p. 1


# RCRA Box 1883 Prepped by Ollie Stewart



## Document

Number: 

# 39 ) ll-B-20 0 Docket Number: 

# A-90-1 9

Printed 12/3/200810:42:12 AM

Sheet 39of 171P. 2 

# A-90-1 9 ll-B-20 0 

# MEMORANDU M TO : Proces s Vent s Docke t A-90-1 9 FROM : DATE : Wand aFloy d

Decembe r

199 1 SUBJECT : HO N NESHAP : Industr y Characteristics /

Vinyliden e Chlorid e Attache di s aproduct-proces s summar y (PPS ) for

th e productio n o

f Vinyliden e Chloride vi adehydrochlorinatio n o f 1,1,2-trichloroethane . Thi s PP S wa s develope da s par t o f th e Industria l Profil e projec t

i n support

o f th e Hazardou s Organi c NESHA P (HON ) regulatory program . Informatio n i n thi s PP S i s use da s abasi s for emission s an dcos t impac t estimate s for

th e HO N program . Liste dbelo w ar e th e key reference s use di n developin g th e attache dPPS . Kirk-Othmer . Encyclopedi ao f Chemical Technology . 3rdedition . Joh n Wiley & Sons , New York , 1985 . pp . 764,766 . EPA-450/3-80-028c . Organi c Chemical Manufacturin g vol . 8 : Selecte dProcesses . December , 1980 . pp . II-6 , 11-1 5 t o 111-17 , IV-15 , IV-1 9 t o IV-20 , V-7 . Weissermel , Klau s an dArpe , Hans-Jurgen . Industria l Organi c Chemistry . Verla g Chemie , New York , 1978 . p . 197 . Austin , Georg e T . Shreve' s Chemical Proces s Industries . 5t hedition . McGraw-Hil l Boo k Company , New York , 1984 . pp . 660-661 . 198 9 Directory o

f Chemical Producer s USA . SR I International , California , 1989 . p . 1058 . 

# Th e Correspondin g .Quality . Ass^aas e xDoeymen t i s Docket Ite m , A-90-1 9 ll-B-25 2P. 3



### Preparer : 

## Date : t/il/to Reviewer : ADMINISTRATIV E NOTE S 

## Pr<jdntt-Proce$ $ Cttfc 

# 1AX Hour s spen t o n thi s PP S 

### P- P Nam e DeA^Jroc/i/ar>.»«/he»
_ / / / , i - - (fsXtzJi/ose/rtAaA,* Incomplet e Item s (part s o f for m yo u canno t complete ) (lin e # an d description ) Dat e Cleare d Initial s

Chemical s missin g CA

S number s

Plan t wit h Cit vbu t n o Count y(plan t name , city , state )P. 4



### Preparer : 

# Date : $/tf/to

Z Reviewer : 

## CheBica l Nam

e 

## PRODUCT-PROCES S SUMMAR Y(PPS ) Alternativ e Cheutfca

l 

# CAS ? I I f

35 + 

# U- Z)A AJtrO£ /Aj, Ujt* 

# lJ> Kare a Fftfll

r CKeiRfct T Nun&e r CHEMICA I SPECIFI C INFORMATIO N 1. 0 U.S . Productio

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e sam e referenc e informatio

nfo r an y answer s belo

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R(Circl e oneKjimion s o f koNo r million s o f gallon s 1. 2 U , S > Capacity

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0- /_^_^_* / 1. 3 M , S . tapasn y Utilisation * '.& {* » $TEN^ N ^ <&& ffflpttft * t^<£s£: 

# report s ,~~/~<r Produc t Pric e 1, 4 1. 5 I> $ 1. 7 

## 1.7. 1 Averag

e Pric e w-^-t- r 1.7. 2 tffttts af

^mj^fWT^Q^irm^r S/gallon

1. 8 Comment

sP. 5

1 

## 2. 0 ' Chemica l End-Us e Re f # _____ • Pg * ___£2_ , Re f Yea r __ f ' * *

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. Producer s Re f # _____ _P g # _J_____ , Re f Yea r^ ^ ldteM|s^9 f Pr^lMi&fCPl e we ) ^lto7is^rjcg^_or—millio n o f galop s 3. 2 Name , Location , an d Capacit y Location , Proces s Use d (us e P- P # ) 

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% Nat' l

_ _ £ Viabl e (v/n l Capacit y 

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## P-P 5 P- P 6 4. 1 Documentatio no f P-P s Exclude d

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### '-6genatio

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# tf
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Generi c Reactio n
4. 4 Explai n ho

wyo u selecte d th e reactio n typ e i n lin e 4.3 .P. 9



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### 111-1 5

VINYLIDEN

E CHLORIDE Vinyliden

e chlorid

e i s produced domesticall y b y th e dehydrochlorinatio no f 1,1,2-trichloroethan e a s represente

d b y th e followin

g reaction: 8 

### ' 13 

### ' 1 4


### CH2CI-CHCI 2 + (1,1,2-trichloroethane ) NaO H (sodiu m hydroxide ) CH 2 

### =CC1 2 

### (vinyliden

e chloride ) NaC l 

### H, 0

(sodiu m (water ) chloride ) Th e reactio

ni s carrie

d ou t inth e liqui d phas e a

t a temperatur e o f about 100°C , wit ha relativel y

dilut e ( 5 t

o 1 0 w t % ) sodiu

m hydroxid

e solution . Produc t yield s ar e believed to range fro m 8 5 t o 90%. 1 3 

### Figure III- 5 represent s a flo w diagra m fo r a proces s inwhichvinyliden e chlorid

e i s produced fro

m 1,1,2-trichloroethane. 8 

### ' 13 

### ' 1 4 

### Concentrate d sodiu m hydroxid

e solutio n(strea

m 1 ) i s dilute

d wit hwate r (strea m 2 ) t o 5 to 10 % concentratio n an d combine

d wit h1,1,2-trichloroethan e fee d (strea

m 3) , wit hunreacte

d 1,1,2-tri chloroethan

e (strea

m 16 ) recycle

d fro m th e distillatio

nsectio

no f th e process , an d wit ha recycle

d sodiu m hydroxide—sal t solutio n(strea

m 8) . Th

e combine

d fee d strea m (4 ) i s further mixed t o provide dispersa l o f th e insolubl e organi c phas e inth

e aqueou s phas e befor e i t i s fe d to th e dehydrochlorinatio nreactor . Th e dehydrochlorinatio nreacto

