Polyester Mortars - ACS Symposium Series (ACS Publications)

5 Polyester Mortars RAYMOND B. SEYMOUR

Downloaded by UCSF LIB CKM RSCS MGMT on December 1, 2014 | http://pubs.acs.org Publication Date: November 27, 1979 | doi: 10.1021/bk-1979-0113.ch005

University of Southern Mississippi, Hattiesburg, MS 39401

While commercial polyesters are r e l a t i v e l y new, they were synthesized by Berzelius i n 1849 by the condensation of glycerol and t a r t a r i c acid. The first commercial polyesters called Glyptals were produced i n the early part of the 20th Century by the controlled condensation of t r i f u n c t i o n a l glycerol and difunctional phthalic anhydride. Vorlander described unsaturated polyesters which were produced from ethylene glycol and maleic anhydride i n 1894, but commercial unsaturated polyesters were not introduced u n t i l the 1920's. The first commercial free radical-curable unsaturated polyesters were produced by Kienle and Hovey, who condensed difunctional glycols, such as ethylene glycol with phthalic anhydride and an unsaturated aliphatic acid such as o l e i c acid. The name alkyd, which was derived from the prefix i n alcohol and the suffix i n incorrectly spelled "akyd" was used to describe these important polyesters. The degree of unsaturation i n these oil-modified alkyds was controlled by the amount and type of unsaturated acid used i n the formation of the polyester. These unsaturated polymers cured or "dried" through auto-oxidation by oxygen from the air which reacted with the unsaturated carbon atoms on the surface of the freshly deposited film. This crosslinking reaction, l i k e that of the "drying" of oil-based paints, was catalyzed by heavy metal s a l t s , such as lead or cobalt salts of organic acids. Alkyds, which are some of the most important paint resins, are produced at an annual rate i n excess of 300 thousand tons. Carothers repeated Vorlander's synthesis of ethylene glycol maleates but found that the crosslinking reaction of these s o l i d unsaturated polyesters was too slow to be of p r a c t i c a l use. 1

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0-8412-0523-X/79/47-113-061$05.00/0 © 1979 American Chemical Society

In Plastic Mortars, Sealants, and Caulking Compounds; Seymour, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 1979.


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COMPOUNDS

E l l i s and Rust solved t h i s problem by d i s s o l v i n g the s o l i d unsaturated p o l y e s t e r s i n a l i q u i d v i n y l monomer, such as v i n y l acetate.-2>10 However, the l e s s v o l a t i l e and more widely a v a i l able styrene monomer was used i n s t e a d o f v i n y l acetate f o r most of the f i b e r g l a s s - r e i n f o r c e d "low p r e s s u r e " p o l y e s t e r p l a s t i c s t h a t were produced during World War I I and s i n c e that time. A t y p i c a l f o r m u l a t i o n f o r a general purpose unsaturated p o l y e s t e r r e s i n i s as f o l l o w s : — p h t h a l i c anhydride (2 moles), maleic anhydride (1 mole), and propylene g l y c o l (3.15 moles). The unsaturated p o l y e s t e r obtained by the thermal condensation of these r e a c t a n t s and removal of water plus excess propylene g l y c o l i s d i s s o l v e d i n styrene (2.7 moles) c o n t a i n i n g 0.01% of hydroquinone i n h i b i t o r . This unsaturated p o l y e s t e r i s then cured by the a d d i t i o n of a peroxy compound, such as benzoyl peroxide which produces f r e e r a d i c a l s (R.) f o r the c r o s s l i n k i n g r e a c t i o n . A simulated equation f o r these r e a c t i o n s i s as f o l l o w s : HO - OH + A r ( C 0 ) 0 + C=C(C0 )2° ~> 2

2

Unsaturated P o l y e s t e r + ArC=C + R.

