U.S. patent application number 14/420017 was filed with the patent office on 2015-07-16 for polyarylene sulfide and a preparation method thereof.
This patent application is currently assigned to SK Chemicals CO., LTD.. The applicant listed for this patent is SK CHEMICALS CO., LTD.. Invention is credited to Sung-Gi Kim, Se-Ho Lee.
Application Number | 20150197605 14/420017 |
Document ID | / |
Family ID | 50068360 |
Filed Date | 2015-07-16 |
United States Patent
Application |
20150197605 |
Kind Code |
A1 |
Lee; Se-Ho ; et al. |
July 16, 2015 |
POLYARYLENE SULFIDE AND A PREPARATION METHOD THEREOF
Abstract
The present invention relates to a polyarylene sulfide having
more improved miscibility with other polymer materials or fillers,
and a method of preparing the same. At least part of end groups of
the main chain of the polyarylene sulfide is carboxyl group
(--COOH) or amine group (--NH.sub.2).
Inventors: |
Lee; Se-Ho; (Gyeonggi-do,
KR) ; Kim; Sung-Gi; (Gyeonggi-do, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SK CHEMICALS CO., LTD. |
Seongnam-si, Gyeonggi-do |
|
KR |
|
|
Assignee: |
SK Chemicals CO., LTD.
Seongnam-si, Gyeonggi-do
KR
|
Family ID: |
50068360 |
Appl. No.: |
14/420017 |
Filed: |
August 6, 2013 |
PCT Filed: |
August 6, 2013 |
PCT NO: |
PCT/KR2013/007081 |
371 Date: |
February 6, 2015 |
Current U.S.
Class: |
528/363 ;
528/389 |
Current CPC
Class: |
C08L 81/02 20130101;
C08G 75/14 20130101; C08L 81/04 20130101; C08G 75/02 20130101 |
International
Class: |
C08G 75/14 20060101
C08G075/14 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 7, 2012 |
KR |
10-2012-0086423 |
Claims
1. A polyarylene sulfide of which at least part of end groups of
the main chain is carboxyl group (--COOH) or amine group
(--NH.sub.2).
2. The polyarylene sulfide according to claim 1, showing the peak
of 1600 to 1800 cm.sup.-1 or 3300 to 3500 cm.sup.-1, in a FT-IR
spectrum.
3. The polyarylene sulfide according to claim 2, wherein the
relative height intensity of the peak of 1600 to 1800 cm.sup.-1 or
3300 to 3500 cm.sup.-1 is 0.001 to 10%, when the height of the ring
stretch peak shown at 1400 to 1600 cm.sup.-1 is assumed as the
intensity of 100%, in the FT-IR spectrum.
4. The polyarylene sulfide according to claim 1, wherein the
melting temperature is 265 to 290.degree. C.
5. The polyarylene sulfide according to claim 1, wherein the number
average molecular weight is 5,000 to 50,000.
6. The polyarylene sulfide according to claim 1, wherein the melt
viscosity measured with a rotational viscometer at 300.degree. C.
is 10 to 50,000 poise.
7. The polyarylene sulfide according to claim 1, wherein the
tensile strength measured according to ASTM D 638 is 100 to 900
kgf/cm.sup.2.
8. The polyarylene sulfide according to claim 1, wherein the
elongation measured according to ASTM D 638 is 1 to 10%.
9. The polyarylene sulfide according to claim 1, wherein the
flexural strength measured according to ASTM D 790 is 100 to 2,000
kgf/cm.sup.2.
10. The polyarylene sulfide according to claim 1, wherein the
impact strength measured according to ASTM D 256 is 1 to 100
J/m.
11. A method of preparing the polyarylene sulfide according to
claim 1, including the steps of: polymerizing a reactant including
a diiodoaromatic compound and sulfur element; and adding a compound
having carboxyl group or amine group thereto while carrying out the
polymerization step.
12. The method according to claim 11, wherein the compound having
carboxyl group or amine group includes one or more compounds
selected from the group consisting of 2-iodobenzoic acid,
3-iodobenzoic acid, 4-iodobenzoic acid, 2,2'-dithiobenzoic acid,
2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 2,2'-dithiodianiline,
and 4,4'-dithiodianiline.
13. The method according to claim 11, wherein the compound having
carboxyl group or amine group is added thereto in the amount of
0.0001 to 5 parts by weight, based on 100 parts by weight of the
diiodoaromatic compound.
14. The method according to claim 11, wherein the compound having
carboxyl group or amine group is added thereto when the degree of
the polymerization reaction is progressed 90% or more, wherein the
degree of polymerization reaction is determined by the ratio of
present viscosity to target viscosity.
15. The method according to claim 11, wherein the diiodoaromatic
compound is one more compounds selected from the group consisting
of diiodobenzene, diiodonaphthalene, diiodobiphenyl,
diiodobisphenol, and diiodobenzophenone.
16. The method according to claim 11, wherein polymerizing step is
carried out for 1 to 30 hours by varying the temperature and
pressure from the initial reaction condition of 180 to 250.degree.
C. and 50 to 450 torr to the final reaction condition of 270 to
350.degree. C. and 0.001 to 20 torr.
17. The method according to claim 11, further including the step of
melt-mixing the reactant including the diiodoaromatic compound and
sulfur element, before the polymerizing step.
18. A shaped article, including the polyarylene sulfide according
to claim 1.
19. The shaped article according to claim 19, which is a form of
film, sheet, or fiber.
Description
TECHNICAL FIELD
[0001] The present invention relates to a polyarylene sulfide
having more improved compatibility with other polymer materials or
fillers, and a method of preparing the same.
BACKGROUND OF THE INVENTION
[0002] Now, polyarylene sulfide is a representative engineering
plastic, and the demand for the products being used in a high
temperature and corrosive environment or the electronic goods is
increasing due to its high heat resistance and chemical resistance,
flame resistance, electric insulation, and so on.
[0003] Among the polyarylene sulfides, polyphenylene sulfide (PPS)
is one and only commercially on sale now. The commercial
preparation process of PPS being applicable until now is the method
of carrying out a solution polymerization of p-dichlorobenzene
(pDCB) and sodium sulfide in a polar organic solvent such as
N-methylpyrrolidone. The method is known as Macallum process.
[0004] However, when the polyarylene sulfide is prepared by such
Macallum process, a salt type by-product may be formed in a
solution polymerization process using sodium sulfide, and thus
there is a disadvantage of requiring a washing or drying process
for eliminating a salt type by-product or a residual organic
solvent. Furthermore, since the polyarylene sulfide prepared by
such Macallum process is a powder form, the post processability and
workability may decrease.
