Title: Aromatic polyester
Abstract: The present invention provides an aromatic polyester which is obtained by condensation polymerization reaction of terephthalic acid, 2,6-naphthalenedicarboxylic acid and acylated product obtained by acylation of parahydroxybenzoic acid and hydroquinone with fatty acid anhydride, wherein said aromatic polyester satisfy the following conditions (A) to (D), and the acylation and/or the condensation polymerization reaction are conducted in the presence of heterocyclic organic compound containing at least two nitrogen atoms:
(A): Number of moles of a monomer unit derived from parahydroxybenzoic acid (UNIT (1)) is 54-62 moles per 100 moles of UNIT (1), a monomer unit derived from hydroquinone (UNIT (2)), a monomer unit derived from terephthalic acid (UNIT (3)) and a monomer unit derived from 2,6-naphthalenedicarboxylic acid (UNIT (4)) in total; (B): Number of moles of UNIT (2) is 19-23 moles per 100 moles of UNIT (1), UNIT (2), UNIT (3) and UNIT (4) in total; (C): The molar ratio of UNIT (3) and UNIT (4), which is represented by the following formula (I) is 0.23-0.35:
wherein [(3)] and [(4)] represent number of moles of respective UNIT (3) and UNIT (4); (D): Total number of moles of UNIT (3) and UNIT (4) is 0.95-1.05 moles per one mole of UNIT (2).
Patent Number: 6,890,988 Issued on 05/10/2005 to Hosoda, et al.
| Inventors:
|
Hosoda; Tomoya (Ibaraki, JP);
Harada; Hiroshi (Nishitokyo, JP);
Okamoto; Satoshi (Tsukuba, JP)
|
| Assignee:
|
Sumitomo Chemical Company, Limited (Osaka, JP)
|
| Appl. No.:
|
372301 |
| Filed:
|
February 25, 2003 |
Foreign Application Priority Data
| Feb 27, 2002[JP] | 2002-051035 |
| Current U.S. Class: |
524/720; 524/442; 525/437; 525/444; 528/190; 528/193; 528/194; 528/198; 528/199; 528/206; 528/212 |
| Intern'l Class: |
C08L 005/34.77; C08G064/00 |
| Field of Search: |
528/190,193,194,198,206,212
525/437,444
524/442,720
|
References Cited [Referenced By]
U.S. Patent Documents
| 5710237 | Jan., 1998 | Waggoner et al.
| |
| 5969083 | Oct., 1999 | Long et al.
| |
| 6121369 | Sep., 2000 | Stack et al.
| |
| 2002/0055607 | May., 2002 | Okamoto et al.
| |
| Foreign Patent Documents |
| WO 9745469 | Dec., 1997 | WO.
| |
Primary Examiner: Acquah; Samuel A.
Attorney, Agent or Firm: Sughrue Mion, PLLC
Claims
1. An aromatic polyester which is obtained by condensation polymerization reaction
of terephthalic acid, 2,6-naphthalenedicarboxylic acid and acylated product obtained
by acylation of parahydroxybenzoic acid and hydroquinone with fatty acid anhydride,
wherein said aromatic polyester satisfy the following conditions (A) to (D), and
the acylation and/or the condensation polymerization reaction are conducted in
the presence of heterocyclic organic compound containing at least two nitrogen atoms:
(A): Number of moles of a monomer unit derived from parahydroxybenzoic acid (UNIT
(1)) is 54-62 moles per 100 moles of UNIT (1), a monomer unit derived from hydroquinone
(UNIT (2)), a monomer unit derived from terephthalic acid (UNIT (3)) and a monomer
unit derived from 2,6-naphthalenedicarboxylic acid (UNIT (4)) in total;
(B): Number of moles of UNIT (2) is 19-23 moles per 100 moles of UNIT (1), UNIT
(2), UNIT (3) and UNIT (4) in total;
(C): The molar ratio of UNIT (3) and UNIT (4), which is represented by the following
formula (I) is 0.23-0.35:
wherein [(3)] and [(4)] represent number of moles of respective UNIT (3)
and UNIT (4);
(D): Total number of moles of UNIT (3) and UNIT (4) is 0.95-1.05 moles per one
mole of UNIT (2).