r i s continuousl y

purged wit hnitrogen(strea m 5 ) t o preven t th

e accumulatio

no f monochloroacetylene impurit y inth e vinyliden

e chlorid e product , a ste

p that result s ina proces s emissio nsourc e (ven

t A) . Th e two-phas e reactor effluent (strea m 6 ) i s separate

d int o tw

o streams . Th

e aqueou s phas e (strea m 7) , compose

d o f a sodiu

m hydroxide—sal t solutio nsaturate

d wit horgani c compounds , i s split . On e fractio

n(strea

m 8 ) i s recycle

d t o th e dehydrochlorinatio

nreactor . Th

e othe r fractio

n(strea

m 9 ) i s combine

d wit h th e botto m strea m (14 ) fro

m th e dryin g colum nan d fe d t o th e strippin

g column , wher e stea

m (10 ) i s introduce

d countercurrentl y

to stri p mos t o f th e dissolve

d organic s fro

m th e aqueou s phase . Th e organic s (strea

m 11 ) are remove

d overhea

d an d are combine

d wit hth

e organi c phas e (strea m 12 ) fro

m th e phas e separato

r a s fee d to th e dryin g column . Th

e strippe

d aqueou s phas e i s remove d a s th e botto m strea m (sourc e F ) an

d discharge

d t o th e wastewate r treatment system .P.1 1



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Th e dryin g colum nbotto m strea m (14) , whichcontain s mos t o f th e residua l water , i s recycle

d t o th e strippin

g column . Th

e drying-colum

noverhea

d strea m (15 ) passe s t

o th e finishin

g column , wher e th

e overhea

d strea m (16) , compose

d primaril y o f unreacte

d 1,1,2-trichloroethane , i s remove d an d recycle

d to th e dehydrochlori natio nreactor . Th

e refine

d vinyliden

e chloride produc t i s remove d a s th e botto m strea m (17 ) an

d transferre

d to storag

e inpressurized tanks . Fro m storag e th e vinyliden

e chlorid

e ma y b e transferre

d b y pipeline fo

r interna l us e (strea m 18 ) o r loade d (strea

m 19 ) int o tan

k truck s an

d tan k car s fo

r off-sit e consumption . Th e dehydrochlorinatio nreactor purge ven t (A ) an d th e distillatio

ncolum n vents , (B ) whichreleas e primaril y noncondensabl e gases , are source s o f proces s emissions . Storage emission s (ven t C ) are th

e emission s fro

m storag e o f 1,1,2-trichloroethane . Handlin g emission s (ven

t D ) resul t fro

m th e loadin

g o f vinylidene chlorid e int o tan k truck s an

d railroa

d tan k cars . Wit hpressurized tank s used fo r vinylidene chlorid e storag

e n o significant emission s fro m produc t storage occur . Fugitiv e emission s (E ) occu r whenleak s develo p invalve s or i npum p o r compressor seals . Whe

nproces s pressure s are highe r tha nth e coolin

g wate r pressure , VO C ca nlea k int o th

e coolin

g wate r an

d escap e a s fugitiv

e emission s fro

m th e coolin

g tower . Secondar

y emission s ca

noccu r whenwastewate r discharge d fro m th e strippin

g colum n(source F ) i s sen t t o a wastewate r treatment syste m an d th e containe

d VOC ar e desorbed .P.1 2



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### Fig . III-5 . Flo w Diagra mfo r Vinyliden e Chlorid e fro m1,1,2-Trichloroethan e'

» 

# vvER A Unite d State s Offic e o f Ai r Quality EPA-450/3-80-028 c Environmenta l Protectio n Plannin g an d Standard s Decembe r 198 0 Agency Researc h Triangl e Par k N C 2771 1 Ai r 

# Organi c Chemica l Manufacturin g Volum e 8 : Selecte d Processe s

PROPERT

Y O f EP A LIBRAR

Y RTP,.N O

### Tabl e II-2 . Productio n Capacit yfo r 1,1,1-Trichloroethane , Perchloroethylene , Trichloroethylene , an d Vinyliden e Chlorid e

197 9 Capacity

(Mg/yr ) Compan y Location 1,1,1-Tricliloroethan c Perchloroethylene Trichloroethylene Vinylidene Chloride Diamon d Shamroc k Do w

D u Pont Ethy l PP G Stauffe r Vulca n Dee r Park , TX

Freeport , TX Pittsburg , CA Plaquemine , L

A Corpu s Christi , T

X Bato nRouge , L

A Lak e Charles , L

A Louisville , K

r Geismar , L

A Wichita , K S Tota l 204,00 0 136,00 0
159,00 0 90,00 0 589,00 0 75,00 0 68,00 0 18,00 0 54,00 0 73,00 0 23,00 0 91,00 0 32,00 0 68,00 0 23.00 0 525,00 0 b 6 8

2 0 9 1 00 0 

### '
00 0 00 0 2 3 c

,000—4 5

8 8 ooo d 00 0

179,00 0 Se e re f 2 . 23,000-Mg/y

r capacit

y uni t placed o

nstandb

y i nearl y 197 8 (ref 2) . Capacit y

dat a not available . Include s 23,000-Mg/y r expansio

ncomplete

d i n197 8 (re

f 9) . Mos t o f thi s capacity (88,00 0 Mg/yr ) wa s place d o nstand-b y wit hth

e shutdow

n o f PPG' s vinyliden

e chloride—base d 1,1,1-trichloroethan e process . I



# __ r

### mmmmm
111-1 5

D . VINYLIDEN E CHLORID E Vinyliden e chlorid e i s produce d domesticall y by th e dehydrochlorinatio no f 1,1,2-trichloroethan e a s represente d by the followin g reaction: 8 ' 13 ' 1 4
CH2CI-CHCI 2 + NaO H (1,1,2-trichloroethane ) (sodiu m hydroxide ) CH 2 =CC1 2 (vinyliden e chloride ) NaC l + H 2 0 (sodiu m (water ) chloride )
Th e reactio ni s carrie d ou t i nthe liqui d phas e a t a temperatur e o f abou t 100°C , wit ha relativel y dilut e ( 5 t o 1 0 w t % ) sodiu m hydroxid e solution . Produc t yield s ar e believe d t o rang e fro m 8 5 t o 90%. 1 3 Figur e III- 5 represent s a flo w diagra

m fo r a proces s i nwhic hvinyliden e chlorid e i s produce d fro

m 1,1,2-trichloroethane. 8 ' 13 ' 1 4 Concentrate d sodiu m hydroxid e solutio n(strea

m 1 ) i s dilute d wit hwate r (strea m 2 ) t o 5 t o 10 % concentratio n and combine d wit h1,1,2-trichloroethan e fee d (strea m 3) , wit hunreacte d 1,1,2-tri chloroethan e (strea m 16 ) recycle d fro m the distillatio nsectio no f the process , and wit ha recycle d sodiu m hydroxide—sal t solutio n(strea m 8) . Th e combine d fee d strea

