WO2004078826A1 - Biodegradable alphatic polyester ionomeric resin and its preparing method - Google Patents
Biodegradable alphatic polyester ionomeric resin and its preparing method Download PDFInfo
- Publication number
- WO2004078826A1 WO2004078826A1 PCT/KR2003/000943 KR0300943W WO2004078826A1 WO 2004078826 A1 WO2004078826 A1 WO 2004078826A1 KR 0300943 W KR0300943 W KR 0300943W WO 2004078826 A1 WO2004078826 A1 WO 2004078826A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- aliphatic polyester
- ionomeric resin
- glycol
- polyaliphatic
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6888—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
Definitions
- the present invention relates to biodegradable aliphatic polyester
- ionomeric resin and a preparing method thereof, more particularly to aliphatic
- polyester ionomeric resin with significantly improved biodegradability prepared
- polyester resin is an aromatic compound with large
- polyaliphatic carboxylic acid to prepare an aliphatic polyester resin composition.
- biodegradable aliphatic polyester ionomeric resin and a preparing method thereof.
- FIG. 1 shows ⁇ H-NMR spectrum of the aliphatic polyester ionomeric resin
- FIG. 2 is a non-contact mode AFM (atomic force microscope) photograph
- FIG. 3 is a non-contact mode AFM photograph of the aliphatic polyester
- the present invention relates to biodegradable aliphatic polyester
- ionomeric resin comprising glycol 41 to 54 wt% of polyaliphatic (including cyclic
- polymers are chemically bonded to the alkali metal sulfonate.
- the present invention also relates to a method of preparing biodegradable
- the present invention provides environment-friendly biodegradable
- polyaliphatic glycol having at least two hydroxyl groups and polyaliphatic
- carboxylic acid having at least two carboxyl groups which has significantly
- ionomer refers to a material containing a small number of ionic
- the present invention is prepared by adding an ionic compound to polyaliphatic
- glycol and polycarboxylic acid to introduce ionic groups to the polymer chain of
- polyaliphatic glycol those having 2 to 20 carbon atoms, including cyclic
- glycol those having hydroxyl groups at both
- diol or its structural isomer such as ethylene glycol, 1,3-
- propanediol 1,2-butanediol, 1,4-butanediol,
- 1,6-hexanediol and 1,9-nonanediol may be used alone or in combination.
- 1,6-hexanediol and 1,9-nonanediol may be used alone or in combination.
- glycol having ether groups diethylene glycol, triethylene glycol or polyethylene
- glycol (molecular weight being 900 or smaller) may be used alone or in
- polyaliphatic carboxylic acid an acid anhydride thereof or a derivative
- polyaliphatic carboxylic acid selected from
- oxalic acid malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
- anhydride thereof or a derivative thereof may be used alone or in combination.
- the polyaliphatic glycol is used in 41 to 54 wt%, and the polyaliphatic
- carboxylic acid is used in 36 to 52 wt%. If the content of the polyaliphatic glycol
- the resulting polymer may have a low molecular weight.
- ionic compound aliphatic or aromatic alkali metal sulfonate
- sodium aliphatic or aromatic sulfonate may be used.
- sodium aliphatic or aromatic sulfonate preferably sodium aliphatic or aromatic sulfonate
- dibutyl-5-sulfoterephthalate may be used alone or in combination.
- ionic compound is used in 1 to 23 wt%. If the content is below 1 wt%, the ionic
- melt polymerization becomes difficult because the ionic salt becomes less soluble.
- biodegradable aliphatic polyester ionomeric resin of the present invention is a biodegradable aliphatic polyester ionomeric resin of the present invention.
- the monomers may be
- titanium butoxide, tin chloride or tetraisopropyl titanate may be used alone or in
- the catalyst is used in 0.05 to 2 wt% for the total aliphatic polyester
- ionomeric resin weight If the catalyst content is below 0.05 wt%, it becomes difficult to increase molecular weight because the catalyst activity does not last
- the polymer may be discolored. If the
- condensation polymerization temperature is below 220 ° C, the reaction is
- the polycondensation is carried out under high
- the aliphatic polyester ionomeric resin of the present invention comprising
- polyaliphatic glycol polyaliphatic carboxylic acid and ionic compound
- Oligomer prepared in the esterification step was cooled to 100 ° C, and 0.58 g of
- titanium isopropoxide catalyst was added. After mixing well, pressure was applied.
