 |
Description  |
|
|
BACKGROUND OF THE INVENTION
This invention relates to functional resins derived from polyamines and a
process for producing the same.
Many reports on the synthesis of functional resins having carbon-carbon
unsaturated bonding portions at side chains of polymers can be divided
into the following two categories.
One of them includes a process wherein a vinyl compound having an allyl
group (CH.sub.2 .dbd.CHCH.sub.2 --), which is poor in polymerizability, in
its molecule is synthesized and only a vinyl group is selectively
polymerized to yield a functional resin having unsaturated groups at side
chains; or a process wherein a compound having a functional group (e.g. an
epoxy group) which is capable of ring opening polymerization, and a vinyl
group and only the ring portion is subjected to ring opening
polymerization to yield a functional resin.
The other of them includes a process wherein a suitable resin is selected
as a support, which is reacted with a compound having a suitably modified
carbon-carbon unsaturated bonding portion to yield a functional resin.
Examples of the former category are syntheses of functional resins having
unsaturated groups at side chains by subjecting, for example, acrylic acid
(or methacrylic acid) allyl ester, vinyl ethylene oxide, or methacrylic
acid glycidyl ester to anion polymerization for polymerizing only the
ethylene oxide rings selectively [e.g. M. Dorati, et al: Makromol. Chem.
vol. 60, pp. 233-235 (1963); G. Allen, et al: Polymer vol. 5, pp. 553-557
(1964); T. Otsu, et al: Makromol. Chem. vol. 71, pp. 150-158 (1964)]. But
these processes are not suitable for industrially practical syntheses of
functional resins, since various problems arise in that side reactions
such as partial polymerization occur during monomer synthesis, which
results in making the separation and purification of the monomer
difficult. In the case of applying the functional resins to a special use,
the unsaturated groups which are active portions become too active to use.
Ionic polymerization is a relatively difficult polymerization technique;
and during the polymerization, some unsaturated groups which should be
retained as they are as unreacted portions at side chains participate in
the polymerization to cause a crosslinking reaction, which results in
making the produced resin insoluble.
Examples of the latter category are functional resins obtained by reacting
polyvinyl alcohol with cinnamic acid chloride. Such resins are available
commercially as photosensitive resins but have a defect in that the
development by using neutral water is difficult.
The latter functional resins are usually coated on a glass or metal plate,
and exposed to light or heat as an energy source to crosslink unsaturated
groups at side chains among polymers to give an insolubilized coating
film. When the resin is applied to such a utility, the resin should be not
only good in film-forming properties and flexibility but also good in
adhesiveness to glass, wooden plate and metal. But the above-mentioned
functional resins are not always sufficient as to adhesiveness.
On the other hand, in order to enhance the reactivity of functional resins
having functional groups at side chains, it is necessary to facilitate the
association between a reactive portion and a substance to be reacted. For
such a purpose, it is desirable that the main chain portion is flexible,
and the side chain portion is long to some extent and flexible so as to be
bent freely. In other words, the main chain portion is preferably a
support having no rigid ring portions and no hetero atoms such as a sulfur
atom and an oxygen atom. Further, in order to show good adhesiveness to
glass, wood, metal and the like material, these functional resins should
have functional groups which show large affinity to these materials at
side chains. Production of such functional resins satisfying the
above-mentioned requirements has not been reported yet.
SUMMARY OF THE INVENTION
Objects of this invention are to provide functional resins satisfying the
above-mentioned requirements and a process for producing the same.
This invention provides a functional resin having repeating units of the
formula:
##STR1##
wherein X is not present or an organic acid; Y is a carbon-carbon double
bond-containing group represented by the formula:
##STR2##
n is an integer of 10 or more; j and k are integers and the ratio of j/j+k
and k/j+k are larger than zero but smalller than one; and t is zero or an
integer of 1.
This invention also provides a process for producing a functional resin
having repeating units of the formula (I) which comprises reacting a
polyallylamine or polyvinylamine having repeating units of the formula:
##STR3##
wherein X is not present or an organic acid; n is an integer of 10 or
more; and t is zero or an integer of 1, with an epoxy group-containing
allyl compound of the formula:
##STR4##
wherein Y is a carbon-carbon double bond-containig group represented by
the formula:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an infrared spectrum of the functional resin obtained in Example
1.
