Composition of urea formaldehyde foam insulation

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Composition of urea formaldehyde foam insulation

NATIONAL RESEARCH COUNCIL OF CANADA DIVISION OF BUILDING RESEARCH

DBR INTERNAL REPORT NO. 501

C O l P O S I T I O N OF UliEA FORPIALDEHYDE F O M I I N S U L A T I O N

by P.G. S i m

Checked by: Approved by: L

.

W . Gold Date: J u n e 1985 Prepared for: R e c o r d s P u r p o s e s

ABSTRACT

The

a v a i l a b l e l i t e r a t u r e on t h e c o m p o s i t i o n of u r e a formaldehyde foam i n s u l a t i o n (UFFI), a s of J u l y 1984, i s s u r v e y e d and

summarized. T h i s r e p o r t i s a c o m p i l a t i o n of a l l s u c h i n f o r m a t i o n a v a i l a b l e t o t h e a u t h o r . The c h e m i c a l s p o s s i b l y used i n t h e f o r m u l a t i o n of

UFFI

a r e l i s t e d i n a v a r i e t y of c a t e g o r i e s , based upon t h e i r u s e s , r e a l o r c l a i m e d , i n t h e p r o d u c t i o n of t h e foam. The a c t u a l c o m p o s i t i o n s of foams u s e d p r o b a b l y v a r i e d w i d e l y , f o r a number of r e a s o n s . Some d i s c u s s i o n of p o s s i b l e v a r i a b i l i t y i s given.

COMPOSITION OF UREA FORMALDEHYDE FOAM INSULATION by

P.G. Sim

INTRODUCTION

The f o l l o w i n g i s a l i s t of i n g r e d i e n t s p o s s i b l y u s e d i n t h e p r o d u c t i o n of u r e a formaldehyde foam i n s u l a t i o n (UFFI). The t h r e e major components were:

Resin Concent r a t e

Surf a c t a n t u s u a l l y combined i n one m i x t u r e Acid C a t a l y s t

These

were

u s u a l l y blown i n t o a foam w i t h a i r and moulded b e f o r e t h e p o l y m e r i z a t i o n r e a c t i o n had proceeded f a r enough t o g i v e a r i g i d m a t r i x . A g r e a t v a r i e t y of c h e m i c a l s may have been added t o e a c h of t h e b a s i c

components, f o r d i v e r s p u r p o s e s and i n v a r i o u s amounts.

The f o l l o w i n g l i s t i s compiled from

a l l

d a t a a v a i l a b l e a s of March 2 1 , 1984. The s o u r c e s were a l m o s t e n t i r e l y p a t e n t a p p l i c a t i o n s , which a r e n o t o r i o u s l y i m p r e c i s e . I f r e a d e r s h a v e , o r come a c r o s s , a d d i t i o n a l

c o m p o s i t i o n a l d a t a , t h e y a r e a s k e d t o k i n d l y a d v i s e t h e D i v i s i o n . In Canada, t h e r e were 16 CNHC a c c e p t a n c e numbers i s s u e d t o UFFI

m a n u f a c t u r e r s u n d e r t h e CHIP program. The a c t u a l number of c o m p o s i t i o n s i s c e r t a i n l y much h i g h e r , f o r a v a r i e t y of r e a s o n s . Chief among t h e s e i s t h a t t h e m a n u f a c t u r e r s changed t h e c o m p o s i t i o n s of t h e i r p r o d u c t s p e r i o d i c a l l y . Some of t h e s e changes a r e r e f l e c t e d i n t h e p a t e n t s b u t many may n o t be; f o r example, changes i n s u p p l i e r s of p r i n c i p a l c h e m i c a l s would n o t be n o t e d i n p a t e n t s b u t c o u l d r e p r e s e n t a s i g n i f i c a n t change i n c o m p o s i t i o n . Many o t h e r changes may have t a k e n p l a c e w i t h o u t n o t i f i c a t i o n , a s t h e m a n u f a c t u r e r s modified t h e i r p r o d u c t s i n a n a t t e m p t t o meet t h e d r a f t CGSB s t a n d a r d . F u r t h e r , s i n c e e a c h m a n u f a c t u r e r s o l d two components, c r u d e r e s i n and c a t a l y s t / f o a m i n g m i x t u r e , t h e number of p o s s i b l e c o m b i n a t i o n s i n c r e a s e s t o a t least 256. There was no r e q u i r e m e n t f o r any i n s t a l l e r t o u s e r e s i n and c a t a l y s t from t h e same m a n u f a c t u r e r . A f i n a l c o m p l i c a t i o n i s t h a t t h e s o l e q u a l i t y c o n t r o l o n - s i t e was t h e t i m e t a k e n f o r a sample of t h e foam t o set.

A s t h e day wore on and t h e t e m p e r a t u r e changed, a d j u s t m e n t s t o t h e r e s i n / c a t a l y s t r a t i o would be r e q u i r e d t o g i v e a c o n s t a n t s e t t i n g time. Thus, i t i s p o s s i b l e t o have many d i f f e r e n t compositions i n t h e same house. The n e t r e s u l t of a l l t h e s e f a c t o r s i s t h a t t h e v a r i e t y of compositions i n houses i n Canada mst be c o n s i d e r e d v i r t u a l l y l i m i t l e s s a n d e a c h sample of foam must be t r e a t e d

as

unique.

For t h e p u r p o s e s of t h i s summary, a l a r g e number of Canadian p a t e n t a p p l i c a t i o n s

were

r e a d . The t a b l e below i s a l i s t of a l l t o which t h e a u t h o r had a c c e s s . I f any a r e wrong, h e would a p p r e c i a t e n o t i f i c a t i o n .