2. The aromatic polyester according to claim 1 wherein said heterocyclic organic
base compound is imidazole compound represented by the general formula
##STR3##
wherein R
1, R
2, R
3 and R
4 each independently
represents hydrogen atom, alkyl group having 1 to 4 carbon atoms, hydroxymethyl
group, cyano group, cyanoalkyl group having 1 to 4 carbon atoms, cyanoalkoxy group
having 1 to 4 carbon atoms, carboxyl group, amino group, aminoalkyl group having
1 to 4 carbon atoms, aminoalkoxy group having 1 to 4 carbon atoms, phenyl group,
benzyl group, phenylpropyl group or formyl group.
3. The aromatic polyester according to claim 1 wherein the amount of said heterocyclic
organic base compound added is from 0.001 to 1 part by weight per 100 parts by
weight of UNIT (1), UNIT (2), UNIT (3) and UNIT (4) in total.
4. An aromatic polyester obtained by solid phase polymerization of the aromatic
polyester according to claim 1.
5. A molded article obtained by molding a composition comprising the aromatic
polyester according to claim 4.
6. The molded article according to claim 5 which further comprising filler and
the filter content is 10-400 parts by weight per 100 parts by weight of the aromatic polyester.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an aromatic polyester obtained from parahydroxybenzoic
acid, hydroquinone, terephthalic acid and 2,6-naphthalenedicarboxylic acid.
2. Prior Art
Aromatic polyesters obtained by polymerization of (1) parahydroxybenzoic
acid, (2) hydroquinone,(3) terephthalic acid and (4) 2,6-naphthalenedicarboxylic
acid have been already known.
##STR1##
Specifically, U.S. Pat. No. 5,969,083 reports that when number of moles
of monomer unit derived from (1) is 53.8 moles per 100 moles of the monomer units
derived from (1) to (4) in total which constitute the aromatic polyester; and when
the value which is represented by the following formula (I) is 0.2 or 0.4:
wherein [(3)] and [(4)] represent number of moles of the monomer unit derived
from (3) and the monomer unit derived from (4),
the resulting aromatic polyester has a low melting point and low viscosity, and
thus a molded article obtained therefrom exhibits a high heat distortion temperature
(i.e., a deflection temperature under load) and excellent tensile elongation.
Further, Japanese laid open patent publication WO 97/45469 reports that
when number of moles of monomer unit derived from (1) is 55.6 moles per 100 moles
of the monomer units derived from (1) to (4) in total; and when the value represented
by the formula (I) is 0.4, the resulting aromatic polyester has a low melting point,
and thus a molded article obtained therefrom is excellent in tensile strength,
tensile elongation, flexural strength and a modulus of flexural elasticity, and
has a high heat distortion temperature (i.e., a deflection temperature under load).
The present inventors studied on aromatic polyesters containing monomer unit
derived from (1) at 54-62 moles per 100 moles of the monomer units drived from
(1) to (4) in total which constitute the aromatic polyester, and having the value
represented by the formula (I) of 0.23-0.35, and revealed that the molded article
obtained from the aromatic polyester has insufficient impact strength.
An object of the present invention is to provide an aromatic polyester which
gives
a molded article having excellent mechanical strength such as tensile, flexure
and the like with excellent heat resistance such as a heat distortion temperature,
and having excellent impact strength even with an aromatic polyester obtained from
(1) parahydroxybenzoic acid, (2) hydroquinone,(3) terephthalic acid and (4) 2,6-naphthalenedicarboxylic
acid, containing the monomer unit derived from (1) at 54-62 moles per 100 moles
of the monomer units derived from (1) to (4) in total, and having the value represented
by the aforementioned formula (I) of 0.23-0.35
SUMMARY OF THE INVENTION
The present invention relates to an aromatic polyester which is obtained by condensation
polymerization reaction of terephthalic acid, 2,6-naphthalenedicarboxylic acid
and acylated product obtained by acylation of parahydroxybenzoic acid and hydroquinone
with fatty acid anhydride, wherein said aromatic polyester satisfy the following
conditions (A) to (D), and the acylation and/or the condensation polymerization
reaction are conducted in the presence of heterocyclic organic compound containing
at least two nitrogen atoms.
(A): Number of moles of a monomer unit derived from parahydroxybenzoic acid
(hereinafter referred to "UNIT (1)") is 54-62 moles per 100 moles of the unit (1),
a monomer unit derived from hydroquinone (hereinafter referred to "UNIT (2)"),
a monomer unit derived from terephthalic acid (hereinafter referred to "UNIT (3)")
and a monomer unit derived from 2,6-naphthalenedicarboxylic acid (hereinafter referred
to "UNIT (4)") in total.