m (4 ) i s furthe r mixe d t o provid e dispersa l o f the insolubl e organi c phase i nth e aqueou s phas e before i t i s fe d t o the dehydrochlorinatio nreactor . Th e dehydrochlorinatio nreacto r i s continuousl y purge d wit hnitroge n(strea m 5 ) t o preven t the accumulatio no f monochloroacetylen e impurit y i nthe vinyliden e chlorid e product , a ste p tha t result s i na proces s emissio nsourc e (ven t A) . Th e two-phas e reacto r effluen t (strea m 6 ) i s separate d int o tw o streams . Th e aqueou s phase (strea m 7) , compose d o f a sodiu m hydroxide—sal t solutio nsaturate d wit horgani c compounds , i s split . On e fractio n(strea m 8 ) i s recycle d t o the dehydrochlorinatio nreactor . Th e othe r fractio n(strea m 9 ) i s combine d wit h th e bottom

strea m (14 ) fro

m th e dryin g colum nan d fe d t o the strippin g column , wher e stea

m (10 ) i s introduce d countercurrentl y t o stri p mos t o f the dissolve d organic s fro

m the aqueou s phase . Th e organic s (strea m 11 ) ar e remove d overhea d an d ar e combine d wit hthe organi c phas e (strea m 12 ) fro

m the phas e separato r a s fee d t o the dryin g column . Th e strippe d aqueou s phas e i s remove d a s the botto m strea m (sourc e F ) an d discharge d t o the wastewate r treatmen t system .

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Fig . III-5 . Flo w Diagra mfo r Vinyliden e Chlorid e fro m1,1,2-Trichloroethan eP.2 8

111-1 7

Th e dryin g colum

nbotto

m strea m (14) , whic hcontain s mos t o f the residua l water , i s recycle d t o th e strippin g column . Th e drying-colum noverhea d strea

m (15 ) passe s t o th e finishin g column , wher e th e overhea d strea m (16) , compose d primaril y o f unreacte d 1,1,2-trichloroethane , i s remove d an d recycle d t o th

e dehydrochlori natio nreactor . Th e refine d vinyliden e chlorid e produc t i s remove d a s the botto m strea m (17 ) an d transferre d t o storag e i n pressurize d tanks . Fro m storag e the vinyliden e chlorid e ma y b e transferre d by pipelin e fo r interna l us e (strea m 18 ) o r loade d (strea

m 19 ) int o tank truck s and tank car s fo r off-sit e consumption . Th e dehydrochlorinatio nreacto r purg e ven t (A ) an d the distillatio ncolum n vents , (B ) whic hreleas e primaril y noncondensabl e gases , ar e source s o f proces s emissions . Storag e emission s (ven t C ) ar e the emission s fro m storag e o f 1,1,2-trichloroethane . Handlin g emission s (ven t D ) resul t fro m th e loadin g o f vinyliden e chlorid e int o tank truck s and railroa d tank cars . Wit hpressurize d tank s use d fo r vinyliden e chlorid e storag e n o significan t emission s fro m produc t storag e occur . Fugitiv e emission s (E ) occu r whe nleak s develo p i n valve s o r i n pum p o r compresso r seals . Whe nproces s pressure s ar e highe r tha nthe coolin g wate r pressure , VO C ca nlea k int o th e coolin g wate r an d escap e a s fugitiv e emission s fro m th e coolin g tower . Secondar y

emission s ca n occu r whe nwastewate r discharge d fro m the strippin g colum n(sourc e F ) i s sen t t o a wastewate r treatmen t syste m an d th e containe d VO C ar e desorbed .

unu • - ..——J—9mm ILI I l l m lip—UI"*fB~g~«~WW~WPi.1j.».takL_S. . ..tv.*.—_*M*- i 

### IV-1 5

doe s no t includ e storage , handling , fugitive , o r secondar y emissions . Th e compositio n an d flo w o f th e uncontrolle d emission s i nth e ga s fro m th e reacto r ven t (A) , i n th e ga s fro

m th e dryin g colum

nven t (B) , an d i nth e ga s fro m th e distillatio n vent s (C ) ar e give ni nTable s IV-10—1 2 respectively. 4 

### ' 16 

### ' 1 7


### D . VINYLIDEN E CHLORID E Th e proces s flo

w diagra m (Fig . III-5 ) fo r th e productio no f vinyliden e chlorid e fro m 1,1,2-trichloroethan e represent s th e processe s use d by Dow Chemica l Company 5 

### ' 1 8 

### an d PP G Industries , currentl y th e onl y

domesti c producer s o f vinyliden e chloride. 2 

### ' 3 

### Emission s fro

m the reacto r ven t (A ) ar e compose d o f vinyliden e chloride , monochloro acetylene , and nitroge nand resul t fro m th e purgin g o f th e reacto r t o preven t the accumulatio no f monochloroacetylen e i nthe liqui d vinyliden e chlorid e product . A nestimat e o f th e reacto r ven t ga s compositio ni s give ni nTabl e IV-13 . A nestimat e o f th e compositio no f th e distillatio ncolum nven t (B) , th e othe r sourc e o f proces s emissions , i s give ni nTabl e IV-14 . Th e estimate d quantitie s o f emission s fro

m bot hsource s (vent s A an d B ) ar e base d o ninformatio nfro m tw o plants 6 

### ' 1 8 

### and th e tota l i s give ni nTabl e IV-7 . 

# I

•mmptwrnmP.3 0


### IV-1 9

n . KI - T V ^ Estimate d Compositio n o f Ven tGa s fro m ^RLcror'sectioro f aVinyliden e Chlorid e Plan t 

### a

Componen t Compositio n (w t % ) Vinyliden e chlorid e Monochloroacetylen e Nitroge n 5 6 8 3 6 Emissio n Rati o

(g/kg) b 

### 6. 2 0. 9 4. 0

a 

### Se e ref s 3 , 4 , an

d 5 . b g 

### o f emission s pe r k g o f produc t produced .



# iIV-2 0
Table IV-14 . Estimate d Compositio no f Distillatio n Ven t Ga s fro

m a Vinyliden e Chlorid e Plant 3

Componen t Vinyliden e chlorid e Nitroge n

a Se e re f 18 . Compositio n (w t % ) 5 0 5 0 Emissio nRati o

(g/kg) b 0. 7 0. 7

g o f emission s pe r k g o f produc t produced .

