS IN THERMOSETTING RESIN FIELD F i r e s t o n e ( 3 ) has a l r e a d y reported that l i q u i d 1, 2-PBD can be used f o r i n s u l a t i n g m a t e r i a l s l i k e the u s u a l thermosetting r e s i n s . I n s u l a t i n g m a t e r i a l s o f cured s y n d i o t a c t i c 1, 2-PBD p l u s f i l l e r s show as good p r o p e r t i e s as those o f l i q u i d 1,

2-PBD.

APPLICATION TO PHOTO-SENSITIVE POLIMER FIELD Since 1, 2-PBD i s e a s i l y cured by U.V. i r r a d i a t i o n , i t can be regarded as a p h o t o - s e n s i t i v e polymer. I f a p h o t o - s e n s i t i z e r i s added to 1, 2-PBD, the s e n s i t i v i t y o f the compounds i s s i m i l a r to t h a t o f other commercial photo-polymers. Moreover, adding a c r o s s - l i n k i n g agent l i k e d i a z i d compound, the compound c o n t a i n i n g these three components i n d i c a t e s i t s s u p e r i o r s e n s i t i v i t y compared with other p h o t o - s e n s i t i v e polymers. For example, adding k% o f p h o t o - s e n s i t i z e r (p, p tetramethyl-diamino-benzophenone) to the polymer, the 1, 2-PBD was c r o s s - l i n k e d by U.V. i r r a d i a t i o n (low pressure mercury lamp, f



TAKEUCHI

ET AL.

1,2-Polybutadiene

Applications

31

"50 100 " 150 F i l m thickness (M)

Figure 2. Relationship between film thickness and C0 gas permeability

Cure time (min.)

Figure 3.

2

Table 2.

Cure curves obtained with JSR curelastometer

Comparison between 1, 2-PBD and v a r i o u s rubbers i n outdoor exposure w e a t h e r a b i l i t y t e s t Time of Exposure: Location:

one month in summer

Kobe City, Japan Outdoor Exposure Test Results

White stock formulation

Change in hardness

SBR > BR > EPDM > l,2-PBD

Change in Tensile strength

SBR > EPDM > BR = 1.2-PBD

Change in Elongation

BR > SBR > 1,2-PBD = EPDM

Crack appearance (after 30 days' exposure)

Black stock formulation

BR > SBR > 1,2-PBD > EPDM (muth) (little) (slight) (none)

Change in color

BR > SBR > EPDM > 1,2-PBD

Change in hardness

BR = EPDM > SBR > 1,2-PBD

Change in Tensile strength

EPDM = SBR > BR »

Change in Elongation Crack appearance (after 30 days' exposure)

1,2-PBD

BR > 1,2-PBD = EPDM > SBR SBR = BR » (much) (little)

1,2-PBD = EPDM (none) (none)


32

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d i s t a n c e 5cm) and the exposed step numbers o f the step t a b l e t (21 steps) made by Kodak Co. f o r the purpose o f measuring the photos e n s i t i v i t y put the 19th step a t 30 sec. I t i s suggested that h i g h p h o t o - s e n s i t i v i t y o f 1, 2-PBD makes u s e f u l i t a photos e n s i t i v e polymer.


A unique P l a s t i c M a t r i x has been developed by Nippon P a i n t Co., u t i l i z i n g the p h o t o - s e n s i t i v i t y , the low s o f t e n i n g temperature and the good flow property o f 1, 2-PBD having 25% c r y s tallinity* An o r d i n a r y l e t t e r p r e s s p l a t e system i s shown i n t h i s schematic arrangement. ORIGINAL (Master P l a t e ) Metal Engraving Photopolymezr Plate

MATRIX

DUPLICATE

Paper Mat

Lead Stereo Type

Plastic Matrix (Photocuring)

Plastic Printing Plate (Thermoplastic)

They wanted t o improve the system f o r reasons o f l a b o r h e a l t h c o n d i t i o n s and environment, and considered that the l e a d p r i n t i n g p l a t e should be changed t o an other p r i n t i n g p l a t e ( f o r example, polypropylene). Therefore, i t i s necessary f o r the improvement that the paper mache matrix i s changed to an other matrix by which any p r i n t i n g system could be produced. Some necessary c o n d i t i o n s o f the matrix are the r e a p p e r a n c i v i l i t y o f the r e l i e f images on the master p l a t e , and the t h e r m a l s t a b i l i t y when the r e l i e f images on the matrix are t r a n s c r i b e d to the p r i n t i n g p l a t e by press-molding. 1, 2-PBD having 25% c r y s t a l l i n i t y i s a good r e a p p e r a n c i v i l i t y o f the r e l i e f images on the master p l a t e , because o f i t s h i g h flow p r o p e r t i e s , but the thermal s t a b i l i t y o f 1, 2-PBD i s no good a t s o f t e n i n g temperature of polypropylene. C o n s i d e r i n g that the thermal deformation temperature o f c r o s s - l i n k i n g m a t e r i a l i s g e n e r a l l y i n c r e a s e d higher than t h a t o f non c r o s s - l i n k i n g m a t e r i a l , they s t u d i e d the improvement o f the thermal deformation temperature to c r o s s - l i n k only surface o f 1, 2-PBD. T h e i r d e s i r e d p l a s t i c matrix was comp l e t e d by photo-curing the surface o f 1, 2-PBD p l a t e with U.V. irradiation. Photograph IV shows t h a t the p l a s t i c matrix before U.V. i r r a d i a t i o n i s l i f t e d from the master p l a t e . The matrix i s impressed by a r o l l e r o r h y d r a u l i c p r e s s onto these p l a t e s a f t e r the preheated 1, 2-PBD p l a t e i s p l a c e d on the master p l a t e . Photograph V shows that the surface o f 1, 2-PBD matrix i s photocured by U.V. i r r a d i a t i o n . Photograph VI shows that the r e l i e f



3.

