Ionomer Interpenetrating Polymer Network Coatings from

Chapter 21

Downloaded by NANYANG TECHNOLOGICAL UNIV on October 13, 2017 | http://pubs.acs.org Publication Date: April 18, 1988 | doi: 10.1021/bk-1988-0367.ch021

Ionomer Interpenetrating Polymer Network Coatings from Polyurethane and Vinyl Chloride Copolymer H. X . Xiao, K . C. Frisch, and S. Al-Khatib Polymer Institute, University of Detroit, Detroit, MI 48221 Opposite charge group containing ionomer pseudo-interpenetrating polymer network (IPN) coatings were prepared from a carboxyl-containing vinyl chloride copolymer (VMCC) and polyurethanes (PUs) with and without tertiary amine nitrogen in the polymer backbone at various PU-VMCC compositions. The morphology and physical properties of the ionomer pseudo-IPN coatings were compared with those of nonionomer pseudo-IPN coatings. The ionomer pseudo-IPN coatings exhibited improved mechanical properties and higher adhesive strength and did not reveal any phase separation as determined by thermomechanical analysis and scanning electron microscopy. I n t e r p e n e t r a t i n g polymer networks (IPNs) a r e a unique blend o f c r o s s l i n k e d polymers i n which t h e c h a i n s o f t h e two p o l y m e r s a r e h e l d t o g e t h e r by permanent entanglements formed by homocross-1inking o f t h e component p o l y m e r s . The d e g r e e o f i n t e r p é n é t r a t i o n d e p e n d s upon t h e m i s c i b i l i t y between t h e c o n s t i t u e n t polymers. Most p o l y m e r p a i r s a r e n o t compatible because, i n c o n t r a s t t o low-molecular weight m a t e r i a l s , t h e e n t r o p y o f m i x i n g two m a c r o m o l e c u l e s c o n t a i n i n g a l a r g e number o f segments i s r e l a t i v e l y small w h i l e the enthalpy o f mixing i s u s u a l l y p o s i t i v e o r near zero, unless s p e c i f i c i n t e r a c t i o n s are present (1-10). To achieve m i s c i b i l i t y , the presence o f s p e c i f i c i n t e r a c t i o n s i s u s u a l l y r e q u i r e d and t h e s e i n c l u d e : hydrogen bonding, (11-17) c h a r g e - t r a n s f e r complexes, (18-20) a n i o n - c a t i o n i n t e r a c t i o n (2-9, 21, 22) and i o n dipole interactions. (23-27) These specific i n t e r a c t i o n s g e n e r a l l y give r i s e t o the remarkable p r o p e r t i e s o f the r e s u l t i n g polymer blends, a l l o y s , and IPNs. Pseudo or semi-IPNs are combinations o f l i n e a r with c r o s s l i n k e d polymers r e s u l t i n g i n v a r i o u s d e g r e e s o f interpénétration. (28-34) I n t e r e s t i n polyurethane ionomers has increased i n the l a s t decade because of t h e i r growing uses i n waterbased coating, adhesives, medical, and semiconductor applications. However, r e l a t i v e l y l i t t l e information has been published regarding the synthesis and 0097-6156/88/0367-0311$06.00/0 © 1988 A m e r i c a n C h e m i c a l Society

Dickie et al.; Cross-Linked Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1988.