### V- 7
Tabl e V-4 . Estimate s o f Controlle d VOC Emission s fro m a Vinyliden

e Chlorid

e Process 3



### Sourc e Reacto r ven t Distillatio n ven t Tota l Uncontrolle d VO C

Emissio n Rati o (g/kg) b 

### 7. 1 0. 7 7. 8 Contro l Devic e

Incineratio n Aqueou s scrubbe r VO C Emissio n Reductio n (% ) 

### 9 8 9 0 Controlle d VO C

Emissio n Rati o (g/kg) b 

### 0.1 4 0.0 7 0.2 1 See ref s 2 an

d 8 . g o f emission s pe r k g o f vinyliden

e chlorid

e produced .

^P—«———«M— <P.3 3

' »


# "io ! ST - 7^ p - 0O?39/i/ e \<f&9 C.X. ^ 

# 198 9 DIRECTOR

Y O F CHEMICA L PRODUCER S UNITE D STATE S O F AMERICA

Informatio n i n thi s Director y i s fo r th e sol e an d privat e us

e o f sponsor

s o f th a Director y o f Chemica l Producers Program .



### QAP'J M * »P-?AR Y V

# fclil 33 3 RAVENSWOO O AVENU E MENL O PARK
. CALIFORNI A9402 5 (415)859-362 7 FAX : (415)326-551 2 TWX : 910-373-204 6 TELEX : 33448 6

Copyrigh t O 198 9 SR I rmamational . Unauthorize d us e or reproductio n o

f al l o r an y par t o f thi s documen t <

s prohibited . Printe

d i n US A198 9 DIRECTORY O F CHEMICA L PRODUCER S UNITE D STATE S PRODUCT S Vmy l aeatat a viny l cMorid a ethylen e terpolyme r rtsin s (See : Plastic

s an d Resins

) Vinyiacetonitril e (See : Ally l cyanide) Vinylbenzen e (See : Styrene) p-Vinylbanzenesulfoni c acid , sodiu m sal t (See : Sodiu m fistyren e sulfonate ) Viny l benzy l chlorid e monome r Do wChemica l U.S A Midland , Michiga n Viny l bromid e monome r Ethy l Corporatio n Cnemical s Grou p Magnolia , Arkansa s Viny l buty l ethe r (See : n-Buty l viny l ether ) N-Vinylcarbazol e Polysciences , Inc . Warrington , Pennsylvani a Vinylcarbino l (See : Ally l alcohol ) Viny l chloride-ethyleri e copolyme r resin s (See : Ethylene viny l chlorid e copolyme rresin s unde rPlastic s an d Resins

) Viny l chlorid e monome r (Chloroethylene ) (VCM) Borde n Chemical s an d Plastics Partnershi p DowChemica l U.S A Formosa Plastics Corporatio n U.S A Georgi a Gul f Corporatio n Th e BFGoodric h Compan y BFGoodric h Chemica l Grou p Occidenta l Petroleu m Corporatio n Occidenta l Chemica l Corporation , subsidiar y Plastics & Polymer

s Divisio n PV C Resin s an d Fabricate d Products Grou p PP G Industries , In c Chemical s Grou p Vista Chemica l Compan y Geismar , Louisian a Oyste r Creek , Texa s Plaquemine , Louisian a Bato n Rouge , Louisian a Poin t Comfort , Texa s Plaquemine , Louisian a Calver t City . Kentuck

y L a Porte , Texa s

Dee r Park , Texa s Lak e Charles , Louisian a Lak e Charles , Louisian a TOTA L Annua l Capacit y (Million s o

f Pounds) 80 0 70 0 10S 0 40 0 S8 0 1Q0 0 100 0 130 0

10S 0 65 0 72 0 9,25 0 Process

Ethylene-oxychlor i natio n Ethylene-oxychlorinatio n Ethylene-oxychlorinatio n Ethylene-oxychlorinatio n

Ethylen e Ethylene-oxychlorinatio n Ethylene-oxychlorinatio n Source : SR I Internationa l estimate s as o f Januar y 1 , 1989 . Viny l 2-chloroethy i ethe r Interchem , Inc . Alcola c subsidiar

y Sedalia , Missour i Viny l chloroformat e PC R Inc . Gainesville , Florid a Viny l cyanid e (See : Acrylonitrile ) 4-Vinyl- 1 -cyclohexen e (Butadien e dimer ) (4-Ethenyl- 1 - cyclohexene ) (1,2,3,6-Tetrahydrostyrene ) Unio n Carbid e Corporatio n Chemical s an d Plastics Busines s Grou p Specialt y Chemical s Divisio n Institute , Wes t Virgini a Vinylen e carbonat e Polysciences , In c Warrington , Pennsylvani a Vinylethylen e (See : 1,3-Butadiene ) Viny l ethy l ethe r (See : Ethy l viny l ether ) Viny l ferrocen e

. Paris h Chemica l Compan y Viny l fluorid e (Fluoroethylene ) E . I . d u Pon t d e Nemours & Company , In c Chemical s an d Pigment s Departmen t Fraon * Products Divisio n Vlnytformi c aci d (See : Acryli cacid ) Orem , Uta h

Louisville , Kentuck

y Vinylformi c aci d ester s (See : Acrylat e esters)

/Vinyliden e chlorid e monome r (1, 1 -Dichloroethylene ) / Do wChemica l U.S A Freeport , Texa s [ PP G Industries , In c V Chemical s Grou p Lak e Charles . Louisian a Vinyliden e fluorid e (See : 1,1-Difluoroethylene ) Viny l isobuty l ethe r (See : Isobuty l viny l ether ) Viny l methy l ethe r (See : Methy l viny l ether ) 5-Viny l norbomen e (VBCH ) Unio n Carbid e Corporatio n Chemical s an d Plastics Busines s Grou p .. . . • Specialt y Chemical s Divisio n Institute , Wes t Virgini a Viny l octadecy l ethe r (See : Octadecylviny l ether ) 2-Vinytpyridin e Reill y Industries , In c 4-Vinylpyridin e Reill y Industries , In c Indianapolis , Indian a Indianapolis , Indian a Viny l pyridin e late x (See : Styrene-butadiene-2-vinylpyridin e late x unde r Elastomers ) 1-Vinyl-2-pyrrolidinon e GA F Corporatio n GA F Cnemicals , subsidiar y Calver t City . Kentuck

y

105 8 SR I Internationa l

# AL-W ) 

# Shreve' s Chemica l Proces s Industrie s GEORG E T . AUSTI N ProfessorEmeritus of

Chemical

Engineering Washington State University 

# Fift h Editio n

McGraw-Hil l Boo kCompan y Ne w Yor k St . Loui s Sa

n Francisc o Aucklan dBogotaHambur g Johannesbur g Londo n Madri dMexic o Montrea l Ne w Delh i Panam a

