p. 1 

# OAR Box 1413 Prepped by Ollie Stewart



### Document

Number: 

# 4 ) 11-1- 4 Docket Number: 

# A-94-5 2

Printed 7/9/20083:11:20PM

Sheet 4 of 114/-— , • * «•_..!.,»— r * s "*»"_s i / . ' / . - • • o s . P. 2 

## A.04-6 2

SOUT H COAS

TAI R QUALIT

YMANAGEMEN TDISTRIC T RULE DEVELOPMEN TDIVISIO N

STAF F REPORT PROPOSE D RUL E 1162 - POLYESTE R RESI N OPERATION S

Januar y23 , 198 7

Prepare d by : Moustaf a Elsheri f

Senio rA.Q . Enginee r Reviewe d by : Davi d E . Schwie n

A.Q . Engineerin g Manage r Approve d by : Larr yM . Bowe n

Directo ro f Rul e Developmen tP. 3



## " I

I . EXECUTIV E SUMMAR Y Propose d Rul e 116 2 - Polyeste r Resi n Operation s (PRO ) i s designe d t o reduc e Volatil e Organi c Compoun d (VOC ) emission s fro mproductio n o r rewor k facilitie s tha t us e polyeste r resin . Polyeste r resi n i s a materia l uniquel ycapabl e o f meetin g a wid e variet yo f specifi c proces s an d end-produc t requirements . Product s mad e fro mthi s materia l includ e boa t o r yach t hulls , storag e tanks , automobil e fron t ends , fishin g rods , pools , spas , chairs , showe r and tu b enclosures , an

d panels . Fo r years , th e Distric t ha s looke d a t th e emission s fro mPR O 3 s a nuisance , primaril ybecaus e on e o f th e reactant s i s styrene , a malodorou s chemica l wit h a ver ylo wodo r threshol d (0. 1 ppm) . j Neithe r th e EPA» s Contro l Techniqu e Guideline s (CTG ) no r th e Stat e

. Implementatio n Pla n (SIP ) addresse s th e contro l o f VO C emission s fro m -PRO . Althoug h emission s and reduction s o f emission s fro mPR O ar e no t include d i n th e Ai r Qualit yManagemen t Pla n (AQMP) , staf f ha s determine d tha t th e tota l estimate d VO C emission s fro mPR O i s 22 tons/day . Ther e ar e tw o mai n source s o f VO C emissions : th e firs t i s th e productio n proces s i n whic h a VOC-typ e monomer , suc h a s styren e (1 4 tons/day) , i s used ; an d th e second i s th e cleanin g proces s i n whic h aceton e ( 8 tons/day ) i s primaril yuse d a s a cleanin g solvent . Staf f ha s determine d tha t thi s Rul e wil l achiev e a tota l VO C emissio n reductio n o f u p t o 12. 6 tons/da y(5. 6 tons/da yfro mth e productio n proces s and 7 tons/da yfro mth e cleanin g process) . Staf f ha s confirme d tha t complianc e wit h thi s Rul e ma yb e achieve d b y eithe r modificatio n o f tn e chemica l reactant s o r b yth e additio n o f film-formin g additive s (vapor-suppresse d resins) . Add-o n contro l equipmen t suc h a s incinerators , carbo n adsorbers , o r condenser s ar e technicall yfeasibl e bu t ar e no t expecte d t o b e economicall yviabl e fo r th e majorit yo f polyeste r resi n fabricators . Accordin g t o th e staff' s cos t analysis , th e cost-effectivenes s fo r thes e thre e contro l equipmen t technique s wil l var yfro m$19,00 0 t o $48,00 0 pe r to n o f VO C emissio n reduction . Th e cos t o f complianc e throug h proces s change s o r additiv e technolog yi s expecte d t o b e minima l i f materia l saving s i s considered . Th e propose d Rul e include s exemption s fo r ge l coa t us e and fo r us e o f corrosion-resistan t material s (unti l Jul y1 , 1990) , du e t o th e unavailabilit yo f low-emissio n technology . I n addition , dail y recordkeepin g wil l mor e tha n likel yb e require d fo r al l facilities . II . BACKGROUN D Currently , VO C emission s fro mPR O ar e no t regulate d b yth e District . Rul e 442 , whic h applie s i n genera l t o th e contro l o f VO C emission s fro mP. 4

-2
-

solvent- j use d i n productio n processes , doe s no t appl yt o PRO . Th e primaryreaso n fo r thi s i s th e monome r (primaril ystyrene ) use d i n thes e processe s i s considere d a ra wmateria l an d no t a solvent . I t i s polymerize d t o becom e a par t o f th e fina l cure d product . I n 1982 , a repor t wa s publishe d b yth e Ai r Resource s Boar d (ARB ) base d o n a stud

ydon e b

yScienc e Application , In c (SAI) . Th e repor t discusse s Californi a VO C emission s fro mPR O and variou s type s o f contro l technology . Th e repor t recommende d tha t th e infonnatio n obtaine d throug h thei r surve yshoul d b e incorporate d int o loca l emissio n inventorie s sinc e n o comprehensiv e detaile d inventoryo f polyeste r resi n operation s existed . Als o recommende d wa s th e us e o f vapor-suppressan t additive s an d othe r materia l change s t o contro l emissions . However , th e repor t faile d t o addres s emission s fro mth e us e o f cleanin g materials . Currently , th e Ba yAre a AQMD , th e Shast a Count yAPCD , an d th e Ventur a Count yAPC D hav e rule s fo r PRO . Non e o f thes e rule s wer e appropriat e fo r th e man ydivers e PRO s i n th e District . I n orde r t o develo p a rul e suitabl e fo r thi s area , staf f hel d severa l interna l workshops , tw o publi c workshops , manyindividua l an d group conferences , an d mad e severa l fiel d observation s t o evaluat e an d discus s th e curren t technologie s i n th e polyeste r resi n industry . III . POLYESTE R RESI NOPERATION S Thi s sectio n briefl ydescribe s th e chemistr yo f polyeste r resin , th e industrystructure , th e manufacturin g process , an d th e cleanu

p operation . A . Chemistr yo f Polyeste r Resi n Polyeste r resi n product s offe r a combinatio n o f propertie s suc h as : hig h strengt h an

d dimensiona l stabilit ywit h lo wweight ; corrosio n resistance ; excellen t dielectri c properties ; opportunitie s fo r part s consolidatio n an d desig n flexibility ; lo wfinis h cost ; an d moderat e toolin g cost . Th e fabricatio n o f polyeste r resi n product s require s a comple x chemica l reaction . Asimpl e introductio n wil l hel p explai n th e term s and th e processe s (pleas e se e Appendi x A) . Ther e ?r e tw o typo c ? f resins . Th e firs t typ e i s general-purpos e res: : ns . A

n exampl e i«

> orthophthali c resins , whic h ar e use d b yth e majorit yo f th e polyeste r resi n fabricators . Thes e orthophthali c resin s ar e lower-cos t resin s and the ysatisf yi m: t o f th e produc t specificatio n requirements . Th e secon d typ e i s corrosion-resistan t resin s suc h a s halogenated , bisphenol-A , furan , viny l ester, and isophthalic . Thes e resin s ar e relativel ycostl yand thei r uniqu e molecula r structure s allo wthe mt o resis t acids , alkalie s and solvents .P. 5

