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Thermosetting phenolphthalein-based copolymers
THERMOSETTING PHENOLPHTHALEIN-BASED COPOLYMERS* V. V. KORSHAK, V. A . SERGE~/'EV, V. K . SHITIKOV, A . A . SEVEROV, I . K I t . NAZMUTDII~'OVA, S. G. ZHELTAKOVA, V. F . BURLUTSKII, B . A . KISELEV
and V. V. YAREME~KO Organometallic Compounds Institute, U.S.S.R. A c a d e m y of Sciences
(Raceived 16 June 1967)
OgR previous work had shown [1] that phenolphthalein (PHP) yields thermosetting polymers with formaldehyde; the carbon present will be largely converted by thermal treatment up to 900°C to a carbonized polymer. We therefore thought it worth our while to study the properties of polymers produced from a P H P mixture with phenol and formaldehyde (FA). Table 1 below lists the results of the thermogravimetric study of crosslinked copolymers produced by the copolycondensation of phenol-FA resol (PFAR) with the methyl derivatives of P H P (MPHP) [2], using different weight ratios. TXBLE 1. RESULTS OF THE THERMAL TREATMENT OF P F A R : M P H P COMPOSITIONS Starting components PFAR
MPHP
Car ° Intense bonized decomp. Tit Tltt rage*,% polymer loss/rain yield,
Elemental analysis, % copo!ymer carbon, polymer
%
H
0 (by diff.)
6.02 4"89 5.14 5"06 5"36 6"76 5'29 5"93 5"90
20-96[ 21.26 20.28 19.31 18.73 17.36 18.87 18.03 16.00
C yield,
% i
20 40 50 60 70 80 90 100
100 80 60 5O 40 30 20 10
]425 410 415 425 435 445 450 450 455
515 520 535 535 540 540 540 535 535
1.81 1.64 1.55 1.42 1.41 1-6I 1.64 2.00 2.00
59"0 60.3 61.7 63.4 64.7 64.3 64.0 63.0 57.6
73.02 73.85 74"58 75.63 75.91 75-88 75.84 76-14 78.00
92.86 0.77 6.37 94.79 1.00 4.2I 95.44 0.92 3.64 95.05 1.05 3.80 95.90 1.04 4.06 95.63 1.03 3.34 95.38 0-95 2.67 95.11 0.90 3.99 95.26 0.68 4.06
76"6 77"4 78"9 79'7 81"7 81"0 80"5 78"7 70"3
* The p o l y m e r was heated for 1 h r to 900°C. t T I a n d T I I - - t e m p e r a t u r e a t which the polymgr samples lost 10 an~ 2 0 % weight respectively.
The above Table shows an increase of the P F A R content in the mixture to cause an initial increase of the carbonize~[ polymer yield at 900°C, followed by a decrease. The largest yield (64.7%) was found to arise from a copolymer * Vysokomol. soyed. A10: No. 5, 1085-1091, 1968. 1258
Thermosetting phenolphthalein.based copolymers
1259
produced from 60~/o w/w PFAR and 40~/o w/w MPHP. This copolymer also had the smallest rate of intense decomposition. Another fact evident from the Table is that an increase of the weight of PFAR present increased the carbon quantity in the copolymer. The carbon participating in the formation of the solid carbonized polymer, however, increased only to a certain maximum and then decreased again. A maximum was reached with the copolymer based on 60 PFAR: 40 MPHP ~ w/w, i.e. an 81.7~/o C content. This result can be explained by additional crosslinking due to the lactone ring of P H P in the presence of PFAR [3], according to the following scheme OH |
OH f H ~
OH I --CH2
--_~
OH
OH
/\ I
o
OH
OH
i ~ / CH2 I
|
OH
This reaction is similar to that of pyromeUitic anhydride with aromatic compounds (diphenyl, terphenyl, anthracene, n~phthalene), which was described by Pohl and Engelhardt [4]. The synthesis of the PHP-phenol-FA copolymers was carried out also by directly condensing phenol and P H P with FA. I t was not necessary to use a solvent in this case, nor to make use of the laborious operation of recovering the methyl derivative of PHP. Where the phenol content was 3 4 0 % wfw relative to PHP, the reaction mixture was homogeneous in formalin at 90-100°0. This PHP-containing copolymers (PHP-40 in future) was produced by directly reacting the starting component mixture with an aqueous FA solution. To clarify the influence of the number of crosslinking bonds on the properties and particularly the heat resistance of PHP-40, it was produced by reacting 1 mole of phenol with 1-2, 1.5 and 1.8 moles FA in the presence of a 25~o
1260
V.V. KO~SHAKet al.