312

CROSS-LINKED POLYMERS


p r o p e r t i e s of ionomer pseudo-IPNs. The purpose of the p r e s e n t s t u d y was t o s t u d y t h e e f f e c t s o f o p p o s i t e c h a r g e g r o u p s i n i o n o m e r p s e u d o - I P N s b a s e d on polyurethanes and a v i n y l c h l o r i d e copolymer. Experimental A. Raw M a t e r i a l s The raw m a t e r i a l s used i n t h i s s t u d y a r e presented i n Table 1. The p o l y e t h e r p o l y o l and s h o r t c h a i n d i o l s were d e g a s s e d a t 80-90 C under vacuum overnight t o remove any moisture. MEK was t r e a t e d with m o l e c u l a r s i e v e s 4A o v e r n i g h t t o remove any moisture p r i o r to use. The o t h e r m a t e r i a l s were u s e d a s received. B. Procedures (1) PREPARATION OF POLYURETHANES (PU): A r e s i n k e t t l e under dry n i t r o g e n was charged with H MDI. A mixture o f 1,4-butanediol, or N-methyldiethanolamine, and poly-(oxytetra-methylene) g l y c o l (PTMO) was added a t an NCO/OH r a t i o of 2:1. The r e a c t i o n was c a r r i e d o u t a t 100 C f o r about two h o u r s u n t i l t h e t h e o r e t i c a l i s o c y a n a t e content, as determined by the di-n-butylamine t i t r a t i o n method (27) , was reached. The PU p r e p o l y m e r w i t h o r without t e r t i a r y amine n i t r o g e n groups was d i s s o l v e d i n d r y MEK t o o b t a i n a p r e p o l y m e r s o l u t i o n o f 30-40% solids. I t was then mixed with a mixture of 1,4-BD/TMP (4:1 by equiv. r a t i o ) a t an NCO/OH = 1.05/1.0 r a t i o i n t h e p r e s e n c e o f T-12 c a t a l y s t (0.05% based on t o t a l weight). The r e a c t i o n mixture was c a s t i n a metal mold t r e a t e d w i t h a r e l e a s e agent a t ambient temperature. A f t e r standing 3-5 hours a t room temperature, the mold was p l a c e d i n an oven and post-cured a t 100 C f o r 16 hours. The s a m p l e s were t h e n c o n d i t i o n e d i n a d e s i c c a t o r f o r one week before t e s t i n g . (2) VINYL CHLORIDE COPOLYMER: A copolymer from v i n y l c h l o r i d e , v i n y l a c e t a t e and m a l e i c a c i d (VMCC) (1% o f m a l e i c a c i d ) was d i s s o l v e d i n MEK t o o b t a i n a homogeneous s o l u t i o n of about 30% s o l i d s . A s t a b i l i z e r T h e r m o l i t e 25, was added t o t h e above s o l u t i o n a t 0.5% (by wt.) based on the s o l i d s content o f VMCC. (3) P R E P A R A T I O N OF P s e u d o - I P N s : The prepolymer and VMCC s o l u t i o n s were mixed a t d i f f e r e n t PU/VMCC r a t i o s . The c a t a l y s t and the c r o s s l i n k i n g agent f o r PU were added a t an NCO/OH r a t i o o f 1.05. The mixtures were then c a s t i n metal molds (treated with a r e l e a s e agent) a t ambient t e m p e r a t u r e t o o b t a i n f i l m samples of c a . 40-60 m i l s t h i c k n e s s f o r determination o f the s t r e s s - s t r a i n p r o p e r t i e s . The PU c r o s s - l i n k i n g r e a c t i o n was c a r r i e d o u t a t 80°C f o r 2-3 hours and postcured a t 100 C f o r 16 hours. The f i l m samples were then c o n d i t i o n e d i n a d e s i c c a t o r f o r one week b e f o r e testing. The above s o l u t i o n s were a l s o c o a t e d on


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TABLE 1

Polymer

Network

Coatings

313

RAW MATERIALS

Designation

Description

Supplier

Terathane 1000(PTMO) H MDI

Poly(1,4-oxytetramethylene) glycol MW=1000 Dicyclohexylmethane 4,4 d i i s o c y a n a t e 1,4-Butanediol

Du Pont Co. Mobay Chem Co. Du Pont Co. Celanese Chem.Co. M &T Chem.Co. Penwalt Co. Union carbide Corp.

12

1

1,4 BD TMP

Trimethylolpropane

T-12

Dibutyltin dilaurate

N-MDEA

N-methyldiethanolamine

VMCC

Thermolite MEK

Poly ( v i n y l c h l o r i d e - v i n y l acetate-maleic a c i d ) . MW = 15000, maleic a c i d = 1% 25 . T h e r m o s t a b i l i z e r of PVC Methylethyl ketone Molecular s i e v e s 4A

M &T Chem.Co. Eastman Chem.Co. Eastmen Chem.Co.