-3
-

B . Industr y

Structur e I t i s estimate dtha t ther e ar e approximatel y 100 0 firms , eac hwit h les s than3 0 employees , conductin g polyeste r resi noperation s i n th e District . Mos t o f thes e companie s fabricat e thei r product s b y spray-up , han

dlay-up , andcontact-moldin g type s o f processes . Approximatel y

5 0 firms , wit hove r 3 0 employee s each , ar e involve d i nautomate dprocesse s suc ha s paneling , pultrusion , o r filament-winding . I nadditio nt o the fabricators , ther e ar e estimate dt o b e abou t 70 0 rewor k andrepai r shop s fo r automobiles , boat s an

dothe r products . Th e tota l amoun t o f polyeste r resi nmaterial s use dthroughou t the Distric t i s approximatel y 12 8 millio nlbs/year s (mostl y orthophthalic) . Thi s include s 7 millio nlbs/yea r fo r corrosion-resistan t applications . Th e amoun t o f aceton e use di s abou t 600,00 0 gals/year . Figur e 1 show s th e distributio nb y produc t an

dTabl e 1 show s th e amoun t o f polyeste r resi nusag e distribute db

y process . Fo r spray-up , han

dlay-upan

dcontac t moldin g processes , ge l coa t i s th e firs t materia l t o b e applie dt o th e mol dan dbecome s th e ultimat e finis hfo r th e product . Thi s ge l coa t mus t for m a stron g chemica l bon

dt o th e fiberglas s laminate . Vapo r suppressan t additive s fo

r th e ge l coa t wil l mak e tha t bondin g impossible . Also , sprayabl e viscositie s canno t b e achieve da t monome r level s les s tha n3 5 percent . Fo r thes e reasons , som e provision s o f thi s Rul e wil l no t appl y

t o ge l coa t application . Fabricator s tha t mak e corrosion-resistan t product s ar e concerne d abou t long-ter

m liabilitie s associate dwit hthei r product s an dmus t mee t rigi dperformanc e standards . Currently , th e amoun t o f corrosion-resistan t material s use di nth e Distric t i s onl y 7 millio npound s per year . Staf f believe s tha t 3- 5 year s ar e neede d t o develo pmodification s o f material s t o mee t th e genera l requirement s o f the Rule . Fo r thes e reasons , som e provision s o f thi s Rul e wil l no t appl y t o corrosion-resistan t application s unti l 1990 .FIGURE 1



# Estimate dResi n Use d Distributio n b y Produc t

40 % 

### Percen to

f Tota l

30 % -

20 % -



### 10 % h

0 % 

### Pool/Sp aAut

o Tank s Marble Bath Fixt . Othe rBoa tPanel s



# Product s H H Resi n Use d iP. 7

- 5 - TABL E 1 ESTIMATE D SCAQM

D POLYESTE R RESI N USAG E (LB S PE R YEAR )

CLOSE D MOLDIN G BMC , SMC , RESI N APPLIE D A TPRESS , INJECTIO N 3,500,00 0

OPEN MOLDIN G SPRAY-U P 50,000,00 0 CONTINUOU S LAMINATIO N 2-4,000,00 0 CASriN G 22,500,00 0 HAN D LAY-U P 15,300,00 0 FILAMEN TWINDIN G 3,400,00 0 PULTRUSIO N 1,300,00 0 OTHE R 8,000,00 0

TOTA L 128,000,00 0P. 8



### -6
-

C . Manufacturin g Proces s I n general , ther e ar e severa l productio n method s use d i n thi s industry . Asurve yo f th e PR O i n th e Distric t show s tha t th e simultaneou s us e o f mor e tha n on e metho d account s fo r th e vas t majorit yo f resi n use . Th e followin g ar e th e mos t commo n productio n methods : 1 . Spray-up Mor e tha n hal f o f th e industr yuse s som e for mo f spra y applicatio n o f resi n ont o a mol d (se e Figur e 2) . Fiberglas s rovin g i s fe d int o a speciall ydesigne d "choppe r gun " whic h chop s th e rovin g int o approximatel yone-inc h lengths ; th e gu n simultaneousl yspray s a predetermine d amoun t o f resi n and catalys t int o th e ope n mold ; and th e tw o chemica l ingredient s ar e mixe d outsid e th e gu n a s the yexi t (outsid e mix ) o r insid e th e gu n (interna l mix) . O f al l th e productio n methods , th e spray-up proces s ha s th e highes t potentia l fo r VO C emissions . Atomizatio n o f resi n create s a n enormou s surfac e are a o f expose d resin , thu s enhancin g VO C los s throug h evaporation .

FIGUR E 2 

## Spray-U p

Mol d

Resi n Catalys tP. 9



### -7 -

2 . HandLay-u

p Thi s methodbegin s wit hfittin g choppe dstrand s o f fiberglas s o r wove nfiberglas s rovin g int o a nopenmold , by

hand . Catalyze dresi ni s the nadde dan d "wetted-out " i nth e fiberglas s strand s b y us e o f rollers , brushes , o r squeegee s (se e Figur e 3) . Thi s metho dproduce s a highe r strength-to-weigh t rati o produc t compare dt o product s mad e wit hspray^upmethods . A relativel y

larg e surfac e o f resi ni s expose dt o th e atmospher e for mos t o f th e productio ncycl e an dhelp s creat e a rathe r hig

hVO C emissions . A commo npractic e inth e industr y i s t o combin e spray-u pan d handlay-u

pmethods .

FIGURE 3 

## Han d LayJJ p

Roller Ma t Impregnated wit h Resi n Mol dP.1 0

- 8 -

3 . Continuou s Laminatio n• Continuou s stran dfiberglas s roving s ar e choppe dan devenl y distribute dont o acontinuously-movin g shee t o f cellophan e o r othe r typ e o f non-adherin g plasti c sheetin g (se e Figur e 4) . Th e choppe dglas s laye r

i s the nsaturate dwit hpre-catalyze d resi nan dcovere dwit hasecon dshee t o f cellophane . Th

e glass/resi ncomposit e sandwiche dbetwee nth e cellophan e sheetin g i s the npulle dthroug haformin g di e an dpasse d throug hacurin g oven . Th e emergin g cure dpane l i s the n strippe do f

it s cellophan e covering , trimme dalon g th e edges , andcu t t o th e desire dlength . The VO C emissio npe r

uni t weigh t o f produc t i s no t hig hbecaus e mos t

o f th e proces s tha t ha s apotentia l t o emi t VO C i s containe dwithi nth e to p an d botto mcellophan e sheets .