aqueous ammonia solution as catalyst. Table 2 shows the results of the thermogravimetric testing of such copolymers. The Table shows t h a t the increase of the FA mole fraction from 1.2 to 1.8 reduced the carbonized polymer yield and the carbon content. These findings point to a smaller tendency of the methyl group carbon to participate TABLE
2.
CONDITIONS
INFT.UENCE ON
THE
OF
THE
CARBO2CIZED
SYNTHESIS POLYMER
YIELD
Starting components, moles total phenol
FA
1 1
,
1
Yield of carboCarbon nized po- yield, % lymer, °//o
1.2 1.5 1"8
64.7 63.4 61"4
82"3
80"1 79"8
in the carbonized polymer formation, compared with the carbon of the aromatic part of P H P 40 produced from 1 mole phenols and 1.2 mole FA, which gave the largest carbonized polymer yield (64.7%) and carbon content (82.3%). The temperature regime of producing a test batch in the "Karbolit" factory T,°C
80
'~ 80
ZO z
o
l
i
6
7
J
~ 60 .o
goo
Time,hp FlO. 1
T~°C FIG. 2
FIG. 1. Temperature regime during PHP-40 production. FIo. 2. Thermogravimetric decomposition curves: 1--PHP-40; 2--PHP-FA and 3--phenolFA polymer. is shown in Fig. 1. The duration of the reaction in the PHP-40 production was about 6 hr. A temperature reduction at about 1.5 hr reaction time was due to the introduction of the formalin solution, which was at room temperature, and t h a t after 5.5 hr reaction time was due to the water removal under vacuum from the reaction mass. The PHP-40 product had good solubility in alcohol, acetone and in other organic solvents; it contained about 5.8% of free phenol. The gel and setting times of the copolymer on a dish at 150°C were 5 and 50 min respectively. The thermosetting copolymer, after repeated alkaline treatment,
Thermosetting phenolphthalein-based copolymers
126'1
followed b y neutralization, had a static ion-exchanging capacity of 24 mg NaOH/g copolymer. Figure 2 shows the thermogravimetrie curves of PHP-40 (curve 1) and, for comparison, those of the P H P - F A {curve 2) and phenol-FA {curve 3) polymers. From this diagram one can see the different nature of the decomposition of P H P - 4 0 at up to 900°C, compared with the other two polymers. This difference starts to show in the intense decomposition range (350-550°C), in which the P H P - 4 0 decomposes more slowly than the P H P - F A polymer, but more rapidly than the phenol-Fa polymer. The continuation of heating to 900°C makes P H P - 4 0 decompose at a lower rate than both the other polymers. The decomposition rates of P H P - 4 0 at different temperatures are shown in Fig. 3; these were determined on a Paulik, Paulik and Erdei derivatograph. The comparison of these rates of P H P - 4 0 with those of the other two, made earlier [1], showed the former to have a more uniform rate of decomposition in the range 350-600°C, irrespective of the peaks, which are present at the Same temperatures (peaks at 370, 470 and 570°C). The liberated, gaseous pyrolysis products of P H P - 4 0 contained 10.6 ml/g COs, while the P H P - F A yielded 3 times as much C02, i.e. 31.5 ml/g. Figure 4 shows the rates of gas evolution as a function of temperature when P H P - 4 0 was heated to 900°C in 60 min. An outstanding feature seen here, compared with the polymers based on P H P and phenol [I], is the absence of a maxim u m on the gas evolution rate curve around 470°C; the intense gas evolution is only observable in the range 650-670°C, and this appears to be the initial stage of the carbonization process.