(B): Number of moles of UNIT (2) is 19-23 moles per 100 moles of UNIT (1),
UNIT (2), UNIT (3) and UNIT (4) (hereinafter referred to "UNITS (1-4)") in total.
(C): The molar ratio of UNIT (3) and UNIT (4), which is represented by the
following formula (I) is 0.23-0.35:
wherein [(3)] and [(4)] represent number of moles of respective UNIT
(3) and UNIT (4).
(D): Total number of moles of UNIT (3) and UNIT (4) is 0.95-1.05 moles per
one mole of UNIT (2).
Hereinafter, the aromatic polyester defined above is referred to "the
present polyester".
The present invention also relates to an aromatic polyester obtained
by solid phase polymerization of the present polyester. Hereinafter, the aromatic
polymer obtained by the solid phase polymerization is referred to "the present
polyester (2)".
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention is explained in detail below.
The content of UNIT (1) in the present polyester is from 54 to 62 moles, preferably
from 55 to 60 moles of UNIT (1) per 100 moles of UNITS (1-4) in total which constitute
the present polyester.
The content of UNIT (2) is from 19 to 23 moles, preferably from 20 to 22.5 moles
per 100 moles of UNITS (1-4) in total which constitute the present polyester.
The content of UNIT (3) and UNIT (4) is from 0.95 to 1.05 moles, preferably from
about 0.98 to about 1.02 moles, and particularly preferably from about 1.00 mole
per 1 mole of UNIT (2) which constitute the present polyester.
When the molar ratio of UNIT (3) and UNIT (4) in the present polyester is represented
by the following formula (I):
wherein [(3)] and [(4)] represent number of moles of respective UNIT (3)
and UNIT (4) which constitute the present polyester, the ratio is from 0.23 to
0.35, preferably from 0.25 to 0.30.
As charged amount of a monomer as a raw material of polymer usually directly
reflects
the contents of the monomer unit derived from the material in the polymer, the
content of UNIT (1), UNIT (2), UNIT (3) or UNIT (4) may be regarded as identical
to the content of parahydroxybenzoic acid, hydroquinone, terephthalic acid or 2,6-naphthalenedicarboxylic
acid used respectively, in the present invention.
The fatty acid anhydride used in producing the present polyester may include
for example, acetic anhydride, propionic anhydride, butyric anhydride, isobutyric
anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, monochloroacetic
anhydride, dichloroacetic anhydride, trichloroacetic anhydride, monobromoacetic
anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic
anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride,
maleic anhydride, succinic anhydride, β-bromopropionic anhydride and the
like. Two or more fatty acid anhydrides may be used.
Among the fatty acid anhydrides, acetic anhydride, propionic anhydride, butyric
anhydride and isobutyric anhydride are preferred, and in particular, acetic anhydride
is suitable.
The amount of the fatty acid anhydride to be used is usually from about 1.0 to
about 1.25 equivalents, preferably from about 1.0 to about 1.2 equivalents, and
particularly preferably from about 1.03 to about 1.15 equivalents per one equivalent
in total of phenolic hydroxyl groups of parahydroxybenzoic acid and hydroquinone.
When the fatty acid anhydride is used at 1.0 equivalent or greater, it is preferred
that sublimation of the raw monomer materials are likely to be suppressed during
the condensation polymerization reaction. When the fatty acid anhydride is used
at 1.25 equivalents or less, it is preferred that coloring of the resulting aromatic
polyester is likely to be reduced.
The present polyester is aromatic polyester obtained by carrying out the reaction
in the presence of a heterocyclic organic base compound containing two or more
nitrogen atoms during the acylation and/or condensation polymerization reaction.
The heterocyclic organic base compound containing two or more nitrogen atoms
herein includes for example, imidazole compounds, triazole compounds, dipyridyl
compounds, phenanthroline compounds, diazaphenanthrene compounds, 1,5-diazabicyclo[4.3.0]non-5-ene,
1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0] unde-7-cene, N,N-dimethylaminopyridine
and the like.
The imidazole compound includes for example, imidazole compounds represented
by the following formula (II)
##STR2##
wherein R
1, R
2, R
3 and R
4 each
independently represents hydrogen atom, alkyl group having about 1 to 4 carbon
atoms, hydroxymethyl group, cyano group, cyanoalkyl group having about 1 to 4 carbon
atoms, cyanoalkoxy group having about 1 to 4 carbon atoms, carboxyl group, amino
group, aminoalkyl group having about 1 to 4 carbon atoms, aminoalkoxy group having
about 1 to 4 carbon atoms, phenyl group, benzyl group, phenylpropyl group, formyl
group or the like.