CANADIAN PATENTS RELATING TO UREA FORMALDEHYDE FOAM INSULATION

A p p l i c a t i o n o r Date I s s u e d o r

P a t e n t Number A p p l i e d f o r A p p l i c a n t D e s c r i p t i o n -

1. 308,569 1931 Feb. 10 Alphonse Gams, Gustave Widmer, S o c i e t y of Chemical I n d u s t r y of B a s l e 2. 408,139 1942 O c t . 20 L.S. Meyer, Alaskon Company I n c o r p o r a t e d 3. 416,856 1943 Jkc.

7

K.E. Kipper, American Cyanamid Co.

4. 455,331 1948 Mar. 22 Lawrence E. Daly Dominion Rubber Co. Ltd., M o n t r e a l , QuB. Canada 5. 455,332 1 9 4 8 M a r . 22 William J. C l a y t o n and Edward R. Svendson, Dominion Rubber Co. Ltd., M o n t r e a l , QuB. Canada A p r o c e s s of making c o n d e n s a t i o n p r o d u c t s of carbamides and a l d e h y d e s , p a r t i c u l a r l y of u r e a formaldehyde. I n s u l a t i n g m a t e r i a l and method of m a n u f a c t u r e , c o n s i s t i n g of f o r m a l - dehyde u r e a r e s i n foam. Aqueous e m u l s i o n c o m p r i s i n g a w a t e r s o l u b l e formaldehyde r e s i n , a n a c r y l i c ester of a l i p h a t i c a l c o h o l and a v i n y l ester of a l i p h a t i c a c i d w i t h a i d of e m l s i f i e r and f r o t h i n g a g e n t . P a r t i c u l a r l y u r e a formaldehyde r e s i n . Porous x e r o g e l made from melamine- formaldehyde c o n d e n s a t i o n p r o d u c t s . Very l i g h t w e i g h t m u l t i - c e l l u l a r m a t e r i a l , w i t h d e n s i t y less t h a n 2 l b / f t 3 , w i t h e x c e l l e n t a c o u s t i c and i n s u l a t i n g p r o p e r t i e s . P r o d u c t t h a t i s r e s i l i e n t and r e s i s t a n t t o burning. Method of c o n t i n u o u s l y f o r m i n g a r t i c l e s of s o l i d i f l e d p l a s t i c foam from m i x t u r e s of t h e r m o s e t t i n g r e s i n s and t h e r m o p l a s t i c r e s i n s .

Use of u r e a f o r m a l d e h y d e r e s i n f o r t h i s p u r p o s e .

.

455,868 1948 Apr. 12 W i l l i a m J. C l a y t o n , Dominion Rubber Co. L t d . , M o n t r e a l , Q u B . Canada 7. 470,900 1951 J a n . 16 L.S. Meyer, L i bbey-Owens- Ford Glass Co.

8. 4 7 7 , 0 8 1 1951 S e p t . 1 8 C.H. C u p p e t t , Newark P l a s t e r Co., New York U.S.A. 9. 494,753 1 9 5 3 J u l y 2 8

D.

Gonda, K e n t , England 10. 575,580 1959 May 12 N. Brown,

E.I.

DuPont d e Nemours Co.

,

U.S.A. 11. 700,942 1964 Dec. 29 G.H. J u s t i c e , A l l i e d Chemical Gorp., New York U.S.A. 12. 709,001 1 9 6 5 May 4 F r i t z S t a s t i n g a n d F r i t z Graf

.

,

B.A.S.F., L u d w i g s h a f e n , R h e i n , Germany F o r m a t i o n of a d e s e n s i t i z e d foam, w i t h s l o w e r g e l l i n g r a t e s , by t h e a d d i t i o n of a w a t e r s o l u b l e s a l t o r b a s e of a d i v a l e n t m e t a l , t o r e a c t w i t h p h o s p h o r i c a c i d . P r o d u c t i o n o f h a r d e n e d u r e a f o r m a l d e h y d e r e s i n foam o f improved c o m p r e s s i o n s t r e n g t h . P r o d u c t i o n of gypsum b o a r d u s i n g a p a r t i a l c o n d e n s a t i o n p r o d u c t of u r e a a n d f o r m a l d e h y d e . C o n s t r u c t i o n of s t r u c t u r a l b u i l d i n g u n i t s o r p a n e l s f o r s o u n d a b s o r b i n g p u r p o s e s . Urea f o r m a l d e h y d e r e s i n s o l i d foams h a v i n g a c l o s e d c e l l s t r u c t u r e . Urea f o r m a l d e h y d e r e s i n foams i n which t h e f o r m a l d e h y d e o d o r i s s u b s t a n t i a l l y s u p p r e s s e d a n d a p r o c e s s f o r p r e p a r i n g s u c h foams by a d d i n g ammonium b i c a r b o n a t e o r ammonium c a r b o n a t e w i t h a t e r p e n e . Composite expanded p l a s t i c c o n s i s t i n g of particles of p o r o u s p l a s t i c w i t h t h e i n t e r s t i c e s f i l l e d w i t h a c u r e d p l a s t i c foam. P o r o u s p l a s t i c may b e p o l y s t y r e n e o r poly-

v i n y l c h l o r i d e and t h e c u r e d p l a s t i c may be u r e a formaldehyde foam. 13. 711,750 1965 June 15 R.H.G. Penner &

R. Thompson, S u r r e y , England

14. 716,119 1 9 6 5 A u g . 1 7 G.H. J u s t i c e , A l l i e d Chemical Corp., New York U.S.A.

15. 726,785 1966 Jan. 25 F.L. K e l l e y & R.L. Wells, A l l i e d Chemical Corp., New York U.S.A.

16. 747,334 1966 Nov. 29 R.W. L i l l i e , New J e r s e y , U.S.A., A l l i e d Chemical Corp.

,

New York, U.S.A.