FIG. 2 is an infrared spectrum of the functional resin obtain in Example 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The term "functional resin" in this invention means a resin having
unsaturated groups of the formula: CH.sub.2 .dbd.Ch--at side chains in the
formula (I) and being able to be crosslinked when exposed to light or heat
or reacted with a special reagent.
The functional resin of this invention has repeating units of the formula:
##STR6##
wherein X is not present or an organic acid; Y is a carbon-carbon double
bond-containing group represented by the formula:
##STR7##
n is an integer of 10 or more; j and k are integers and the ratio of j/j+k
and k/j+k are larger than zero but smaller than one; and t is zero or an
integer of 1.
Examples of the organic acid in the definition of X are a carboxylic acid
such as acetic acid.
The functional resin having the repeating units of the formula (I) is
obtained by introducing substituents each having a hydroxyl group and
carbon-carbon double bond(s) at side chains of polyallylamine or
polyvinylamine. By applying the crosslinking properties of these
unsaturated groups, it is possible to form a protective film or colored
protective film for a substrate material by coating said resin alone or in
admixture with a colorant and/or an antiseptic agent on a glass plate, a
wooden plate, or a metal plate and heating or exposing to light for
crosslinking and insolubilization.
The functional resin having the repeating units of the formula (I) can be
produced by reacting a polyallylamine or polyvinylamine having repeating
units of the formula:
##STR8##
wherein X, t and n are as defined above, with an epoxy group-containing
allyl compound of the formula:
##STR9##
wherein Y is as defined above.
In the formula (IV), when the "t" is 1, a polyallylamine is represented by
the formula (IV). When the "t" is zero, a polyvinylamine is represented by
the formula (IV).
In the formula (IV), n is an integer of 10 or more, preferably an integer
of 500 or less considering the easiness of preparation of the starting
material, more preferably an integer of 50 to 300.
The starting polymer having repeating units of the formula (IV) is
dissolved in an organic solvent and reacted with the compound of the
formula (V) at a temperature preferably from 0.degree. to 100.degree. C.
for preferably 10 minutes to 10 days.
Examples of the organic solvent are alcohols such as methanol, ethanol,
iso-propanol; methyl Cellosolve and ethyl Cellosolve.
The compound of the formula (V) is preferably used in an amount of 0.2 to
0.8 equivalent weight, more preferably 0.2 to 0.7 equivalent weight, per
equivalent weight of the polyallylamine or polyvinylamine of the formula
(IV).
This invention is illustrated by way of the following Examples, in which
all parts and percents are by weight unless otherwise specified.
REFERENCE EXAMPLE 1
[Synthesis of Polyallylamine]
A polyallylamine.hydrochloride was synthesized by the process taught by
Example 1 of Japanese Patent Unexamined Publication No. 58-201811. That
is, into 1.1 kg of concentrated hydrochloric acid (35%), 570 g (10 moles)
of monoallylamine was dropped with stirring while keeping at 5.degree. to
10.degree. C. with ice cooling. After completion of the dropping, the
water and excess hydrogen chloride were removed by distillation at
60.degree. C. under a reduced pressure of 20 mm Hg using a rotary
evaporator to give white crystals. The crystals were dried over silica
gels for drying at 80.degree. C. under a reduced pressure of 5 mm Hg to
yield 980 g of monoallylamine.hydrochloride containing about 5% of water.
In a 2-liter flask equipped with a stirrer, a thermometer, a reflux
condenser, and a nitrogen introducing pipe, 590 g (6 moles) of the
monoallylamine.hydrochloride and 210 g of distilled water were placed and
dissolved with stirring to give a 70% aqueous solution of
monoallylamine.hydrochloride. The solution was heated to 50.degree. C.
while passing nitrogen gas thereinto. Then, an azo initiator having a
cationic nitrogen atom-containing group, i.e.,
2,2'-bis(N-phenylamidinyl)2,2'-azopropane.dihydrochloride in an amount of
14 g was dissolved in 20 ml of distilled water and added thereto. After
about 2 hours, the flask was cooled with stirring so as to maintain the
solution temperature at 48.degree. to 52.degree. C. by removing the heat
generated. The generation of heat was stopped after 10 hours from the
addition of the initiator, so that the stirring was stopped to continue
the polymerization for additional 60 hours at 50.degree..+-.1.degree. C.
while standing still. Thus, there was obtained a colorless, transparent,
viscous solution. The resulting solution was poured into a large amount of
methanol to give a white polymer precipitate. The precipitate was filtered
using a glass filter and washed with methanol. The thus obtained
precipitate was crushed finely without drying, and extracted with methanol
for 15 hours using a Soxhlet extractor to remove unpolymerized
monoallylamine.hydrochloride. After the extraction, drying at 50.degree.