Specific examples of the imidazole compound include for example, imidazole,
1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1-ethylimidazole, 2-ethylimidazole,
4-ethylimidazole, 1,2-dimethylimidazole, 1,4-dimethylimidazole, 2,4-dimethylimidazole,
1-methyl-2-ethylimidazole, 1-methyl-4ethylimidazole, 1-ethyl-2-methylimidazole,
1-ethyl-2-ethylimidazole, 1-ethyl-2-phenylimidazole, 2-ethyl-4-methylimidazole,
2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole,
2-phenyl-4-methylimidazole, 1-cyanoethyl-2-meithylimidazole, 1-cyanoethyl-2-phenylimidazole,
4-cyanoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-methylimidazole, 1-(cyanoethylaminoethyl)-2-methylimidazole,
N-[2-(2-methyl-1-imidazolyl)ethyl]urea, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-methylimidazoletrimelitate,
1-cyanoethyl-2-phenylimidazoletrimelitate, 1-cyanoethyl-2-ethyl4-methylimidazoletrimelitate,
1-cyanoethyl-2-undecylimidazoletrimelitate, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-S-triazine,
2,4-diamino-6-[2′-undecylimidazolyl(-(1′))-ethyl-S-triazine], 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1′)]-ethyl-S-triazine,
1-dodecyl-2-methyl-3-benzylimidazolium chloride, N,N′-bis(2-methyl-1-imidazolylethyl)urea,
N,N′-(2-methyl-1-imidazolylethyl)adipoamide, 2,4-dialkylimidazole-dithiocarboxylic
acid, 1,3-dibenzyl-2-methylimidazolium chloride, 2-phenyl-4-methyl-5-hydroxymethylimidazole,
2-phenyl-4,5-dihydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-bis(cyanoethoxymethyl)imidazole,
2-methylimidazole isocyanuric acid adduct, 2-phenylimidazole•isocyanuric
acid adduct, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-S-triazine•isocyanuric
acid adduct, 2-alkyl-4-formylimidazole, 2,4-dialkyl-5-formylimidazole, 1-benzyl-2-phenylimidazole,
imidazole-4-dithiocarboxylic acid, 2-methylimidazole-4-dithiocarboxylic acid, 2-undecylimidazole-4-dithiocarboxylic
acid, 2-heptadecylimidazole-4-dithiocarboxylic acid, 2-phenylimidazole-4-dithiocarboxylic
acid, 4-methylimidazole-5-dithiocarboxylic acid, 4-dimethylimidazole-5-dithiocarboxylic
acid, 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid, 2-undecyl-4-methylimidazole-5-dithiocarboxylic
acid, 2-phenyl-4-methylimidazole-5-dithiocarboxylic acid, 1-aminoethyl-2-methylimidazole,
1-(cyanoethylaminoethyl)-2-methylimidazole, N-(2-methylimidazolyl-1-ethyl)urea,
N,N′-(2-methylimidazolyl(1)-ethyl)-adipoyldiamide, 1-aminoethyl-2-ethylimidazole,
4-formylimidazole, 2-methyl-4-formylimidazole, 4-methyl-5-formylimidazole, 2-ethyl-4-methyl-5-formylimidazole,
2-phenyl-4-methyl-4-formylimidazole and the like.
The triazole compound includes for example, 1,2,4-triazole, 1,2,3-triazole, benzotriazole
and the like.
The dipyridyl compound includes for example, 2,2′-dipyridyl, 4,4′-dipyridyl
and the like.
The phenanthroline compound includes for example, pyrimidine, purine, 1,7-phenanthroline,
1,10-phenanthroline and the like.
The diazaphenanthrene compound includes for example, pyridazine, triazine, pyrazine,
1,8-diazaphenanthrene and the like.
Among them, the imidazole compound represented by the general formula (I) is
preferred, and the imidazole compound represented by the general formula (I), wherein
R
1 is an alkyl group having 1 to 4 carbon atoms and each of R
2
and R
3 is hydrogen atoms, is particularly preferred in light of
a color tone, and moreover, 1-methylimidazole and 1-ethylimidazole are most preferred
on behalf of their ready availability.
The content of the heterocyclic organic base compound is usually from about 0.001
to about 1 part by weight per 100 parts by weight of UNITS (1-4) in total which
constitute the present polyester, and is preferably from 0.05 to 0.5 part by weight
in light of color tone and productivity.