Unsaturated P o l y e s t e r Crosslinked Polyester

Several reviews on unsaturated p o l y e s t e r r e s i n technology are available.A2>13,IS,Π Network polymers were produced by i n s i t u f r e e r a d i c a l i n i t i a t e d p o l y m e r i z a t i o n o f d i e t h y l e n e b i s ( a l l y l carbonate) during World War I I and u n f i l l e d c l e a r c a s t i n g s of t h i s r e s i n are s t i l l a v a i l a b l e under the trade name of CR-39 (16), This monomer was a l s o copolymerized w i t h d i a l l y l phthalate and prepolymers of the l a t t e r c a l l e d DAP to produce p o l y e s t e r s . i ^ ' l ^ The heat r e s i s t a n c e of p o l y e s t e r s may be improved by the a d d i t i o n of t r i a l l y l cyanurate as one of the monomers-1^ and t h e i r flame r e s i s t a n c e may be reduced by r e p l a c i n g part of the p h t h a l i c anhydride by chlorendic,2Q t e t r a c h l o r o p h t h a l i c , 2 1 tetrabromop h t h a l i c a n h y d r i d e ^ r the D i e l s - A l d e r adduct of hexachloropentadiene and t e t r a h y d r o p h t h a l i c anhydride.-^ The f i r e r e t a r d a n t p r o p e r t i e s of p o l y e s t e r s have a l s o been improved by the use of e x t e r n a l flame r e t a r d a n t s , such as antimony oxide and organic halogen compounds,-^ borates, b a s i c magnesium carbonate and alumina t r i h y d r a t e (ΑΤΗ).25 » 26 The f l e x i b i l i t y of unsaturated p o l y e s t e r s may be improved by r e p l a c i n g some of the p h t h a l i c anhydride by a l i p h a t i c d i b a s i c a c i d s , such as a d i p i c , a z e l a i c , s e b a c i c , d i g l y c o l i c o r dimer vegetable o i l a c i d s and by r e p l a c i n g propolyene g l y c o l by dipropylene g l y c o l or higher homologs such as t r i p r o p y l e n e glycol. The r e s i s t a n c e of unsaturated p o l y e s t e r r e s i n s t o s o l v e n t s and c o r r o s i v e s may be improved by the use o f i s o p h t h a l i c o r t e r e p h t h a l i c a c i d i n place of p h t h a l i c anhydride and by the use of h i g h l y branched d i o l s , such as 2 , 2 , 4 - t r i m e t h y l - l , 3 - p e n t a n e d i o l , 1,3-cyclohexanediol, hydrogenated b i s phenol A or the r e a c t i o n 0



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product of the l a t t e r and propylene oxide i n place o f propylene glycol. The c h a r a c t e r i s t i c b r i t t l e n e s s o f unsaturated p o l y e s t e r r e s i n s was overcome by reinforcement w i t h s i l a n e - t r e a t e d f i b e r g l a s s . While over 750 thousand tons o f these r e i n f o r c e d p l a s t i c s are produced annually i n the U.S., the emphasis i n t h i s chapter w i l l be on room t e m p e r a t u r e - c u r a b l e - f i l l e d unsaturated p o l y e s t e r mortars o r concrete. As discussed i n Chapters 1 and 7, these anaerobic p o l y e s t e r mortars are w i d e l y used as m a t e r i a l s o f construction.— As described i n Chapter 1, the o r i g i n a l s i l i c a - f i l l e d unsaturated p o l y e s t e r mortar, c a l l e d V i t r o p l a s t i s used as a g r o u t i n g composition f o r j o i n i n g b r i c k s f o r f i l l i n g c r a c k s , as a m o n o l i t h i c f l o o r o r w a l l c o a t i n g , and as a c a s t i n g composition f o r a r t i c l e s , such as d r a i n pipes and bathroom f i x t u r e s . A t y p i c a l two package p o l y e s t e r cement c o n s i s t s of an unsaturated p o l y e s t e r (41), c e l l u l o s e acetate b u t y r a t e o r p o l y v i n y l acetate (1.8) and Ν,Ν-dimethylaniline (1) d i s s o l v e d i n styrene (18). This l i q u i d (binder) i s i n t i m a t e l y mixed w i t h a f i l l e r c o n s i s t i n g of graded s i l i c a o r s o l i d g l a s s spheres (15.5), t a l c (23), t i t a n i u m d i o x i d e (1.0) and benzoyl peroxide (1.0). The s e t t i n g time of t h i s mortar may be r e g u l a t e d by the amount of benzoyl peroxide i n i t i a t o r used i n the f o r m u l a t i o n . I t i s advantageous t o add s i l a n e o r t i t a n a t e c o u p l i n g agents to the f i l l e r i n order t o a i d the m i x i n g , i n c r e a s e the adhesion between the r e s i n and f i l l e r and t o reduce the v i s c o s i t y o f the mortar. Thixotropes, such as pyrogenic s i l i c a may be added t o c o n t r o l the flow o f the mortar on v e r t i c a l s u r f a c e s . I t i s e s s e n t i a l that the c o n c e n t r a t i o n o f v o l a t i l e styrene monomer be kept w i t h i n acceptable l i m i t s .-^S- The c o n c e n t r a t i o n of v o l a t i l e s may a l s o be reduced by the use o f higher b o i l i n g monomers, such as v i n y l t o l u e n e o r t e r t . b u t y l s t y r e n e . The latter23>2Q l l as graded aggregate f i l l e r s w i l l reduce the shrinkage when the r e s i n cures.31 (The normal shrinkage i s about 17%.) The r e s i s t a n c e o f p o l y e s t e r concrete t o hot water may be improved by the use o f TMPD g l y c o l p o l y e s t e r s , d i a l l y l p h t h a l a t e o r c r o s s - l i n k i n g a c r y l i c resins.-22 The water r e s i s t a n c e of " c u l t u r a l marble" produced from c l a y or calcium c a r b o n a t e - f i l l e d p o l y e s t e r mortars has been improved by t r e a t i n g the f i l l e r w i t h a s i l a n e , such as gammamethacryloylpropyltriethoxysilane.23 The translucency of " c u l t u r e d marble" may be improved by the use o f ΑΤΗ as a f i l l e r . The p h y s i c a l p r o p e r t i e s of a t y p i c a l room temperature-cured p o l y e s t e r concrete i s as f o l l o w s : B a r c o l hardness (50), t e n s i l e s t r e n g t h (500 kg cm~ ), e l o n g a t i o n (0.45%), compressive s t r e n g t h (1400 kg cm" ) f l e x u r a l s t r e n g t h (1050 kg c m ) and heat d e f l e c t i o n (41°C). The l a t t e r may be increased by 30° by the use of fumaric a c i d i n s t e a d of maleic a c i d . P l a s t i c concrete produced from general purpose p o l y e s t e r and f i l l e d w i t h limestone has l i m i t e d r e s i s t a n c e t o a c i d s and a l k a l i s , a s