314



aluminum panels f o r measurement of t h e Gardner and l a p shear s t r e n g t h .

impact

Instrumental Techniques and Measurements The t e n s i l e strength, modulus, and e l o n g a t i o n a t b r e a k were measured on an Instron T e n s i l e T e s t e r a t a c r o s s h e a d speed o f 20 i n . / m i n (ASTM D-412) and t h e hardness by means of a Shore A Durometer (ASTM D-2240). The impact r e s i s t a n c e of the pseudo-IPN c o a t i n g s was measured on a Gardner-SPI modified V a r i a b l e Height Impact T e s t e r using both t h e d i r e c t and t h e i n d i r e c t techniques. A TMS-2 Thermomechanical A n a l y z e r (Perkin-Elmer) was used t o determine the g l a s s t r a n s i t i o n temperatures of the ionomer pseudo-IPNs a t temperatures ranging from -100 C t o +100°C and 0.01 mm of p e n e t r a t i o n range, 80g of p e n e t r a t i n g weight, and a heating r a t e o f 10 C/min. The chemical r e s i s t a n c e was measured by p l a c i n g t h e c o a t e d panels i n t o a 10% NaOH of HC1 s o l u t i o n a t room temperature f o r one week. The r e v e r s e s i d e and the edges of the panels were c o a t e d w i t h wax t o p r o t e c t t h e metal s u r f a c e s from chemical a t t a c k . To observe the morphology of the pseudo-IPNs with and w i t h o u t o p p o s i t e c h a r g e g r o u p s , s a m p l e s were p r e p a r e d by f r e e z e - f r a c t u r i n g i n l i q u i d n i t r o g e n and a p p l y i n g a g o l d c o a t i n g of a p p r o x i m a t e l y 200 A t h i c k n e s s . M i c r o g r a p h s were o b t a i n e d by u s i n g a P h i l l i p s S c a n n i n g Electron Microscope Model SEM 505. R e s u l t s and D i s c u s s i o n A. E f f e c t o f D i f f e r e n t Compositions of PU/VMCC on t h e M e c h a n i c a l P r o p e r t i e s of Pseudo-IPN Coatings with and without Opposite Charge Groups As shown i n Figures 1 and 2,the pseudo-IPN c o a t i n g s w i t h o p p o s i t e charge groups e x h i b i t e d improved p r o p e r t i e s due t o n e u t r a t i z a t i o n of the carboxyl groups i n VMCC by t h e t e r t i a r y amine n i t r o g e n i n the PU,as shown i n t h e f o l l o w i n g schemes: -COO As a r e s u l t , the m i s c i b i l i t y between t h e PU network and the VMCC l i n e a r chains was g r e a t l y improved and both t e n s i l e and l a p shear strength were enhanced compared t o t h e m a t e r i a l s without opposite charge groups i n which o n l y hydrogen b o n d i n g between c a r b o x y l and u r e t h a n e c o u l d form i n s t e a d o f i o n i c bonds. I t has been known t h a t t h e m i s c i b i l i t y between p o l y ( v i n y l c h l o r i d e ) and p o l y e s t e r s depends upon the CH /C=0 r a t i o , (28) and t h a t the chain length o f t h e


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Ionomer

Interpenetrating

Polymer

Network

Coatings


4000

3000

Φ IPN-C1 w i t h O O O O s i t e charge grouos 2000 Θ

IPN-C2 w i t h o u t charee ^rouns

ormosite

1000

95/5 100/0

80/20 70/30 75/25 PU/VHC

60/40

50/50

Comnosition

F i g u r e 1. E f f e c t o f d i f f e r e n t c o m p o s i t i o n s o f PU/VMCC on t h e t e n s i l e s t r e n g t h o f semi-IPN c o a t i n g s w i t h o r w i t h o u t o p p o s i t e charge g r o u p s .