Pari s Sao Paul o Singapor e Sydne y Toky o Toront o 

# RADIA N LIBRAR Y RESEARC H TRIANGL E PARK . N CLibrary of Congres s Catalogin g i n Publicatio n Dat a Shreve , Randolp h Norris , 1885-197 5 Shreve' s Chemical proces s industries . Include s index . 1 . Chemistry , Technical . I . Austin , Georg e T , 1914 - TP145.S 5 198 4 660. 2 ISBN 0-07-057147- 3 2 . Chemical industry . II . Title . 83-13629 , Copyrigh t© 1984 , 1977 , 195 6 by McGraw-Hill , Inc. Al l right s reserved . Copyrigh t194 5 by McGraw-Hill . Inc . Al l right s reserved . Printed in th e Unite d States o

f America . Excep ta

s permitte d underth e Unite d States Copyrigh tAc

to f 1976 , n o par to f this publicatio n ma

y b e reproduce d o

rdistribute d in an

y for m o rb y an y means , o

rstored in a dat abas e orretrieva

l system , withou tth e priorwritten permission o f th e publisher . 3456789 0 DOC/DO C 8987 6 

### ISB N Q-Q7-0S71M7- 3

Th e editor s forthis boo

kwere Joa

n Zseleczk

y an d Rit aMargolies , th e designe rwa s Jules Perlmutter . and th e productio n superviso rwas Thomas G. Kowalczvk . I twas setin Caledoni aby Universit y Graphics . Inc . Printe d and bound by R . R . Donnelle y & Son

s Company

i~L*L66 0 Chap. 3 4 Plaatic Industries ticize db y wate r

an di s completel y solubl e i n a n exces s o f water . Polyviny l alcoho l react s wit h a n aldehyd e unde r

th e influenc e o

f hea t an di n th e presenc e o

f a n aci dcatalyst , suc h a s sulfuri c o r

hydrochlori c acid , an dth e resul t i s atypica l acetal . Polyviny l butyra l i s forme da s follows :

—C

H —CH. , —CH
I" I 0 -CH.,

—+ C3H 7CH 0
H 0

I H —C H —CH. , —C

H — CH 2 - I" I 0 —C H —0
Th e correspondin g forma l an daceta l are :

-C H —CH. , —CH

—CH 2 - II 0 —C H —0 I H Forma l -C H —CH2 —CH—CH 2 — II 0—C H —0 I CH. , Aceta l I n actua l commercia l production , th e hydrolysi s an dcondensatio n reaction s ar e neve r carrie d t o completio n becaus e i t ha s bee n foun dtha t

th e presenc e o

f residua l acety l an dhydroxy l group s give s th e resin s bette r properties . Polyviny l butyra l i s usuall y extrude da s ashee t for th e interlaye r

fo r safety glass . Some polyviny l acetal s ca n b e compression-molde da t temperature s fro m10 0 t o 130° C an dinjec
tion-molde da t

temperature s fro m17 0 t o 190°C . Polyviny l formal s can b e molde db y eithe r compressio n o r

injection , dependin g upo n th e softenin g point . Vinylidene Resins. Thi s clas s o f resin s wa s introduce di n 194 0 an di s forme db y th e polymerizatio n o

f th e monomeri c vinyliden e chloride , CH 2 =CC1 2 , o r vinyliden e fluoride . Thes e .resin s ma y b e represente das : H C l H C l H C l H C l I I I I I I I I —C—C—C—C—C—C—C—C — I I I I I I I I H aH C

l H C l H C l o r th e monome r

ma y b e copolymerize dwith viny l chlorid e t o giv e ane w produc t represente d as : H aH C l H C l H C l H C l I I I I I I I I I I —C—C—C—C—C—C—C—C—C—C — I I . 1 I I I I I I I H H H C

l H C l H C l H H Th e resin s forme db y copolymerizatio n rang e fro maflexibl e materia l havin g asoftenin g poin t o f abou t 70° C t o ahard , thermoplasti c soli dwithasoftenin g poin t o f 180°C . Thei r highe r softenin g poin t

indicate s agreate r

degre e o f crystallin e character . I

f th e fibrous crys tal s ar e not

oriented , th e vinyliden e chlorid e ha s atensil e strengt ho f 5 5 MPa , whic h i s an ordinar y value . I

f th e crystal s ar e oriente db y drawing , however , th e tensil e strengt hmay b e increase dt o abou t

41 0 MPa . Thes e resin s ma y b e fabricate db y compressio n o r injectio n moldin g or accurat e c

c STYRENEI tio n o f eth \ polymeriz a tio n a t mo ' weight , w l catalyst s si ' ula r weig h 85° C i n a Th e visco i 200°C , t o • Th e extruc l with acryl o Anothe r p-methy l s

i t o produc e ACHYLIC

Hi acryli c aci c merizatio n o r in soluti c ar e increas i use dbecau : len t optica l thei r excel h clamps . Em 

### Alloying Th e proper l polymers . T ar e no t full ; ylen e oxid e microscope , i s muc heas i ones . On e o f tl adher e tog e in g polyme i compatibili :

w Mod. Ph 3I A Bette r M DuBoi s a M Polyme rManufacturing Processes 66 1 moldin g o r

extrusio n with th e us e o

f speciall y develope dtechnique s an dequipmen t t o obtai n accurat e contro l o

f propertie s an dshape .

e r carrie d hydroxy l STYRENE RESINS. 30Monomeri c styren e (Chap . 36 ) i s mad e b y th e pyrolysis-dehydrogena
tio n o f ethylbenzene , whic hi s synthesize dfro methylen e an dbenzene . Th e factor s tha t affect polymerizatio n o

f th e monome r

ar e th e temperatur e an dpurit y o f th e styrene . Polymeriza
tio n at moderat e temperature s withou t catalyst s produce s resin s o f hig haverag e molecular weight , whic himpar t

hig hviscosit

y t o thei r solutions . I

f th e temperatur e i s increase dan d catalyst s suc ha s benzoy l peroxide , oxygen , o r stanni c chlorid e ar e added , th e averag e molec
ular weigh t an dviscosit

y ten dt o decrease . Styren e o f 99.5 % purity , whe n heate dt o 8 0 t o 85° C i n astainless-stee l kettle , polymerize s t o a3 5 o r 4 0 percen t

conversio n i n 4 0 t o 6 0 h . Th e viscou s solutio n i s passe ddow n atower , with zone s o f increasin g temperatur e u p t o 200°C , t o stri p of

f th e unconverte dmonome r an dt o tak e of

f th e polyme r

i n amolte n state . Th e extrude dproduc t

i s coole dan dgranulated . A blen do f acrylonitrile-butadien e rubbe r withacrylonitrile-styren e resin s produce s AB S plastics . Anothe r variatio n o