- FIG. 2 is
- FIG. 3 is a non-contact mode AFM photograph of the aliphatic
- polyester ionomeric resin prepared according to Comparative Example 1.
- Dispersed ion clusters measuring about 50 nm were found in FIG. 2, but not in FIG.
- Resin film with thickness ranging from 0.2 to 0.25 mm was cut into 2 x 5 cm size.
- the aliphatic polyester ionomeric resin of the present invention As described above, the aliphatic polyester ionomeric resin of the present invention
- the aliphatic polyester ionomeric resin of the present invention may be any suitable aliphatic polyester ionomeric resin.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a biodegradable aliphatic polyester ionomeric resin and its preparing method. More specifically, the present invention relates to a biodegradable aliphatic polyester ionomeric resin and its preparing method wherein said biodegradable aliphatic polyester ionomeric resin comprises a multivalent aliphatic glycol having at least two hydroxyl groups and a multivalent aliphatic carboxylic acid having at least two carboxyl groups as active ingredients and is further added with an ionic salt so that said ion can be incorporated into said polymer chain thereby remarkably improving biodegradability.
Description
BIODEGRADABLE ALIPHATIC POLYESTER IONOMERIC RESIN AND ITS
PREPARING METHOD
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to biodegradable aliphatic polyester
ionomeric resin and a preparing method thereof, more particularly to aliphatic
polyester ionomeric resin with significantly improved biodegradability prepared
by adding an ionic compound to polyaliphatic glycol having at least two hydroxyl
groups and polyaliphatic carboxylic acid having at least two carboxyl groups, and
a preparing method thereof.
Description of the Related Art
Commonly used polyester resin is an aromatic compound with large
molecular weight, which is produced by poly condensation of terephthalic acid
and ethylene glycol or terephthalic acid and 1,'4-butanediol. It is widely used in
fibers, bottles, films and so forth. However, since the aromatic polyester resin is
hardly decomposed when it is wasted, it often leads to serious environmental
pollution.
Accordingly, it has been under high social demands to develop
biodegradable plastics which may replace synthetic plastics considering
convenience and durability.
It is well known that aliphatic polyester is biodegradable (Journal of
Macromol. Sci-Chem., A-23(3), 1986, 393-409). It has been applied to the medicinal,
agricultural and fishery industries, as a result, researches on its use are in progress.
Biodegradable aliphatic polyester and copolyester resin compositions and
their preparing method thereof are disclosed in Korea Patent Publication Nos. 98-
082074, 99-009593, 00-0019012 and 01-0055721. However, the improvements of
the above-mentioned aliphatic polyester resin compositions have been largely
restricted to mechanical and physical properties, but not much advance was made
in biodegradability.
Although the conventional aliphatic polyesters exhibit a bit improved
biodegradability than aromatic polyester resins, they are disadvantageous in that
they decompose very slowly in nature thus not helping to reduce the
environmental pollution to the level of satisfaction.
SUMMARY OF THE INVENTION
The present inventors have found that biodegradability is greatly
improved when ionic compound is added to polyaliphatic glycol and
polyaliphatic carboxylic acid to prepare an aliphatic polyester resin composition.
Therefore, it is an object of the present invention to provide new
biodegradable aliphatic polyester ionomeric resin and a preparing method thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows αH-NMR spectrum of the aliphatic polyester ionomeric resin
prepared according to the Example 2 of the present invention.
FIG. 2 is a non-contact mode AFM (atomic force microscope) photograph
of the aliphatic polyester ionomeric resin prepared according to the Example 2 of
the present invention.
FIG. 3 is a non-contact mode AFM photograph of the aliphatic polyester
ionomeric resin prepared according to the Comparative Example 1 of the present
invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention relates to biodegradable aliphatic polyester
ionomeric resin comprising glycol 41 to 54 wt% of polyaliphatic (including cyclic
aliphatic), 36 to 52 wt% of polyaliphatic carboxylic acid or acid anhydride thereof
and 1 to 23 wt% of aliphatic or aromatic alkali metal sulfonate, wherein the resin
polymers are chemically bonded to the alkali metal sulfonate.