[0005] Accordingly, a method of melt-polymerizing the reactants
including diiodoaromatic compounds and sulfur element was suggested
as the method of preparing the polyarylene sulfide such as PPS and
the like. Such method does not form a salt type by-product and not
use an organic solvent in the preparation process of the
polyarylene sulfide, and thus it does not require an additional
process for eliminating them. Furthermore, since the polyarylene
sulfide prepared finally has a pellet form, there is an advantage
of easy post processability and good workability.
[0006] However, in the case of the polyarylene sulfide prepared by
the melt-polymerization method, the ends of the main chain were
composed of iodine and most aryl groups (representatively,
benzene). Therefore, there was a disadvantage of that such
polyarylene sulfide was inferior in the compatibility with other
polymer materials or all sorts of reinforcements or fillers like
glass fiber and the like due to the characteristics of its main
chain structure.
[0007] Due to this, it was hard to compound the polyarylene sulfide
prepared by the melt-polymerization method with other polymer
materials or fillers for securing optimized properties suitable to
various uses, and it was difficult to show optimized properties
even if it was compounded with them.
DETAILS OF THE INVENTION
OBJECTS OF THE INVENTION
[0008] It is an aspect of the present invention to prepare a
polyarylene sulfide having more improved compatibility with other
polymer materials or fillers, and a method of preparing the
same.
[0009] It is another aspect of the present invention to provide a
shaped article including the polyarylene sulfide.
TECHNICAL MEANS
[0010] The present invention provides a polyarylene sulfide of
which at least part of end groups of the main chain is carboxyl
group (--COOH) or amine group (--NH.sub.2).
[0011] The present invention also provides a method of preparing
polyarylene sulfide, including the steps of: polymerizing a
reactant including a diiodoaromatic compound and sulfur element;
and adding a compound having carboxyl group or amine group thereto
while carrying out the polymerization step.
[0012] The present invention also provides a shaped article
including the polyarylene sulfide resin.
[0013] Hereinafter, the polyarylene sulfide according to specific
embodiment of the invention, the preparation method thereof, and
the shaped article including the same are explained in more detail.
However, the embodiment is provided only for an example of the
invention, and the scope of the invention is not limited to or by
them and it is obvious to a person skilled in the art that various
modifications are possible in the scope of the invention.
[0014] In this description, "include" or "comprise" means to
include any components (or ingredients) without particular
limitation unless there is no particular mention about them, and it
cannot be interpreted as a meaning of excluding an addition of
other components (or ingredients).
[0015] According to one embodiment of the invention, a polyarylene
sulfide of which at least part of end groups of the main chain is
carboxyl group (--COOH) or amine group (--NH.sub.2) is
provided.
[0016] The present inventors accomplished the present invention, in
the course of studying the method of preparing a polyarylene
sulfide having better compatibility with other polymer materials or
fillers which can be compounded with various materials and can
realize optimized properties suitable to various uses, in the
process of preparing a polyarylene sulfide by melt-polymerizing a
reactant including a diiodoaromatic compound and sulfur
element.
[0017] From the research of the present inventors, it is recognized
that the polyarylene sulfide prepared by prior melt-polymerization
method has the ends of the main chain composed of iodine and most
aryl groups (representatively, benzene) and there is substantially
no functional group in the main chain, and thus there is a
disadvantage of that such polyarylene sulfide is inferior in the
compatibility with other polymer materials, all sorts of
reinforcements such as glass fiber and the like, or fillers.
[0018] However, it is recognized that the polyarylene sulfide of
one embodiment shows good compatibility with other polymer
materials or fillers, since reactive functional groups such as
carboxyl group (--COOH) or amine group (--NH.sub.2) are introduced
to at least part of the ends of the main chain of the same.
Consequently, the polyarylene sulfide of one embodiment can be
suitably compounded with various polymer materials or fillers, and
makes it possible to provide a resin composition and a shaped
article showing the optimized properties suitable to various uses.
Simultaneously with this, the polyarylene sulfide can show good
heat resistance and chemical resistance, and excellent mechanical
properties unique to the polyarylene sulfide.
[0019] The polyarylene sulfide of one embodiment may show the peak
of about 1600 to 1800 cm.sup.-1 derived from carboxyl groups of the
ends of the main chain or the peak of about 3300 to 3500 cm.sup.-1
derived from amine group, in a FT-IR spectrum, when it is analyzed
with FT-IR spectroscopy. At this time, the intensity of the peak of
1600 to 1800 cm.sup.-1 or the peak of 3300 to 3500 cm.sup.-1 may
correspond to the amount of carboxyl groups or amine groups
connected to the ends of main chain.
[0020] According to one example, in the FT-IR spectrum of the
polyarylene sulfide of one embodiment, if the height of the ring
stretch peak shown at about 1400 to 1600 cm.sup.-1 is assumed as
the intensity of 100%, the relative height intensity of the peak of
about 1600 to 1800 cm.sup.-1 or about 3300 to 3500 cm.sup.-1 may be
about 0.001 to 10%, about 0.01 to 7%, about 0.1 to 4%, or about 0.5
to 3.5%. At this time, the ring stretch peak shown at 1400 to 1600
cm.sup.-1 may be what is derived from the arylene group such as
phenylene and the like included in the main chain of the
polyarylene sulfide. Since the height intensity of the peak of
about 1600 to 1800 cm.sup.-1 derived from carboxyl groups or the
peak of about 3300 to 3500 cm.sup.-1 derived from amine groups is
about 0.001 to 10%, about 0.01 to 7%, about 0.1 to 4%, or about 0.5
to 3.5% in comparison to the height intensity of the peak derived
from the arylene group (for example, phenylene group), the
polyarylene sulfide of one embodiment can show good compatibility
with other polymer materials or fillers and can maintain excellent
properties unique to the polyarylene sulfide.
[0021] Meanwhile, the melting temperature of the polyarylene
sulfide of one embodiment may be about 265 to 290.degree. C., about
270 to 285.degree. C., or about 275 to 283.degree. C. Because of
such melting temperature range, the polyarylene sulfide of one
embodiment obtained by melt-polymerization method, to which
carboxyl group or amine group is introduced, can show excellent
heat resistance and flame retardance.