C. under a reduced pressure was conducted to give 533 g (90%) of a
polymer. The polymer was subjected to elementary analysis and NMR spectral
analysis (D.sub.2 O, 270 MHz).
The NMR spectral analysis revealed that the obtained polymer was
polyallylamine.hydrochloride.
The results of the elementary analysis suggested that the
polyallylamine.hydrochloride adsorbed about one molecule of water per 4
monomeric units thereof.
Elementary analysis: (as C.sub.3 H.sub.8 NCl):
______________________________________
C (%) H (%) N (%)
______________________________________
Found 36.71 8.80 13.78
Calcd. 38.51 8.61 14.97
Calcd. as 36.74 8.74 14.28
C.sub.3 H.sub.8 NCl.1/4H.sub.2 O
______________________________________
The number average molecular weight (Mn) of the polyallylamine obtained by
osmotic pressure measurement in an aqueous solution of sodium chloride was
8500.
Dehydrochlorination treatment of the polyallylamine.hydrochloride was
carried out as follows. Sodium hydroxide in an amount of 80 g was
dissolved in 350 ml of methanol. To this solution, 187 g of the
polyallylamine.hydrochloride was added and stirred at 45.degree. C. for 16
hours. After cooling to room temperature, 142 g of anhydrous sodium
sulfate was added thereto for dehydration of neutralization water and
allowed to stand for 24 hours.
After filtration of a precipitate present in the reaction solution, there
was obtained 360 ml of a methanol solution containing 29% of
polyallylamine having a molecular weight (Mn) of about 5700 (average
degree of polymerization 100).
Dehydrochlorination percent of the polyallylamine.hydrochloride measured by
conductometric titration using the methanol solution of polyallylamine was
97.0%.
REFERENCE EXAMPLE 2
[Synthesis of Polyvinylamine]
Polyvinylamine.hydrochloride was synthesized by the process taught by D. J.
Dawson, et al [J. Am. Chem. Soc. vol. 98, pp 5996-6000 (1976)]. That is,
in a 5-liter four-necked flask equipped with a stirrer, a thermometer, a
distillation head, 1 liter of water was placed and stirred. Then, 1412 g
of acetone-wetted poly(N-vinylacetoamide) cake [containing 424 g (4.98
moles) of poly(N-vinylacetoamide) measured at a dry state] together with
200 ml of water was added to the flask and boiled. After removing the
acetone by distillation (maximum distillation temperature 100.degree. C.),
the mixture was cooled and treated with 522 ml of 12N hydrochloric acid.
When reflux was resumed in an atmosphere of argon, incompletely hydrolyzed
products began to precipitate after 20 hours. When 50 ml of water was
added thereto, the solution became clear. After 40 hours, the clouded
solution was treated with 100 ml of water, and the solution was added,
while warm, to isopropanol with rapid stirring to form a precipitate. The
product was filtered, washed with 6 liters of isopropanol and dried at
100.degree. C. for 14 hours under a reduced pressure to yield 415 g of
slightly colored white powdery solid.
The proton titration (calculated value 12.6 milliequivalent/g, measured
value 11.5 milliequivalent/g) and the elementary analysis revealed that
the resulting solid comprised 91% (378 g) of polyvinylamine.hydrochloride
and 9% of residual isopropanol. After purifying the above-mentioned solid
by dialysis, the aqueous solution was added to 12N HCl in an amount 25
times as large as by volume to give a precipitate of
polyvinylamine.hydrochloride.
Elementary analysis: (as C.sub.2 H.sub.6 NCl).sub.n :
______________________________________
C (%) H (%) N (%)
______________________________________
Calcd. 30.20 7.60 17.61
Found 30.75 8.26 16.89
______________________________________
Dehydrochlorination treatment of the obtained polyvinylamine.hydrochloride
was carried out in the same manner as described in Reference Example 1
except for using 157 g of the polyvinylamine.hydrochloride in place of 187
g of polyallylamine.hydrochloride. As a result, there was obtained 350 ml
of methanol solution containing 21% of polyvinylamine having a molecular
weight (Mn) of about 5600 (average degree of polymerization 130).
Dehydrochlorination percent of the polyvinylamine.hydrochloride measured by
conductometric titration was 95.4%.