f polystyren e i s arecentl y introduce dpol y p-methy l styrene , PMS . Th e p-methy l styren e i s prepare dfro mtoluen e an dethylene , an dit i s claime dtha t

thi s i s cheape r t o produc e tha n styrene . Superio r propertie s ar e anothe r

plu s for th e PM S ove r

polystyrene 31

. ACRYLIC

RESINS AND PLASTICS." Th e methyl , ethyl , an dbuty l ester s o f acryli c an dmeth
acryli c acid s ar e polymerize dunde r th e influenc e o

f heat , light , an dperoxides . Th e poly
merizatio n reactio n i s exothermi c an dma y b e carrie dout i n bul k for castings , o r

b y emulsion , o r i n solution . Th e molecular weigh t decrease s a s th e temperatur e an dcatalys t concentratio n ar e increased . Th e polymer s ar e noncrystallin e an dthu s ver y clear . Suc hresin s ar e widel y use dbecaus e o

f thei r clarity , brilliance , eas e o f forming , an dligh t

weight . The y hav e excel
len t optica l propertie s an dar e use dfor camera , instrument , an dspectacl e lenses . Becaus e o f thei r excellen t dielectri c strengt hthe y ar e ofte n use dfo r high-voltag e lin e spacer s an dcabl e clamps . Emulsion s ar e widel y applie da s textil e finishes an dpaints .

ite d 

### Alloying and Blending 33 Th e propertie s o

f man y plastic s ca n b e greatl y modifie db y blendin g o r alloyin g tw o o r

mor e polymers . Th e term s ar e ofte n use dinterchangeably , bu t technically , blend s ar e mixture s tha t ar e no t full y compatible , an dalloy s ar e mixture s tha t ar e fully compatibl e suc ha s polyeth
ylen e oxid e an dpolystyrene . Th e blend s appea r a s separat e phase s whe n viewe dunde r a microscope . Thes e combination s ar e takin g ove r a n increasin g shar e o

f th e marke t

becaus e it i s muc heasie r

t o develo p desirabl e propertie s b y mixin g know n plastic s tha n b y creatin g ne w ones . On e o f th e problem s associate dwith blend s an dalloy s i s ho w t o mak e th e component s adher e together . On e approac hi s t o introduc e acompatibilize r whic hcreate s interpenetrat
in g polyme r

network s b y providin g aphysica l link betwee n semicompatibl e materials . Most compatibilizer s ar e bloc k copolymer s an dthe y produc e a n interwove n matri x o f physicall y

M Mod. Plast. 5 2 (6 ) 1 6 (1975) ; Hydrocarbon Process. 5 8 (9 ) 18 5 (1979) ; MPE , 1981-1982 . 31 A Bette r Styren e Goe s Commercial , Chem. Week. 13 0 (7 ) 4 2 (1982) . 32 DuBoi s an dJohn , Plastics, 6thed. , Va n Nostran dReinhold , Ne w York , 1981 . M Polyme r

Alloys , Chem. Week

13 2 (9 ) 7 2 (1983) .

# Klau s Weisserme l Hans-Jiirgen Arp e 

# Industria l Organi c Chemistr

y Importan t Ra w Material s an d Intermediate s Translate db

y Alexander Mulle n



# Verla g Chemi e • Weinhei

m• Ne w Yor k 197 8«fe: .« .

Prof . Dr . Klau s Weissermel Dr . Hans-Jiirgen Arp e Hoechs t AG Postfac h800 3 2 0 D-623 0 Frankfur

t S O Wes t Germany 

# Prefac e

Cop yEditing : Dr
. Han s F
. Ebe l Thi s book contain s 4 3 Table s CIP-Kurztilefaufnahni e der Deutsche: n Bibliothek Weissermel , Klau s Industria l organi c chemistry : important ra w material s andintermediate s / Klau s Weissermel ; Hans-Jiirge n Arpe . - 1 . Aufl . - Weinheim . Ne w York : Verla

g Chemie . 1978 . Dt . Ausg . u.d.T. : Weissermel . Klaus : Industrielleorganisch e Chemie . ISB N 3-527-25706- 3 (Weinheim) ISB N 0-89573-005- 7 (New York ) NE : Arpe . Hans-Jurgen : © Verlag Chemi e GmbH . D-694 0 Weinheim , 197 8 Al l right s reserve d(includin g thos e o f translatio n int o foreign languages) . N o par t o f thi s book ma y be reproduce di

n .m v for m- b y photoprint , microfilm , o r an y othe r mean s - nor

transmitte dor

translate dinto amachine languag e without written permissio n fro

mih e publishers . Registere dnames , trademarks , nc . use di n thi s book , eir«nvirt».>H

t specific indicatio n thereof

, ar e no t to b e considere d unprotecte db

y law . Printer : Passavi aDruckere i GmbH Passa u Printe di n Wes t Germany Industria l organi c cl a s wel l as , t o a n in e presen t statu s of k n Ther e wa s thu s aa n an dintermediate s < an dt o presen t

i t i n : development , whic t fro mthei r

industria l in g discussion s with Thi s boo k

address e fro mi t th e chemist i manufacturin g pro c glea n informatio n a am i feedstocks alo r discipline s i

n rh o d economist s - will b economi c interrela t Thi s boo k

i s arran g thei r tightes t possi b unavoidable . Th e i

i A s arule , th e man u meri t an dsignific a appficaiton s o

f th e p products ' art " r'requ * existin g technologi c more , economi c o r

r Th e author s endea v informatio n ar e a t

t 1 . Th e mai n text . 2 . Th e synopsi s o f

t 3 . Flo w diagram s i

l Thes e thre e types o o r makin g brie f

n o note s whic h briefl y t o b e rapidl y infor n

## I0--U^o\^ry^CGy&Z-' 9.1. Vinyl-Halogen Compounds 19 7
ch , W . Wit

hethane , however , th e involve dtechnolog y fo r circulatin g the catalys t

melt ha s only bee n employe din apilo t plan t up t o no w {c.f. CH 4 Oxychlorination , Sectio n 2.3.6.1) .

in
o f <ystin
- >nie . bl e :of le d ra - *a s it h m g in
I n n a -n . 9.1.1.4 . Viny l Chloride Applications I n quantitativ e terms , vinyl chloride i s chiefl y employe da s a monome r an dcomonomer

in polymerizations . Only aminor amount , alon g wit

hit s precurso r

EDC , serve s a s startin g mate rial fo r numerou s chlorin e derivative s o f ethan e an dethylen e fo r applicatio n a s solvent s an dextractants . Thes e compound s usedt o b e solely derive dfro macetylene . 1,2-Dichloroethane i s als o useda s solvent fo r resins , asphalt , bitumen andrubber

a s wel l a s extractan t

fo r fats an doils . Combine dwit

htetraethyl
- or

tetramethyllea dit

serve s i n anti
knock agent s t o conver

t almos t non-volatil e leadcompound s into readily volatil e ones . Furthermore , vinyl chlorid e an d1,2-dichloroethan e ar e start in g material s fo

r th e manufactur

e o f vinylidene chloride {c.f. Section 9.1.2 ) an dtri
- an dtetrachloroethylen e {c.f. Sectio n 9.1.4) .
9.1.2 . Vinyliden

e Chlorid e Vinylidene chlorid e (more properl y name dvinyliden e di
chloride , VDC ) i s manufacture dby initially chlorinatin g vinyl chloride or