FIGUR E 4 Rovin g Strand s Rovin g Chopper*

' Formin g Chambe r Resi n 

# ffl Pane l Cellophane Rol

l



## •Hnimitnniii n Resi n 

# Q

1_ _ Pane l Cutte r 

# P

= 3 Cellophane Rewin

d Cellophan e Rol l

_ . Sectio n Trimme rP.1 1


### -9 -

4 . Castin g o rMoldin g Thi s proces s i s bein g more widel yuse d no wb ycompanie s tha t wan t finishe d component s wit h on e o rtw o smoot h surface s (se e Figur e 5) . Continuou s strand s ar e lai d b yhan d int o a mol d an d catalyze d polyeste rresi n i s poure d o rinjecte d int o th e mol d cavity . I n som e cases , th e resi n i s mixe d wit h fiberglas s an d othe radditive s t o for m a putt yo rdough-lik e resin , suc h a s th e resi n i n a Bul k Moldin g Compoun d (BMC ) o r • i n a Shee t Moldin g Compoun d (SMC ) process . Thi s proces s i s " use d fo rhighl ycomple xshape s an d fo rcor e material s tha t requir e added structura l strength . Most o f thes e ar e closed mol d processes . Emissions , i n general , ar e low .

FIGURE 5 

## Resi n Transfe r Moldin gP.1 2

-10 -

5 . Pultrusio n Continuou s rovin g strand s ar e pulle d fro m a cree l throug h a strand-tensionin g devic e int o a resi n bat h (se e Figur e 6) . Whe n thoroughl yimpregnated , th e forme d resin/glas s composit e i s the n passe d throug h a heate d die . Th e finishe d cure d resin/glas s stoc k

i s the n cu t t o th e desire d lengt h an d packaged . Th e mai n VO C emissio n sourc e i s th e ope n resi n bath , sinc e curin g (als o a sourc e o f VO C emissions ) take s plac e i n th e enclose d die .

FIGUR E 6 

## Pultrusio n Strand Tension Device Pul l Roller s Formin g Di e Heate d Di e Hovin g Strand s Resi n Bat h 

# O

Forme d Impregnate d Stran d Cured , ( r \

Puttnided 1 Ra t Stoc kP.1 3

-11 -

6 . Filamen t Windin g

Thi s metho di s becomin g increasingl y popula r for th e manufactur e o f larg e pipes , storag e tanks , an dothe r hollo w vessel s whic hma y

b e subjec t t o grea t interna l pressur e (se e Figur e 7) . Continuou s strandroving s ar e pulle db y a rotatin g mandre l througha strandtensionin g devic e int o a resi nbath . Emergin g fro

m th e resi nbath , the strands , eac huniforml y coated , ar e woundont o a mandre l t o th e shap e an dpatter n require dfor th e finishe dproduct . Th e uni t i s the ncure din a nove no r a t roo

m temperature . Th e requiremen t fo r low-resi n viscosit y

ofte nimplie s th e us e o f highe r monome r concentration , causin g a moderat e VO C emission .

FIGUR E 7 

## Filamen t Windin g Stran d Tensio n Devic e Mandre l Drive

Roving s



## Cree l Windin g Mandre l Resi n Bat hP. M

-12 -

D . Cleanu p Operatio n Cleanu p o f

hands , tools , andspra y gun s i s aver y importan t par t o f th e productio n cycle . Hands , brushes , rollers , an dsqueegee s mus t 1 b e cleane dwit hasolven t (usuall y acetone ) afte r applyin g eac h batc ho f

resin . Also , spra y gun s mus t b e flushe dwit hsolven t afte r eac hus e an

dthroughl y cleane ddaily . Thi s cleanin g prevent s resi n fro

mcurin g on th e tool s andi n th e guns , thu s renderin g the m unusable . Cleanin g solven t

i s usuall y availabl e i n 2-gallo n container s fo r han dcleaning , 5-gallo n container s fo r too l cleanin g an

d3

- t o 5-gallo n container s fo r spra y gun cleaning . Also , mos t resi n gun s hav e aclea n solvent-suppl y lin e connecte ddirectl y t o th e gu n t o flus hth e interna l part s afte r eac huse . IV . EMISSION

S Ther e ar e generall y

tw o majo r source s o f VO C emission s fro m PRO : th e resi nusedi nthe manufacturin g processe s an d th e solven t fro

m th e cleanu poperation s durin g an d afte r the manufacturin g processes . A . Emission s Fro

m the Manufacturin g Proces s VO C emission s wil l dependo nth e amoun t o f material s used , th e typ e o f product s made , manufacturin g methods , and busines s activity . Th e mos t commo nmonome r usedi s styrene . Evaporatio no f styren e fro m ge l coa t o r resi ndurin g th e raw material-applicatio nproces s an ddurin g the curin g perio di s th e mai nsourc e o f VO C emissions . I t i s estimate dtha t up to.1 0 percen t o f th e resi ni s los t a s overspra y

o r b y evaporatio ndurin g th e raw materia l applicatio n process . Inaddition , u p t o 8 percen t o f th e styren e monome r in th e applie dresi no r ge l coa t evaporate s befor e polymerizatio ni s complete . Ther e ar e man y othe r factor s tha t impac t th e styren e evaporation , suc ha s ge l time , temperature , and ai r flow . Figure s 8 , 9 , an

d 1 0 sho w

th e amoun t o f VO C emission s wit heac hfactor . Staf f ha s determine dtha t th e stati c laborator y tes t method s fo r measurin g VO C emission s fro m th e polyeste r resi nmaterial s ar e the bes t an d mos t consisten t method s available . B . Emission s Fro

m the Cleanin g Proces s Cleanin g solven t emission s typicall y accoun t fo r mor e tha n3 6 percen t o f th e tota l plan t VO C emissions . Thes e emission s ar e du e t o th e evaporatio no f solven t fro m the part s bein g cleaned , fro m atomizatio no f solvent , fro m agitatio no f th e solven t during the cleanu pprocess , fro m storag e o f solven t i nope ncontainers , an d fro m imprope r disposa l o f wast e materials .P.1 5

-13
- Th e numbe r o f employee s applyin g th e resi n directl yaffect s tota l solven t emission s becaus e eac h employe e mus t clea n hi s hands , tools , and spra ygun .FIGUR E 8



# Influenc e o f

Ge l Tim e

gm/m £

Fiv e 

# o n 

# Styren e Emission s

Te nFiftee n 

# Minute s H Styren e Emission s Twent y IFIGURE 9



# Influenc e of

Temperatur e o n 

# Styren e Emission s
15 0 

### Styren e Evaporatio n- gm/m 2

10 0

2 5 3 0 3 5



# Ambien t Temperatur e - "

C I Suppresse dResi n H H Standar dResi n Ut IFIGUR E 1 0

20 0


### 15 0 

# Influenc e o f

Ai r Flo w Rat e o n 

# Styren e Emission s Styren e Evaporatio n - gm/m 2

10 0 at i



### Suppresse dResi n

T l 0 0P.1 9

-17 -

V . EMISSIO

NCONTRO

LTECHNIQUE

S The thre e contro l technique s are : proces s change s t o contro l monome r emissions , materia l change s fo r contro l o f

aceton e emissions , and add-o n contro l equipment . • A . Proces s Change s 1 . Modification s t o Materia l Reducin g th e resi nconten t canreduc e th e emissions . Thi s ca n b e accomplishe dby eithe r redesignin g th e product s t o requir e les s resi no r

usin g mor

e filler s an dcolorants . Mos t o f th e time , however , i t

i s difficul t

t o achiev e th e desire dproduc t propertie s by reducin g th e resi ncontent . Th e conversio nt o low-monomer-typ e resin s (35-weigh t percent ) compare dt o th e conventiona l resin s (40