EXAMPLE 1
In a 500 ml three-necked flask equipped with a stirrer, a reflux condenser
and a thermometer, 146 ml of methanol solution containing 22.8 g of the
polyallylamine having the molecular weight of about 5700 synthesized in
Reference Example 1 was placed and 32.0 g of allyl glycidyl ether
(corresponding to 0.7 equivalent weight of allyl glycidyl ether per
equivalent weight of polyallylamine) was dropped thereinto in 30 minutes
at room temperature with stirring.
After dropping, the system was heated to 40.degree. C. and stirring was
continued for 24 hours, followed by cooling to room temperature. Then, the
reaction product was poured into about 400 ml of ether. After removing a
supernatant liquid, ether was added to the produced viscous gum-like
substance with stirring. Then, a supernatant liquid was removed by
decantation. After repeating this procedure several times, the gumlike
substance was dried under a reduced pressure to give 35.0 g of a white
resin.
An infrared spectrum of the obtained resin is shown in FIG. 1. As is clear
from FIG. 1, a broad absorption due to the hydroxyl group and the amino
group is present near 3300 cm.sup.-1. Further, absorptions are seen at 910
cm.sup.-1 and 990 cm.sup.-1 corresponding to the unsaturated C.dbd.C bond
due to the allyl group.
The presence of the unsaturated C.dbd.C bond due to the allyl group was
also shown by .sup.1 H-NMR spectra.
From the results of elementary analysis, the presence of about 5% of water
in the resin was found. After amending the results of elementary analysis
by removing the amount of water, the found values of the resin were in
good agreement with the calculated values as shown below:
______________________________________
C (%) H (%) N (%)
______________________________________
Found 62.98 10.33 10.73
Calcd. 63.13 10.36 10.67
______________________________________
In the above, the calculated value was obtained by taking j/j+k as 0.65
(this value was calculated from .sup.1 H-NMR proton absorption spectra at
300 MHz mentioned below) in the formula (I).
Solubility of the resulting functional resin in various solvents is shown
in Table 1.
TABLE 1
______________________________________
Solvent Solubility*
______________________________________
Water o
Methanol o
Ethanol o
Isopropanol o
Methyl Cellosolve
o
Ethyl Cellosolve o
DMF o
DMSO o
CHCl.sub.3 o
Benzene x
Xylene x
CCl.sub.4 x
THF x
Ethyl acetate x
Ether x
Acetone x
Trichloroethylene
x
______________________________________
Note
*The solubility of 0.1 g of the resin in 10 ml of a solvent.
o: Soluble
x: Insoluble
The starting polyallylamine is soluble in water, methanol, and ethanol, but
the obtained functional resin is also soluble in organic solvents other
than methanol and ethanol as shown in Table 1 and shows considerably
diferenct solubility from the polyallylamine.
From the results of IR, .sup.1 H-NMR, the elementary anaylsis and the
solubility, the chemical structure of the obtained resin is concluded to
be as follows:
##STR10##
Considereing that "n" of the starting polymer is about 100 and no rupture
of the main chain takes place due to the mild reaction conditions, the "n"
in the above formula is estimated as 100.
Further, from the value of absorption intensity of the hydrogen atoms of
the allyl group in the .sup.1 H-NMR proton absorption spectrum at 300
MH.sub.z, the value of j/j+k was 0.6 to 0.7 (0.65 in average).
Further, the obtained resin began to soften at 180.degree. C. and was
decomposed at 200.degree. C. to give brown insoluble material.
EXAMPLE 2
The process of Example 1 was repeated except for changing the amount of
allyl glycidyl ether as shown in Table 2. Preparation conditions and
properties of the resulting functional resins are shown in Table 2.
TABLE 2
______________________________________
Amount of allyl glycidyl ether
22.9 g
18.3 g 13.7 g 9.2 g
______________________________________
Equivalent weight
0.5 0.4 0.3 0.2
to polyallylamine
Yield (g) 31.2 26.8 24.9 21.1
IR absorption
3300 cm.sup.-1
Yes Yes Yes Yes
990 cm.sup.-1 Yes Yes Yes Yes
910 cm.sup.-1 Yes Yes Yes Yes
Allyl group Yes Yes Yes Yes
absorption in
.sup.1 H-NMR
Solubility
Methyl Cellosolve
o o o o
Ethyl Cellosolve
o o o x
CHCl.sub.3 o o x x
j/j + k 0.46 0.37 0.26 0.15
n 100 100 100 100
______________________________________
Note
*The value in the structural formula in Example 1.