17. 755,677 1967 Mar. 28 T.A. P i l g r i m , B r i t i s h P l a s t e r W a r d ( H o l d i n g s ) L t d . , London, England To p r o v i d e h e a t i n s u l a t i n g c e l l u l a r m a t e r i a l s which have been r e n d e r e d intumes- c e n t , w i t h t h e u s e of s u l p h u r i c a c i d , ammonium s u l p h a m a t e

,

ammonium c h l o r i d e o r bromide, p y r o p h o s p h o r i c a c i d . Urea formaldehyde r e s i n foams i n which t h e f o r m a l d e h y d e o d o r i s s u p p r e s s e d o r e l i m i n a t e d . P r o c e s s t o s u b s t a n t i a l l y r e d u c e t h e c o n c e n t r a t i o n of m e t h y l 0 1 g r o u p s . To p r o v i d e a u r e a

formaldehyde foam where t h e i n i t i a l formaldehyde i s c o n t r o l l e d and r e c u r r e n c e o f f o r m a l - dehyde o d o r i s p r e v e n t e d . Add s m a l l p o r t i o n o f u r e a t o aqueous a c i d i c h a r d e n e r p r i o r t o foaming and mixing. P r o c e s s and a p p a r a t u s f o r p r o d u c i n g l a m i n a t e d pane 1 s. For c o n t i n u o u s l y p r o d u c i n g s t r u c t u r a l p a n e l s h a v i n g foamed c o r e s . To p r o v i d e a c e l l u l a r u r e a formaldehyde which i s n o t crumbly o r f r i a b l e . A c e l l u l a r UF r e s i n i n which c e l l s a r e s o t h i n t h a t t h e a v e r a g e b u l k of s o l i d between c e l l s d o e s

n o t e x c e e d t o t a l volume of s o l i d r e s i n p e r u n i t ; volume of c e l l u l a r r e s i n

i s 2.2%.

18. 781,531 1968

Mar.

26 A l f r e d Kuhlkamp, Foam p l a s t i c c o n s i s t i n g A l b r e c h t Moschel of a n amino a l k y l a t i o n and Rudolf p r o d u c t of a poly-

Nowack, Farbwerke c a r b o x y h a l o m e t h y l e s t e r Hoechs t w i t h f o r m a l d e h y d e a n d A k t i e n g e s e l l s - t h e r e a c t i o n p r o d u c t of c h a f t F r a n k f u r t a polyamine a n d C02 i n am Main, Germany t h e p r e s e n c e of a n o r t h o - e s t e r of T i o r Z r o r a n a l c h o l a t e of Al. Foam p l a s t i c where t h e h a l o m e t h y l e s t e r i s r e p l a c e d by a n a c e t o - a c e t y l a t e d o r a cyano- a c e t y l a t e d m e t h y l e s t e r . 19. 790,647 1968 J u l y 23

P.R.

Temple & Method o f t r e a t i n g u r e a

F. B r a s c o , f o r m a l d e h y d e r e s i n foam A r t h u r D. L i t t l e t o p r e v e n t c r a c k i n g o r I n c . , Cambridge, d i s i n t e g r a t i o n o f Mass., U.S.A. m a t e r i a l s on f i n a l d r y i n g . 20. 793,370 1968 Aug. 27 D.S. S h r i v e r , A p p a r a t u s f o r c o n t i n u - R.R. MacGregor & o u s l y p r o d u c i n g s t r o n g W.P. Moore, c l o s e d c e l l u r e a A l l i e d Chemical f o r m a l d e h y d e foams. Corp.

,

New York

U.S.A. P r o c e s s f o r b l e n d i n g a n a q u e o u s u r e a f o r m a l - d e h y d e r e s i n s o l u t i o n w i t h a foamed h a r d e n i n g s o l u t i o n . 21. 8 1 7 , 9 3 6 1969 J u l y 1 5 G.H. J u s t i c e & P r o c e s s f o r p r e p a r i n g R.L. W e l l s , f l a m e - r e t a r d a n t u r e a A l l i e d Chemical f o r m a l d e h y d e i n s u l a t i n g Corp., New York foams w i t h o u t e x c e s s i v e

U.

S.A. s h r i n k a g e d u r i n g c u r i n g

and d r y i n g .

22. 8 2 8 , 8 0 3 1969 Dec. 2 P.J. Mason, Foam r e t a r d a n t , non- A l l i e d Chemical s h r i n k i n g u r e a f o r m a l - Corp.

,

New York d e h y d e foams.

U.S.A.

A d d i t i o n of e t h y l e n e g l y c o l t o r e s i n p r i o r t o foaming.

23. 857,350 1970 Dec. 1 H. Wilmsen P r o c e s s f o r t h e Essen, Germany p r o d u c t i o n of foamed

aminoplas t r e s i n s . To improve p h y s i c a l c h a r a c t e r i s t i c s by improving s t r u c t u r e of c e l l w a l l s .

24. 860,909 1971 Jan. 12 T.A. P i l g r i m , To p r o v i d e a new foam BPB I n d u s t r i e s m a t e r i a l s u i t a b l e f o r Ltd., Landon, t h e p r o d u c t i o n of England moulded a r t i c l e s and

t h e r m a l i n s u l a t i o n e s p e c i a l l y i n i n s u l a t i n g b u i l d i n g p a n e l s . P e l l e t s of expanded u r e a formaldehyde r e s i n bonded t o g e t h e r by a m a t r i x of r i g i d foamed r e s i n ( p o l y u r e t h a n e ) . 25. 864,607 1971 Feb. 23 A l f r e d Renner, P r o c e s s f o r t h e Ciba Ltd., m a n u f a c t u r e of porous Bach, S w i t z e r l a n d s o l i d s of c r o s s - l i n k e d u r e a formaldehyde p o l y c o n d e n s a t i o n p r o d u c t s h a v i n g a n i n t e r n a l s u r f a c e a r e a g r e a t e r t h a n 10 m2/g.