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but i s more r e s i s t a n t to aqueous s a l t s o l u t i o n s than h y d r a u l i c cements. The r e l a t i o n s h i p s between molecular s t r u c t u r e and r e s i s t a n c e to c o r r o s i v e s and t e s t s f o r such r e s i s t a n c e have been described.24,35 The chemical r e s i s t a n c e of p o l y e s t e r concrete i s r e l a t e d to the unsaturated p o l y e s t e r s used and the styrene content of the cured p l a s t i c s . The c o r r o s i v e r e s i s t a n c e of these cements to a c i d s , a l k a l i e s , s a l t s , and o x i d i z i n g chemicals, such as c h l o r i n e d i o x i d e , may be improved by using b i s phenol A d i a c r y l a t e ( v i n y l e s t e r ) as the prepolymer and by adding g l a s s f l a k e s to the mixture of s i l i c a f i l l e r and coupling a g e n t s . — Spode, which i s a w e l l known manufacturer of chinaware, i s now producing i t s p l a t e s , cups, and saucers i n molds cast from p o l y e s t e r mortar.27 P o l y e s t e r cements are a l s o being used as r o o f i n g c o m p o s i t i o n ^ and a mixture of p o l y e s t e r r e s i n and P o r t l a n d cement c a l l e d E s t e r c r e t e i s being used t o surface bridges. 29 U l t r a v i o l e t r a d i a t i o n - c u r a b l e f i l l e d urethane dimethacylate cements have been used as d e n t a l r e s t o r a t i v e compositions.42 While r e l a t i v e l y l a r g e o b j e c t s may be c a s t i n molds from p o l y e s t e r mortars, molds are not always e s s e n t i a l . For example, a reproducton of the 20 m long John Paul Jones f i r s t s h i p , the Providence, was f a b r i c a t e d by a p p l y i n g a p o l y e s t e r mortar to f i b e r glass-reinforced polyester planking. The r e a c t i o n i n r e j e c t i o n molding process (RIM), which has been used f o r l a r g e polyurethane moldings, may a l s o be used w i t h f i l l e d p o l y e s t e r s (RRIM). L i k e w i s e , much h y d r a u l i c cement a r t may be adapted to p o l y e s t e r cement technology. Both of these cements have been r e i n f o r c e d w i t h s i l i c a and asbestos. A c t u a l l y , over 3 m i l l i o n tons of asbestos has been used a n n u a l l y , world wide, f o r the reinforcement of h y d r a u l i c cements t o produce composite corrugated sheet and pipe. Some of the asbestos f i l l e r i n h y d r a u l i c cements has been replaced by f i b r i l l a t e d polypropylene. More than 500 thousand s h e l l p i l e s of t h i s f i b r i l l a t e d p o l y p r o p y l e n e - f i l l e d P o r t l a n d cement, c a l l e d " C a r i c r e t e " are produced annually i n England. 41 > 42 One may ask, why a hydrophobic f i b e r , l i k e polypropylene, was used w i t h P o r t l a n d cement i n s t e a d of a more compatible f i b e r , such as f i b r i l l a t e d p o l y v i n y l a l c o h o l ? L i k e w i s e , one may a l s o ask why the l a t t e r has not been used t o upgrade p o l y e s t e r concrete? Presumably, the answer t o the f i r s t question i s , those w i t h e x p e r t i s e i n h y d r a u l i c cements are not w e l l versed i n organic polymer science and technology. The answer to the second i s t h a t , i n s p i t e of l a r g e s c a l e use of f i b e r g l a s s - r e i n f o r c e d p o l y e s t e r s and " c u l t u r e d marble", too few organic polymer s c i e n t i s t s and t e c h n o l o g i s t s are i n t e r e s t e d i n i n v e s t i g a t i n g p o l y e s t e r concrete. F o r t u n a t e l y , as discussed by Dr. Ohama i n Chapter 7, some i n v e s t i g a t i o n are being undertaken and these should lead to dramatic improvements i n c o n s t r u c t i o n through the use of p o l y e s t e r concrete. 1


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Polyester Mortars - ACS Symposium Series (ACS Publications)

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