When the amount to be used is 0.001 part by weight or greater, the impact strength
tends to be improved, and when it is 1.0 part by weight or less, to control the
end point of the reaction tends to become easier.
The heterocyclic organic base compound containing two or more nitrogen atoms
may render present for a period of time during the acylation or condensation polymerization
reaction, or during the acylation and condensation polymerization reaction. Specific
time period for adding the compound may include for example, prior to the acylation
reaction, during the acylation reaction, after the acylation reaction and prior
to the condensation polymerization reaction, during the condensation polymerization
reaction, and the like.
Next, the process for the production of the present polyester is explained
in detail with references to the specific examples.
In the acylation reaction, parahydroxybenzoic acid and hydroquinone are first
mixed with the fatty acid anhydride. For the purpose of simplification, it is preferred
that terephthalic acid and 2,6-naphthalenedicarboxylic acid that are monomers of
UNIT (3) and UNIT (4) having a carboxyl group can be concurrently mixed therewith.
Then, stirring is conducted under nitrogen atmosphere usually at about 130 to about
160° C. for 10 minutes to 30 hours, preferably at about 140 to about 160°
C. to obtain acylation product.
Then, the present polyester can be obtained by the condensation polymerization
of the acylation products derived from parahydroxybenzoic acid and hydroquinone
with terephthalic acid and 2,6-naphthalenedicarboxylic acid, and fatty acid is
generated as by-product.
The condensation polymerization reaction is usually conducted at a temperature
in the range of from about 130 to about 400° C. while raising the temperature
at a rate of from about 0.1 to 50° C./min. It is more preferred that the reaction
is conducted preferably at a temperature in the range of from about 150 to about
350° C. while raising the temperature at a rate of from about 0.3 to about
5° C./min.
Upon the condensation polymerization reaction of the acylation products derived
from parahydroxybenzoic acid and hydroquinone with terephthalic acid and 2,6-naphthalenedicarboxylic
acid, the generated by-product fatty acid and unreacted fatty acid anhydride are
usually evaporated and distilled out from the system in order to shift the equilibrium.
In addition, by refluxing a part of the fatty acid which was distilled out so
that it returns to the reaction vessel, the acylation products, terephthalic acid,
2,6-naphthalenedicarboxylic acid, And the like which evaporate or sublime in association
with the fatty acid can also be returned to the reaction vessel.
For the purpose of accelerating the condensation polymerization reaction to increase
the polymerization rate, a slight amount of a catalyst may be added as needed as
long as object of the present invention is not obstructed. The catalyst which may
be added includes for example: germanium compounds such as germanium oxide and
the like; tin compounds such as stannous oxalate, stannous acetate, dialkyl tin
oxides, diaryl tin oxides and the like; titanium compounds such as titanium dioxide,
titanium alkoxide, alkoxy titanium silicates and the like; antimony compounds such
as antimony trioxide and the like; metal salts of an organic acid such as sodium
acetate, potassium acetate, calcium acetate, zinc acetate, ferrous acetate and
the like; Lewis acids such as boron trifluoride, aluminum chloride and the like;
amines; amides; inorganic acids such as hydrochloric acid, sulfuric acid and the like.
For the acylation reaction and the condensation polymerization reaction, a batch
apparatus or the like can be used equipped with a stirring apparatus such as anchor
blade, Faudler blade, comb-shaped agitating blade and the like.
It is recommended that thus resulting aromatic polyester is further subjected
to solid phase polymerization to obtain the present polyester (2). A process for
the solid phase polymerization may include for example, a process in which the
aromatic polyester obtained by the condensation polymerization reaction is cooled
and ground, and thereafter heated usually to about 230° C.-370° C. as
is in a solid state, and the like. The solid phase polymerization is usually conducted
under the reduced pressure or under an inert gas atmosphere such as nitrogen gas
and the like.
By regulating the reaction temperature and the reaction time in the condensation
polymerization reaction and the solid phase polymerization as well as distillation
rate of the by-product fatty acid and the like generated in the condensation polymerization
reaction and the like, flow beginning temperature of the resulting aromatic polyester
can be controlled. For example, when the reaction time in the solid phase polymerization
is shortened, aromatic polyester having low flow beginning temperature can be obtained.
When the reaction time in the solid phase polymerization is prolonged, aromatic
polyester having high flow beginning temperature can be obtained.