26. 868,964 1971 Apr. 20 H a r l a n G. Freeman P r o c e s s f o r making a & Maurice G. c e l l u l a r foam from a G i l l e r n , m o d i f i e d a l d e h y d e Weyerhauser Co., c o n d e n s a t i o n r e s i n Tacoma, ( r e a c t e d w i t h a n Washington, a r o m a t i c amine), w i t h U.S.A. blowing a g e n t blended i n t o t h e r e s i n p r i o r t o c u r i n g .

27. 873,922 1971 June 22 D. Hanton, To make p h e n o l f o r m a l - Compagnie d e dehyde foams which a r e S a i n t Gobaine, of u n i f o r m d e n s i t y , Neuilly-sur- f r e e of c a v e r n s and S e i n e , France f i r e r e s i s t a n t . 28. 876,146 1971 J u l y 2 0 D.H. Ogden, Method of p r o d u c i n g B r i t i s h Indus- c o n t i n u o u s l y low- t r i a l P l a s t i c s d e n s i t y s e l f - s u s t a i n i n g Ltd., Manchester foam. England

R e q u i r e s t h a t b o t h t h e r e s i n and t h e h a r d e n e r be i n d i v i d u a l l y foamed b e f o r e t h e y a r e mixed t o g e t h e r .

29. 1,013,499 1977 J u l y 5 M. Widmann, Urea formaldehyde foam, Borden P r o d u c t s two-component system Ltd., Canada c o n s i s t i n g of a n aqueous s o l u t i o n of UF r e s i n and aqueous s o l u - t i o n of a foaming a g e n t . S p e c i a l l y d e s i g n e d gun t o produce t h e foam. 30. 1,028,099 1978 Mar. 14 B. R o l l e t & New m l t i c e l l u l a r

M. G r u f f a x , r i g i d polymers. France ConcCdC

a

Rhane Poulenc, SA France 31, 1,028,100 1978

Mar.

14 B. R o l l e t & M u l t i c e l l u l a r m a t e r i a l s . M. G r u f f a x , France Concede 3 Rhi3ne Poulenc, SA France

32. 1,031,100 1978 May 9 Arnold G i l l e r , P r o c e s s f o r making Richard S t r a u s s , a n aqueous f i r e - Hans Weiner and r e t a r d a n t c o m p o s i t i o n D i e t e r c a p a b l e of forming a Zacharowski, foam l a y e r . Hoessht A k t i e n g e s e l l s c h a f t Germany ( F e d e r a l R e p u b l i c o f ) 33. 1,031,125 1978 May 16 D. A. Hubbard, P r o c e s s f o r p r o d u c i n g I m p e r i a l Chemical moulded expanded UF I n d u s t r i e s , Lt d., p r o d u c t s by a d d i n g a U.K. c a t a l y s t t o t h e UF

r e s i n s o l u t i o n which c a u s e s g e l l i n g and c u r i n g of t h e r e s i n s o l u t i o n . 34. 1,033,498 1978 June 20 J.A.G. Gent,

H.O. L a r s e n & S. Barfoed, K o n i n k l i j k e Emballage Z n d u s t r i e / V a n

Leer,

B.V., N e t h e r l a n d s Improvement i n t h e p r o c e s s of p r e p a r i n g poly f u r a n foams by p o l y m e r i z i n g f u r f u r y l a l c o h o l i n t h e p r e s e n c e of a s t r o n g a c i d . The d e n s i t y of foams c a n b e c o n t r o l l e d by

t h e amount of p r e p o l y m e r i n t h e f u r f u r y l a l c o h o l . 35. 1,044,846 1978 Dec. 19 Radmachers Bayer

A k i e n g e s e l l - s c h a f t

,

Germany

36. 1,044,864 1978 Dec. 26 R. Kader, Mauser Kommandi t g e s e l l - s c h a f t

,

Germany 37. 1,056,099 1979 June 5 H. Wilmsen, Ge rmany 38. 1,058,456 1979 J u l y 17 H. Glesemann, Germany 39. 1,066,879 1979

Nov.

27 G.V. L i n d s t r o m , Sweden P r o d u c t i o n of foams by a d d i n g a n a c i d h a r d e n e r t o a n a q u e o u s s y s tem c o n t a i n i n g u r e a f o r m a l - dehyde u s i n g b o r o n p h o s p h a t e a s a h a r d e n e r . A r t o f e x t r u d i n g t h e r m o p l a s t i c materials. Improved a p p a r a t u s f o r e x t r u d i n g a l e n g t h o f s o f t t h e r m o p l a s t i c i n t h e f o r m of a t u b e . P r o c e s s f o r p r e p a r a t i o n of flame-proof s y n t h e t i c r e s i n foam. Based upon s y n t h e t i c r e s i n s f o r m u l a t e d i n a q u e o u s m e d i a i n which a s y n t h e t i c r e s i n i s foamed a n d i s s u b s e - q u e n t l y c u r e d by a c a t a l y s t . Improved l i g h t d e n s i t y s h a p e d m a t e r i a l s t h a t may b e u s e d a s s t r u c t u r a l members s u c h as s y n t h e t i c foam b o a r d s o r p a n e l s f o r i n s u l a t i o n , w i t h p a r t i a l l y o p e n c e l l u l a r s t r u c t u r e . To p r o v i d e a method a n d a p p a r a t u s f o r a t l e a s t two c h e m i c a l r e a c t i o n components, o n e o f which i s c a u s e d t o foam a n d t h e o t h e r a t o m i z e d t o a e r o s o l foam. P a r t i c u l a r l y c e l l u l a r p l a s t i c f r o m u r e a f o r m a l d e h y d e c o n d e n s a t e .

