Monomer reactivity ratios in the copolymerization of calcium acrylate with hexahydro-1,3,5-triacryloyltriazine

Ts. A. GOGUADZEet al.

2078

styrene have minima, which is different from the d H ~ (T) curve for P P F S found in this work (Fig. 2). We would like to thank F. S. Florinskii, a member of the laboratory of M. M. K o t o n of the Institute of Macromolecular Compounds, for presenting the specimens of polyparafluorostyrene. CONCLUSIONS

(I) The proton and fluorine magnetic resonance spectra of polyparafluorostyrene have been studied in the temperature range 20-150 °. The curves are symbatie and there is no change in the width and second moment of the NMI~ lines up to the softening point, 125 °. (2) Theoretical AH~ and AH~ values have been calculated for the rigid P P F S lattice. Taking account of the intermolecular contribution, these values are very similar to those observed experimentally at room temperature. (3) The effect of torsional vibrations of the radicals o]1 AH~ and - d H h~} has been determined theoretically. The effect is found weaker in P P F S than PFMS, which was studied before, and at reasonable vibration amplitudes it is not outside experimental error. (4) It is concluded that the results of the present work support the proposition that there are in-phase torsional vibrations in polyhalogene styrenes below Translated by V. ALFOI~D

the softelfing point.

REFERENCES 1. R. A. ABDRASHITOV, N. M. BAZHENOV, M. V. VOL'KENSHTEIN, A. I. KOL'TSOV and A. S. KHACHATUROV, Vysokomol. soyed. 5: 405, 1963 2. $. H. VAN VLECK, Phys. Rev. 74: 1168, 1948 3. T. M. BIRSHTEIN and O. B. PTITSYN, Vysokomol. soyed. 2: 628, 1960 4. E. R. ANDREW, J. Chem. Phys. 18: 607, 1950 5. R. KOSFELD, Kolloid-Z. 172: 182, 1960

MONOMER REACTIVITY RATIOS IN THE COPOLYMERIZATION OF CALCIUM ACRYLATE WITH HEXAHYDR0-1,3,5-TR!ACRYLOYLTRIAZINE* TS. A. G O G U A D Z E , V. V. K O R S H A K a n d •. Y E . O G N E V A D. I. Mendeleyev Chemico-Technological Institute, Moscow

(Received 21 December 1963)

TO STRENGTHEN unduly wet soils [1] we have proposed copolymerization of water-soluble monomers to form a three-dimensional copolymer. Calcium acry* Vysokomol. soyed. 6: No. 10, 1875-1879, 1964.

Copolymerization of CaA with HI-IT

2079

late (CaA) and hexahydro-l,3,5-triacryloyltriazine (HHT) were used as the initial monomers. Copolymerization of CaA and H H T has not, so far, been studied, nor have we found any data in the literature on the copolymerization of CaA with other unsaturated compounds. Thinius, Walter and Lommatsch [2] studied the copolymerization of H H T with styrene and methyl methacrylate but the reactivity ratios of these monomers during copolymerization were not determined. I n this paper we describe an attempt to investigate copolymerization of CaA with HHT, determine the copolymerization constants of these monomers and evaluate the differential composition of the copolymers obtained. I n view of the fact that the initial monomers contain several double carbmlcarbon independent bonds which do not differ in ability to eopolymerize, the modified Mayo and Lewis i~tegral equation was used to calculate copolymerization constants [3]: I ,.,=

1 log-[Me ]

1--P'-[M-1]'n] !'I

p;log

Emd:m/ i'

[M1]'n

[M0]._n] i log [~I1] -~-'°g - -

[M10].n

l - - p ' [lVl0]"ml

(1)

~ - - P ' [M°] • m

p'--(1--r'l)/(1--r'.)),

(2)

where n and m are the numbers of double bonds in monomers M 1 and 5Io, respectively. We found t h a t calculation from this equation leads to less deviation of r 1 and r 2 from the mean values obtained by determination of the copolymerization constant according to the "intersection method" than from the unmodified Mayo and Lewis equation. The reactivity ratios of radicals to monomer molecules M1 and M 2 were calculated from equations (3) and (4): rl=--'rl,

!

m

r2= - - ' r~.