315


316


g y l c o l i n t h e e s t e r s p l a y s an i m p o r t a n t r o l e i n the m i s c i b i l i t y . (28) Pandyopadhyay and Shaw (29) i n d i c a t e d t h a t t h e p o l y u r e t h a n e based on PTMO e x h i b i t e d poor m i s c i b i l i t y w i t h PVC c o m p a r e d t o o n e b a s e d o n p o l y c a p r o l a c t o n e g l y c o l due t o the f a c t t h a t the PTMObased PU p h y s i c a l l y b o n d e d w i t h PVC c o u l d n o t be p r o d u c e d as r e a d i l y as with p o l y - c a p r o l a c t o n e g l y c o l based PU with PVC. (28) The hydrogen bonding between the carboxyl groups i n VMCC and t h e urethane groups i n the PU without t e r t i a r y amine n i t r o g e n was n o t s t r o n g enough t o improve t h e m i s c i b i l i t y o f the two polymer systems presumably due t o t h e v e r y low c o n c e n t r a t i o n o f carboxyl groups i n t h e VMCC. The pseudo-IPNs without o p p o s i t e c h a r g e groups e x h i b i t e d low s t r e s s - s t r a i n p r o p e r t i e s and low l a p shear strength. On t h e o t h e r hand, t h e pseudo-IPNs w i t h o p p o s i t e c h a r g e groups, even a t low c o n c e n t r a t i o n o f i o n i c bonds, e x h i b i t e d r e l a t i v e l y h i g h s t r e s s - s t r a i n p r o p e r t i e s and l a p shear s t r e n g t h . I n c r e a s i n g the c o n c e n t r a t i o n o f VMCC r e s u l t e d i n more b r i t t l e m a t e r i a l s with lower t e n s i l e and l a p shear strength. The maximum t e n s i l e s t r e n g t h o f t h e pseudo-IPNs appeared a t about the 80:20 r a t i o o f PU/VMCC f o r b o t h pseudo-IPNs w i t h and w i t h o u t o p p o s i t e charge groups. Presumably the maximum entangle-ment between t h e VMCC c h a i n s a n d t h e PU n e t w o r k a l s o o c c u r r e d a t t h i s composition ( Figure 1 ) . The maximum l a p shear strength o f the pseudo-IPNs, however, appeared a t about t h e 75:25 c o m p o s i t i o n f o r ionomer pseudo-IPNs w i t h o p p o s i t e charge groups and 70:30 composition f o r the pseudo-IPNs without o p p o s i t e charge groups (Figure 2) . A l l the pseudo-IPNs without opposite charge groups e x h i b i t e d v e r y p o o r e l o n g a t i o n due t o t h e i r p o o r miscibility. The r e l a t i v e l y high t e n s i l e s t r e n g t h s o f the 75:25 and the 80:20 r a t i o s o f PU/VMCC could be due t o t h e h i g h e r degree of i n t e r p e n e - t r a t i o n between t h e c h a i n s o f VMCC and t h e PU networks r e s u l t i n g f r o m improved m i s c i b i l i t y because of hydrogen bonding between the c a r b o x y l and urethane groups ( Figure 1 ) . B. Gardner Impact S t r e n g t h of Pseudo-IPNs with and without Opposite Charge Groups The ionomer pseudo-IPN coatings with o p p o s i t e charge groups gave b e t t e r r e s u l t s than the pseudo-IPNs without o p p o s i t e c h a r g e groups due t o t h e i r g r e a t e r flexibility. The i m p a c t s t r e n g t h d e c r e a s e d w i t h i n c r e a s i n g c o n c e n t r a t i o n o f VMCC due t o i t s i n h e r e n t b r i t t l e n e s s (Table 2 ) . C. Solvent and Chemical Resistance o f Pseudo-IPN Coatings As shown i n Table 3, both pseudo-IPNs with and without opposite charge groups e x h i b i t e d poor s o l v e n t


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Polymer

Network

Coatings

317

50α

400-


300.

200

u to

jB 100

IPN-C1 w i t h o p p o s i t e charge groups IPN-C2 w i t h o u t charge groups

95/5

80/20

100/0

70/30 75/25

opposite

60/40

50/50

F i g u r e 2. E f f e c t o f d i f f e r e n t c o m p o s i t i o n s o f PU/VMCC on t h e l a p s h e a r s t r e n g t h o f semi-IPN c o a t i n g s w i t h o r w i t h o u t o p p o s i t e charge g r o u p s .