[0022] And, the number average molecular weight of the polyarylene
sulfide may be about 5,000 to 50,000, about 8,000 to 40,000, or
about 10,000 to 30,000. The polydispersity index defined as the
weight average molecular weight divided by the number average
molecular weight may be about 2.0 to 4.5, about 2.0 to 4.0, or
about 2.0 to 3.5. Because the polyarylene sulfide of one embodiment
has such polydispersity index and molecular weight range, it can
show excellent mechanical properties and processability and can be
processed into various shaped articles for various uses.
[0023] Furthermore, above polyarylene sulfide of one embodiment may
have the melt viscosity of about 10 to 50,000 poise, about 100 to
20,000, or about 300 to 10,000, which is measured with a rotational
viscometer at 300.degree. C. The polyarylene sulfide of one
embodiment having such melt viscosity can show superior mechanical
properties in company with excellent processability.
[0024] For example, the polyarylene sulfide of one embodiment may
have the tensile strength of about 100 to 900 kgf/cm.sup.2, about
200 to 800 kgf/cm.sup.2, or about 300 to 700 kgf/cm.sup.2, which is
measured according to ASTM D 638, and the elongation of about 1 to
10%, about 1 to 8%, or about 1 to 6%, which is measured according
to ASTM D 638. Furthermore, the polyarylene sulfide of one
embodiment may have the flexural strength of about 100 to 2,000
kgf/cm.sup.2, about 500 to 2,000 kgf/cm.sup.2, or about 1,000 to
2,000 kgf/cm.sup.2, which is measured according to ASTM D 790, and
the impact strength of about 1 to 100 J/m, about 5 to 50 J/m, or
about 10 to 20 J/m, which is measured according to ASTM D 256. Like
this, the polyarylene sulfide of one embodiment can show good
compatibility with other polymer materials or fillers and can
exhibit excellent properties.
[0025] The polyarylene sulfide of one embodiment may show good
compatibility with various thermoplastic resins such as
polyvinylalcohol-based resins, vinylchloride-based resins,
polyamide-based resins, polyolefin-based resins, polyester-based
resins, and the like; various thermoplastic elastomers such as
polyvinylchloride-based elastomers, polyolefin-based elastomers,
polyurethane-based elastomers, polyester-based elastomers,
polyamide-based elastomers, polybutadiene-based elastomers, and the
like; or various reinforcements/fillers such as glass fiber, carbon
fiber, boron fiber, glass bead, glass flake, talc, calcium
carbonate, and the like. Therefore, above polyarylene sulfide of
one embodiment can be compounded with other various polymer
materials or fillers and show excellent synergistic effect, and it
becomes possible to realize the properties optimized to various
purposes.
[0026] As an example, it was recognized that the elongation was
elevated about 10 times from about 2.2% to about 25.2%, the impact
strength was elevated about 3 times from about 17 J/m to about 54
J/m by compounding about 90 weight % of the polyarylene sulfide of
one embodiment of which carboxyl group is introduced to the end
group of the main chain, and about 10 weight % of thermoplastic
elastomer. Furthermore, it was recognized that the tensile strength
was largely elevated from about 602 kgf/cm.sup.2 to about 1750
kgf/cm.sup.2 by compounding about 60 weight % of the polyarylene
sulfide of one embodiment of which amine group is introduced to the
end group of the main chain, and about 40 weight % of glass fiber.
Therefore, it can be known from the improved properties caused by
such compounding that the polyarylene sulfide of one embodiment can
show good compatibility with other various polymer materials or
fillers, and consequently can exhibit excellent synergistic
effects.
[0027] When the polyarylene sulfide of one embodiment is compounded
with other polymer materials or fillers, it is preferable to mix
about 10 to 99 weight % or about 50 to 90 weight % of the
polyarylene sulfide and about 1 to 90 weight % or about 10 to 50
weight % of one or more components selected from the group
consisting of thermoplastic resin, thermoplastic elastomers, and
fillers. A shaped article having excellent properties preferable to
various uses can be prepared by shaping such mixture with a method
of biaxial extrusion and the like.
[0028] Meanwhile, according to another embodiment of the invention,
a method of preparing the polyarylene sulfide is provided. Such
method of another embodiment may include the steps of polymerizing
a reactant including a diiodoaromatic compound and sulfur element;
and adding a compound having carboxyl group or amine group thereto
while carrying out the polymerization step.
[0029] In the preparation method of another embodiment, the
compound having carboxyl group or amine group may be added thereto
when the degree of polymerization reaction of the diiodoaromatic
compound and sulfur element is progressed about 90% or more, or
about 90% or more and less than 100%, (for example, in the latter
part of the polymerization reaction), wherein the degree of
polymerization reaction is determined by the ratio of present
viscosity to target viscosity. The degree of polymerization
reaction can be determined as the ratio of present viscosity to
target viscosity. For this, an objective molecular weight of the
polyarylene sulfide and a target viscosity corresponding to the
objective molecular weight are set up, and the present viscosity
according to the degree of polymerization reaction is measured. At
this time, the present viscosity may be differently measured by a
method well-known to a person skilled in the art in accordance with
the scale of reactor. For example, when the polymerization is
carried out in a relatively small polymerization reactor, it may be
measured by using a viscometer after taking a sample from the
reactor where the polymerization reaction is progressing. On the
other hand, when the reaction is carried out in a huge continuous
polymerization reaction, the present viscosity may be measured
continuously in real time with a viscometer installed in the
reactor itself.
[0030] Like this, the polyarylene sulfide of one embodiment of
which carboxyl group (--COOH) or amine group (--NH.sub.2) is
introduced to at least part of end groups of the main chain can be
prepared by adding and reacting the compound having carboxyl group
or amine group in the latter part of the polymerization reaction of
the reactant including the diiodoaromatic compound and sulfur
element. Particularly, since the compound having carboxyl group or
amine group is added in the latter part of the polymerization
reaction, proper amount of carboxyl group or amine group can be
introduced to the end groups of the main chain, and the polyarylene
sulfide of one embodiment having not only good compatibility with
other polymer materials or fillers but also excellent properties
unique to the polyarylene sulfide can be prepared effectively.
[0031] Meanwhile, in the preparation method of another embodiment,
an arbitrary monomer compound having carboxyl group or amine group
may be used as the compound having carboxyl group or amine group.
As the examples of the compound having carboxyl group or amine
group, 2-iodobenzoic acid, 3-iodobenzoic acid, 4-iodobenzoic acid,
2,2'-dithiobenzoic acid, 2-iodoaniline, 3-iodoaniline,
4-iodoaniline, 2,2'-dithiodianiline, or 4,4'-dithiodianiline may be
used, and various compounds having carboxyl group or amine group
can be used in addition.