- t o 50-weigh t percent ) i s aviabl e metho dfo r th e contro l o f

som e o f th e emissio n problem s previousl y describe d(se e Figur e 11) . Severa l companie s hav e beenmarketin g suc hresin s fo r severa l years . Th e cos t o f low-monome

r resin s i s slightl y highe r thanth e cos t o f conventiona l resins . Th e reductio ni ntota l styren e emission s canreac h4 0 percent , b y weight , whe naconventiona l resi n i s replace dby alow-styren e resin . .FIGUR E1 1 

# Influenc e o f

Styren e Conten t o n 

# Styren e Emission s

12 0 

### Styren e Evaporatio n - gm/m 2

32 % Styren e 

# Minute s 35 % Styren e -* ~ 40 % Styren e -B

_44 % Styren e 0 0 I

T l h oP.2 1 -19 -
Anothe r emissio nreductio noptio ni s t o reduc e th e resi n molecula r

weigh t t o th e poin t

where resin , a t

onl y 3 5 percen t styrene , woul dexhibi t alo w enoug hviscosit y t o readil y we t th e reinforcemen t

materials . Unfortunately , resi nwit hlow monome r conten t migh t b e unacceptabl e fo r

th e manufactur e o f som e product s becaus e th e resi nwoul db e more viscou s and difficul t t o spray , mold , o r

injec t (se e Figur e 12) . Also , reductio ni nmolecula r weigh t usuall y i s accomplishe dby a correspondin g los s o f

desire dpropertie s (mechanica l o r physical ) whic hals o coul dseverel y limi t th e acceptabilit y o f som e products . Recently , amodifie dphotoinitiato r polyeste r

resi nwas developed , bu t

i t i s stil l unde r

analysis . Th

e ne w photoinitiato r

resi ni s aone-componen t resi nwhichcure s withou t additive s whe

nexpose dt o long-wav e ultraviole t light . Th e mos t significan t

advantag e o f

thi s syste mi s th e rapi d curin g (les s ge l time) . Inaddition , th e cur e develop s fro m th e outside , whic hgreatl y limit s styren e evaporation . Additiona l advantage s are : o arapi dandcontrolle drat e o f cure . o no mixin g an

dmeterin g o f

ra w material s i s required , o ther e i s minimal wast e fromunuse dresin , o les s cleanin g i s neede dbetwee nresi napplications . Th e initia l testin g o f

thi s modifie dresi nshow s a4 0 percen t reductio ni nemission s compare dt o the•emission s fro mth e conventiona l resins . Thi s photoinitiato r additiv e coul db e use dt o produc e mos t

o f th e polyeste r

resi nproduct s tha t

ar e u p t o one-inc hthick . A fina l optio ni s th e replacemen t o f par t o r al l o f th e styren e wit hanothe r

monomer . Th

e searc hfo r

suc hamonome

r ha s bee n th e subjec t

o f researc hby man

y companie s fo r

som e time . Th

e idea l material , o f

course , i s amonome

r wit hal l o f th e desirabl e qualitie s o f styren e (goo dthinnin g capacity , goo dmechanica l properties , andeas e o f polymerzation) ; and on e whic hi s alow-VO

C emitter , andi s cost-effectiv e a s a styren e substitute . 2 . Suppresse dResin s Th e mos t promisin g technolog y toda y fo r reducin g VD

C emission s i s th e us e o f

suppresse dresins . Thes e resin s decrees * VO C emission s by entrappin g som e o f th e monome

r tha t woul d otherwis e vaporiz e durin g th e exothermi c curin g o f th e resi n (se e Figur e 13) • Th

e suppressin g agen t

consist s o f

paraffi n o r wax-lik e material s tha t ar e adde dt o th e polyeste r resin . Th e paraffi nbuild s afil mo nth e surfac e o f

th e laminat e whic hphysicall y block s th e polymer surfac e fro

moxyge ni nth e ai r an da t th e sam

e tim e reduce s styren e evaporation .FIGURE 1 2



# Viscosit y vs . Percen t Styren e (a t

2 0 C ) 160 0 Viscosit y CP S 140 0 120 0 100 0 80 0 60 0 40 0 f

20 0 

### 0 0 Han d Lay-U p Spray-U p 

### 1 0 \

\



### 2 0 3 0 4 0 

# Percen t Styren e *~ ~ Resi n i r o o i



### 5 0 6 0

r o r oFIGURE 1 3



# Compariso no f

Suppresse dResi n an d 

# Standar dResi n Styren e Evaporatio n - gm/m 2

2 0 4 0 6 0 

# Tim e i n Minute s Afte r Laminatin g

— " ~ Suppresse dResi n' Standar dResi n i r o

8 0

t o c oP.2 4

-22 - Suppresse dresin s wil l reduc e VO C emission s by abou t

M O percent , by weight . Thes e resin s ar e price dslightl y highe r tha nth e conventiona l resins . However , suppresse dresin s wil l achiev e materia l saving s whic hshoul doffse t th e differenc e i n price . Differen t

brand s o f

suppresse dresin s var y i n performanc e an

dmetho do f

suppression . (Mor

e specifi c informatio ni s unavailabl e du e t o claim s o f confidentiality. ) Presently , afe

w manufacturer s hav e experience ddifficult y wit hdelamination , aseparatio nbetwee nlayer s o f applie d resin . Thi s happen s becaus e th e suppresse dresi nleave s a thi n fil mo f

wa x o nth e surfac e whic hcanb e detrimenta l t o th e adhesio no f

asubsequen t

lamination . 3 . Closed-Mol dProces s Use o f aclosed-mol dproces s i s a nexcellen t

wa y t o reduc e styren e emissions . Som e o f thes e processe s ar e th e Resin-Transfe r

Moldin g (RTM

) process , th e Sheet-Moldin g Compoun d(SMC ) process , an dth e Bulk-Moldin g Compoun d(BMC ) process . Thes e processe s ar e use donl y fo r small-siz e products . B . Clean-u p Solven t

(Acetone ) Emissio nReduction s Thre e method s t o reduc e aceton e emission s are : correctio no f employe e wor

k habits , reclamatio no f spen t acetone , andus e o f solven t substitutes . 1 . Correctio no f

Employe e Wor

k Habits . Aceton e i s usuall y availabl e fo r eac hemploye e i na2-gallo n containe r

fo r handcleaning , a5-gallo ncontaine r fo r too l cleaning , an

da5-gallo ncontaine r fo r spray-gu ncleaning . Also , mos t

spra y gun s hav e aclean-aceton e fee dlin e t o flus h th e interna l part s afte r eac huse . Unfortunately , man

y fabricators ' practice s an dwor k habit s whe nhandlin g andusin g aceton e ar e les s tha nideal . Limitin g th e issuanc e o f

aceton e t o th e employee , andprope r trainin g anddiligen t

supervisio nwit hregar dt o th e prope r us e an d handlin g o f

acetone , wil l reduc e solven t emissions . 2 . Reclamatio no f

Spen t Aceton e Ther e ar e tw

r option s fo r

th e contro l o f

s-jtut-aceton e emissions : on-sit e recover y o r off-sit e recover y a t

a commercia l solven t

reclaimin g facility ; bot hoffe r economi c an denvironmenta l benefits . Som e manufacturer s simpl y dispos e o f spen t aceton e by allowin g i t t o si t i nopencontainer s an devaporate . On-sit e aceton e reclamatio nthroug hth e us e o f adistillatio nuni t