EXAMPLE 3
In a 1-liter three-necked flask equipped with a stirrer, a reflux condenser
and a thermometer, 730 ml of methanol solution containing 114 g of the
polyallylamine having the molecular weight of about 5700 synthesized in
Reference Example 1 was placed and 114.5 g of allyl glycidyl ether
(corresponding to 0.5 equivalent weight of allyl glycidyl ether per
equivalent weight of polyallylamine) was dropped thereinto in 1.5 hours at
room temperature with stirring.
After continuing the reaction at 40.degree. C. for 24 hours with stirring,
the methanol used as a solvent was removed by distillation under a reduced
pressure using an evaporator.
Further, in order to remove the water, 300 ml of ethanol was added to the
reaction solution and the procedure of distillation under a reduced
pressure using an evaporator was repeated three times. The residue was
dissolved in 1000 ml of chloroform. An insoluble substance was removed by
centrifugation. The supernatant liquid was placed in the three-necked
flask and stirred, cooled with ice and subjected to dropping of 132 g of
acetic acid at 15.degree. C. or lower in one hour.
The chloroform was removed by distillation using an evaporator to reduce
the volume about 1/3. The resulting solution was poured into ethyl acetate
to produce a precipitate, which was sufficiently washed with ethyl acetate
and dried under a reduced pressure to give 290 g of a solid material.
FIG. 2 shows an infrared spectrum of the resulting product. As is clear
from FIG. 2, there are absorptions corresponding to the unsaturated
C.dbd.C bond due to the allyl group at 910 cm.sup.-1 and 990 cm.sup.-1 and
a broad absorption due to the hydroxyl group at 3400 cm.sup.-1. Further,
an absorption due to the carbonyl group in acetate salt is detected at
1700 cm.sup.-1.
The presence of the absorption of the allyl group was shown by .sup.1 H-NMR
spectra.
From the results of elementary analysis, the presence of about 6% of water
in the resin was demonstrated. After amending the results of elementary
analysis by removing the amount of water, the found values of the resin
were in good agreement with the calculated values.
Solubility of the resulting functional resin in various solvents is shown
in Table 3.
TABLE 3
______________________________________
Solvent Solubility*
______________________________________
Water o
Methanol o
Ethanol o
Isopropanol o
Methyl Cellosolve
o
Ethyl Cellosolve o
DMF o
DMFSO o
CHCl.sub.3 o
Benzene x
Xylene x
CCl.sub.4 x
THF x
Ethyl acetate x
Ether x
Acetone x
Trichloroethylene
x
______________________________________
*See Table 1.
Polyallylamine.acetate is soluble in water, methanol and ethanol, while the
resulting resin is also soluble in solvents in which the
polyallylamine.acetate is not soluble, for example, isopropanol, ethyl
Cellosolve, etc.; this means that the solubility of the resulting resin is
different from that of the polyallylamine.acetate.
From the results of IR, .sup.1 H-NMR, the elementary analysis and the
solubility, the chemical structure of the obtained resin is concluded as
follows:
##STR11##
EXAMPLE 4
In a 300-ml three-necked flask equipped with a stirrer, a reflux condenser,
and a thermometer, 146 ml of methanol solution containing 17.3 g of the
polyvinylamine having the molecular weight of about 5600 synthesized in
Reference Example 2 was placed and 32.0 g of allyl glycidyl ether
(corresponding to 0.7 equivalent weight of allyl glycidyl ether per
equivalent weight of polyvinylamine) was dropped thereinto in 30 minutes
at room temperature with stirring.
After continuing the stirring at 40.degree. C. for 24 hours, the flask was
cooled naturally to room temperature. After removing a supernatant liquid,
ether was added to the produced viscous gum-like substance with sufficient
stirring. Then, a supernatant liquid was removed by decantation. After
repeating this procedure twice, the gum-like substance was dried under a
reduced pressure to give 32.5 g of a white resin.
The obtained resin showed in an infrared absorption (IR) spectrum
absorptions corresponding to the unsaturated C.dbd.C bond due to the allyl
group at 910 cm.sup.-1 and 990 cm.sup.-1, and a broad absorption due to
the hydroxyl group and the amino group at near 3300 cm.sup.-1.