The present invention also relates to a method of preparing biodegradable
aliphatic polyester ionomeric resin comprising the steps of esterifying at 170 to
220 °C of a mixture comprising 41 to 54 wt% of polyaliphatic (including cyclic
aliphatic) glycol, 36 to 52 wt% of polyaliphatic carboxylic acid or acid anhydride
thereof and 1 to 23 wt% of aliphatic or aromatic alkali metal sulfonate, and
performing polycondensation at 220 to 260 °C by adding a polycondensation
catalyst.
Hereunder, the present invention is described in more detail.
The present invention provides environment-friendly biodegradable
aliphatic polyester ionomeric resin prepared by adding an ionic compound to
polyaliphatic glycol having at least two hydroxyl groups and polyaliphatic
carboxylic acid having at least two carboxyl groups, which has significantly
improved biodegradability due to the ions inserted in the polymer chain, and a
preparing method thereof.
In general, ionomer refers to a material containing a small number of ionic
groups in the nonpolar polymer chain. Since the polar ions present in the
nonpolar chain attract each other, it has totally different physical properties from
those of other polymers. The biodegradable aliphatic polyester ionomeric resin of
the present invention is prepared by adding an ionic compound to polyaliphatic
glycol and polycarboxylic acid to introduce ionic groups to the polymer chain of
the polyester resin. Hence, the aliphatic polyester resin has significantly
improved biodegradability.
As polyaliphatic glycol, those having 2 to 20 carbon atoms, including cyclic
aliphatic glycol, may be used. As glycols, those having hydroxyl groups at both
ends or those having ether groups may be used. As glycol having hydroxyl
groups at both ends, diol or its structural isomer, such as ethylene glycol, 1,3-
propanediol, neopentylglycol, propylene glycol, 1,2-butanediol, 1,4-butanediol,
1,6-hexanediol and 1,9-nonanediol, may be used alone or in combination. For the
glycol having ether groups, diethylene glycol, triethylene glycol or polyethylene
glycol (molecular weight being 900 or smaller) may be used alone or in
combination.
As polyaliphatic carboxylic acid, an acid anhydride thereof or a derivative
thereof, those having 2 to 12 carbon atoms, including cyclic aliphatic carboxylic
acid, are preferable. For example, polyaliphatic carboxylic acid selected from
oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
sebacinic acid, azelaic acid, nonanedicarboxylic acid and dimethylsuccinic acid, an
anhydride thereof or a derivative thereof may be used alone or in combination.
The polyaliphatic glycol is used in 41 to 54 wt%, and the polyaliphatic
carboxylic acid is used in 36 to 52 wt%. If the content of the polyaliphatic glycol
is below 41 wt%, the resulting polymer may have a low molecular weight. In
contrast, if it exceeds 54 wt%, the reaction is proceeded at a slower rate.
As an ionic compound, aliphatic or aromatic alkali metal sulfonate,
preferably sodium aliphatic or aromatic sulfonate, may be used. For example,
sodium 1,4-dihydroxybutanesulfonate, sodium dimethyl-5-sulfoisophthalate,
sodium diethyl-5-sulfoisophthalate, sodium dibutyl-5-sulfoisophthalate, sodium
dimethyl-5-sulfoterephthalate, sodium diethyl-5-sulfoterephthalate or sodium
dibutyl-5-sulfoterephthalate may be used alone or in combination. The above
ionic compound is used in 1 to 23 wt%. If the content is below 1 wt%, the ionic
compound does not offer significant effect. In contrast, if it exceeds 50 wt%, the
melt polymerization becomes difficult because the ionic salt becomes less soluble.
The biodegradable aliphatic polyester ionomeric resin of the present
invention with ionic compound introduced, has inherent viscosity of ranging from
0.1 to 2.3, melting point of ranging from 104 to 114 °C and glass transition
temperature of ranging from -22 to 3 °C . More importantly, it has 1.2 to 5 times
superiorities in biodegradability to the conventional aliphatic polyester resins.
Hereunder, the preparing method of aliphatic polyester ionomeric resin of
the present invention is described in detail.
First, 41 to 54 wt% of polyaliphatic (including cyclic aliphatic) glycol
having at least two hydroxyl groups, 36 to 52 wt% of polyaliphatic carboxylic
acid having at least two carboxyl groups, an acid anhydride thereof or a derivative
thereof and 1 to 23 wt% of ionic compound are added at 170 to 220 °C for
esterification. If the reaction temperature is below 170 °C, the esterification is
proceeded at a slower rate. In contrast, if it exceeds 220 °C, the monomers may be
decomposed.