(3) (4)

The differential composition of the copolymer was calculated from the Mayo and Lewis differential equation for copolymer composition [4]: [ml]

[M °] r I • [M1° ] q-[1~I ° ]

[rod - [M°~ r2" [M°] -k DI°] "

(m)

Experimental data concerning the composition of products obtained by copolymerization of CaA and HHT, with various monomer ratios in the initial mixture, are shown in Table 1. H H T content in the initial monomer mixture did not exceed 7.48 moles-~, since at higher H H T concentration only the H H T homopolymer forms.

2080

Ts. A. GOGUADZEet a l .

As c a n be seen f r o m Table 1, H H T c o n t e n t in t h e c o p o l y m e r is always higher t h a n in the initial m i x t u r e which indicates a high a c t i v i t y in c o p o l y m e r i z a t i o n with acrylic acid (AA). TABLE 1. COPOLYMERIZATIONOF CALCIUMACRYLATE(CaA) AND HEXAHYDRO-1,3,5-TRIACRYL. OYLTRIAZINE(HHT)

Series of experiments

Composition of initial monomer mixture ~o by wt.

moles-~o

CaA

HHT

Mo

M0

98 96 94 92 90

2 4 6 8 10

98.54 97.06 95.56 94-05 92.52

1.46 2.94 4.44 5.95 7.48

Nitrogen Copolymer content yield, % of the by wt. eopolymer, % by wt. 7-03 2.65 3.29 4.22 6.68

0.72 1.26 1-53 2.27

2.46

Copolymer composition ~o by wt. CaA

ttHT

moles-~o m1

95.73 4.27 96.741 92.53 7 - 4 7 94.10 90.93 9.07 92.71 ] 86.54 13.46 90.16 85.41 14.59 87.52

m2 3"26 5"90 7"29 9"84 12'48

Figure 1 presents a n e x p e r i m e n t a l curve of c o p o l y m e r composition p l o t t e d f r o m the d a t a of Table 1 with coordinates m~----f(M°), where M ° is the m o l a r p r o p o r t i o n of I-IHT in the initial m o n o m e r m i x t u r e ; m s is the m o l a r p r o p o r t i o n

I

o,ot

c..

E.O05

#

0-05 010 M~ , molecular propoption

0I5

FIG. 1. Experimental curve showing eopolymer composition. of H H T in the copolymer. The shape of the curve over t h e diagonal shows t h a t the calculated values of r I a n d r 2 for this s y s t e m should be within the r a n g e rll.

Copolymerization of CaA with H H T

2081

To calculate the copolymerization constant according to an integral equation u s e d t o d e t e r m i n e c o m p o s i t i o n , t h e v a l u e o f p a r a m e t e r p ' has t o be e s t a b l i s h e d . W h e r e m i x t u r e a n d c o p o l y m e r c o m p o s i t i o n s d o n o t coincide, p a r a m e t e r p ' will be n e g a t i v e . T o e l u c i d a t e this Fig. 2 p r e s e n t s t h e r e l a t i o n M ° - - ( m 2 / M °) (the c u r v e w a s p l o t t e d f r o m t h e d a t a in T a b l e 1). I t c a n be scent f r o m Fig. 2 t h a t , w i t h n o n e o f t h e initial m o n o m e r m i x t u r e s , does t h e c o p o l y m e r f o r m e d h a v e t h e s a m e c o m p o sition as t h a t o f t h e initial m i x t u r e , i.e. t h e r e is n o a z e o t r o p i e m i x t u r e o f t h e s e 1712