The flow beginning temperature of the present polyester (2) is usually from about
250 to about 400° C., and particularly preferably from about 270 to about
370° C.
The flow beginning temperature herein refers to a temperature at which the melting
viscosity of the polyester indicates 4800 Pa·s (48000 poise) when it is extruded
from a nozzle at a temperature elevation rate of 4° C./minute under load of
9.8 MPa (100 kg/cm
2), using a capillary type rheometer equipped with
a die having the inner diameter of 1 mm and the length of 10 mm.
Weight-average molecular weigh of the present polyester (2) is usually
from about 10000 to about 50000.
The molded article according to the present invention can be obtained in general,
by blending the present polyester (2) with filler and the like as needed, followed
by molding.
Examples of the filler includes glass fiber such as milled glass fiber,
chopped glass fiber and the like; inorganic fillers such as glass beads, hollow
glass bulbs, glass powder, mica, talc, clay, silica, alumina, potassium titanate,
wollastonite, calcium carbonate (heavy, light, colloidal and the like), magnesium
carbonate, basic magnesium carbonate, sodium sulfate, calcium sulfate, barium sulfate,
calcium sulfite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium
silicate, silica sand, silica rock, quartz, titanium oxide, zinc oxide, iron oxide
graphite, molybdenum, asbestos, silica alumina fiber, alumina fiber, gypsum fiber,
carbon fiber, carbon black, white carbon, diatomaceous earth, bentonite, sericite,
white sand, black lead and the like; metal or nonmetal whisker such as potassium
titanate whisker, alumina whisker, aluminum borate whisker, silicon carbide whisker,
silicon nitride whisker and the like; and the like. Among them, glass fiber, glass
powder, mica, talc, carbon fiber and the like are suitable.
Two or more of the fillers described above may be used in the molded article
according to the present invention. Further, the amount of the filler to be blended
in the molded article is usually about 400 parts by weight or less, preferably
from about 10 to 400 parts by weight, and more preferably from about 10 to 250
parts by weight per 100 parts by weight of the present polyester (2).
The filler may be those subjected to surface treatment. Methods for the surface
treatment include for example, a method in which a surface treatment agent is adsorbed
to the filler surface, a method in which a surface treatment agent is added when
the present polyester (2) and the filler are kneaded, and the like.
Examples of the surface treatment agent include reactive coupling agents
such as silane coupling agents, titanate coupling agents, borane coupling agents
and the like; lubricants such as higher fatty acids, higher fatty acid esters,
metal salts of higher fatty acid, fluorocarbon surfactants and the like.
The molded article according to the present invention may contain additives,
thermoplastic resin and the like. Examples of the additive include: mold release-improving
agents such as fluorine resins, metal soaps and the like; nucleating agents; antioxidants;
stabilizers; plasticizers; slipping agents; color protection agents; coloring agents;
ultraviolet light absorbers; antistatic agents; lubricants; flame retardants; and
the like.
Examples of the thermoplastic resin include polycarbonates, polyamides,
polysulfones, polyphenylene sulfides, polyphenylene ethers, polyether ketones,
polyetherimides and the like.
A process for producing the molded article includes for example: a process in
which
raw materials involving the present polyester (2), a filler, additives and the
like are added to a kneading machine such as single screw extruder, twin-screw
extruder, Banbury mixer, roller, Brabender, kneader and the like, followed by melting
and kneading, and then the materials are supplied to a molding machine such as
extrusion molding machine, injection molding machine, compression molding machine,
blow molding machine and the like to execute molding; a process in which the raw
materials are previously admixed using mortar, Henschel mixer, ball mill, ribbon
blender or the like, and thereafter, the addition, melting and kneading, and molding
in a similar manner to those as described above is carried out; a process in which
the raw materials are added to a reaction vessel followed by mixing; a process
in which the raw materials are supplied into a molding machine, and then molded
along with melting and mixing; and the like.
The molded articles according to the present invention can be molded into those
having various types of shapes such as fibers, films and the like. Moreover, as
they are excellent in formability, mechanical properties, electrical properties,
chemical resistance, heat resistance, oil resistance and impact resistance, they
can be used for, for example, machine parts such as cog wheels, gears, bearings,
motor accessories and the like; electric and electronic parts such as switches,
coil bobbins, relays, connectors, sockets and the like; accessories for office
and information equipment such as printers, copying machines, facsimile terminal
equipments, video cartridge recorders, video cameras, flexible disk drives, hard
disk drives, CD-ROM drives, magnetic optical disk drives and the like; process
associated parts for producing semiconductors such as IC trays, wafer carriers
and the like; cooking utensils such as pans for microwave cooking, ovenwares for
a bench oven and the like; i.e., large-sized molded articles and molded articles
having a complicated shape and the like.