6
;~0
/00
ZOO 300 z~OOSO0 600 7GO 800 T, oC
O Joo
$80
700
r,"c
$00
FIG. 3 FIG. 4 FIG. 3. Decomposition rate of PHP-40 during thermal treatment up to 900°C. FIG. 4. Differential rate of gas evolution from PHP-40 during thermal processing up to 900°C. Table 3 lists the results of mechanical strength testing during the shift of steel plates jointed b y compositions based on P H P - 4 0 {composition 1) and those based on a phenol-FA polymer {composition 2). The shear strength produced b y composition 1 is larger, regardless of the time or temperature of ageing the samples. For example, 24 hr at 350°C gave a shear strength of 24 kg/cm 2 to steel plates joined b y composition 1, while the joint was fractured in the case of composition 2.
1262
V . V . K o R s m ~ x et aJ.
T A B L E 3. S H E A R S T R E N G T H Ilq T H E CASE OF S T E E L P L A T E S J O I N E D B Y M E A N S OE D I F F E R E N T COMPOSITIONS
Shear strength, kg/em 2 at testing temp. 5 hr ageing at 300°C
testing temp., °C
Composition
24 hr ageing at350°C
testing temp., °C
PHP-40 (1) Phenol-FA (2)
20
300
350
20
181 175
48 --
22 16
75 103
300[
350
20
350
52 45
15 7
14 0
24 0
T h e use o f P H P - 4 0 as a n a d h e s i v e w i t h c o n s t r u c t i o n a l m a t e r i a l in p r a c t i c e was e x a m i n e d b y p h y s i c o - m e c h a n i c a l t e s t i n g o f " p u r e " samples, a n d also arm o u r e d plastics b a s e d on this m a t e r i a l . T h e m e c h a n i c a l t e s t i n g o f h a r d e n e d a n d pressed s a m p l e s of 15 × 10 × 4 m m (7-8 k g / c m ~) w a s carried o u t on a D i n s t a t in t h e p o l y m e r physics l a b o r a t o r y o f t h e 0 r g a n o m e t a l l i c C o m p o u n d s S y n t h e s i s I n s t i t u t e o f t h e U.S.S.R. A c a d e m y o f Sciences. TABLE 4. ~.ECHANICALPROPERTIES
Polymer PHP-40 Phenol-FA
OF P O L Y M E R S
Spec. rebounce, Static flexing, kg cm/cm s kg/cm 2 5"4 1"9
239 395
TABLE 5. MECHANICALPROPERTIESOF SOMEARMOUREDPLASTICS Sample Plastic glass with 30% PHP-40 Ditto with 30~o phenol-FA polymer Plastic glass with 30% PHP-FA polymer Textotil with 30% PHP-40 Ditto after thermal treatment to 900°C
Spec. rebounce, Static flexing, kg cm/cm' kg/cm ~ 24.1
965
17.8
645
70.1 26.5
2068 1300
10.0
1600
T a b l e 4 lists t h e m e c h a n i c a l p r o p e r t i e s of P H P - 4 0 a n d gives t h o s e of t h e p h e n o l - F A p o l y m e r for c o m p a r i s o n . T a b l e 4 shows t h a t t h e r e are slight differences in t h e m e c h a n i c a l s t r e n g t h of t h e m e n t i o n e d p o l y m e r s . Quite different results were o b t a i n e d w h e n m a t e r i a l s were used as binders of glass, asbestos a n d s o m e o t h e r fibres.