[0032] Furthermore, the compound having carboxyl group or amine
group may be added thereto in the amount of about 0.0001 to 5 parts
by weight, about 0.001 to 3 parts by weight, or about 0.01 to 2
parts by weight, based on 100 parts by weight of the diiodoaromatic
compound. Proper amount of carboxyl group or amine group can be
introduced to the end groups of the main chain by adding such
amount of the compound having carboxyl group or amine group, and
consequently, the polyarylene sulfide of one embodiment having not
only good compatibility with other polymer materials or fillers but
also excellent properties unique to the polyarylene sulfide can be
prepared effectively.
[0033] Meanwhile, in the preparation method of another embodiment,
the polyarylene sulfide is prepared basically by the method of
polymerizing the reactant including the diiodoaromatic compound and
sulfur element, and consequently, the polyarylene sulfide having
superior mechanical properties to prior Macallum process can be
prepared.
[0034] At this time, the diiodoaromatic compound may be one or more
compounds selected from the group consisting of diiodobenzene
(DIB), diiodonaphthalene, diiodobiphenyl, diiodobisphenol, and
diiodobenzophenone, but not limited to or by them, diiodoaromatic
compounds that alkyl group or sulfone group is connected to above
compounds as a substituent or an oxygen or nitrogen atom is
included in the aromatic group may also be used. There are various
diiodocompound isomers of diiodoaromatic compounds depending on the
position of iodine atoms, and a compound having iodine at
para-position like para-diiodobenzene (pDIB),
2,6-diiodonaphthalene, or p,p'-diiodobiphenyl may be used more
preferably.
[0035] And, the form of sulfur element which reacts with the
diiodoaromatic compound is not limited particularly. Generally,
sulfur elements exist in a cyclooctasulur (S8) form in which 8
atoms are connected at room temperature. However, if not such form,
any solid type or liquid type sulfur which can be used commercially
may be used without particular limitation.
[0036] Furthermore, the reactant may further include a
polymerization initiator, a stabilizer, or a mixture thereof. As
the polymerization initiator, one or more initiator selected from
the group consisting of 1,3-diiodo-4-nitrobenzene,
mercaptobenzothiazole, 2,2'-dithiobenzothiazole,
cyclohexylbenzothiazole sulfenamide, and butylbenzothiazole
sulfonamide may be used, for example, but it is not limited to or
by them.
[0037] And, common stabilizer for polymerization reaction or resins
may be used as the stabilizer unlimitedly.
[0038] Meanwhile, during the polymerization reaction, a
polymerization inhibitor may be added thereto at the time when the
polymerization is somewhat progressed. At this time, any
polymerization inhibitor which can terminate the polymerization by
eliminating iodine group included in the polymerized polymer can be
used without particular limitation. Specifically, one or more
compounds selected from the group consisting of diphenyl suldife,
diphenyl ether, diphenyl, benzophenone, dibenzothiazole disulfide,
monoiodoaryl compound, benzothiazoles, benzothiazolesulfenamides,
thiurams, dithiocarbamates, and diphenyl disulfide may be used.
[0039] More preferably, the polymerization inhibitor may be one or
more compounds selected from the group consisting of iodobiphenyl,
iodophenol, iodoaniline, iodobenzophenone, 2-mercaptobenzothiazole,
2,2'-dithiobisbenzothiazole,
N-cyclohexylbenzothiazole-2-sulfenamide,
2-morpholinothiobenzothiazole,
N,N-dicyclohexylbenzothiazole-2-sulfenamide, tetramethylthiuram
monosulfide, tetramethylthiuram disulfide, zinc
dimethyldithiocarbamate, zinc diethyldithiocarbamate, and diphenyl
disulfide may be used.
[0040] Meanwhile, the time of adding the polymerization inhibitor
may be determined by considering the molecular weight of the
polyarylene sulfide to be polymerized finally. For example, the
inhibitor may be added at the time of that about 70 to 100 wt % of
the diiodoaromatic compound included in the initial reactant are
reacted and exhausted.
[0041] And, the polymerization reaction may be carried out in any
condition which can initiate the polymerization of the reactants
including the diiodoaromatic compound and sulfur element. For
example, the polymerization reaction may be carried out in a
temperature-rising and pressure-reducing reaction condition. At
this time, the condition may be carried out for about 1 to 30 hrs
while varying the temperature and pressure condition from the
initial reaction condition of about 180 to 250.degree. C. and about
50 to 450 torr to the final reaction condition of about 270 to
350.degree. C. and about 0.001 to 20 torr. For more concrete
example, the polymerization reaction may be carried out with the
final reaction condition of about 280 to 300.degree. C. and 0.1 to
0.5 torr.
[0042] Meanwhile, the preparation method of the polyarylene sulfide
according to another embodiment may further include the step of
melt-compounding the reactants including the diiodoaromatic
compound and sulfur element before the polymerization reaction. The
condition of the melt-compounding is not limited as long as all of
the reactants are melted and compounded, and for example, the
process may be carried out at the temperature of about 130.degree.
C. to 200.degree. C. , or about 160.degree. C. to 190.degree.
C.
[0043] Like this, by carrying out the melt-compounding step before
the polymerization reaction, it is possible to carry out succeeding
polymerization reaction more easily.
[0044] Furthermore, in the preparation method of polyarylene
sulfide according to another embodiment, the polymerization
reaction may be carried out in the presence of a nitrobenzene-based
catalyst. And, when the melt-compounding step is carried out before
the polymerization reaction as disclosed above, the catalyst may be
added in the melt-compounding step. As the nitrobenzene-based
catalyst, 1,3-diiodo-4-nitrobenzene, or 1-iodo-4-nitrobenzene may
be used but it is not limited to or by them.
[0045] According to still another embodiment of the invention, a
shaped article including the polyarylene sulfide of above
embodiment is provided. The shaped article may solely consist of
the polyarylene sulfide or may further include other polymer
materials and/or reinforcements/fillers. The polyarylene sulfide
shows excellent compatibility with other polymer materials and/or
reinforcements/fillers, and makes it possible to provide a resin
composition or a shaped article having superior properties by being
mixed (for example, compounded) with them. At this time, the
polymer materials and/or reinforcements/fillers which can be
compounded with the polyarylene sulfide are same as disclosed
above.
[0046] Such shaped article may include about 10 to 99 weight % or
about 50 to 90 weight % of the polyarylene sulfide and about 1 to
90 weight % or about 10 to 50 weight % of one or more components
selected from the group consisting of thermoplastic resin,
thermoplastic elastomers, and fillers. And, by shaping the resin
composition satisfying above content range with a method such as
biaxial extrusion, the shaped article having excellent properties
and applicable to various uses can be obtained.