40. 1,098,650 1981 Mar. 31 H.L. Korf, Improved s o l i d u r e a Rapco Foam Inc., formaldehyde r e s i x foam U. S . A . and a method of makixg

i t .

A d d i t i o n o f c a r b o h y d r a t e . 41. 1,111,599 1981 Oct. 27 KunoWagner, P r o c e s s f o r making a n

Manfred Dhan and a m i n o p l a s t foam

Ranns P. M u l l e r , c o m p r i s i n g a hardened Bayer Aktienge- r e a c t i o n p r o d u c t of a n s e l l s c h a f t

,

a l d e h y d e and a n a t l e a s t Germany ( F e d e r a l b i f u n c t i o n a l modified R e p u b l i c o f ) a,w u r e a o r a,w d i u r e t h a n e o r a n a,w b i u r e t o r a n a , w b i s - a n t h r a n i l a t e .

Where p o s s i b l e , i n d i c a t e d maximum l e v e l s of some of t h e a d d i t i v e s h a v e been g i v e n . O f t e n , t h e r e a r e o n l y b r i e f comments, which have been i n c l u d e d i n q u o t a t i o n marks, a l o n g w i t h t r a d e names of some of t h e i n g r e d i e n t s a n d v a r i o u s o t h e r comments. Compositional i n f o r m a t i o n t e n d s t o be somewhat vague; one f i n d s comments s u c h a s :

"I may mix r e s i n and c a t a l y s t i n any p r o p o r t i o n s from 1:4 t o 1:50"

"The r e s i n t o c a t a l y s t r a t i o may be i n t h e r a n g e from 1 t o a b o u t 1.5 t o 1 t o a b o u t 2.3"

S i m i l a r gems a r e s c a t t e r e d t h r o u g h t h e c l a i m s . I n g e n e r a l ,

p a r t i c u l a r l y f o r t h e more r e c e n t c o m p o s i t i o n s , t h e a c t u a l d r i e d foam c a n end up c o n t a i n i n g s o m e t h i n g l e s s t h a n 50% u r e a formaldehyde r e s i n s o l i d s ,

i . e , i t a p p e a r s p o s s i b l e t o have foam i n p l a c e t h a t i s c h i e f l y a d d i t i v e ! I n what f o l l o w s , t h e i n f o r m a t i o n a v a i l a b l e h a s been s p l i t i n t o s e v e r a l s u b - c a t e g o r i e s . Various foams c o u l d c o n t a i n one o r more c h e m i c a l s from each c a t e g o r y , o r t h e c a t e g o r y may n o t be r e p r e s e n t e d a t a l l .

-

A l l foams m s t c o n t a i n a t l e a s t one r e p r e s e n t a t i v e from t h e Acid C a t a l y s t , S u r f a c t a n t , and R e s i n and R e s i n Co-reactants c a t e g o r i e s . Other g r o u p s of c h e m i c a l s may be r e p r e s e n t e d depending on t h e m a n u f a c t u r e r and s p e c i a l c h a r a c t e r i s t i c s d e s i r e d .

Some Chemicals P o s s i b l y Used i n t h e F a b r i c a t i o n of UFFI Acid C a t a l y s t s p h o s p h o r i c a c i d

-

most l i k e l y ; o t h e r s a r e g e n e r a l l y more e x p e n s i v e o x a l i c t a r t a r i c s u l p h u r i c h y d r o c h l o r i c f o r m i c

p-toluene s u l p h o n i c a c i d s a c e t i c c h l o r a c e t i c a c r y l i c m a l o n i c c i t r i c s u l p h u r o u s n i t r i c sulphami c l a c t i c p o l y p h o s p h o r i c t e t r a p h o s p h o r i c w a t e r - s o l u b l e ammonium hydrogen s u l p h a t e s of t h e g e n e r a l formula: R N H ~ + HS0,- R may be H, a l k y l , c y c l o a l k y l , h y d r o x y a l k y l , o r a r y l May be up t o

10-152

of a c i d i n f i n a l f o r m u l a t i o n . R e s i n and R e s i n C o - r e a c t a n t s

Resins a r e , i n g e n e r a l , m i x t u r e s of methyl01 and p o l y m e t h y l o l u r e a s . These may be p r e p a r e d i n s i t u , by r e a c t i o n of u r e a and formaldehyde, o r be s u p p l i e d a s a v i s c o u s l i q u i d r e s i n ( w a t e r s o l u t i o n ) . A d d i t i v e s may be u s e d t o modify t h e c r o s s - l i n k i n g p r o c e s s , t o a c t a s p o l y m e r i z a t i o n t e r m i n a t o r s o r t o g i v e h a r d e r o r s o f t e r foams. Some a r e : f u r f u r y l a l c o h o l f u r f u r a l g l y c o l s me lamine

u r e a

-

added t o make a ' h a r d e r ' foam t h i o u r e a d i c y a n d i a m i d e benzoquanamine a n i 1 i n e pheno 1 a l k y l

-

phenols a c e t a l d e h y d e a c r o l e i n c r o t o n a l d e h y d e benzaldehyde g l y o x a l

1 ) Primary aromatic amines of t h e formula:

F I G U R E 1

where

Y l

and

Y 2

may be any o f :

H, Cl-Cs

a l k y l

n i s i n t h e range 1-2.

Y

( ~ ) n

may be r e p l a c e d by:

-SO2-, -NH-,

-0-,

-S-, -C=C-,

o r

-S-S-.

12

2) Bis(aminoary1) compounds, of the general formula:

R R '

H 2 N

mxaNH2

F I G U R E 2

R,R' may be alkoxyl, -H,

-0H,

-NO2, -NH2, S O O H or C I X s

alkyl;

X

may be any

of the C(Y1Y2)n groups mentioned above.