Thermosetting phenolphthalein-basecl copolymors
1263
Tables 5-7 enumerate the results of mechanical testing of certain armoured (reinforced) plastics. These Tables show that articles made from a polymer containing P H P had better mechanical properties than those based on phenol-FA polymer. For example, the use of PHP-40, and also of P H P - F A polymer as jointing compound with fibre glass yielded materials with similar mechanical properties to those given by plastic glass based on a mixture with epoxide polymers (Table 6, the two last samples). This appears to be explained by the large adhesion of the binder to the mineral fibre due to the presence of polar lactone groups. The asbo-abrasive materials based on PHP-containing copolymer also had good physico-mechanical properties.
TABLE 6. M E C H A N I C A L P R O P E R T I E S OF GLASS PLASTICS
Fibreglass K T - I I with PHP-40 Phenol-FA Mixture of 50% P H P - 4 0 and 50% P H P - e p o x i d e polymer Mixture of 50% phenolF A with 50% P H P epoxide polymer
P o l y m e r Breaking content, strength, % kg/cm s
Separn. strength, kg/cm'
Shear strength, kg/cm 2
Brinel Adhesive hardness, strength, kg/em 2 kg/cm I
43"2 44.9
1800 1004
3020 1520
205 264
294.5 211.5
46"1
1337
2230
162
247.0
36"1
2050
3150
262
250"9
234 200
T A B L E 7 . M E C H A N I C A L P R O P E R T I E S OF PLASTIC GLASS
F r a c t u r e resistance during static flexing, k g / c m ' Material based on
Elongation strength, kg/cm I
Compression' strength, kg/cm 2
testing t e m p e r a t u r e , ° C 20 Plastic glass of P H P - 4 0 modified with organo-Si polymer D i t t o of phenol-FA modified with an organo-Si polymer
300
20
20
3256
1810
4607
3316
2610
1250
3705
1610
Table 8 lists the properties of absotcxtolit coatings based on PHP-40 and a Bakelite paint of type A. It shows that replacement of the phenol-FA paint b y PHP-containing binder yielded a material which had only half the moisture absorption capacity.
1264
V. V. KORSHAK et a~. TABLE 8. PROPERTIES OF
Preparation method
AN
ASBOTEXTOLIT COVERING
Volatiles in soaked textile,
Adhesive
% Pressmoulding, 5 kg/cm ~ Ditto Vacuum-forming Ditto
Bakelite paint type A PHP-40 PHP-40 Bakelite paint type A PHP-40
Polymer content,
%
Water swelling at 6 arm in 3 days,
Spec. gray.,
g/cm a
To
7"1 7'1 5"0
38.55 44-15 47.30
3.2 1.07
1.54 1.57 1.51
4.9 4.1
47.75 58-6
6"23 3"75
1.31 1-39
1.49
CONCLUSIONS (1) Copolymers were synthesised from phenol a n d phenolphthalein, a n d their h e a t resistance was examined. (2) T h e p h e n o l p h t h a l e i n - c o n t a i n i n g copolymers were f o u n d to h a v e b e t t e r h e a t resistance t h a n t h e p h e n o l - f o r m a l d e h y d e polymers. (3) I t was f o u n d t h a t a r m o u r e d materials (fibre glass, textolites, a s b o t e x t o lites), based on phenolphthalein-eontaining copolymers, h a d b e t t e r p h y s i e o m e chanical properties t h a n similar materials based on p h e n o l f o r m a l d e h y d e p o l y mer.