The presence of the unsaturated C.dbd.C bond due to the allyl group was
also demonstrated by .sup.1 H-NMR spectra.
From the results of elementary analysis, the presence of about 5% of water
in the resin was demonstrated. After amending the results of elementary
analysis by removing the amount of water, the found values of the resin
were in good agreement with the calculated values as shown below:
______________________________________
C (%) H (%) N (%)
______________________________________
Found 61.02 9.05 11.30
Calcd. 60.38 9.91 12.18
______________________________________
Solubility of the obtained resin in various solvents is shown in Table 4.
TABLE 4
______________________________________
Solvent Solubility*
______________________________________
Water o
Methanol o
Ethanol o
Isopropanol o
Methyl Cellosolve
Ethyl Cellosolve o
DMF o
DMSO o
CHCl.sub.3 o
Benzene x
Xylene x
CCl.sub.4 x
THF x
Ethyl acetate x
Ether x
Acetone x
Trichloroethylene
x
______________________________________
*See Table 1.
The starting polyvinylamine is soluble in water, methanol, ethanol and
isopropanol, but insoluble in DMF (dimethylformamide), DMSO (dimethyl
sulfoxide) and CHCl.sub.3. In contrast, the obtained resin is also soluble
in DMF, DMSO and CHCl.sub.3, in which the starting polyvinylamine is
insoluble as mentioned above. Thus, the solubility of the obtained resin
is clearly different from that of the polyvinylamine.
From the results of IR, .sup.1 H-NMR, the elementary analysis and the
solubility, the chemical structure of the obtained resin is concluded as
follows:
##STR12##
EXAMPLE 5
The process of Example 4 was repeated except for changing the amount of
allyl glycidyl ether as shown in Table 5. Preparation conditions and
properties of the resulting functional resins are shown in Table 5.
TABLE 5
______________________________________
Amount of allyl glycidyl ether
22.9 g
18.3 g 13.7 g 9.2 g
______________________________________
Equivalent weight to
0.5 0.4 0.3 0.2
polyvinylamine
Yield (g) 26.5 23.8 21.0 18.6
IR absorption
3300 cm.sup.-1
Yes Yes Yes Yes
990 cm.sup.-1 Yes Yes Yes Yes
910 cm.sup.-1 Yes Yes Yes Yes
Allyl group Yes Yes Yes Yes
absorption in
.sup.1 H-NMR
Solubility
Methyl Cellosolve
o o o o
Ethyl Cellosolve
o o o x
CHCl.sub.3 o o x x
j/j + k 0.45 0.36 0.26 0.16
n 130 130 130 130
______________________________________
*The value in the structural formula in Example 4.
EXAMPLE 6
1-Diallylamino-2,3-epoxypropane was synthesized according to the process
disclosed in J. Polym. Sci., vol. 59 (167), pp S1-S2 (1962) by F. W.
Michelotti.
The processes described in Examples 1 and 4 were repeated, respectively,
except for using 42.9 g of 1-diallylamino-2,3-epoxypropane (corresponding
to 0.7 equivalent weight of 1-diallylamino-2,3-epoxypropane per equivalent
weight of polyallylamine or polyvinylamine, respectively) in place of 32.0
g of allyl glycidyl ether. As a result, there were obtained 46.3 g of
polyallylamine-modified resin and 42.7 g of polyvinylamine-modified resin,
respectively.
From IR absorption spectra of the two kinds of obtained resins, absorptions
corresponding to the unsaturated C.dbd.C bond due to the allyl group at
910 cm.sup.-1 and 990 cm.sup.-1 and a broad absorption due to the hydroxyl
group and the amino group at 3300 cm.sup.-1 were observed.
The presence of the unsaturated C.dbd.C bond due to the allyl group was
also shown by .sup.1 H-NMR spectra.
The found values of the two obtained resins were in good agreement with the
calculated values. Solubilities of the obtained resins in various solvents
are shown in Table 6 (polyallylamine-modified resin) and Table 7
(polyvinylamine-modified resin).
TABLE 6
______________________________________
Solvent Solubility*
______________________________________
Water o
Methanol o
Ethanol o
Isopropanol o
Methyl Cellosolve
o
Ethyl Cellosolve o
DMF o
DMSO o
CHCl.sub.3 o
Benzene x
Xylene x
CCl.sub.4 x
THF x
Ethyl acetate x
Ether x
Acetone x
Trichloroethylene
x
______________________________________
*See Table 1.