I

I

2

I

I

I

5

10

6

I~I~ . moles %

FIG. 2. m2/M°=/(M °) relation. m o n o m e r s . C o n s e q u e n t l y , p a r a m e t e r p ' will b e n e g a t i v e . A r b i t r a r i l y a s s u m i n g p a r a m e t e r p ' t o be 1 a n d 2, f r o m t h e m o d i f i e d i n t e g r a l e q u a t i o n o f c o m p o s i t i o n (1) w e c a l c u l a t e d c o p o l y m e r i z a t i o n c o n s t a n t s r 1 a n d r 2. T h e r e s u l t s are s h o w n in T a b l e 2. TABLE 2. DETERMINATIONOF COPOLYMERIZATIONCONSTANTS Composition of the initial monomer mixture, moles M1

'0

0 Ms

0.01077 0'01055 0.01033 0.01011 0"0099

0.00016 0'00032 0.00048 0.00064 0.0008

Unreaeted, moles

log A*

log tM°A [M1]

M1

og

10.0004571

0.0141

0.00918 0.00057 i 0.0418 0.00923 0.000725!, 0.0302

p'=--I

p'=--2

rI

rl

tM01 LlVJ..:,]

Ms

0"01003 0"000136 I 0.0310 0"0102810"0003 0.0Ill

0.01

l

0"0704 0.0278 0.0212 0.0504 0.0426

0.2858 0.0158 0.0069 0-0078 0.0607

0.0386 0.0162 0.0073 0.0060 0.0116

r2

r2

0"59 1"68 0"28i 1"93

0.2 2.4310.24! 1.98 0.44 2.0 0 5 6 174 0.56 1.74 0'50i 1-68

057 17110.45! 174 i

* A=[1--p' ([M1].n):([M2].m)]/[1--p'([MO].n):([M0].m)], where n is the number of double bonds in the CaA monomer(M1),equal to two; m is the numberof double bonds in the/tilt monomer(M2), equal to three.

Copolymerization constants were graphically determined ("intersection m e t h o d " ) . T h e m e a n c o p o l y m e r i z a t i o n c o n s t a n t s o f C a A (rl) a n d H H T (r~) are: rl----0.56:L 0.02; r 2 = 1.71-4-0.03.

Ts. A. GOGUADZEet al.

2082

The p r o d u c t of the c o p o l y m e r i z a t i o n c o n s t a n t s reflects t h e t e n d e n c y of radicals to alternate. I n our case rl.re----0.9576_~0-96 which proves a r a n d o m arr a n g e m e n t of m o n o m e r residues in t h e copolymers. C o p o l y m e r composition w a s established f r o m t h e r~ a n d re values a n d calcul a t e d f r o m t h e M a y o a n d Lewis differential equation. This calculation is fully p r o p o r t i o n a l since t h e degree of conversion in c o p o l y m e r i z a t i o n was negligible a n d did nob exceed 7°./0 b y wt. (see Table 1). S u b s t i t u t i n g t h e r 1 a n d r e values o b t a i n e d in e q u a t i o n (5) t h e [me] values were found. Since [ml] / - [m2] ----100 m o l e s - X , [ml] values were o b t a i n e d b y solving this equation. The results of t h e calculation are s h o w n in Table 3. T A B L E 3. C O P O L Y M E R C O M P O S I T I O N O B T A I N E D F R O M r 1 A N D r~ V A L U E S C A L C U L A T E D FOR VARIOUS MONOMER RATIOS IN THE INITIAL MIXTURE

Series* of experiments, No.

Composition of initial monomer mixture, moles-~o

98.54 97.06 95.96 94.05 95.52

Calculated differential composition of the copolymer, moles- %

[M0]

[ml]

[m~]

1-46 2-94 4.44 5.95 7.47

97.43 94.95 92.37 90.90 87.46

2.57 5.O5 7.63 9.10 12.54

* The serial n u m b e r s o f experiments are the same as m Table 1.