Translated by K. A. ALLEN REFERENCES 1. V. A. SERGEYEV, V. V. KORSHAK and V. K. SHITIKOV, Vysokomol. soyed. A 9 : 1952, 1967 (Translated in Polymer Sei. U.S.S.R. 9: 9, 2202, 1967) 2. Russian Authors Cert. No. 172489, 1962; Byull. isobretenii, No. 13, 70, 1965 3. R. Mc NEILL and D. E. WEISS, Austral. J. Chem. 12: 643, 1959; Proe. 4th Conf. Carbon, Buffalo 1959, 281, 1960 4. H. A. POHL and R. H. ENGELHARDT, J. Phys. Chem. 66: 100, 1962
and V. V. YAREME~KO Organometallic Compounds Institute, U.S.S.R. A c a d e m y of Sciences
(Raceived 16 June 1967)
OgR previous work had shown [1] that phenolphthalein (PHP) yields thermosetting polymers with formaldehyde; the carbon present will be largely converted by thermal treatment up to 900°C to a carbonized polymer. We therefore thought it worth our while to study the properties of polymers produced from a P H P mixture with phenol and formaldehyde (FA). Table 1 below lists the results of the thermogravimetric study of crosslinked copolymers produced by the copolycondensation of phenol-FA resol (PFAR) with the methyl derivatives of P H P (MPHP) [2], using different weight ratios. TXBLE 1. RESULTS OF THE THERMAL TREATMENT OF P F A R : M P H P COMPOSITIONS Starting components PFAR
MPHP
Car ° Intense bonized decomp. Tit Tltt rage*,% polymer loss/rain yield,
Elemental analysis, % copo!ymer carbon, polymer
%
H
0 (by diff.)
6.02 4"89 5.14 5"06 5"36 6"76 5'29 5"93 5"90
20-96[ 21.26 20.28 19.31 18.73 17.36 18.87 18.03 16.00
C yield,
% i
20 40 50 60 70 80 90 100
100 80 60 5O 40 30 20 10
]425 410 415 425 435 445 450 450 455
515 520 535 535 540 540 540 535 535
1.81 1.64 1.55 1.42 1.41 1-6I 1.64 2.00 2.00
59"0 60.3 61.7 63.4 64.7 64.3 64.0 63.0 57.6
73.02 73.85 74"58 75.63 75.91 75-88 75.84 76-14 78.00
92.86 0.77 6.37 94.79 1.00 4.2I 95.44 0.92 3.64 95.05 1.05 3.80 95.90 1.04 4.06 95.63 1.03 3.34 95.38 0-95 2.67 95.11 0.90 3.99 95.26 0.68 4.06
76"6 77"4 78"9 79'7 81"7 81"0 80"5 78"7 70"3
* The p o l y m e r was heated for 1 h r to 900°C. t T I a n d T I I - - t e m p e r a t u r e a t which the polymgr samples lost 10 an~ 2 0 % weight respectively.
The above Table shows an increase of the P F A R content in the mixture to cause an initial increase of the carbonize~[ polymer yield at 900°C, followed by a decrease. The largest yield (64.7%) was found to arise from a copolymer * Vysokomol. soyed. A10: No. 5, 1085-1091, 1968. 1258
Thermosetting phenolphthalein.based copolymers
1259
produced from 60~/o w/w PFAR and 40~/o w/w MPHP. This copolymer also had the smallest rate of intense decomposition. Another fact evident from the Table is that an increase of the weight of PFAR present increased the carbon quantity in the copolymer. The carbon participating in the formation of the solid carbonized polymer, however, increased only to a certain maximum and then decreased again. A maximum was reached with the copolymer based on 60 PFAR: 40 MPHP ~ w/w, i.e. an 81.7~/o C content. This result can be explained by additional crosslinking due to the lactone ring of P H P in the presence of PFAR [3], according to the following scheme OH |
OH f H ~
OH I --CH2
--_~
OH
OH
/\ I
o
OH
OH
i ~ / CH2 I
|
OH
This reaction is similar to that of pyromeUitic anhydride with aromatic compounds (diphenyl, terphenyl, anthracene, n~phthalene), which was described by Pohl and Engelhardt [4]. The synthesis of the PHP-phenol-FA copolymers was carried out also by directly condensing phenol and P H P with FA. I t was not necessary to use a solvent in this case, nor to make use of the laborious operation of recovering the methyl derivative of PHP. Where the phenol content was 3 4 0 % wfw relative to PHP, the reaction mixture was homogeneous in formalin at 90-100°0. This PHP-containing copolymers (PHP-40 in future) was produced by directly reacting the starting component mixture with an aqueous FA solution. To clarify the influence of the number of crosslinking bonds on the properties and particularly the heat resistance of PHP-40, it was produced by reacting 1 mole of phenol with 1-2, 1.5 and 1.8 moles FA in the presence of a 25~o
1260
V.V. KO~SHAKet al.