3)

Amino naphthalenes, of the general formula:

F I G U R E 3

where R may be +HZ in any unsubstituted ring position, or 2-0H or 8-0H, if

the amino is in the 1-position.

iii

I

1

diaminopyridine

2,6

-

3,4

-

pyrrole

N

-

methylpyrrole

2,4

-

dimethylpyrrole

4,6

-

diaminopyrimidine

aldehyde

-

epoxide mixtures, where the epoxy compound has more than one

resorcinol

4

-

aminosalicylic acid

3,5

-

diaminobenzoic acid

o

-

hydroxyaniline

m

-

hydroxyaniline

o

-

phenylenediamine

m

-

phenylenediamine

p

-

phenylenediamine

1,2,4, or 1,3,5

-

triaminobenzene

2

-

amino

-

5

-

nitro phenol

2

-

aminoresorcinol

m

-

methoxyaniline

2,4,6

-

triaminotoluene

2,4

-

diaminodiphenylamine

1,3

-

diamino

-

4

-

methoxy benzene

1,4

-

diamino

-

2

-

nitro benzene

-

2,4

-

diaminophenol

2,4

-

diaminotoluene

2,4

-

diaminoacetanilide

m

-

xylylenediamine

3,3 dimethoxybenzidine

4,4

-

oxydianiline

o

-

toluidine

4,4

-

diaminodiphenylmethane

4,4

-

diaminodiphenylsulphone

3,3

-

diaminobenzidine

4,4

-

diaminodiphenylamine

4,4

-

diaminostilbene

4,4

-

methylenedianiline

4,4

-

diamino diphenyl disulphide

1,5

-

diaminonaphthalene

1,8

-

diaminonaphthalene

1

-

amino

-

5

-

naphthol

1

-

amino

-

2

-

naphthol

2,7

-

diaminonaphthalene

1,2

-

diaminonaphthalene

t

rioxane

paraformaldehyde

vinyl

-

cyclohexane dioxides

limonene dioxide

dicyclopentadiene dioxide

ethylene glycol-bia (3,4

-

epoxy

-

tetra hydro

-

dicyclopentadiene

-

8

-

yl) ether

(3,4

-

epoxy

-

tetrahydrodicyclopentadiene

-

8

-

yl)

-

glycidylether

epoxidized polybutadienes, epoxidized copolymers of butadiene

with ethylenically unsaturated compounds such as styrene or vinyl

acetate

diethylene glycol-bis (3,4

-

epoxy

-

cyclohexane

-

carboxylate)

bis

-

3,4

-

epoxy

-

cyclohexyl methylsuccinate

3,4

-

epoxy

-

6

-

methyl cyclohexylmethyl

-

methylauccinate

3,4

-

epoxy

-

6

-

methyl cyclohexane carboxylate

3,4

-

epoxy

-

6

-

hexahydrobenzal

-

3,4

-

epoxy

-

cyclohexane

1,l

-

dimethanol

epoxidized soybean oil

a l l y 1 g l y c i d y l e t h e r g l y c i d y l a c r y l a t e g l y c i d y l m e t h a c r y l a t e p o l y g l y c i d y l esters from t h e r e a c t i o n of a d i c a r b o x y l i c a c i d , s u c h a s s u c c i n i c , a d i p i c , p h t h a l i c o r t e r e p h t h a l i c , w i t h e p i c h l o r o h y d r i n o r g l y c e r o l d i c h l o r o h y d r i n g l y c i d y l e t h e r s of p o l y h y d r i c p h e n o l s , e.g., of p h e n o l s s u c h a s : 2,2

-

b i s ( p

-

hydroxyphenyl)

-

p r o p a n e r e s o r c i n o l hydroquinone 4,4

-

dihydroxybenzophenone b i s

-

( 4

-

hydroxyphenyl)

-

e t h a n e 1 , 5

-

d i h y d r o x y n a p h t h a l e n e 4,4

-

d i h y d r o x y b i p h e n y l p o l y g l y c i d y l e t h e r s of p o l y h y d r i c a l c o h o l s , s u c h a s : g l y c e r i n e e t h y l e n e g l y c o l p r o p y l e n e g l y c o l d i e t h y l e n e g l y c o l h e x a n e t r i o l p e n t a e r y t h r i t o l t r i m e t h y l o l e t h a n e t r i m e t h y l o l propane d i g l y c e r o l d i p e n t a e r y t h r i t o l succinoguanamine adipoguanamlne a m i n o q u i n a z o l i n e s g u a n a z o l e s s u l p h o n a m i d e s cyanamide S u r f a c t a n t s

Many d i f f e r e n t t r a d e names a r e mentioned. There a p p e a r t o be t h r e e major t y p e s : amines, amides o r s u l p h o n a t e s ; t h e l a t t e r predominate. Some p a r t i c u l a r o n e s mentioned a r e ( ? = b r a n d name unknown t o a u t h o r ) :

Brand Name A c t i v e I n g r e d i e n t ( s )

'Tween 40'

-

' s o r b i t a n monopalmitate p o l y o x y a l k y l e n e d e r i v a t i v e ' 'Nacconol SZA

-

'80% a l k y l a r y l s u l p h o n a t e , h a v i n g pH = 1.5'

?