canreduc e thi s loss . Thes e unit s ar e availabl e i ndifferen t size s i nP.2 5 -23 - orde r t o b e compatibl e wit hth e need s o f variou s PRO. Thes e unit s com

e completel y assemble dan dcanrecove r

9 0 t o 9 7 percen t o f th e solven t

tha t otherwis e i s lost . Thi s approac h• shoul dhel p reduc e th e problem s associate dwit hth e storag e o f dirt y solvents . Som e polyeste r

resi nmanufacturer s dispos e o f spen t aceton e a t anoff-sit e dump . Thi s wil l contribut e t o VO C emission s a t th e dum p site . Spen t

aceton e canb e sen t

t o commercia l facilitie s tha t

specializ e i nreclaimin g aceton e a s wel l a s othe r solvents . A

nadditiona l benefi t

o f thi s metho di s tha t th e polyeste r

resi nfabricato r

canals o hav e th e off-sit e reclamatio nfacilit y dispos e o f soli dwast e include di nth e spen t acetone . 3 . Use o f

Solven t Substitute s Polyeste r

resi nmateria l manufacturer s hav e recentl y develope d low-VOC , water-base dmaterial s t o replac e aceton e fo r cleanin g hands , tools , an

dspra y equipment . Thes e type s o f material s ar e no w successfull y use dby mos t o f th e fabricators . However , aceton e i s usuall y use di nsmal l quantitie s t o di p tool s andspra y equipmen t fo r afina l cleanin g i norde r t o remov e th e wate r

fro mth e ite mbein g cleaned . Wor k i s ongoin g t o improv e th e ne w solven t

substitut e product s an dt o eliminat e th e fina l us e o f acetone . C . Add-onControl s Fou r type s o f

add-o ncontro l equipmen t wer e investigated : incineration , absorption , adsorption , an dcondensation . 1 . Incineratio n Thermal o r

catalyti c incinerator s ar e availabl e t o contro l emission s fro

mspra y booths , oven s androo mexhausts . I natherma l incinerato r th e solvent-lade nai r i s expose dt o a temperatur e o f

1000 ° t o 1500° Fanddirec t flam e contac t

fo r a perio do f

0. 3 t o 0. 6 seconds . Inth e catalytic , incinerato r th e operatin g temperature s ar e 600 ° t o 750° Flower . I neithe r case , th e importan t

incineratio ndesig nfactor s are : wast e ga s strea mflo w rate , residenc e time , temperature , an dwast e ga s hea t content . Bothincinerator s ca nb e designe dt o achiev e 9 0 t o 9 9 percen t remova l efficiency . However , withi n th e District , incinerator; : hav e not , i ngeneral , bee nuse da s emission-contro l device s i nth e PRO . (One fabricato r

use s incineratio nonl y whe

nth e VO C emission s excee dacertai n limi t s o i t ca ncomply wit hRegulatio nnil , Ne w Sourc e Review. ) Incineratio ni s mos t effectiv e whe

nth e pollutan t

t o b e controlle di s a t

ahig hconcentratio nandha s ahig h heatin g value . Typically , polyeste r resi noperation s hav e lo w VO C concentration s i nthei r exhaust s an dhig hexhaus t ai rP.2 6

-24 - flows . Thes e condition s resul t i nlo w hea t

conten t exhaus t streams , thu s leadin g t o tiig hsupplementa l fue l requirement s an dincreasin g operatin g costs . Therefore , incineratio ni s no t usuall y economicall y feasibl e fo r mos t PRO . 2 . Absorptio n Throug hth e us e o f

absorption , aceton e andstyren e emission s ar e remove dfro

mth e exhaustin g contaminate dai r strea mby direc t contac t wit haliquid . Th

e absorptio ntake s plac e b y a chemica l reactio nwit hon e o r mor e components , sodium hydroxid e o r

amixtur e o f

sodiumhydroxid e an

dsodiu m hypochlorite , i nth e water-base dliquid . Th e estimate d contro l efficienc y i s a t leas t 7 0 percent . Absorptio nha s no t

beenuse dt o contro l styren e an daceton e emission s i nth e District . Furthe r investigatio nan

dtestin g woul dhav e t o b e don e t o determin e it s applicabilit y fo r th e PRO; a s apar t

o f this , th e impac t

o f th e resultin g liqui dand soli dwast e disposa l wouldhav e t o b e determined . 3 . Adsorptio n Carbo nadsorptio ni s acommo ncontro l techniqu e fo r removin g VO C emission s froma

n ai r stream . Whe

nth e carbo nreache s th e saturatio n point , ho t ai r O r stea mi s use dt o regenerat e th e adsorben t

carbon . However, activate dcarbo ncanserv e a s a catalyti c agen t

fo r th e polymerizatio no f som e monomers . I f hig hmolecula r

weigh t polymer s ar e produced , the nth e adsorben t

surfac e ca nbecom

e foule dan

dregeneratio nma

y no t b e possible . Also , th e presenc e o f aceton e emission s i nth e ai r strea mcoul dreduc e th e adsorptio nefficiency , sinc e aceton e ha s arelativel y hig hhea t o f adsorption , thereby , syste meffectivenes s i s reduce dwhe nth e temperatur e rises . I naddition , particulat e matte r generate di nth e proces s ca n clo g th e adsorbent , thereb y reducin g it s effectivenes s an d increasin g th e pressur e dro p throug hth e system . 4 . Condensatio n Ther e ar e tw

o type s o f

condensers . Th

e firs t typ e i s a surfac e condense r

where exhaus t

ai r strea mi s coole dwit ha fluid , bu t

doe s no t

com e int o direc t

contac t wit hth e air . The secon dtyp e i s acontac t condense r

where th e exhaus t

ai r strea mi s spraye dwit hachille dliquid . Bot htype s ar e generall y no t

practica l becaus e mos t PR O exhaust s hav e VO

C concentration s belo w 100 0 ppm , andcondenser s wor k effectivel y wit hhigher-VO C streams . COS T ANALYSI

S Whil e al l th e emissio ncontro l technique s describe di nthi s repor t are , i nprinciple , applicabl e t o mos t o f th e polyeste r

resi nfabricators , thei r implementatio ncost s var y considerably .P.2 7 -25 - Th e tota l capita l cost s liste dbelo w were base donvendo r price s o f

th e basi c equipmen t

an daccessories . Uni t

electricit y an dnatura l ga s cos t wer e obtaine dfro

mSouther nCaliforni aEdiso nCompan y an dSouther n .Californi aGa s Company, respectively . A typica l polyeste r

resi nfabricato r

was selecte dfo r

thi s cos t analysi s study . Thre e control-equipmen t scenario s wer e evaluated . A . Material s Use