1,2-dichloroethan e t o 1,1,2-trichloroethan e whic h is the n dehydrochlorinate dwit haqueou s Ca(OH) 2 o r

NaO H at approx . 100 ° C t o VDC : application s o f VCM : I . PV C an dnumerou s copolymer s mai n applicatio n area s for PVC : buildin g an delectrica l industries , automobil e constructio n 2 . intermediat e product s (als o EDC ) fo r manufactur e of

solvent s an dextractants ,'gCljC-CH j (methylchloroform ) C1 2 C = CHC 1 (trichloroethylene ) CI 2 C = CC1 2 (tetrachloroethylene ) an dth e monome r

H 2 C - CCI 2 (vinyliden e chloride , VDC )

vinyliden e chlorid e manufactur e (two
step) : 1 . conversio n o

f VC M o r

1,2-dichloro
ethan e int o 1,1,2-trichloroethan e 2 . dehydrochlorinatio n wit haqueou s alkal i

es s :he
5) he H,C«CHC 1 -^Cl*
- C1CH,-CH»C I + Cit ; ClCHjCHC H 'fO 

### 0)

-*- H,C-CC1 , Vinylidene chlorid e can b e readil y copolymerize dwit hvinyl chloride an dothe r

monomers . Th e polymer s ar e use dt o coa t cellulos e hydrate films an dpolypropen e i n orde r t o reduc e air an dwater permeability . application s of vinyliden e chloride : a s comonome r

withVC M (85 % VD C + I S % VCM , 'Saran' ) for

coatin g o f films (cel
lulos e hydrat e an dpolypropene) , wit h A N (30 % VD C + 70 % AN ) for flame resistan t acryli c fiber sP.4 3 

# I OIH I

. V

Yor k

Yor k RGE R

kele y 

### ^^^^ |



# KIRK-OTHME

R I 

# ENCYCLOPEDI

A O F 1 CHEMICA L TECHNOLOGY I
THIR D EDITIO N 1

^M

A WILEY-INTERSCIENC E PUBUCATIO N 

## Joh n Wile y & Son s NE W YOR K• CHICHESTE R• BRISBANE • TORONT O

# I ••*«* »

Copyrigh t ©

197 8 b v Joh n Wile y & Sons , Inc . Al l right s reserved . Publishe d simultaneousl y i n Canada . N o pa n o f thi s boo k

ma y b e reproduce d b y an y means , no r transmitted , no r translate d int o a machin e languag e withou t th e writte n permissio n o f th e publisher . Library o f

Congres s Catalogin g i n Publicatio n Data : Mai n entr y unde r title : Encyclopedi a o f chemica l technology . A t hea d o f title : Kirk-Othmer . " A Wiley-lnterscienc e publication. " .Include s bibliographies . 1 . Chemistry , Technical-Dictionaries . I . Kirk , Raymon d Eller , 1890-1957 . II . Othmer , Donal d Frederick , 1904 - III . Grayson , Martin . IV . Eckroth , David . V . Title : Kirk-Othme r encyclopedi a o f chemica l tech nology . TP9.E68 5 197 8 660 ' .0 3 ISB N 0-471-02037- 0 77-1582 0 Pag e { Vll l I I X i XX I XXV I XXVII I XXI X 12 0 12 0 12 0 12 0 12 0 ! 1 0 12 0 

## n o 62 3 52 3 62 4 73 3 93 2 96 2 Lin e

Printe d i n th e Unite d State s o f Americ a

### i>

. v k 76 4 VINYUDEN E CHLORID E AN D PVD C



### VINYLIDEN E CHLORID E AN D POLY(VINYLIDEN E CHLORIDE ) Th e mos t valuabl e propert y o

f pol y (vinyliden e chloride ) [9002-85-1](PVDC ) an dit s copolymer s i s low permeabilit y t o awid e rang e o f gase s an dvapors . Th e mos t seriou s deficienc y i s therma l instabilit y a t melt-processin g temperatures . Th e tech
nique s use dt o overcom$(i^y&taT&liTy7ft > 

### copolymerizatio n an dplasticization , wer e develope da t

Th e Do w Chemica

l Company durin g th e 1930 s (1) . Th e commercializatio n o f thes e polymers unde r

th e trad e nam e Sara n began i n 1939 . I n th e Unite dStates , Sara n i s ageneri c ter mfo r hig hVDC-conten t

polymers . ( A lette r followin g th e nam e i s use db y Do w t o indicat e th e typ e o

f comonomer , eg , Sara n A fo

r th e homopolymer , B fo

r copolymer s withviny l chlorid e (VC) , an dFfo r copolymer s withacrylonitril e (AN). ) In othe r countries , Sara n i s stil l atrademar k o f Th e Dow Chemica l Company . Th e synonymou s us e o f poly(vinyliden e chloride ) an d Sara n ha s resulte di n man y material s bein g identifie di n th e literatur e a s poly(vinyl
iden e chloride ) tha t

were actuall y copolymer s o f unknow n composition . Althoug h i t ha avaluabl e properties , th e homopolyme r ha s no t bee n use dt o an y exten t

becaus e o f it s difficult

fabrication . O

f th e many copolymer s tha t hav e been prepared , only thre e type s ar e commerciall y important : vinyliden e chloride-viny l chlorid e copolymer s [9011-06-7], vinyliden e chloride-alky l acrylat e an dmethacrylat e copolymers , an d vinyliden e chloride-acrylonitril e copolymer s [9010-76-8]an dmethacrylonitril e co polymer s [9010-80-4]. Th e literatur e o n vinyliden e chlorid e polymer s throug h 197 2 i s reviewe di n ref