[0047] The shaped article of still another embodiment may be
various shapes of film, sheet, fiber, and the like. And, the shaped
article may be an injection molded article, an extruded article, or
a blown article. In the injection molding process, the mold
temperature may be about 50.degree. C. or more, about 60.degree. C.
or more, or about 80.degree. C. or more in the aspect of
crystallization, and the temperature may be about 190.degree. C. or
less, about 170.degree. C. or less, or about 160.degree. C. or less
in the aspect of deformation of specimen.
[0048] And, if the shaped article is a film or a sheet, it may be
made into an undrawn, a uniaxially drawn, or a biaxially drawn film
or sheet. If it is a fiber, it may be made into an undrawn, a
drawn, or an ultradrawn fiber, and it may be used to a fabric, a
knit, a nonwoven (spunbond, meltblown, or staple), a rope, or a
net.
[0049] Such shaped articles may be used to electric &
electronic parts such as computer parts, architectural elements,
car parts, machine parts, daily necessities, coating parts to which
chemical materials contact, industrial chemical resistant fiber,
and the like.
[0050] In the present invention, further details besides the
disclosure above may be added and subtracted with necessity, and
they are not limited particularly in the present invention.
EFFECTS OF THE INVENTION
[0051] The present invention can provide a melt-polymerized
polyarylene sulfide having excellent compatibility with other
polymer materials or reinforcements/fillers because of carboxyl
group or amine group included at the end of the main chain.
[0052] Such polyarylene sulfide can exhibit excellent properties
optimized to various uses and excellent properties unique to the
polyarylene sulfide by being compounded with other various polymer
materials or fillers.
[0053] Therefore, such polyarylene sulfide can be applied to
various uses including the use of compounding, and can exhibit
excellent properties and effects.
DETAILED DESCRIPTION OF THE EMBODIMENT
[0054] Hereinafter, preferable examples are presented for
understanding the present invention. However, the following
examples are only for illustrating the present invention and the
present invention is not limited to or by them.
Example 1
Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine
Group at the End of the Main Chain
[0055] After completely melting and mixing the reactant including
5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of
1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5L reactor
equipped with a thermocouple capable of measuring the inside
temperature of the reactor and a vacuum line for nitrogen purging
and vacuumizing by heating the same to 180.degree. C., the
polymerization reaction was proceeded by carrying out
temperature-rising and pressure reducing step by step from the
initial reaction condition of 220.degree. C. and 350 torr to the
final reaction temperature of 300.degree. C. and the pressure of 1
torr or less. When the polymerization reaction was proceeded 80%
(the proceeding degree of the polymerization reaction was
identified by the relative viscosity ratio [(present
viscosity/target viscosity)*100%], and the present viscosity was
measured with a viscometer after taking a sample from the reactor
where the polymerization reaction was progressing), 25 g of
2,2'-dithiobisbenzothiazole was added thereto as a polymerization
inhibitor and the reaction was carried out for 1 hr. Subsequently,
after adding 51 g of 4-iodobenzoic acid thereto when the reaction
was proceeded 90% and progressing the reaction under nitrogen
circumstance for 10 mins, the reaction was further progressed with
slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By
this, the polyarylene sulfide resin having carboxyl group or amine
group at the end of the main chain was synthesized. The final resin
obtained by the reaction was prepared into pellets by using a small
strand cutter.
[0056] The polyarylene sulfide resin of Example 1 was analyzed by
FT-IR spectroscopy. At this time, the carboxyl group peak was
recognized at about 1600 to 1800 cm.sup.-1 in the spectrum. It was
also recognized that the relative height intensity of the peak at
about 1600 to 1800cm.sup.-1 was about 3.4% when the height
intensity of the ring stretch peak shown at about 1400 to 1600
cm.sup.-1 was assumed as 100%.
Example 2
Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine
Group at the End of the Main Chain
[0057] After completely melting and mixing the reactant including
5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of
1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5L reactor
equipped with a thermocouple capable of measuring the inside
temperature of the reactor and a vacuum line for nitrogen purging
and vacuumizing by heating the same to 180.degree. C., the
polymerization reaction was proceeded by carrying out
temperature-rising and pressure reducing step by step from the
initial reaction condition of 220.degree. C. and 350 torr to the
final reaction temperature of 300.degree. C. and the pressure of 1
torr or less. When the polymerization reaction was proceeded 80%
(the proceeding degree of the polymerization reaction was
identified by the relative viscosity ratio [(present
viscosity/target viscosity)*100%], and the present viscosity was
measured with a viscometer after taking a sample from the reactor
where the polymerization reaction was progressing), 25 g of
2,2'-dithiobisbenzothiazole was added thereto as a polymerization
inhibitor and the reaction was carried out for 1 hr. Subsequently,
after adding 51 g of 4-iodoaniline thereto when the reaction was
proceeded 90% and progressing the reaction under nitrogen
circumstance for 10 mins, the reaction was further progressed with
slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By
this, the polyarylene sulfide resin having carboxyl group or amine
group at the end of the main chain was synthesized. The final resin
obtained by the reaction was prepared into pellets by using a small
strand cutter.
[0058] The polyarylene sulfide resin of Example 2 was analyzed by
FT-IR spectroscopy. At this time, the amine group peak was
recognized at about 3300 to 3500 cm.sup.-1 in the spectrum. It was
also recognized that the relative height intensity of the peak at
about 3300 to 3500 cm.sup.-1 was about 1.4% when the height
intensity of the ring stretch peak shown at about 1400 to
1600cm.sup.-1 was assumed as 100%.