d Polyeste r

Resi n Ge l Coa t Monome r Percen t (Styrene ) Aceton e Spen t Aceton e Manufacturin g Proces s Operatin g Tim e Emissio n Facto r B . Contro l Equipmen t Incineratio n Adsorptio n Absorptio n Interes t Rat e Equipmen t Lif e C . Operatin g Cos t Labo r Electricit y Ga s Maintenance , Ta x & Ins . Styren e Aceton e 90 0 Lb/Da y 10 0 Lb/Da y 45 % 1 0 Gal/Da y 4 Gal/Da y Combinatio n o f Spray-U p and Han d Lay-Up . 8 Hr/Day , 5 Days/Wk , 5 2 Wks/Yr . Us e 0.1 0 poun d o f VO C los t pe r pound o f resi n used . 90 % Efficienc y 70 % Efficienc y 70 % Efficienc y 10 % 1 5 Year s $10.0 0 H r $ 0.0 8 Kw

h $ 6.4 7 M M Bt u 11 % o f Installatio nCapita l $ 0.8 5 L b $1.2 5 L bP.2 8

-26 - Base donth e abov e assumptions , th e cost-effectivenes s i s a s follows : A. Contro l Equipmen t 1 . Incineratio nCos t Th e estimate dannua l operatin g cos t is : Capita l Cos t Labo r Ga s Electricit y 50 % Hea t Recovery Credi t Ne t $195,00 0 3,00 0 700,00 0 12,000 -350,00 0 $560,00 0 Withareductio no f

approximatel y 11. 7 ton s pe r year , th e cost-effectivenes s woul db e abou t

$48,00 0 per/ton . Carbo n Adsorptio n Cos t The estimate dannualize dcos t is : Capita l Cos t Carbo n Labo r Stea m Electricit y Tota l $190,00 0 14,000 . 2,00 0 1,00 0 25,00 0 $232,00 0 Withreductio no i approximatel y 9. 0 ton s pe r year , th e cost effectivenes s woul db e abou t $26,00 0 per/ton .P.2 9

-27
-

3 . Absorptio n Cos t Th e estimate d annua l operatin g cos t is : Capita l Cos t $150,00 0 Labo r 16,00 0 Electricit y 9,00 0 $175,00 0 Wit h reductio n o f approximatel y9. 0 ton s pe r year , th e cost-effectivenes s woul d b e abou t $19,00 0 per/ton . 4 . Spen t Aceton e Reclamatio n Cos t Spen t Aceton e Generate d 830 0 Gal/Yea r Cos t Credi t fo r Recyclin g $0.4 0 pe r gallo n o f aceton e recycle d Annua l Saving s $3,30 0 Aceton e Recovere d(90 % Recovery ) Recyclin g yield s acos t saving s o f

abou t $134/Tons . I nothe r words , i t

wil l pay fo r

itsel f i nles s tha non e year . B . Goo dHousekeepin g Goo dhousekeepin g an demploye e trainin g ar e goo dlow-price-contro l technique s fo r

reducin g VO

C emission s fro

mPRO . Staf f

found , durin g severa l fiel dinspections , tha t mos t fabricators ' practice s an dwor k habit s ar e les s tha nideal . Most o f th e problem s ar e i n th e are ao f

resi nsprayin g an dmaterial s handlin g an dar e readil y correctabl e withprope r employe e trainin g anddiligen t supervision . The us e o f

close dcontainer s fo r storin g fres han dspen t cleanin g material s an

dwast e polyester-resi nmaterial s reduce s evaporatio n losse s andals o reduce s odo r problems . Improve dhousekeepin g practice s wil l resul t i nacos t

savin g t o th e fabricator s b

y th e eliminatio n o f

unnecessar y evaporatio nlos3 . C . Material s Modificatio nCost s The mos t promisin g material s modificatio nmethod s fo r reducin g VO

C emission s fro

mth e polyeste r

resi noperation s are : 1 . Use o f

low monome

r polyeste r

resi nmaterials .P.3 0

-28 - 2 . Us e o f vapo rsuppressant . 3 . Us e o f resin s wit halowe r

molecula r

weight . 4 . Us e o f photoinitiato r

polyeste r

resins . 5 . Replacemen t

o f styren e wit hothe r

low-VO C materials . Al l o f th e abov e approache s ar e cost-effective ; however , t o b e sur e tha t th e us e o f

suc hmaterial s i nsom e product s i s no t

accompanie d by acorrespondin g los s o f desire dproperties , additiona l researc h an ddevelopmen t

i s required . VI . SIGNIFICAN

T IMPACT S A. Energ y Impac t Th e energ y

impac t wil l be minimal . Th e majorit y o f the fabricator s wil l compl y

b y reformulatin g material s andwil l no t consume additiona l amount s o f energ y o r generat e additiona l wastes . B . Economic Imoac t Smal l fabricator s wil l b e abl e t o us e th e suppresse dresi no r low-monome

r resin . Bot

har e availabl e andcost-effective . The cos t impac t wil l b e minimal . C . Environmenta l Impac t Thes e propose dcontro l measure s wil l no t resul t i nan y wate r pollutio no r i

nan y increas e i nsoli dwast e disposal . Th e reductio ni nemission s o f reactiv e organic s shoul dreduc e ozon e formatio ni nthe Distric t a s wel l a s reduc e th e potentia l fo r odo r nuisance . D . Distric t

Impact s 1 . Enforcemen t Th e majo r

impac t t o th e Enforcemen t

Divisio nstem s fromtw o Rul e requirements : clean-u p an drecordkeeping . Th e Enforcemen t

Divisio nestimate s 4. 5 additiona l inspector s wil l b e neede dt o implemen t th e Rul e afte r

on e year . Th

e nee dwil l b e rediir.f

i to 2 inspector s t o maintai nadequat e enforcemen t thereafter . 2 . Sourc e Testin g Staf f expect s tha t

approximatel y 2 0 hour s pe r yea r wil l b e neede dfo r

testin g an

y ne w add-o ncontro l equipment .P.3 1 -29 -

3 . Laborator y Additiona l laborator y sample s wil l b e require di norde r t o determin e complianc e wit hth e reformulatio nrequirements . A n estimate d200-30 0 hour s pe r year wil l b e neede dt o analyz e thes e samples . 4 . Engineerin g Engineerin g Divisio nestimate s tha t 2. 5 enginee r year s wil l b e require dto proces s th e new application s tha t wil l resul t fro m th e adoptiono f thi s Rule . VII . COMMENTS A . EPA ; N o comments were receive dfromth e EPA. B . AR B Th e AR B find s Rul e 116 2 acceptabl e an dha s n o suggestion s fo r revision . C . PUBLI C Al l o f th e publi c comment s wer e channele dthroug hth e Societ y o f th e Plastic s Industry , Inc . (SPI) . Comment : Recommen

dtha t "Polyeste r

Resi nOperations " b e change dt o "Polyeste r

Resi nMoldin g Operations " t o preven t confusio n wit hPolyeste r

Resi nProducin g Operations . Reply : Propose dRul e 116 2 define s PR O a s th e fabricatio no r rewor k o f product s mad

e fro mpolyeste r

resi nmaterials . Th e propose dRule , therefore , doe s no t appl y t o th e productio no f

polyeste r

resi nmaterials . Comment : Change th e definitio no f "Approve dComposit e System " sinc e th e industr y refer s t o bot hresi nmateria l and reinforcements . I naddition , chang e "additives " t o "formula " i nth e sam

e definition . R eply : Th

e propose dRul e wa s change dt o "Approve dLow-VO C Emission s Resi nSystem. " Th e definitio napplie s t o additivc c technology . Complianc e b y change s i n formulatio ni s th e optio ndescribe dby subparagrap h (b)(1)(A)(iv) . Comment : Includ e definition s ib r ge i coat s an amonomers . Reply : Th

e propose dRul e include s bot hdefinitions .P.3 2

-30 - Comment : Reference s t o "closed-mold " shoul db e change dt o

"molding. " Ther e ar e pultrusio nprocesse s whic hma y no t f i t th e definitio no f