-

d i b u t y l n a p h t h a l e n e s u l p h o n i c a c i d 'Nansa HS 8 0 '

-

sodium a l k y l benzene s u l p h o n a t e ' 'Nansa HS 8 5 S t

-

sodium d o d e c y l benzene s u l p h o n a t e ' 'Nansa HS 30'

-

' m o d i f i e d HS 8 5 S t

'Nansa LES 42'

-

b l e n d o f HS 8 5 S, l a u r y l e t h e r s u l p h a t e and magnesium x y l e n e s u l p h o n a t e

'Nansa 100'

-

HS 8 5 S , m o d i f i e d by t h e a d d i t i o n of e t h o x y l a t e d f a t t y a c i d a l k y l o l amides

'Crop01 60' 'Teepol 514' 'Teepol 610' ' B e l l o i d

NW'

'

Arquad S-50

'

-

sodium s u l p h o s u c c i n a t e

-

b l e n d of a l k y l benzene s u l p h o n a t e s and s e c o n d a r y a l k y l s u l p h a t e s

-

' s o f t s e c o n d a r y a l k y l s u l p h a t e s '

-

sodium s a l t of s u l p h o n a t e d c o a l t a r f r a c t i o n

-

50% i s o - p r o p a n o l and 50% a l k y l t r i m e t h y l ammonium c h l o r i d e , where t h e a l k y l component i s d e r i v e d from soybean o i l f a t t y a c i d s '

-

' t r i e t h a n o l a m i n e s a l t of benzene s u l p h o n i c a c i d '

-

'sodium d i b u t y l phenyl pheno d i s u l p h a t e '

-

' b u t y l a t e of n a p h t h a l e n e s u l p h o n i c a c i d '

-

'sodium a l k y l s u l p h a t e ' c a t i o n i c q u a t e r n a r y ammonium b a s e s f a t t y a l c o h o l s u l p h a t e s o r s u l p h o n a t e s a l k y l a r y l s u l p h o n a t e s s u l p h o s u c c i n i c a c i d ester s a l t s monoglyceride s u l p h a t e s ' t e r t i a r y amido-amines, q u a t e r n i z e d w i t h d i m e t h y l s u l p h a t e

'

S u r f a c t a n t s may be up t o 10% i n f i n a l p r o d u c t , b u t g e n e r a l l y a r e 1-22. P r o t e c t i v e C o l l o i d s

These p e r f o r m much t h e same t a s k a s t h e s u r f a c t a n t s , i . e . , t h e y f a c i l i t a t e t h e f o r m a t i o n of s t a b l e foams.

-

sodium s a l t of c a r b o x y m e t h y l c e l l u l o s e m e t h y l c e l l u l o s e e t h y l c e l l u l o s e h y d r o x y e t h y l c e l l u l o s e

-

p o l y ( v i n y l a l c o h o l s )

-

w a t e r s o l u b l e polymers o r co-polymers of a c r y l i c o r m e t h a c r y l i c a c i d

-

0 . 1

-

10% by w e i g h t may b e added. A n t i - H y d r o l y s i s Agents U s u a l l y added t o r e d u c e t h e f r e e a c i d c o n t e n t of t h e f i n a l r e s i n and t h e r e b y lower t h e r a t e a t which t h e foam b r e a k s down, o r e l s e t o r e a c t w i t h any e v o l v e d HCHO. d i c y a n d i a m i d e r e s o r c i n o l melamine p o l y ( v i n y l a l c o h o l s ) ' d i v a l e n t m e t a l h y d r o x i d e s l u r r y '

-

Ca(OH)2, Ba(OH)2 g u a n y l u r e a c a l c i u m cyanamide ' g u a n i d i n e d e r i v a t i v e s ' h e x a m e t h y l e n e t e t r a m i n e May be u p t o 10% of t h e s e p r e s e n t .

Cosmetic Agents

They a r e s o c a l l e d b e c a u s e t h e y a r e compounds u s u a l l y added t o make t h e foam more s o c i a l l y a c c e p t a b l e , i n a v a r i e t y of ways.

Deodorants: Added t o r e d u c e HCHO odour f u r f u r a l f u r f u r y l a l c o h o l r e s o r c i n o l ammonium b i c a r b o n a t e ammonium c a r b o n a t e u r e a m e l a m i n e t u r p e n t i n e borne01 camphor p o l y ( v i n y l a l c o h o l ) p h e n o l s e s s e n t i a l o i 1s t r i e t h y l a m i n e 'few % by w e i g h t

'

.

Crack Reducers: c a r b o h y d r a t e s g l y c o l s

Some o t h e r compounds may b e added f o r a p p e a r a n c e s s a k e : CaC12

-

' t o g i v e u n i f o r m c e l l s i z e '

-

'may be r e p l a c e d by any a l k a l i n e e a r t h s a l t t o g i v e t h e same 2

-

-

e f f e c t ; a n y s a l t of B e , Mg, Ca, S r o r Ba w i t h h a l i d e , C03

,

HC03,

2- 3

-

3- 2- 2

-

3

-

-

SO,

,

PO,

,

B03

,

CrO,

,

Cr207

,

As0,

,

CN-

,

c i t r a t e , NO3,

a c e t a t e , f o r m a t e , o r a n y o t h e r o r g a n i c o r i n o r g a n i c a c i d c a p a b l e of f o r m i n g water s o l u b l e s a l t s .

Some b l o c k s of foam may have been t r e a t e d w i t h g a s e o u s ammonia t o n e u t r a l i z e e x c e s s a c i d . T h i s t r e a t m e n t i s o n l y mentioned w i t h r e s p e c t t o t h e p r o d u c t i o n of foam s u i t a b l e f o r f l o r i s t s ' mounting b l o c k s . R e s i n S t a b i l i s e r s These a r e added t o t h e c r u d e r e s i n t o e x t e n d i t s s h e l f l i f e . e t h y l e n e g l y c o l d i e t h y l e n e g l y c o l p r o p y l e n e g l y c o l b u t y l e n e g l y c o l b u t e n e d i o l b u t y n e d i o l h e x e n e d i o l f u r f u r y l a l c o h o l

g l y c e r o l

p e n t a e r y t h r i t o l

May be up t o 5% by weight of t h e r e s i n . R e s i n S o l u b i l i z e r s