TABLE 7
______________________________________
Solvent Solubility*
______________________________________
Water o
Methanol o
Ethanol o
Isopropanol o
Methyl Cellosolve
o
Ethyl Cellosolve o
DMF o
DMSO o
CHCl.sub.3 o
Benzene x
Xylene x
CCl.sub.4 x
THF x
Ethyl acetate x
Ether x
Acetone x
Trichloroethylene
x
______________________________________
As is clear from the results of solubilities, the two obtained resins are
different from the starting polyallylamine and polyvinylamine in the
solubilities and are soluble in organic solvents such ethyl Cellosolve,
CHCl.sub.3, etc.
The results of elementary anaylses are as follows:
(i) the functional resin derived from polyallylamine
______________________________________
C (%) H (%) N (%)
______________________________________
Found 68.56 11.66 14.32
Calcd. 67.81 10.78 14.81
______________________________________
(ii) The functional resin derived from polyvinylamine
______________________________________
C (%) H (%) N (%)
______________________________________
Found 66.30 10.83 15.77
Calcd. 65.94 10.44 16.43
______________________________________
From the results of IR, .sup.1 H-NMR, the elemetary analyses and the
solubilities, the chemical structures of the two obtained resins are
concluded to be as follows:
(i) Functional resin derived from polyallylamine:
##STR13##
(ii) Functional resin derived from polyvinylamine:
##STR14##
EXAMPLE 7
The process of Example 1 was repeated except for using each polyallylamine
having molecular weight (Mn) of about 1500 or 2300 produced according to
Synthesis Example 1 to give two kinds of functional resins.
When the polyallylamine having the molecular weight of about 1500 was used,
the yield was 31.2 g and when the polyallylamine having the molecular
weight of about 2300 was used, the yield was 32.4 g.
From the IR absorption spectra and .sup.1 H-NMR spectra of the two obtained
resins, the presence of the allyl group was demonstrated.
The solubilities of the obtained resins were the same as that shown in
Table 1 in Example 1.
From the results of elementary analyses, the presence of about 5% of water
in the two obtained resins was admitted. After amending the results of
elementary analyses by removing the amount of water, the found values of
the resins were in good agreement with the calculated values as shown
below:
(i) Functional resin derived from polyallylamine
(Mn=c.a. 1500)
______________________________________
C (%) H (%) N (%)
______________________________________
Found 63.84 10.81 11.05
Calcd. 63.12 10.34 10.49
______________________________________
(ii) Functional resin derived from polyallylamine
(Mn=c.a. 2300)
______________________________________
C (%) H (%) N (%)
______________________________________
Found 62.78 10.11 10.93
Calcd. 62.10 10.30 10.58
______________________________________
From the results of IR, .sup.1 H-NMR, the elementary analyses and the
solubilities, the chemical structures of the two obtained resins are
concluded as follows:
##STR15##
(i) Functional resin derived from polyallylamine (Mn=c.a. 1500)
n=26, j/j+k=0.67
(ii) Functional resin derived from polyallylamine
(Mn=c.a. 2300)
n=40, j/j+k=0.66
EXAMPLE 8
The functional resins obtained in Examples 1 to 7 and the starting
polyallylamine obtained in Synthesis Synthesis Example 1 were dissolved in
methyl Cellosolve or methanol so as to make the solid content about 10%
and coated on glass plates, iron plates, aluminum plates and wooden
plates.
Each coated film was dried at 150.degree. C. for 1 hour in the air and the
state of each film was observed by the naked eye.
The results are shown in Table 8.
TABLE 8
______________________________________
State of film
Functional resins obtained
Substrate in Examples 1 to 7
Polyallylamine
______________________________________
Glass o x
Iron o x
Aluminum o x
Wood o x
______________________________________
Note
o: Good state without cracks
x: Cracks and peelingoff took place.
As is clear from Table 8, the functional resins obtained in Examples 1 to 7
show by far better surface state of the coated films and adhesiveness than
those of the starting polyallylamine.
As mentioned above, the functional resins of this invention have excellent
properties in that the main chain portion is flexible, and the side chain
portions have desired length, are flexible and cable of bending, and
further at terminals have carbon-carbon double bonds which can be
crosslinked when exposed to heat and light. Therefore, the functional
resins of this invention can be used as protective films for various
substrates, coating compositions, adhesives, and the like.
* * * * *
|
|
 |
|
 |
Description |
|