By shaping the molded article of the present invention into film form or sheet
form, it can be used for display device parts, electrical insulation films, films
for a flexible circuit board, packaging films, films for recording medium and the like.
Additionally, the molded article shaped into fibrous form such as continuous
fiber, short fiber, pulp and the like can be used for clothing materials, heat
resistant thermal insulating materials, reinforcing materials for FRP, rubber reinforcing
materials, ropes, cables, nonwoven fabrics and the like.
The present invention is hereinafter explained by way of Examples, however, the
present invention is not limited by the Examples.
EXAMPLE 1
<Acylation Reaction>
Into a polymerization chamber replaced with nitrogen, were added 835.63 g of
parahydroxybenzoic acid ((M1), 6.05 mol), 272.52 g of hydroquinone ((M2), 2.475
mol), 123.35 g of terephthalic acid ((M3), 0.742 mol), 374.55 g of 2,6-naphthalenedicarboxylic
acid ((M4), 1.733 mol), 1349.55 g of acetic anhydride (13.22 mol) and 0.163 g of
1-methylimidazole as a heterocyclic organic base compound. After the mixture was
stirred at room temperature for 15 minutes, the temperature thereof was elevated
with stirring. When the inner temperature became 145° C., stirring was continued
for 30 minutes while the same temperature was kept.
<Condensation Polymerization Reaction>
Next, under a similar nitrogen atmosphere, the temperature of the mixture was
elevated from 145° C. to 310° C. over 3 hours while distilling out the
distilled by-product acetic acid and unreacted acetic anhydride. Thereafter, 1.426
g of 1-methylimidazole (hereinafter referred to as MI) was further added thereto,
and yielded an aromatic polyester after stirring the mixture at the same temperature
for 1 hour. Thus resulting aromatic polyester was cooled to room temperature, ground
with a grinding machine to give aromatic polyester powder (particle diameter being
about 0.1 mm-about 1 mm).
<Solid Phase Polymerization>
After the temperature of the powder obtained as described above was elevated
under a nitrogen atmosphere from 25° C. to 250° C. over 1 hour, it was
further elevated from the same temperature to 301° C. over 8 hours. Then,
the powder was kept at the same temperature for 5 hours to complete the solid phase
polymerization. Thereafter, the powder post solid phase polymerization was cooled,
and the powder post cooling (aromatic polyester) was subjected to measurement of
the flow beginning temperature using a flow tester (manufactured by Shimadzu Corporation,
"CFT-500 type"), which gave the result of being 323° C.
<Production Example of a Molded Article 1>
To the resultant aromatic polyester, was blended milled glass at 40% by weight,
and thereafter, the mixture was granulated at 350° C. using a twin-screw extruder
Thus resulting pellet was subjected to injection molding using an injection molding
machine at the cylinder temperature of 350° C. and at the mold temperature
of 130° C. The resulting molded article was subjected to measurement of the
flow beginning temperature in a similar manner described above, accompanied by
measurement of the tensile strength, impact strength and deflection temperature
under load as shown below. The results are summarized in Table 1.
(1) Tensile Strength
Tensile strength was measured in accordance with ASTM D638 using an ASTM4 dumbbell.
(2) Impact Strength
Impact strength was measured using a test article (without a notch) of 6.4×12.7×64
mm in accordance with ASTM D256.
(3) Deflection Temperature Under Load
A deflection temperature under load was measured in accordance with ASTM D648
at
1.82 MPa (18.6 kg/cm
2 load) using a test article having length of 127
mm, width of 12.7 mm and thickness of 6.4 mm.
EXAMPLE 2-5 Comparative Examples 1-2
In Examples 2-5, monomers (M1)-(M4), acetic anhydride and MI at a weight illustrated
in Table 1 were mixed, and the acylation reaction and condensation polymerization
reaction was carried out in accordance with Example 1. Then, the solid phase polymerization
was carried out until the reaction mixture reaches to the temperature (referred
to as solid phase polymerization temperature) described in Table 1.
In Comparative Example 1-2, similar operation to Example 1 was conducted except
that MI was not added and that the solid phase polymerization temperature was changed.