After the esterification is completed, polycondensation is proceeded at 220
to 260 °C in the presence of polycondensation catalyst. For the polycondensation
catalyst, magnesium acetate, tetrapropyl titanate, zinc acetate, tetrabutyl titanate,
dibutyl tin oxide, tetrapropyl titanate, calcium acetate, titanium isopropoxide,
titanium butoxide, tin chloride or tetraisopropyl titanate may be used alone or in
combination. The catalyst is used in 0.05 to 2 wt% for the total aliphatic polyester
ionomeric resin weight. If the catalyst content is below 0.05 wt%, it becomes
difficult to increase molecular weight because the catalyst activity does not last
long. In contrast, if it exceeds 2 wt%, the polymer may be discolored. If the
condensation polymerization temperature is below 220 °C, the reaction is
proceeded at a slower rate. In contrast, if it exceeds 260 °C, thermal
decomposition may occur. The polycondensation is carried out under high
vacuum, preferably at 0.1 torr or lower. If the pressure exceeds 0.1 torr, it
becomes difficult to obtain large molecular weight. Preferably, the
polycondensation is proceeded for 50 to 250 minutes, although dependent on the
catalyst content.
The aliphatic polyester ionomeric resin of the present invention comprising
polyaliphatic glycol, polyaliphatic carboxylic acid and ionic compound has
improved water permeability due to introduction of ionic groups in the polymer
chain, and thus significantly improved biodegradability.
EXAMPLES
Hereinafter, the present invention is described in more detail by the
following Examples. However, they shall not be construed as limiting the scope
of the present invention.
Examples 1 to 9 and Comparative Examples 1 to 2 : Preparation of aliphatic
polyester resin
After purging an empty 400 mL 4-bulb condensation reactor with nitrogen
gas, a mixture according to the composition in Table 1 below was added.
Esterification was carried out at 200 °C . After adding the above mixture, the
reaction was terminated 90 to 120 minutes after there is no more evaporation of
water at 200 °C . Water generated during esterification was removed from the
reaction system using a distillator.
After esterification was completed, polycondensation was carried out.
Oligomer prepared in the esterification step was cooled to 100 °C, and 0.58 g of
titanium isopropoxide catalyst was added. After mixing well, pressure was
slowly lowered to high vacuum (0.1 torr or below). Slowly heating to 230 °C,
polycondensation was proceeded for 150 to 180 minutes to obtain polyester resin.
Introduction of sodium ions in the aliphatic polyester ionomeric resin
prepared according to the Example 2 of the present invention was identified by
Η-NMR. The Η-NMR spectrum is shown in FIG. 1.
Ion clusters are formed on the surface of the polyester ionomer. FIG. 2 is
a non-contact mode AFM photograph showing the surface of the aliphatic
polyester ionomeric resin prepared according to the Example 2 of the present
invention. And, FIG. 3 is a non-contact mode AFM photograph of the aliphatic
polyester ionomeric resin prepared according to Comparative Example 1.
Dispersed ion clusters measuring about 50 nm were found in FIG. 2, but not in FIG.
3.
Experimental Example: Physical property measurement of aliphatic polyester
resin
Physical properties of polyester resins prepared in Examples 1 to 9 and
Comparative Examples 1 to 2 were measured by the following method. The
result is shown in Table 2 below.
Inherent viscosity was measured at 30 °C using phenol and 1,1,2,2-
tetrachloroethane. Melting point was determined with a differential scanning
calorimeter (DSC) at a heating rate of 10 °C/min. Glass transition temperature
was determined by the peak value of the tan δ curve using dynamic mechanical
analysis (DMA). Tensile strength and elongation were determined using a
universal testing machine (UTM). Hydrolysis test was performed under pH 12.
Resin film with thickness ranging from 0.2 to 0.25 mm was cut into 2 x 5 cm size.
The samples were completely immersed in caustic soda solution at 40 °C . Weight
loss was checked every day for 30 days.
Table 1
Table 2
As shown in Table 2, the aliphatic polyester ionomeric resin of the present
invention has significantly improved biodegradability.
As described above, the aliphatic polyester ionomeric resin of the present
invention has improved hydrophilicity due to introduction of ionic groups in the
polymer chain. Therefore, it has resulted in significant improvement in
hy dr oly zability .