TABLE 2 IMPACT STRENGTH OF PSEUDO-IPN COATINGS FROM PU AND VMCC WITH AND WITHOUT CHARGE GROUPS Composition of PU/VMCC 100:0 95:5 80:20 75:25 70:30 60:40 50:50 100:0 95:5 80:20 75:25 70:30 60:40 50:50

Opposite Charge Groups NO YES YES YES YES YES YES NO NO NO NO NO NO NO

Impact Strength, i n . l b . Direct Indirect 160 150 150 150 140 140 140 160 140 140 130 130 130 120


160 160 160 150 150 140 120 160 160 130 130 130 120 110

318



TABLE 3

SOLVENT AND CHEMICAL RESISTANCE OF PSEUDO-IPN COATINGS

Composition

Opposite Solvent

of PU/VMCC

Charge Groups

100:0 95:5 80:20 70:30 75:25 60:40 50:50 100:0 95:5 80:20 70:30 75:25 60:40 50:50

NO YES YES YES YES YES YES NO NO NO NO NO NO NO

Resistance a) Resistance b) MEK Xylene 10% HCI 10% NaOH >50 48 48 41 39 36 34 >50 48 45 40 37 37 34

>50 45 45 40 38 35 33 >50 48 48 46 46 45 40

Failure Failure Pass Pass Pass Pass Pass Failure Failure Failure Pass Pass Pass Pass

Failure Pass Pass Pass Pass Pass Pass Failure Failure Failure Pass Pass Pass Pass

^ D o u b l e rub with cotton saturated with s o l v e n t the h i g h e s t rub time without change o f the s u r f a c e was recorded. At room temperature f o r one week.



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319

r e s i s t a n c e with i n c r e a s i n g c o n c e n t r a t i o n s o f VMCC due t o the f a c t t h a t VMCC i s a t h e r m o p l a s t i c , l i n e a r polymer. In c o n t r a s t t o t h e s o l v e n t r e s i s t a n c e , t h e chemical r e s i s t a n c e o f pseudo-IPN c o a t i n g s i n c r e a s e d w i t h i n c r e a s i n g c o n c e n t r a t i o n of VMCC. I t i s i n t e r e s t - i n g t o note t h a t the ionomer pseudo-IPN c o a t i n g s with opposite c h a r g e g r o u p s e x h i b i t e d b e t t e r s o l v e n t and c h e m i c a l r e s i s t a n c e than those without o p p o s i t e c h a r g e groups, p r e s u m a b l y due t o t h e f a c t t h a t a h i g h d e g r e e o f interpénétration occurred between the chains o f VMCC and the PU networks, which was brought about by formation of i o n i c bonds between opposite charge groups. D. G l a s s T r a n s i t i o n Temperatures o f Pseudo-IPN Coatings The T g s f o r both pseudo-IPNs with and without i o n i c bonds (or opposite charge groups) between t h e two polymers a r e shown i n Figure 3. Ionomer pseudo-IPNs with i o n i c bonds only gave s i n g l e T g s f o r each composition. The Tg's increased with an i n c r e a s e o f VMCC i n PU/VMCC composition due t o the i n t r o d u c t i o n o f r i g i d VMCC with a high Tg. In c o n t r a s t , pseudo-IPNs without i o n i c bonds gave two Tg's f o r each composition except a t 100% and 95:5 r a t i o s o f PU/VMCC. These r e s u l t s imply t h a t some phase s e p a r a t i o n had o c c u r r e d i n t h e s e p s e u d o - I P N systems due t o the f a c t t h a t the f r e e energy o f mixing i n the systems may be e i t h e r p o s i t i v e o r zero because of t h e l a c k o f p h y s i c a l i n t e r a c t i o n between t h e two polymers ( i o n i c bonds). As shown i n F i g u r e 3, t h e g l a s s t r a n s i t i o n temperatures o f both PU and VMCC f o r pseudo-IPNs without i o n i c bonds s h i f t e d inward with the Tg of PU s h i f t i n g t o higher temperatures and the Tg of VMCC s h i f t i n g t o lower t e m p e r a t u r e s i n t h e pseudo-IPNs systems without i o n i c bonds. T h i s i m p l i e s t h a t some interpénétration between t h e PU network and t h e VMCC polymer chains had taken p l a c e . Only the 95:5 composition of PU/VMCC e x h i b i t e d a s i n g l e Tg, presumably due t o the f a c t t h a t pseudo-IPNs w i t h low c o n c e n t r a t i o n o f VMCC c o u l d be c o m p a t i b l e through t h e hydrogen bonding between the urethane groups and the carboxyl groups of VMCC. F i g u r e 3 shows the e f f e c t s o f composition on the T g s f o r both ionomer and nonionomer pseudo-IPN. They e x h i b i t good l i n e a r i t y f o r both pseudo-IPNs. Nonionomer p s e u d o - I P N r e v e a l s two l i n e s d u e t o t h e p h a s e separation. The bottom most one i s PU and t h e top most one i s VMCC, b u t t h e y s h i f t e d i n w a r d due t o t h e formation of pseudo-IPN. E. Morphology of Pseudo-IPN Coatings by Scanning E l e c t r o n Microscopy (SEM) !