aqueous ammonia solution as catalyst. Table 2 shows the results of the thermogravimetric testing of such copolymers. The Table shows t h a t the increase of the FA mole fraction from 1.2 to 1.8 reduced the carbonized polymer yield and the carbon content. These findings point to a smaller tendency of the methyl group carbon to participate TABLE
2.
CONDITIONS
INFT.UENCE ON
THE
OF
THE
CARBO2CIZED
SYNTHESIS POLYMER
YIELD
Starting components, moles total phenol
FA
1 1
,
1
Yield of carboCarbon nized po- yield, % lymer, °//o
1.2 1.5 1"8
64.7 63.4 61"4
82"3
80"1 79"8
in the carbonized polymer formation, compared with the carbon of the aromatic part of P H P 40 produced from 1 mole phenols and 1.2 mole FA, which gave the largest carbonized polymer yield (64.7%) and carbon content (82.3%). The temperature regime of producing a test batch in the "Karbolit" factory T,°C
80
'~ 80
ZO z
o
l
i
6
7
J
~ 60 .o
goo
Time,hp FlO. 1
T~°C FIG. 2
FIG. 1. Temperature regime during PHP-40 production. FIo. 2. Thermogravimetric decomposition curves: 1--PHP-40; 2--PHP-FA and 3--phenolFA polymer. is shown in Fig. 1. The duration of the reaction in the PHP-40 production was about 6 hr. A temperature reduction at about 1.5 hr reaction time was due to the introduction of the formalin solution, which was at room temperature, and t h a t after 5.5 hr reaction time was due to the water removal under vacuum from the reaction mass. The PHP-40 product had good solubility in alcohol, acetone and in other organic solvents; it contained about 5.8% of free phenol. The gel and setting times of the copolymer on a dish at 150°C were 5 and 50 min respectively. The thermosetting copolymer, after repeated alkaline treatment,
Thermosetting phenolphthalein-based copolymers
126'1
followed b y neutralization, had a static ion-exchanging capacity of 24 mg NaOH/g copolymer. Figure 2 shows the thermogravimetrie curves of PHP-40 (curve 1) and, for comparison, those of the P H P - F A {curve 2) and phenol-FA {curve 3) polymers. From this diagram one can see the different nature of the decomposition of P H P - 4 0 at up to 900°C, compared with the other two polymers. This difference starts to show in the intense decomposition range (350-550°C), in which the P H P - 4 0 decomposes more slowly than the P H P - F A polymer, but more rapidly than the phenol-Fa polymer. The continuation of heating to 900°C makes P H P - 4 0 decompose at a lower rate than both the other polymers. The decomposition rates of P H P - 4 0 at different temperatures are shown in Fig. 3; these were determined on a Paulik, Paulik and Erdei derivatograph. The comparison of these rates of P H P - 4 0 with those of the other two, made earlier [1], showed the former to have a more uniform rate of decomposition in the range 350-600°C, irrespective of the peaks, which are present at the Same temperatures (peaks at 370, 470 and 570°C). The liberated, gaseous pyrolysis products of P H P - 4 0 contained 10.6 ml/g COs, while the P H P - F A yielded 3 times as much C02, i.e. 31.5 ml/g. Figure 4 shows the rates of gas evolution as a function of temperature when P H P - 4 0 was heated to 900°C in 60 min. An outstanding feature seen here, compared with the polymers based on P H P and phenol [I], is the absence of a maxim u m on the gas evolution rate curve around 470°C; the intense gas evolution is only observable in the range 650-670°C, and this appears to be the initial stage of the carbonization process.