"closed-mold " but , becaus e o f low-VO C emission , los e les s tha n4 percen t weight . Reply : Pultrusio nproces s wit hles s th e 4 percen t weigh t los s wil l b e i ncomplianc e wit hth e "othe r proces s requirement " optio no f subparagrap h(b)(1)(A)(iv) . Comment: Touch-u p o r

repai r shoul db e exemp t

fro mth e subparagrap h (b)(i)(B ) sprayin g requirement s becaus e airles s equipmen t i s neithe r

practica l no r

available . Reply : I f

touch-u p o r

repai r o f asmal l are ai s required , smal l amount s o f

material s ma

y b e applie dwit haconventiona l air-atomize dspra y gun . Th e propose dRul e wil l exempt touch-u p o r

repai r fro mth e subparagrap h(b)(1)(B ) requirements . I

nour•judgment , requirin g tha t thi s operatio nb e don e wit haspra y guntha t ha s asmal l resi n containe r

attache ddirectl y t o th e gun—a s oppose dt o a. hos e connectio nt o alarg e resi ntank—wil l ensur e tha t onl y aminimu

mamoun t o f resi nwil l b e sprayed . Comment : Increas e th e small-use r exemptio nfro

m5 0 pound s pe r

da y t o 25 0 pound s pe r

day . Reply : Neithe r

industr y no r

th e Distric t

ha s dat at o suppor t

a n exemptio nlimit . Distric t staf f believe s tha t

material s modificatio ntechnique s ar e availabl e t o everyone , an d us e o f thi s materia l shoul dhav e onl y aminima l impac t on smal l users . Low-VO

C resi nformulation s wil l cos t almos t th e sam e a s th e conventiona l polyester-resi nmaterials . Therefore , th e propose dexemptio nfo r smal l user s wa s removed . Comment : Metho do f

analysi s shoul db e include di nth e Rule . Reply :

Comment : Reply : comment : The propose dRul e reference s th e District' s "Laborator y

Method s o f

Analysi s fo r

Enforcemen t

Samples " manual whic h contain s th e stati c volatil e emissio ntes t previousl y recommendedby SPI . Soli dwast e suc ha s tri mshoul dno t b e require dt o b e i n aclose dcontainer . Staf f believe s tha t

soli dwast e i s asourc e o f odo r and shoul db e store di naclose dcontainer . Corrosion-resistan t

material s shoul db e permanentl y exempte dfro

mth e provision s o f

subparagrap h(b)(1)(A ) sinc e the y constitut e asmal l portio no f th e tota l use d i nth e District .P.3 3 -31 - Reply : Staf f

believe s tha t

exemptio no f

corrosion-resistan t material s unti l Marc h1 , 1990 shoul dgiv e th e resi n manufacturer s tim e t o transfe r mos t o f th e existin g conventiona l resi n technolog y t o th e corrosion-resistan t materials . Also , staf f believe s tha t

sinc e th e nee do f corrosion-resistan t

material s i s increasing , th e amoun t o f emission s wil l increas e i nth e nea r future . VIII . CONCLUSION

S AN D RECOMMENDATION

S Base do nth e informatio ndescribe dabove , staf f conclude s th e following : A . Neithe r

th e Distric t

no r th e SP I ha s detaile dinformatio no nth e tota l nunbe r

o f polyeste r

resi nfabricators . Staf f estimate s ther e ar e approximatel y 1,05 0 fabricator s and70 0 repai r shop s i nth e District . Thes e fabricator s an drepai r shop s us e 12 8 millio n pound s o f

polyeste r

resi nmaterial s and600,00 0 gallon s o f aceton e pe r year . B . The estimate dtota l VO C emission s fro

mpolyeste r

resi noperation s ar e 2 2 tons/day ; fromth e productio nprocesses , 1 4 tons/day ; an d fromcleanin g processes , 8 tons/day . Th e tota l VO

C emissio n reductio ni s expecte dt o b e 12. 6 tons/day . C . Ther e have-bee n n o emissio ncontro l regulation s fo r thi s industr y becaus e th e developmen t o f technolog y wa s eithe r incomplet e o r

di d no t exist . Technolog y ha s improve ddurin g th e las t 1 2 month s and i s continuin g t o develo p a t arapi dpace . D . Fo r th e majorit y o f

thi s industry , th e add-o ncontro l technique s ar e no t technicall y o r

economicall y feasible . Material s modificatio no r

reformulation , an dadditive s technology , ar e th e mos t promisin g method s fo r complyin g wit hthi s propose dRule . Staff , therefore , recommend s approva l o f Propose dRul e 1162 fo r th e contro l of

VO C emission s fromPolyeste r Resi nOperations .P.3 4

Appendix A CHEMISTR Y O FPOLYESTE

RRESI N Polyeste r

resi nmaterial s hav e bee nclassifie da s plastics . Plastic s ar e variou s syntheti c material s chemicall y create dfro morgani c (carbon-based ) substances . Ther e ar e two basi c type s o f thermoplastic s an dthermosettin g plastics . Thermoplastic s ar e thos e whic hcanb e forme do r shape dby heat ; thi s canb e don e anumbe

r o f time s (physica l change) . Thermosettin g plastic s ar e thos e which , whe nforme do r reacted , requir e o r

giv e of f hea t an dcanno t b e reforme d(chemica l change) . A slightl y bette r

classificatio ntha nplastic s i s polymers . Polyester s ar e polymer s chaine dtogethe r i naparticula r

orde r calle d este r linkage s (tw o carbo nandtw o oxyge natoms) . Polyester s ca nb e broke ndow nint o unsaturate dandsaturated . Th e ter m unsaturate drefer s t o achemica l stat e i nwhic hacompoun dha s chemicall y unsatisfie dreactiv e group s readil y availabl e fo r attachmen t t o othe r groups . I npropose dRul e 116 2 w e dea l onl y wit hunsaturate d polyesters . Th

e saturate dpolyester s ar e represente dby alkyd s (oil-base dpaints ) an

dpolyeste r

fiber s (cloth , rayon , nylon) . Ther e ar e si x type s o f thermosettin g polyme r resins : isophthalic , orthophthalic , halogenated , bisphenol-A , furan , andviny l ester . Th e majorit y o f

th e fabricator s us e orthophthali c fo r mos t o f thei r products . The othe r

resins , calle dcorrosive-resistan t resins , whic h ar e use di napplication s tha t hav e acid , alkal i andsolvent-resistan t requirements , usuall y cos t more tha nth e general-purpos e resi nand requir e th e Underwrite r Laboratories ' approval . 1 . Orthophthali c Resin s Orthophthali c resin s ar e ofte ncalle dgeneral-purpos e polyeste r resins . Th

e differenc e betwee northophthali c an disophthali c resin s i s i nth e positio no f th e tw o COO