The results are summarized in Table 1 together with the molar ratio of (M1) per
total moles of the monomers converted to 100, and the molar ratio of (M3) and (M4)
represented by the formula (I) described above,
| Amount |
(M1) |
835.6 |
835.6 |
911.6 |
873.6 |
911.6 |
| charged (g) |
[mol %] |
[55] |
[55] |
[60] |
[57.5] |
[60] |
| |
(M2) |
272.5 |
272.5 |
242.2 |
257.4 |
242.2 |
| |
[mol %] |
[22.5] |
[22.5] |
[20.0] |
[21.25] |
[20.0] |
| |
(M3) |
123.4 |
102.8 |
109.7 |
106.8 |
91.37 |
| |
[mol %] |
[6.75] |
[5.62] |
[6.0] |
[5.84] |
[5.0] |
| |
(M4) |
374.6 |
401.3 |
332.9 |
366.4 |
356.7 |
| |
[mol %] |
[15.75] |
[16.88] |
[14.0] |
[15.41] |
[15.0] |
| |
MI |
1.43 |
1.43 |
1.41 |
1.42 |
1.42 |
| Monomer |
(M3)/ |
0.30 |
0.25 |
0.30 |
0.275 |
0.25 |
| charging |
[(M3) + (M4)] |
| ratio |
| Solid phase polymerization |
296 |
301 |
292 |
296 |
296 |
| temperature [° C.] |
| Aromatic |
Flow beginning |
323 |
321 |
329 |
322 |
321 |
| poly-ester |
temperature [° C.] |
| Molded |
Flow beginning |
307 |
304 |
312 |
305 |
306 |
| article |
temperature [° C.]# |
| |
Tensile strength |
152 |
153 |
152 |
150 |
143 |
| |
[MPa] |
| |
Tensile elongation |
10.7 |
11 |
10.2 |
10.6 |
9.9 |
| |
[%] |
| |
Flexural strength |
142 |
142 |
148 |
145 |
147 |
| |
[MPa] |
| |
Impact strength |
445 |
468 |
544 |
555 |
596 |
| |
[J/m] |
| |
Deflection |
287 |
286 |
292 |
286 |
286 |
| |
temperature under |
| |
load [° C.] |
| |
TABLE 1-2 |
| |
| |
Comparative example |
| Amount charged |
(M1) |
835.6 |
911.6 |
| (g) |
[mol %] |
[55] |
[60] |
| |
(M2) |
272.5 |
242.2 |
| |
[mol %] |
[22.5] |
[20.0] |
| |
(M3) |
123.4 |
91.37 |
| |
[mol %] |
[6.75] |
[5.0] |
| |
(4) |
374.6 |
356.7 |
| |
[mol %] |
[15.75] |
[15.0] |
| |
MI |
None |
None |
| Monomer |
(M3)/[(M3) + (M4)] |
0.30 |
0.25 |
| charging |
| ratio |
| Solid phase polymerization temperature [° C.] |
303 |
304 |
| Aromatic |
Flow beginning temperature |
322 |
323 |
| polyester |
[° C.] |
| Molded article |
Flow beginning temperature |
306 |
306 |
| |
[° C]# |
| |
Tensile strength [MPa] |
148 |
142 |
| |
Tensile elongation [%] |
9.8 |
9.7 |
| |
Flexural strength [MPa] |
142 |
142 |
| |
Impact strength [J/m] |
390 |
410 |
| |
Deflection temperature under |
282 |
284 |
| |
load [° C.] |
| (M1): 4-hydroxybenzoic acid |
| (M2): hydroquinone |
| (M3): terephthalic acid |
| (M4): 2,6-naphthalenedicarboxylic acid |
| MI: 1-methylimidazole |
| (I): a value represented by: [(M3)]/{[(M3)] + [(M4)]} (mol %) wherein
[(M3)] and [(M4)] represent number of moles of terephthalic acid (M3) and 2,6-naphthalenedicarboxylic
acid unit (4) |
| #a value measured with a pellet (molded article) obtained by granulation. |
Accordingly, the aromatic polyester of the present invention, which
is an aromatic polyester obtained from parahydroxybenzoic acid, hydroquinone, terephthalic
acid and 2,6-naphthalenedicarboxylic acid as monomers, has a low melting point
leading to excellent processing characteristics. Moreover, the molded article obtained
from the aromatic polyester is excellent in mechanical strength such as tensile
strength, flexure strength and the like, with excellent heat resistance such as
heat distortion temperature, and is also excellent in impact strength.
*