6
;~0
/00
ZOO 300 z~OOSO0 600 7GO 800 T, oC
O Joo
$80
700
r,"c
$00
FIG. 3 FIG. 4 FIG. 3. Decomposition rate of PHP-40 during thermal treatment up to 900°C. FIG. 4. Differential rate of gas evolution from PHP-40 during thermal processing up to 900°C. Table 3 lists the results of mechanical strength testing during the shift of steel plates jointed b y compositions based on P H P - 4 0 {composition 1) and those based on a phenol-FA polymer {composition 2). The shear strength produced b y composition 1 is larger, regardless of the time or temperature of ageing the samples. For example, 24 hr at 350°C gave a shear strength of 24 kg/cm 2 to steel plates joined b y composition 1, while the joint was fractured in the case of composition 2.
1262
V . V . K o R s m ~ x et aJ.
T A B L E 3. S H E A R S T R E N G T H Ilq T H E CASE OF S T E E L P L A T E S J O I N E D B Y M E A N S OE D I F F E R E N T COMPOSITIONS
Shear strength, kg/em 2 at testing temp. 5 hr ageing at 300°C
testing temp., °C
Composition
24 hr ageing at350°C
testing temp., °C
PHP-40 (1) Phenol-FA (2)
20
300
350
20
181 175
48 --
22 16
75 103
300[
350
20
350
52 45
15 7
14 0
24 0
T h e use o f P H P - 4 0 as a n a d h e s i v e w i t h c o n s t r u c t i o n a l m a t e r i a l in p r a c t i c e was e x a m i n e d b y p h y s i c o - m e c h a n i c a l t e s t i n g o f " p u r e " samples, a n d also arm o u r e d plastics b a s e d on this m a t e r i a l . T h e m e c h a n i c a l t e s t i n g o f h a r d e n e d a n d pressed s a m p l e s of 15 × 10 × 4 m m (7-8 k g / c m ~) w a s carried o u t on a D i n s t a t in t h e p o l y m e r physics l a b o r a t o r y o f t h e 0 r g a n o m e t a l l i c C o m p o u n d s S y n t h e s i s I n s t i t u t e o f t h e U.S.S.R. A c a d e m y o f Sciences. TABLE 4. ~.ECHANICALPROPERTIES
Polymer PHP-40 Phenol-FA
OF P O L Y M E R S
Spec. rebounce, Static flexing, kg cm/cm s kg/cm 2 5"4 1"9
239 395
TABLE 5. MECHANICALPROPERTIESOF SOMEARMOUREDPLASTICS Sample Plastic glass with 30% PHP-40 Ditto with 30~o phenol-FA polymer Plastic glass with 30% PHP-FA polymer Textotil with 30% PHP-40 Ditto after thermal treatment to 900°C
Spec. rebounce, Static flexing, kg cm/cm' kg/cm ~ 24.1
965
17.8
645
70.1 26.5
2068 1300
10.0
1600
T a b l e 4 lists t h e m e c h a n i c a l p r o p e r t i e s of P H P - 4 0 a n d gives t h o s e of t h e p h e n o l - F A p o l y m e r for c o m p a r i s o n . T a b l e 4 shows t h a t t h e r e are slight differences in t h e m e c h a n i c a l s t r e n g t h of t h e m e n t i o n e d p o l y m e r s . Quite different results were o b t a i n e d w h e n m a t e r i a l s were used as binders of glass, asbestos a n d s o m e o t h e r fibres.