H (carboxyl ) group s i n th e phthali c aci dmolecule . The y ar e o nadjacen t

carbon s (e.g. , i nth e ortho-position ) i northophthali c acid , an dar e separate db y on e carbo n(e.g. , i nth e meta-position ) i nisophthali c acid . Thi s resi nprovide s littl e corrosio nresistance . 2 . Isophthali c Resin s Isophthali c resin s ar e eithe r rigi do r

flexibl e unsaturate d polyeste r

resin s an

dar e base donisophthali c aci dandglycol s o f variou s types . Thes e resin s ar e non-fire-*-retardan t an dar e use d fo r moderat e corrosion-resistanc e application s u p t o 180°F . They generall y exhibi t

excellen t

resistanc e t o water , wea k acids , and alkalies ; an dgoo dresistanc e t o solvent s an dpetroleu mproduct s suc ha s gasolin e an

doil . Th

e flexibl e isophthalic s exhibi t aP.3 5

A- 2 lesse r degre e o f chemica l resistanc e tha n th e rigi d isophthalic s o f highe r molecula r weight . 3 . Chlorendi c Resin s Chlorendi c resin s ar e unsaturate dhalogenate dpolyeste r resin s base don HE

T (hexachlorocyclopentadiene ) aci do r chloredi c anhydrid e reacte dwit hastabl e glycol . Thi s resi ni s suitabl e fo r us e a t elevate dtemperatures , u p t o 350° Fan di s abl e t o handl e aggressive , highl y oxidizin g environments , concentrate dacid s andsom e solvent s ver y well , bu t i s poo r i nalkalin e service . I t canb e formulate dt o achiev e a Clas s I fir e rating . 4 . Bisphenol- A Thi s i s a n unsaturated , rigi d polyeste r mad e b yreactin g biphenol- A wit h propylen e oxid e t o for m a glycol , the n reactin g th e glyco l wit h fumari c aci d t o produc e th e resin . Thi s resi n exhibit s excellen t corrosio n resistanc e t o bot h aci d an d alkal i u p t o 250°F . Thi s i s no t suitabl e fo r stron g oxidizin g conditions . 5 . Viny l Este r Viny l este r

resin s ar e methacrylate depoxie s tha t ar e ver y simila r t o polyester . The

y offe r excellen t

physica l strengt hand , i n general , muc

hbette r impac t strengt htha nrigi dpolyeste r resins . Thes e resin s exhibi t

excellen t

resistanc e t o acids , alkalies , hypochlorite s andman y solvents . The

y ar e preferre dfo r

filamen t winding , especiall y fo r machine-mad e piping . Laminate s ar e goodup t o 250°F . 6 . Fura nResin s Fura n resin s ar e base d o n a fura n polyme r derivativ e o f furfuryl . alcohol . The yexhibi t excellen t resistanc e t o stron g alkalie s and acid s containin g chlorinate d organics , an d ar e superio r i n solven t resistance . However , th e fura n material s ar e no t suitabl e fo r oxidizin g chemical s and shoul d no t b e use d fo r chromi c o r nitri c acids , peroxides , o r hypochlorites . Laminate s ar e goo d u p t o 250°F . A s show n i n Tabl e A , polyme r resin s d o no t resis t al 3 environments , no r d o the yrespon a equall yt o specifi c applications .P.3 6

Resistanc e t o Acid s Resistanc e •t o Alkalie s Resistanc e t o Peroxide s Resistanc e t o Hypo chlorite s Resistanc e t o Solvent s Flam e Retardanc e Therma l Insulatio n Abilit y NOTE : A A- 3

TABL E A COMPARISO NO F PROPERTIE S O F VARIOU S TYPE S O F RESIN S Iso - Ortho
- Halo
- Bisphe

phthali c phthali c genate d nol- A B CA A 3 C C . A C C AB

C CA B B C B B C C AC

AAAA •

= High , B = Moderate , C = Lo w Fura n Viny l Este r AB AA C B

C B AB B C

AA Carbo n Stainles s J

Stee l Stee l B B B B C C

C C AA AA

C C -P.3 7

A- 4 Th e type s an

drelativ e ratio s o f th e variou s raw material s whic har e incorporate dint o a

nunsaturate dpolyeste r determin e the physica l propertie s o f the resin . Ra w material s ar e mixe di na specifi c rati o andar e heate d(cooked) . Th e cooke dmateria l i s calle da bas e resin . Th e bas e resi ni s soli da t roo m temperatur e an

di s late r reduce dwit hmonome r (normall y styrene ) whic hwil l thi nthe polyeste r an deventuall y

reac t wit hit . Th e monome r react s wit hthe bas e resi nbecaus e th e unsaturate dgroup s wil l reac t wit heac hother , bridgin g (cross-linking ) th e polyeste r chain s togethe r unti l on e soli dmas s forms . Th e contro l o f thi s spontaneou s cross-linkin g reactio ni s don e wit hchemica l additive s calle d inhibitors . Usuall y enoug hinhibito r i s adde dt o kee pth e syste m stabl e (liquid ) fo r a minimu m time (thre e month s a t 73°F) . Th e cross-linkin g reactio n(polymerization ) i s a chemica l proces s affecte db

y severa l factor s suc has : temperature , mass , catalysts , promoters , inhibitors , an dcontaminants . Mos t o f th e polyeste r resi n fabricator s us e a catalys t i nthei r operatio nt o overcom e the inhibito r i norde r t o caus e cross-linkin g o f th e polyeste r resin .P.3 8

GLOSSAR Y Definition s Thes e ar e additiona l definition s fo r technica l term s use d b ythi s industry . 1 . Catalys t i s a substanc e adde d t o th e resi n t o mak e i t cur e mor e rapidly . 2 . Cross-linkin g i s a proces s o f joinin g tw o o r mor e polyme r chain s wnic h convert s a thermoplasti c t o a thermosettin g plastic . 3 . Cur e i s th e polymerizatio n o r th e transformatio n fromth e liqui d t o th e soli d stat e o f th e resi n t o achiev e th e desire d physica l properties , includin g hardness . 4 . Fiberglas s i s a fibe r simila r t o woo l o r cotton , bu t mad e from glass . 5 . Ge l Coa t i s a surfac e coat , eithe r colore d o r clear , whic h provide s a cosmeti c enhancemen t an d exposur e protection . 6 . Inhibito r i s a substanc e designe d t o retar d o r preven t a chemica l reaction . 7 . Polyme r i s a larg e chemica l chai n compose d o f identica l cross-linke d groups , suc h a s polystyrene . 8 . Resi n i s an

yo f a clas s o f organi c polymer s o f natura l o r syntheti c origi n use d i n reinforce d product s t o surround an d hol d fibers , an

d i s soli d o r semi-soli d i n th e cure d state . 9 . Thermoplasti c Material s ar e thos e material s tha t repeatedl y softe n whe n heate d an d harde n whe n cooled . 10 . Thermose t Material s ar e thos e material s tha t underg o an irreversibl e chemical-curin g reactio n b yth e actio n o f hea t o r catalyst . 1i . Vapo r Suppressan t i s a substanc e adde d t o th e resi n t o minimiz e th e outwar d diffusio n o f monome r vapo r int o th e atmosphere .