Example 3
Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine
Group at the End of the Main Chain
[0059] After completely melting and mixing the reactant including
5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of
1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5L reactor
equipped with a thermocouple capable of measuring the inside
temperature of the reactor and a vacuum line for nitrogen purging
and vacuumizing by heating the same to 180.degree. C., the
polymerization reaction was proceeded by carrying out
temperature-rising and pressure reducing step by step from the
initial reaction condition of 220.degree. C. and 350 torr to the
final reaction temperature of 300.degree. C. and the pressure of 1
torr or less. When the polymerization reaction was proceeded 80%
(the proceeding degree of the polymerization reaction was
identified by the relative viscosity ratio [(present
viscosity/target viscosity)*100%], and the present viscosity was
measured with a viscometer after taking a sample from the reactor
where the polymerization reaction was progressing), 25 g of
2,2'-dithiobisbenzothiazole was added thereto as a polymerization
inhibitor and the reaction was carried out for 1 hr. Subsequently,
after adding 25 g of 4-iodobenzoic acid thereto when the reaction
was proceeded 90% and progressing the reaction under nitrogen
circumstance for 10 mins, the reaction was further progressed with
slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By
this, the polyarylene sulfide resin having carboxyl group or amine
group at the end of the main chain was synthesized. The final resin
obtained by the reaction was prepared into pellets by using a small
strand cutter. The polyarylene sulfide resin of Example 3 was
analyzed by FT-IR spectroscopy. At this time, the carboxyl group
peak was recognized at about 1600 to 1800 cm.sup.-1 in the
spectrum. It was also recognized that the relative height intensity
of the peak at about 1600 to 1800 cm.sup.-1 was about 2.1% when the
height intensity of the ring stretch peak shown at about 1400 to
1600 cm.sup.-1 was assumed as 100%.
Example 4
Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine
Group at the End of the Main Chain
[0060] After completely melting and mixing the reactant including
5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of
1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5L reactor
equipped with a thermocouple capable of measuring the inside
temperature of the reactor and a vacuum line for nitrogen purging
and vacuumizing by heating the same to 180.degree. C., the
polymerization reaction was proceeded by carrying out
temperature-rising and pressure reducing step by step from the
initial reaction condition of 220.degree. C. and 350 torr to the
final reaction temperature of 300.degree. C. and the pressure of 1
torr or less. When the polymerization reaction was proceeded 80%
(the proceeding degree of the polymerization reaction was
identified by the relative viscosity ratio [(present
viscosity/target viscosity)*100%], and the present viscosity was
measured with a viscometer after taking a sample from the reactor
where the polymerization reaction was progressing), 25 g of
2,2'-dithiobisbenzothiazole was added thereto as a polymerization
inhibitor and the reaction was carried out for 1 hr. Subsequently,
after adding 25 g of 4-iodoaniline thereto when the reaction was
proceeded 90% and progressing the reaction under nitrogen
circumstance for 10 mins, the reaction was further progressed with
slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By
this, the polyarylene sulfide resin having carboxyl group or amine
group at the end of the main chain was synthesized. The final resin
obtained by the reaction was prepared into pellets by using a small
strand cutter.
[0061] The polyarylene sulfide resin of Example 4 was analyzed by
FT-IR spectroscopy. At this time, the amine group peak was
recognized at about 3300 to 3500 cm.sup.-1 in the spectrum. It was
also recognized that the relative height intensity of the peak at
about 3300 to 3500 cm.sup.-1 was about 1.1% when the height
intensity of the ring stretch peak shown at about 1400 to 1600
cm.sup.-1 was assumed as 100%.
Example 5
Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine
Group at the End of the Main Chain
[0062] After completely melting and mixing the reactant including
5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of
1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5L reactor
equipped with a thermocouple capable of measuring the inside
temperature of the reactor and a vacuum line for nitrogen purging
and vacuumizing by heating the same to 180.degree. C., the
polymerization reaction was proceeded by carrying out
temperature-rising and pressure reducing step by step from the
initial reaction condition of 220.degree. C. and 350 torr to the
final reaction temperature of 300.degree. C. and the pressure of 1
torr or less. When the polymerization reaction was proceeded 80%
(the proceeding degree of the polymerization reaction was
identified by the relative viscosity ratio [(present
viscosity/target viscosity)*100%], and the present viscosity was
measured with a viscometer after taking a sample from the reactor
where the polymerization reaction was progressing), 25 g of
2,2'-dithiobisbenzothiazole was added thereto as a polymerization
inhibitor and the reaction was carried out for 1 hr. Subsequently,
after adding 51 g of 2,2'-dithiodibenzoic acid thereto when the
reaction was proceeded 90% and progressing the reaction under
nitrogen circumstance for 10 mins, the reaction was further
progressed with slowly vacuumizing to 0.5 torr or less for 1 hr,
and terminated. By this, the polyarylene sulfide resin having
carboxyl group or amine group at the end of the main chain was
synthesized. The final resin obtained by the reaction was prepared
into pellets by using a small strand cutter.
[0063] The polyarylene sulfide resin of Example 5 was analyzed by
FT-IR spectroscopy. At this time, the carboxyl group peak was
recognized at about 1600 to 1800 cm.sup.-1 in the spectrum. It was
also recognized that the relative height intensity of the peak at
about 1600 to 1800 cm.sup.-1 was about 3.2% when the height
intensity of the ring stretch peak shown at about 1400 to 1600
cm.sup.-1 was assumed as 100%.
Example 6
Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine
Group at the End of the Main Chain
[0064] After completely melting and mixing the reactant including
5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of
1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5L reactor
equipped with a thermocouple capable of measuring the inside
temperature of the reactor and a vacuum line for nitrogen purging
and vacuumizing by heating the same to 180.degree. C., the
polymerization reaction was proceeded by carrying out
temperature-rising and pressure reducing step by step from the
initial reaction condition of 220.degree. C. and 350 torr to the
final reaction temperature of 300.degree. C. and the pressure of 1
torr or less.
[0065] When the polymerization reaction was proceeded 80% (the
proceeding degree of the polymerization reaction was identified by
the relative viscosity ratio [(present viscosity/target
viscosity)*100%], and the present viscosity was measured with a
viscometer after taking a sample from the reactor where the
polymerization reaction was progressing), 25 g of
2,2'-dithiobisbenzothiazole was added thereto as a polymerization
inhibitor and the reaction was carried out for 1 hr. Subsequently,
after adding 51 g of 4,4'-dithiodianiline thereto when the reaction
was proceeded 90% and progressing the reaction under nitrogen
circumstance for 10 mins, the reaction was further progressed with
slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By
this, the polyarylene sulfide resin having carboxyl group or amine
group at the end of the main chain was synthesized. The final resin
obtained by the reaction was prepared into pellets by using a small
strand cutter.
[0066] The polyarylene sulfide resin of Example 6 was analyzed by
FT-IR spectroscopy. At this time, the amine group peak was
recognized at about 3300 to 3500 cm.sup.-1 in the spectrum. It was
also recognized that the relative height intensity of the peak at
about 3300 to 3500 cm.sup.-1 was about 1.3% when the height
intensity of the ring stretch peak shown at about 1400 to 1600
cm.sup.-1 was assumed as 100%.