Thermosetting phenolphthalein-basecl copolymors
1263
Tables 5-7 enumerate the results of mechanical testing of certain armoured (reinforced) plastics. These Tables show that articles made from a polymer containing P H P had better mechanical properties than those based on phenol-FA polymer. For example, the use of PHP-40, and also of P H P - F A polymer as jointing compound with fibre glass yielded materials with similar mechanical properties to those given by plastic glass based on a mixture with epoxide polymers (Table 6, the two last samples). This appears to be explained by the large adhesion of the binder to the mineral fibre due to the presence of polar lactone groups. The asbo-abrasive materials based on PHP-containing copolymer also had good physico-mechanical properties.
TABLE 6. M E C H A N I C A L P R O P E R T I E S OF GLASS PLASTICS
Fibreglass K T - I I with PHP-40 Phenol-FA Mixture of 50% P H P - 4 0 and 50% P H P - e p o x i d e polymer Mixture of 50% phenolF A with 50% P H P epoxide polymer
P o l y m e r Breaking content, strength, % kg/cm s
Separn. strength, kg/cm'
Shear strength, kg/cm 2
Brinel Adhesive hardness, strength, kg/em 2 kg/cm I
43"2 44.9
1800 1004
3020 1520
205 264
294.5 211.5
46"1
1337
2230
162
247.0
36"1
2050
3150
262
250"9
234 200
T A B L E 7 . M E C H A N I C A L P R O P E R T I E S OF PLASTIC GLASS
F r a c t u r e resistance during static flexing, k g / c m ' Material based on
Elongation strength, kg/cm I
Compression' strength, kg/cm 2
testing t e m p e r a t u r e , ° C 20 Plastic glass of P H P - 4 0 modified with organo-Si polymer D i t t o of phenol-FA modified with an organo-Si polymer
300
20
20
3256
1810
4607
3316
2610
1250
3705
1610
Table 8 lists the properties of absotcxtolit coatings based on PHP-40 and a Bakelite paint of type A. It shows that replacement of the phenol-FA paint b y PHP-containing binder yielded a material which had only half the moisture absorption capacity.
1264
V. V. KORSHAK et a~. TABLE 8. PROPERTIES OF
Preparation method
AN
ASBOTEXTOLIT COVERING
Volatiles in soaked textile,
Adhesive
% Pressmoulding, 5 kg/cm ~ Ditto Vacuum-forming Ditto
Bakelite paint type A PHP-40 PHP-40 Bakelite paint type A PHP-40
Polymer content,
%
Water swelling at 6 arm in 3 days,
Spec. gray.,
g/cm a
To
7"1 7'1 5"0
38.55 44-15 47.30
3.2 1.07
1.54 1.57 1.51
4.9 4.1
47.75 58-6
6"23 3"75
1.31 1-39
1.49
CONCLUSIONS (1) Copolymers were synthesised from phenol a n d phenolphthalein, a n d their h e a t resistance was examined. (2) T h e p h e n o l p h t h a l e i n - c o n t a i n i n g copolymers were f o u n d to h a v e b e t t e r h e a t resistance t h a n t h e p h e n o l - f o r m a l d e h y d e polymers. (3) I t was f o u n d t h a t a r m o u r e d materials (fibre glass, textolites, a s b o t e x t o lites), based on phenolphthalein-eontaining copolymers, h a d b e t t e r p h y s i e o m e chanical properties t h a n similar materials based on p h e n o l f o r m a l d e h y d e p o l y mer.
Translated by K. A. ALLEN REFERENCES 1. V. A. SERGEYEV, V. V. KORSHAK and V. K. SHITIKOV, Vysokomol. soyed. A 9 : 1952, 1967 (Translated in Polymer Sei. U.S.S.R. 9: 9, 2202, 1967) 2. Russian Authors Cert. No. 172489, 1962; Byull. isobretenii, No. 13, 70, 1965 3. R. Mc NEILL and D. E. WEISS, Austral. J. Chem. 12: 643, 1959; Proe. 4th Conf. Carbon, Buffalo 1959, 281, 1960 4. H. A. POHL and R. H. ENGELHARDT, J. Phys. Chem. 66: 100, 1962