. 2 . Olde r review s may als o b e o

f interes t (3-4) . Vinylidene Chlorid e Properties . Pur e vinyliden e chlorid e [75-35-4](1,1-dichloroethylene ) i s acolorless , mobil e liqui dwit

hacharacteristi c swee t

odor . It s propertie s ar e summarize di n Tabl e 1 . Vinyliden e chlorid e i s solubl e i n mos t polar an dnonpolar

organi c solvents . It s sol
ubilit y i n wate r

(0.2 5 w t % ) i s nearl y independen t o f temperatur e a t

16-90°C . Manufacture . Vinyliden e chlorid e monomer can b e convenientl y prepare di n th e laborator y b y th e reactio n o f 1,1,2-trichloroethan e withaqueou s alkali : 2 CH 2 ClCHCl a+ Ca(OH)- , • 90" C -* • 2 CH 2 =CC1 2 + CaCl a+ 2 H 2 0 

### Othe r method s ar e base do n bromochloroethane , trichloroethy l acetate , tetrachlo
roethane , an dcatalyti c crackin g o f trichloroethan e (7) . Catalyti c processe s produc e by-produc t

HC l rathe r

tha n les s valuabl e salts , bu t yield s o f vinyliden e chlorid e hav e bee n to o low fo

r commercia l us e o

f thes e processes . However , goo dresult s hav e bee n reporte dwit hmeta l sal t

catalyst s (8-10) . Vinyliden e chlorid e i s prepare dcommerciall y b y th e dehydrochlorinatio n o f 1,1,2-trichloroethan e wit

hlim e or causti c i n sligh t

exces s (2-10% ) (6,11) . A continuou s liquid-phas e reactio n a t

98-99° C yield s c a90% VDC . Causti c give s bette r result s tha n lime . Vinyliden e chlorid e i s purifie db y washin g withwater , drying , an dfractiona l distillation . I t

form s a n azeotrop e with6 w t % methano l (12) . Purificatio n can b e b y distillatio n o

f th e azeotrop e followe db y extractio n o f th e methano l with water ; a n inhibito r i s usuall y adde da t

thi s point . Commercial grade s contai n 200 pp mo f th e monomethy l ethe r

o f hydroquinon e (MEHQ) . Man y othe r inhibitor s fo

r th e poly
merizatio n o

f vinyliden e chlorid e hav e bee n describe di n patents , bu t MEH Q i s th eP.4 6
76 6 VINYLIDEN E CHLORID E AN D PVD C 

### on e mos t ofte n used . Th e inhibito r can b e remove db y distillatio n or b y washin g wit

h 2 5 w t % aqueou s causti c unde r a n iner t atmospher e a t

low temperatures . Fo r man y polymerizations , MEH Q nee dno t b e removed ; instead , polymerizatio n initiator s ar e added . Vinyliden e chlorid e fro mwhic hth e inhibito r

ha s bee n remove d shoul db e refrigerute da t

— 10°C , unde r

u nitroge n ulmospherc , i n tli e clurk , un di

n n nicke l o r bake dphenolic-line dstorag e tank . I f no t use dwithi n on e day , i t

shoul db e reinhibited . Laborator y Polymerization . Vinyliden e chlorid e polymerize s by bot h ioni c an d free-radica l reactions . Processe s base do n th e latte r ar e fa r mor e commo n (13) . Vi
nyliden e chlorid e i s o

f averag e reactivit y whe n compare dwithothe r unsaturate d monomers . Th e chlorin e substituent s stabiliz e radical s i n th e intermediat e stat e o f a n additio n reaction . Sinc e the y ar e als o strongl y electro n withdrawing , the y polariz e th e doubl e bond , makin g i t susceptibl e t o anioni c attack . Fo r th e sam e reason , acar boniu mio n intermediat e i s no t favored . Th e 1,1-disubstitutio n o

f chlorin e atom s cause s steri c interaction s in th e polymer a s i s eviden t

fro mth e hea t

o f polymerizatio n (se e Tabl e 1 ) (14) . Whe n correcte dfo r th e hea t o f fusion , i t i s significantl y les s tha n th e theoretica l valu e o f -83. 7 kJ/mo l (—2 0 kcal/mol ) for

th e proces s o

f convertin g adoubl e bon dt o tw o singl e bonds . Th e steri c strai n apparentl y i s no t importan t

in th e additio n step , becaus e VDC polymerize s easily . No r

i s i t sufficient t o favo r depolymerization ; th e estimate dceilin g temperatur e for PVD C i s c a400°C . Homopolymerization. Th e free-radical polymerizatio n o f VD C ha s bee n carrie d ou t b y solution , slurry ; suspension , an demulsio n methods . Solutio n polymerizatio n in amediu mtha t dissolve s bothmonomer

an dpolymer ha s bee n investigate d(15) . Th e kineti c measurement s lea dt o activatio n energie s an d frequenc y factor s i n th e norma l rang e fo r free-radica l polymerization s o f olefini c monomers . Th e kineti c behavio r o f VD C i s abnorma l whe n th e polymerizatio n i s heterogeneou s (16) . Slurr y polymerization s ar e usuall y use donl y a t th e laborator y level . The y can b e carrie dou t i n bul k or i n commo n solvents , eg , benzene . Poly(vi
nyliden e chloride ) i s insolubl e in thes e medi aan dseparate s fromth e liqui dphas e a s acrystallin e powder . Th e heterogeneity o f th e reactio n make s stirrin g an dhea t transfer difficult ; consequently , thes e reaction s canno t b e easil y controlledo n alarg e scale . Aqueou s emulsio n or

suspensio n reaction s ar e preferre dfo r large-scal e operations . Slurr y reaction s ar e usuall y initiate db y th e therma l decompositio n o f organic per oxide s o r az o compounds . Purel y therma l initiatio n can occur , bu t rate s ar e ver

y slow (17) . Th e spontaneou s polymerizatio n o f VDC , s o ofte n observe dwhe n th e monome r i s store da t

roo mtemperature , i s cause db y peroxide s forme dfromth e reactio n o f VD C wit hoxygen . Ver

y pur e monome r

doe s no t polymeriz e unde r

thes e conditions . Irra
diatio n b y eithe r

u v o r gamm aray s (16,18 ) als o induce s polymerizatio n o f VDC . Th e heterogeneou s natur e o f th e bul k polymerizatio n o

f VD C i s apparen t

from th e rapi ddevelopmen t

o f turbidit y i n th e reactio n mediu mfollowing initiation . Th e turbidit y result s fro mth e presenc e o f minut e PVD C crystals . A s th e reactio n pro gresses , th e crystallin e phas e grow s an dth e liqui dphas e diminishes . Eventually , a poin t i s reache dwher e th e liqui dslurr y solidifie s int o asoli dmass . A typica l conver sion-tim e curv e i s show n i n Figur e 1 fo r abenzoyl-peroxide-catalyze dmas s polymer
izatio n (19) . Th e firs t

stag e o f th e reactio n i s characterize db y rapidl y increasin g rate , whic hlevel s of

f i n th e secon dstag e t o afairl y constan t value ; thi s i s ofte n calle dth e