The aliphatic polyester ionomeric resin of the present invention may
outstandingly reduce environmental pollution when used in place of the
conventional non-decomposable plastics. Because it can be processed into a
variety of plastic gods, including consumer goods, agricultural goods and
industrial films, it is expected to have a great commercial value with regard to
ever-increasing international environment regulations.
While the present invention has been described referring to the preferred
embodiments, those skilled in the art will appreciate that various modifications
and substitutions can be made thereto without departing from the spirit and scope
of the present invention as set forth in the appended claims.
Claims
1. Biodegradable aliphatic polyester ionomeric resin comprising 41 to 54
wt% of polyaliphatic (including cyclic aliphatic) glycol, 36 to 52 wt% of
polyaliphatic carboxylic acid or its acid anhydride, and 1 to 23 wt% of aliphatic or
aromatic alkali metal sulfonate, wherein the resin molecules are chemically
bonded to said alkali metal sulfonate.
2. The biodegradable aliphatic polyester ionomeric resin according to
Claim 1, wherein said aliphatic polyester ionomeric resin has inherent viscosity of
ranging from 0.1 to 2.3, melting point of ranging from 60 to 130 °C and glass
transition temperature of ranging from -50 to 50 °C .
3. The biodegradable aliphatic polyester ionomeric resin according to
Claim 1, wherein said polyaliphatic glycol is a mixture of at least one compounds
selected from the group consisting of ethylene glycol, 1,3-propanediol,
neopentylglycol, propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol,
1,9-nonanediol, diethylene glycol, triethylene glycol and polyethylene glycol.
4. The biodegradable aliphatic polyester ionomeric resin according to
Claim 1, wherein said polyaliphatic carboxylic acid is a mixture of at least one
compounds selected from the group consisting of oxalic acid, malonic acid,
succinic acid, glutaric acid, adipic acid, pimelic acid, sebacinic acid, azelaic acid,
nonanedicarboxylic acid or dimethylsuccinic acid, an anhydride thereof and a
derivative thereof.
5. The biodegradable aliphatic polyester ionomeric resin according to
Claim 1, wherein said aliphatic or aromatic alkali metal sulfonate is a mixture of at
least one compounds selected from the group consisting of sodium 1,4-
dihydroxybutane-2-sulfonate, sodium dimethyl-5-sulfoisophthalate, sodium
diethyl-5-sulfoisophthalate, sodium dibutyl-5-sulfoisophthalate, sodium dimethyl-
5-sulfoterephthalate, sodium diethyl-5-sulfoterephthalate and sodium dibutyl- 5-
sulf oterephthalate .
6. A method of preparing biodegradable aliphatic polyester ionomeric
resin comprising the steps of:
etherifying a mixture at 170 to 220 °C comprising 41 to 54 wt% of
polyaliphatic (including cyclic aliphatic) glycol, 36 to 52 wt% of polyaliphatic carboxylic acid or an acid anhydride thereof and 1 to 23 wt% of aliphatic or
aromatic alkali metal sulfonate; and
performing polycondensation the same at 220 to 260 °C by adding a
polycondensation catalyst.
7. The method of preparing biodegradable aliphatic polyester ionomeric
resin according to Claim 6, wherein said polycondensation catalyst is a mixture of
at least one compounds selected from the group consisting of magnesium acetate,
tetrapropyl titanate, zinc acetate, tetrabutyl titanate, dibutyl tin oxide, calcium
acetate, titanium isopropoxide, titanium butoxide, tin chloride and tetraisopropyl
titanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003230336A AU2003230336A1 (en) | 2003-03-04 | 2003-05-13 | Biodegradable alphatic polyester ionomeric resin and its preparing method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2003-0013403A KR100537211B1 (en) | 2003-03-04 | 2003-03-04 | Biodegradable aliphatic polyester ionomeric resin and its preparing method |
| KR10-2003-0013403 | 2003-03-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004078826A1 true WO2004078826A1 (en) | 2004-09-16 |
Family