C o m p a r i s o n of calculated a n d e x p e r i m e n t a l d a t a for c o p o l y m e r c o m p o s i t i o n (see Tables 1 a n d 3) shows s a t i s f a c t o r y a g r e e m e n t , which p r o v e s t h a t t h e accur a c y of d e t e r m i n a t i o n of r e a c t i v i t y ratios r 1 a n d r~ is sufficient.

EXPERIMENTAL The synthesis of the initial monomers was conducted by the methods described in the literature [5, 6]. The compounds synthesized are colourless crystalline substances. The properties of initial monomers are shown in Table 4. Copolymerization was carried out in polymerization vessels provided with ground stoppers at 2010.05°C. We chose the following standard conditions: copolymerization was effected in a 10~o aqueous solution of the initial monomer mixture; the reaction was initiated with a potassium persulphate-sodium hydrosulphate redox system (0"5~o of total monomer weight); the reaction was inhibited by addition of a 1~o alcoholic solution of hydroquinone in the proportion of 5 ~o of the total monomer weight; decantation of the reaction mixture into methanol; separation of the polymer obtained from the mixture with unreacted monomers by filtration through a porous glass filter; washing with methanol; extraction of copolymers with methanol in 20 hours in a Soxhlet apparatus in order to ensure final purification of the eopolymer from unreacted monomers; drying to constant weight i n v a c u o at 40°C were then carried out.

Copolymerization of CaA with t t H T

2083

TABLE 4. PROPERTIES OF INITIAL5IONOSIERS

Monomer

Elementary composition, %

Method of purifying the monomer

Melting point, °C according calculated

i calculated

found

i I l

CaA

Recrystallization from ethyl alcohol

tlHT

Double reerystallization from hot distilled water

~C 39.56 H 3.24 Ca 22.0 C H N

57-8 6-02 16.8

C 39.01 H 4.81 Ca' 21.22 C H N

57.55 6.04 16.8

to

literature data

Does not melt 157

Solubility in water, %

48.55

> 100

0"77

At least three experiments were carried out with each monomer ratio in the initial mixture. Copolymer composition was calculated from nitrogen content determined b y the Dumas nmthod.

CONCLUSIONS (1) R e a c t i v i t y r a t i o s of A A a n d H H T r a d i c a l s h a v e b e e n c a l c u l a t e d d m ' i n g c o p o l y m e r i z a t i o n of t h e s e m o n o m e r s a p p e a r e d t o be: for C a A r 1 = 0 . 5 6 : t : 0 . 0 2 , for H H T r 2 = 1 . 7 1 q - 0 . 0 3 . (2) C o p o l y m e r c o m p o s i t i o n h a s b e e n c a l c u l a t e d t a k i n g c o p o l y m e r i z a t i o n constants into account. It has been shown that experimental and calculated v a l u e s for c o p o l y m e r c o m p o s i t i o n s a t i s f a c t o r i l y agree. (3) T h e c o p o l y m e r s o b t a i n e d w i t h all t h e m o n o m e r r a t i o s i n t h e i~fitial m i x t u r e were rich in H H T . Translated by E. SmIERE

REFERENCES 1. N. Ye. OGNEVA, V. V. KOItSHAK and Ts. A. GOGUADZE, Auth. Cert. 155451; Byull. izobr., No. 12, 1963 2. K. THINIUS, H. WALTER and G. LOMMATSCH, Plaste und Kautschuk 6: 322, 1959 3. G. S. KOLESNIKOV, Vysokomol. soyed. 6: 559, 1964 4. F. MAYO and F. LEWIS, J. Amer. Chem. Soc. 66: 1594, 1944 5. I. SUDZUKI, Jap. Pat. 5222, 1954; Chem. Abstr. 49: 15948, 1955 6. It. WEGLEIt and It. BALAUFF, Chem. Ber. 81: 527, 1948