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ET AL.

l£-Polybutadiene

Photo IV. The plastic matrix (1,2-PBD) before UV irradiation is lifted from the master plate

Applications

Photo V. The surface of the plastic matrix is photo-cured by UV irradiation

Photo VI. The relief images on the photo-cured matrix are transcribed to the printing plate (PP plate)


33

Deanin; New Industrial Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1974. 4.9 2.8 8.0 2.2 0.75 0.20

Number of Leaves

Diameter of Stem (mm)

Weight of green plant (g) upper part lower part

Weight of dryed plant (g) upper part lower part

0.78 0.20

7.8 2.0

4.6 2.7

10.4

30

1.14

Soil A

0.84 0.25

8.7 2.8

3.2

5.0

12.8

150

5.70

Soil B

0.88 0.28

9.0 2.8

14.2 5.8 3.5

300

11.40

SoilC

Containing 1,2-PBD

Date of sowing: 5 October, 1971 Date of investigation: 15 November, 1971 Note (*) When the film is used as a mulch once a year, the above loading level is equivalent to that of 20 years. (by courtesy of Horticulture Department, Chiba University)

12.5

0

Equivalent quantity of degraded film fragments loaded per 10 ares of ground (depth of soil: 20cm volume of soil: 200m3) (kg)

Height of Plants (cm)

0

No 1,2-PBD content

E f f e c t s o f degraded 1, 2-polybutadiene fragments i n s o i l on the growth o f tomatoes

Loading level of degraded film fragments to the soil in a pot of 30cm diameter (about 7.51) (g)

Table 3-


0.83 0.28

8.5 3.0

6.0 3.0

13.8

450

17.10*

SoilD

3.

TAKEUCHI

ET AL.

1,2-Polybutadiene Applications

35

images on the photo-cured 1, 2-PBD matrix are t r a n s c r i b e d to the p r i n t i n g p l a t e by press-molding a t the s o f t e n i n g temperature o f polypropylene. Many p l a s t i c p r i n t i n g p l a t e s can be molded, u s i n g t h i s photo-curing matrix.


APPLICATION EXAMPLES AS A PHOTO-DEGRADABLE PLASTIC When exposed to the sun, the molded products o f 1, 2-PBD are changed t o e a s i l y crushable form, because o f the occurrence o f hardening d e t e r i o r a t i o n ( ^ ) . Consequently, the hard d e t e r i o r a t e d 1, 2-PBD f i l m s are e a s i l y fragmented with but l i t t l e force due t o photodegradation. When the f i l m i s used as a-mulching f i l m , c h a r a c t e r i s t i c s o f the photodegradable 1, 2-PBD compare to other photodegradable p l a s t i c s ( 5 ) which have l a t e l y been announced as f o l l o w s : 1)

Since 1, 2-PBD i s not p u l v e r i z e d i n t o powder a f t e r photodegradation, there i s no p o s s i b i l i t y o f secondary p o l l u t i o n by powdered dust.

2)

When mixed i n t o s o i l , the photodegraded 1, 2-PBD fragments give no adverse e f f e c t on v e g e t a t i o n and r a t h e r a c c e l e r a t e the growth o f p l a n t s by improving drainage and a e r a t i o n o f the s o i l (Table 3 ) •

3)

Since the photodegraded 1, 2-PBD i s not decomposed by numerous b a c t e r i a i n s o i l s o f Chiba, Japan, i t i s suggested t h a t there i s no r i s k o f high dimension pollutions.

However, the t e s t r e s u l t s propose many problems concerning i t s u t i l i z a t i o n . The p r a c t i c a l u t i l i t y as a photodegradable p l a s t i c should be c a r e f u l l y s t u d i e d to see what would be expected from

it.

CONCLUSION The New Thermoplastic S y n d i o t a c t i c 1, 2-PBD developed by JSR, has been discussed i n some a p p l i c a t i o n s , but the foregoings are s e v e r a l p a r t s o f our developed r e s u l t s . More d e t a i l e d des c r i p t i o n w i l l be given on another o c c a s i o n . JSR announced that the New Thermoplastic S y n d i o t a c t i c 1, 2PBD (JSR RB820 and JSR RB810) i s put on s a l e , a t the 18th o f June. We expect cooperation from a l l i n d u s t r i a l c i r c l e s f o r f u r t h e r development o f 1, 2-PBD u t i l i z a t i o n .


36

NEW

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ACKNOWLEDGEMENTS The authors would l i k e to thank Japan Synthetic Rubber Co., L t d . and Nippon P a i n t Co., L t d . f o r the permission t o p u b l i s h t h i s i n the symposium.


REFERENCE (1)

Y. Takeuchi, A. Sekimoto and M. Abe, T h i s symposium, 1974, 167th ACS Meeting, a t Los Angeles

(2)

S.P. Chen and J.D. F e r r y , Macromolecules 1,

(3)

F i r e s t o n e S y n t h e t i c Rubber & Latex Co., T e c h n i c a l b u l l e t i n

April,

270 (1968)

"FCR-1261" (4)

Y. Takeuchi and A. Sekimoto, Conference on " D e g r a d a b i l i t y o f Polymers and Plastics" 27, 28 Nov. 1973

(5)

G. S c o t t , P l a s t i c - R u b b e r - T e x t i l e , Sept., 361 (1970). Toronto Univ., Canada, C&EN, May 11, 61 (1970). M. Kato, 5 t h Conference f o r Reporting the R e s u l t s o f Polymer Research, Sept. 27, (1971).


New Industrial Polymers

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