Example 7
Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine
Group at the End of the Main Chain
[0067] After completely melting and mixing the reactant including
5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of
1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5L reactor
equipped with a thermocouple capable of measuring the inside
temperature of the reactor and a vacuum line for nitrogen purging
and vacuumizing by heating the same to 180.degree. C., the
polymerization reaction was proceeded by carrying out
temperature-rising and pressure reducing step by step from the
initial reaction condition of 220.degree. C. and 350 torr to the
final reaction temperature of 300.degree. C. and the pressure of 1
torr or less. When the polymerization reaction was proceeded 80%
(the proceeding degree of the polymerization reaction was
identified by the relative viscosity ratio [(present
viscosity/target viscosity)*100%], and the present viscosity was
measured with a viscometer after taking a sample from the reactor
where the polymerization reaction was progressing), 25 g of
2,2'-dithiobisbenzothiazole was added thereto as a polymerization
inhibitor and the reaction was carried out for 1 hr. Subsequently,
after adding 25 g of 2,2'-dithiodibenzoic acid thereto when the
reaction was proceeded 90% and progressing the reaction under
nitrogen circumstance for 10 mins, the reaction was further
progressed with slowly vacuumizing to 0.5 torr or less for 1 hr,
and terminated. By this, the polyarylene sulfide resin having
carboxyl group or amine group at the end of the main chain was
synthesized. The final resin obtained by the reaction was prepared
into pellets by using a small strand cutter.
[0068] The polyarylene sulfide resin of Example 7 was analyzed by
FT-IR spectroscopy. At this time, the carboxyl group peak was
recognized at about 1600 to 1800 cm.sup.-1 in the spectrum. It was
also recognized that the relative height intensity of the peak at
about 1600 to 1800 cm.sup.-1 was about 1.9% when the height
intensity of the ring stretch peak shown at about 1400 to 1600
cm.sup.-1 was assumed as 100%.
Example 8
Synthesis of Polyarylene Sulfide Including Carboxyl Group or Amine
Group at the End of the Main Chain
[0069] After completely melting and mixing the reactant including
5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of
1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5L reactor
equipped with a thermocouple capable of measuring the inside
temperature of the reactor and a vacuum line for nitrogen purging
and vacuumizing by heating the same to 180.degree. C., the
polymerization reaction was proceeded by carrying out
temperature-rising and pressure reducing step by step from the
initial reaction condition of 220.degree. C. and 350 torr to the
final reaction temperature of 300.degree. C. and the pressure of 1
torr or less. When the polymerization reaction was proceeded 80%
(the proceeding degree of the polymerization reaction was
identified by the relative viscosity ratio [(present
viscosity/target viscosity)*100%], and the present viscosity was
measured with a viscometer after taking a sample from the reactor
where the polymerization reaction was progressing), 25 g of
2,2'-dithiobisbenzothiazole was added thereto as a polymerization
inhibitor and the reaction was carried out for 1 hr. Subsequently,
after adding 25 g of 4,4'-dithiodianiline thereto when the reaction
was proceeded 90% and progressing the reaction under nitrogen
circumstance for 10 mins, the reaction was further progressed with
slowly vacuumizing to 0.5 torr or less for 1 hr, and terminated. By
this, the polyarylene sulfide resin having carboxyl group or amine
group at the end of the main chain was synthesized. The final resin
obtained by the reaction was prepared into pellets by using a small
strand cutter.
[0070] The polyarylene sulfide resin of Example 8 was analyzed by
FT-IR spectroscopy. At this time, the amine group peak was
recognized at about 3300 to 3500 cm.sup.-1 in the spectrum. It was
also recognized that the relative height intensity of the peak at
about 3300 to 3500 cm.sup.-1 was about 1.0% when the height
intensity of the ring stretch peak shown at about 1400 to 1600
cm.sup.-1 was assumed as 100%.
Comparative Example 1
[0071] After completely melting and mixing the reactant including
5,130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of
1,3-diiodo-4-nitrobenzene as a reaction initiator in a 5L reactor
equipped with a thermocouple capable of measuring the inside
temperature of the reactor and a vacuum line for nitrogen purging
and vacuumizing by heating the same to 180.degree. C., the
polymerization reaction was proceeded by carrying out
temperature-rising and pressure reducing step by step from the
initial reaction condition of 220.degree. C. and 350 torr to the
final reaction temperature of 300.degree. C. and the pressure of 1
torr or less. When the polymerization reaction was proceeded 80%
(the proceeding degree of the polymerization reaction was
identified by the relative viscosity ratio [(present
viscosity/target viscosity)*100%], and the present viscosity was
measured with a viscometer after taking a sample from the reactor
where the polymerization reaction was progressing), 25 g of
2,2'-dithiobisbenzothiazole was added thereto as a polymerization
inhibitor and the reaction was progressed under nitrogen
circumstance for 10 mins, and the reaction was further progressed
with slowly vacuumizing to 0.5 torr or less and terminated when the
viscosity reached the target viscosity. By this, the polyarylene
sulfide resin having neither carboxyl group nor amine group at the
end of the main chain was synthesized. The final resin obtained by
the reaction was prepared into pellets by using a small strand
cutter.
[0072] The polyarylene sulfide resin of Comparative Example 1 was
analyzed by FT-IR spectroscopy. At this time, it was recognized
that there was neither carboxyl group peak nor amine group peak at
about 1600 to 1800 cm.sup.-1 or about 3300 to 3500 cm.sup.-1 in the
spectrum.
Comparative Example 2
[0073] Product name Z200 of DIC Co., Ltd. in which the polyarylene
sulfide made by Macallum process was compounded with an elastomer
was used as Comparative Example 2.
Experimental Example 1
Evaluation on Basic Properties of Polyarylene Sulfide
[0074] The properties of polyarylene sulfides of Examples 1 to 8
and Comparative Example 1 were evaluated by the following
methods:
[0075] Melting Temperature (Tm)
[0076] By using a differential scanning calorimeter (DSC), after
elevating the temperature of the specimen from 30.degree. C. to
320.degree. C. with a scanning speed of 10.degree. C./min and
cooling to 30.degree. C., the melting temperature was measured
while elevating the temperature from 30.degree. C. to 320.degree.
C. again with a scanning speed of 20.degree. C./min.
[0077] Number Average Molecular Weight (Mn) and Polydispersity
Index (PDI)
[0078] After dissolving the polyarylene sulfide in
1-chloronaphthalene at 250.degree. C. for 25 minutes with stirring
so as to be 0.4 wt % solution, the polyarylene sulfide was divided
in order in the column of a high temperature gel permeation
chromatography (GPC) system (210.degree. C.) by flowing the
solution with the flow rate of 1 mL/min, and the intensity
corresponding to the molecular weight of the divided polyarylene
sulfide was measure by using a RI detector. After making a
calibration line with a standard specimen (polystyrene) of which
the molecular weight was known, the relative number average
molecular weight (Mn) and polydispersity index (PDI) of the measure
sample was calculated.