These may be added t o c l a r i f y o r lower t h e v i s c o s i t y of t h e bulk r e s i n . methanol e than01 b u t a n o l s p e n t a n o l s hexano 1s methyl e t h y l k e t o n e e t h y l a c e t a t e b u t y l a c e t a t e t o l u e n e e t h y l benzene x y l e n e s hexane h e p t a n e (must be mixed w i t h o t h e r s o l v e n t s ) . Flame R e t a r d a n t s t e t r a h y d r o x y methylphosphonium c h l o r i d e t e t r a b r o m o b i s p h e n o l dibromobutene d i o l dibromopropenal sodium bromide c h l o r a l h y d r a t e f u r f u r a l f u r f u r y l a l c o h o l d i m e t h y l methane phosphonate b o r i c a c i d boron o x i d e borax b o r i c a c i d esters boron t r i c h l o r i d e boron t r i b r o m i d e boron n i t r i d e boron p h o s p h a t e boron t r i f l u o r i d e e t h e r a t e boron t r i f l u o r i d e methanol boron t r i f l u o r i d e monethylamine t r i m e t h o x y l b o r o x i n e May b e up t o 10% p r e s e n t .

The phosphonate mentioned may be r e p l a c e d by any o t h e r phosphonate d e r i v e d from t h i s one by s u b s t i t u t i n g any o r a l l of t h e methyl groups by e t h y l .

A g e n e r a l f o r m u l a f o r t h e p h o s p h o n a t e s i s : 0 '2-62 a d d e d , b e s t i s 3.5%'

u

CH30

-

P

-

OCH3 II CH3 I n g e n e r a l , t h i s g r o u p d i d n o t a p p e a r t o be v e r y e f f e c t i v e and p r o b a b l y d i d n o t go i n t o any commercial p r o d u c t .

C h l o r a l h y d r a t e may be r e p l a c e d by any o t h e r d e r i v a t i v e formed by t h e r e a c t i o n of i t w i t h : ammonia, a l c o h o l s , a l k y l e n e g l y c o l s , p h e n o l s , a c e t o n e , o r by 2 , 3 d i b r o m o p r o p a n o l o r by 'any o t h e r h a l o g e n a t e d compound c o n t a i n i n g a t l e a s t t h r e e c a r b o n atoms'.

Some compounds were a l s o added i n a few c a s e s t o g i v e good c h a r r i n g p r o p e r t i e s : p e n t a e r y t h r i t o l g l y c e r o l s u g a r s ' p o l y h y d r i c a l c o h o l s ' There may be up t o 10% of t h i s l a s t g r o u p p r e s e n t , b u t g e n e r a l l y l e s s was added.

Other compounds t h a t may h a v e been t r i e d a r e : t r i s h a l o a l k y l p h o s p h a t e s ( ' T r i s ' )

d i c y a n d i a m i d e melamine

t r i m e t h y l a m i n e s u l p h a t e d i c h l o r o b i s p h e n o l

P l a s t i c i z e r s and Anti-Shrink Anents p o l y ( v i n y l a l c o h o l ) p o l y ( v i n y l a c e t a t e ) p o l y ( e t h y l e n e g l y c o l s ) ( v a r i o u s

MW

r a n g e s and p r o f i l e s ) h y d r o x y m e t h y l a t e d p o l y ( v i n y l a l c o h o l ) s o r b 1 to 1 s i m p l e s a c c h a r i d e s

-

f r u c t o s e , g l u c o s e , m a l t o s e , s u c r o s e p e n t a e r y t h r i t o l g l y c e r o l ' p o l y h y d r i c a l c o h o l s

'

melamine ( p r o b a b l y u s e d more a s c o - r e a c t a n t ) ' e m l s i f i e d p o l y v i n y l r e s i n ' ' e m u l s i f i e d p o l y a c r y l i c a c i d r e s i n ' May be up t o 30% by w e i g h t of t h e s e .

Dimethyl formamide (DMF) may h a v e been added a s a c o s o l v e n t f o r some of t h e s e .

F i l l e r s and E x t e n d e r s wood f l o u r s t a r c h d e x t r o s e g l a s s o r m i n e r a l f i b r e s m i n e r a l powder c a l c i u m s i l i c a t e k a o l i n mica t r a s s powder t a l c s l a t e powder m i n e r a l wool s l a g wool foundry s l a g wool barium s u l p h a t e a l k a l i n e e a r t h o r heavy m e t a l p h o s p h a t e s z i r c o n i u m o r l e a d compounds i r o n o x i d e t i t a n i u m d i o x i d e chromium o x i d e

Few X _{may have been added t o some f o r m u l a t i o n s .}

Blowing Agents

These a g e n t s a r e u s e d t o c r e a t e g a s b u b b l e s f o r foam g e n e r a t i o n . Air was used i n t h e g r e a t e s t number of c a s e s , b u t mention i s made of a d d i n g g a s g e n e r a t o r s t o t h e m i x t u r e i n some c l a i m s . b u t a n e dichlorotetrafluoroethane c h l o r a l h y d r a t e ( b u t no mention of what t o r e a c t w i t h )

-

C02 l i b e r a t i n g compounds

-

low b o i l i n g p o i n t p o l y h a l o g e n a t e d s a t u r a t e d f l u o r o c a r b o n s

-

lower a l i p h a t i c e t h e r s .

-

f r e o n s urea/NaN02/HC1

No amounts mentioned

-

'few X ' _{i n some c a s e s .}

The l a s t m i x t u r e i s o n l y mentioned once and i t

i s

hoped t h a t i t n e v e r went i n t o any commercial p r o d u c t . I f i t d i d , t h e r e may be n i t r o s o u r e a s p r e s e n t i n some foams.

C o l o u r i n g Agents