f

f

M i c r o g r a p h s o f pseudo-IPN c o a t i n g s w i t h o u t opposite charge groups are shown i n Figure 4 (from A - l t o C - l ) a t d i f f e r e n t c o m p o s i t i o n s o f PU/VMCC and magnifications. F i g u r e 4 ( A - l and A-2) are micrographs



320


F i g u r e 3 · E f f e c t o f the c o m p o s i t i o n i n the ionomer and nonionomer IPN on t h e g l a s s t r a n s i t i o n temperature.



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F i g u r e 4. M i c r o g r a p h s o f semi-IPN w i t h and w i t h o u t o p p o s i t e charge groups by s c a n n i n g e l e c t r o n m i c r o s c o p y (SEM).

of 100% polyurethanes a t 5 χ 10 and 10 m a g n i f i c a t i o n , respectively. In Figure 4 ( B - l & C - l ) , the composition of PU/VMCC was changed from 80:20 t o 50:50. A l l o f t h e micrographs e x h i b i t e d obvious phase s e p a r a t i o n , i n which t h e w h i t e p a r t i c l e s o f VMCC d i s p e r s e d i n t o the dark matrix o f t h e PU. Upon i n c r e a s i n g the c o n c e n t r a t i o n o f VMCC, t h e a r e a o f t h e d i s p e r s e d phase o f VMCC was increased with the VMCC p a r t i c l e s i n c l o s e proximity t o each other. In c o n t r a s t , the micrographs of the ionomer pseudoIPN c o a t i n g s with opposite charge groups, Figure k (A-2 t o G-2) , d i d not r e v e a l any phase s e p a r a t i o n . No white p a r t i c l e s o f the VMCC phase were v i s i b l e i n t h e d a r k m a t r i x o f t h e PU phase. Presumably t h e i o n i c bonds between the carboxyl and t e r t i a r y amine groups provided t h e b e s t o p p o r t u n i t y f o r interpénétration between the l i n e a r chains o f VMCC and the networks o f PU t o prevent any p o s s i b l e phase separation from the ionomer pseudoIPN microphase. The p h y s i c a l p r o p e r t i e s o f ionomer


322

CROSS-LINKED

POLYMERS


pseudo-IPNs with opposite charge groups were o b v i o u s l y improved compared t o t h e pseudo-IPNs w i t h o u t o p p o s i t e charge groups as p r e v i o u s l y mentioned (see F i g u r e s 1 and 2) . Conclusions The m i s c i b i l i t y between poly ( v i n y l c h l o r i d e ) and poly-urethanes based on poly (oxytetramethylene) glycol can be improved by i n t r o d u c i n g opposite charge groups t o form i o n i c bonds. The improvement i n m i s c i b i l i t y from i o n i c bonds between the two polymer systems provided t h e best chance f o r i n t e r p e n e - t r a t i o n between t h e l i n e a r c h a i n s o f VMCC and the PU networks i n order t o o b t a i n good p h y s i c a l p r o p e r t i e s o f t h e ionomer p s e u d o - I P N c o a t i n g s from PU and VMCC.

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