[0079] Melt viscosity (Poise)
[0080] The melt viscosity (hereinafter, `M.V.`) was measured at
300.degree. C. by using a rotating disk viscometer. In frequency
sweep measuring method, angular frequency was measured from 0.6 to
500 rad/s, and the viscosity at 1.84 rad/s was defined as the melt
viscosity (M.V.).
[0081] The properties measured according to above methods are
listed in the following Table 1:
TABLE-US-00001 TABLE 1 Number Melting Average Polydispersity Melt
temperature Molecular Index Viscosity Classification (.degree. C.)
Weight (PDI) (Poise) Example 1 278.6 17,667 2.9 2,940 Example 2
278.3 17,614 2.9 2,200 Example 3 278.8 17,435 2.8 2,830 Example 4
278.6 17,224 2.8 2,770 Example 5 277.5 17,338 2.9 2,350 Example 6
277.7 17,152 2.9 2,930 Example 7 278.3 17,531 2.8 2,470 Example 8
278.7 17,582 2.8 2,530 Comparative 280.5 17,267 2.8 2,420 Example
1
Experimental Example 2
Evaluation on Mechanical Properties of Polyarylene Sulfide
[0082] The mechanical properties of polyarylene sulfides of
Examples 1 to 8 and Comparative Example 1 were evaluated by the
following methods:
[0083] Tensile Strength and Elongation
[0084] The tensile strength and the elongation of the polyarylene
sulfide specimens prepared according to Examples 1 to 8 and
Comparative Example 1 were measured according to ASTM D 638
method.
[0085] Flexural Strength
[0086] The flexural strength of the polyarylene sulfide specimens
prepared according to Examples 1 to 8 and Comparative Example 1
were measured according to ASTM D 790 method.
[0087] Impact Strength (Izod)
[0088] The impact strength of the polyarylene sulfide specimens
prepared according to Examples 1 to 8 and Comparative Example 1 was
measured according to ASTM D 256 method.
[0089] The mechanical properties measured according to above
methods are listed in the following Table 2:
TABLE-US-00002 TABLE 2 Impact Tensile Flexural Strength Strength
Elongation Strength (J/m, Classification (kgf/cm.sup.2) (%)
(kgf/cm.sup.2) Notched) Example 1 612 2.2 1,430 17 Example 2 602
1.2 1,422 20 Example 3 622 2.1 1,433 18 Example 4 614 1.3 1,442 17
Example 5 628 2.2 1,455 18 Example 6 605 1.2 1,428 17 Example 7 611
2.3 1,435 17 Example 8 618 1.3 1,447 19 Comparative 605 1.2 1,453
19 Example 1
[0090] The specimens were prepared by compounding the polyarylene
sulfide of Examples 1 to 8 and Comparative Example 1 with other
components according to the following methods:
[0091] Compounding of Polyarylene Sulfide and Glass Fiber (GF)
[0092] After drying the polymerized resin, the compounding was
carried out with a small twin-screw extruder under the condition of
the extrusion die temperature of 300.degree. C. and the screw speed
of 200 rpm while adding 40 parts by weight of glass fiber to 60
parts by weight of the resin.
[0093] Compounding of Polyarylene Sulfide and Elastomer
[0094] The mixing extrusion was carried out under the condition of
the extrusion die temperature of 300.degree. C. and the screw speed
of 200 rpm while adding 10 parts by weight of Lotader (Grade
AX-8840, made by Arkema), the elastomer, to 90 parts by weight of
the resin.
[0095] The mechanical properties of the compounded specimens were
evaluated by the same way as the polyarylene sulfide specimens and
are listed in the following Table 3. Furthermore, the properties of
the specimen of Comparative Example 2, a commercialized compounded
specimen, are compared with Examples and Comparative Example 1 in
the following Table 3:
TABLE-US-00003 TABLE 3 Tensile Flexural Impact Strength Elongation
Strength Strength Classification (kgf/cm.sup.2) (%) (kgf/cm.sup.2)
(J/m, Notched) Example 1 + 583 25.2 1,030 54 Elastomer 10% Example
2 + 1,750 1.8 2,440 85 GF 40% Example 3 + 577 20.5 1,010 48
Elastomer 10% Example 4 + 1,740 1.8 2,400 83 GF 40% Example 5 + 564
24.3 1,010 52 Elastomer 10% Example 6 + 1,770 1.8 2,480 86 GF 40%
Example 7 + 568 18.7 1,005 45 Elastomer 10% Example 8 + 1,750 1.8
2,420 82 GF 40% Comparative 556 2.5 950 17 Example 1 + Elastomer
10% Comparative 1,700 1.7 2,300 77 Example 1 + GF 40% Comparative
660 15.7 940 76 Example 2
[0096] According to Tables 2 and 3, it was recognized that the
elongation was elevated about 10 times from about 2.2% to about
25.2 and the impact strength was elevated about 3 times from about
1 7J/m to about 54 J/m by compounding the polyarylene sulfide of
Example 1 of which carboxyl group is introduce to the end of the
main chain with the thermoplastic elastomer. And, it was recognized
that the tensile strength was largely elevated from about 602
kgf/cm.sup.2 to about 1750 kgf/cm.sup.2 by compounding the
polyarylene sulfide of Example 2 of which amine group is introduced
to the end group of the main chain with glass fiber. Therefore, it
can be known from the properties elevated by such compounding that
the polyarylene sulfides of Examples can show good compatibility
with other various polymer materials or fillers, and consequently
can exhibit excellent synergistic effects.
[0097] On the other hand, it was recognized that the polyarylene
sulfide of Comparative Example 1 was inferior in the compatibility
with other polymer materials or fillers and the synergistic effects
caused by compounding was not so big.
[0098] Furthermore, the compounded specimen of Comparative Example
2 was a commercialized specimen prepared by compounding the
polyarylene sulfide which was obtained by Macallum process and was
known to be good in the compatibility with other polymer materials
and several % of elastomer. However, such compounded specimen of
Comparative Example 2 also showed not enough elongation improvement
by compounding with elastomer, in comparison with Examples, and it
seems to have the problems (deterioration in processability and
workability due to the powder form) of polyarylene sulfide obtained
by Macallum process.
* * * * *