ID=32960165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2003/000943 WO2004078826A1 (en) | 2003-03-04 | 2003-05-13 | Biodegradable alphatic polyester ionomeric resin and its preparing method |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100537211B1 (en) |
| AU (1) | AU2003230336A1 (en) |
| WO (1) | WO2004078826A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700050A (en) * | 2015-07-15 | 2017-05-24 | 大爱感恩科技股份有限公司 | Composition for preparing hydrophilic polyester, hydrophilic polyester, and preparation method of hydrophilic polyester |
| CN116813897A (en) * | 2023-05-22 | 2023-09-29 | 苏州奥凯高分子材料股份有限公司 | PET nucleating agent and preparation method and application thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100952724B1 (en) | 2006-12-12 | 2010-04-13 | 주식회사 엘지화학 | Method for Synthesizing Biodegradable Polyester Containing Aliphatic and Aromatic Compound |
| KR100983019B1 (en) * | 2008-03-14 | 2010-09-17 | 한양대학교 산학협력단 | Organic-inorganic hybrid complex, method for preparing the organic-inorganic hybrid complex, and artificial hard tissue comprising the same |
| KR101386222B1 (en) * | 2012-06-27 | 2014-04-17 | 롯데케미칼 주식회사 | Preparation method of aliphatic polyester resin |
| KR101716004B1 (en) * | 2014-11-11 | 2017-03-13 | 롯데케미칼 주식회사 | Preparation method of aliphatic copolyester resin |
| KR102607932B1 (en) * | 2021-06-01 | 2023-12-01 | (주)포스코이앤씨 | Eco-friendly biodegracable resin based dust reducing agent and manufacturing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR940014497A (en) * | 1992-12-24 | 1994-07-18 | 김준웅 | Thermoplastic Biodegradable Resin and Manufacturing Method Thereof |
| JPH093299A (en) * | 1995-06-15 | 1997-01-07 | Tonen Chem Corp | Polypropylene composition |
| US6018004A (en) * | 1994-11-15 | 2000-01-25 | Basf Aktiengesellschaft | Biodegradable polymers, preparation thereof and use thereof for producing biodegradable moldings |
| US6368710B1 (en) * | 2000-12-19 | 2002-04-09 | E. I. Du Pont De Nemours And Company | Sulfonated aliphatic-aromatic copolyesters |
| JP2002171846A (en) * | 2000-09-29 | 2002-06-18 | Sekisui Chem Co Ltd | Biodegradable film for agriculture |
-
2003
- 2003-03-04 KR KR10-2003-0013403A patent/KR100537211B1/en not_active IP Right Cessation
- 2003-05-13 AU AU2003230336A patent/AU2003230336A1/en not_active Abandoned
- 2003-05-13 WO PCT/KR2003/000943 patent/WO2004078826A1/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR940014497A (en) * | 1992-12-24 | 1994-07-18 | 김준웅 | Thermoplastic Biodegradable Resin and Manufacturing Method Thereof |
| US6018004A (en) * | 1994-11-15 | 2000-01-25 | Basf Aktiengesellschaft | Biodegradable polymers, preparation thereof and use thereof for producing biodegradable moldings |
| JPH093299A (en) * | 1995-06-15 | 1997-01-07 | Tonen Chem Corp | Polypropylene composition |
| JP2002171846A (en) * | 2000-09-29 | 2002-06-18 | Sekisui Chem Co Ltd | Biodegradable film for agriculture |
| US6368710B1 (en) * | 2000-12-19 | 2002-04-09 | E. I. Du Pont De Nemours And Company | Sulfonated aliphatic-aromatic copolyesters |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700050A (en) * | 2015-07-15 | 2017-05-24 | 大爱感恩科技股份有限公司 | Composition for preparing hydrophilic polyester, hydrophilic polyester, and preparation method of hydrophilic polyester |
| CN106700050B (en) * | 2015-07-15 | 2018-11-30 | 大爱感恩科技股份有限公司 | It is used to prepare composition, the hydrophilic polyester and preparation method thereof of hydrophilic polyester |
| CN116813897A (en) * | 2023-05-22 | 2023-09-29 | 苏州奥凯高分子材料股份有限公司 | PET nucleating agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100537211B1 (en) | 2005-12-16 |
| KR20040078454A (en) | 2004-09-10 |
| AU2003230336A1 (en) | 2004-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2797945C (en) | Aliphatic-aromatic copolyesters and their mixtures | |
| JPH06293826A (en) | Thermoplastic biodegradable resin and its production | |
| KR20110112340A (en) | Copolyesters with enhanced tear strength | |
| NZ201954A (en) | Linear polyesters containing hydroxy-bis(hydroxyalkoxy)-xanth-9-one residues | |
| KR20110112339A (en) | Copolyesters with enhanced tear strength | |
| US4097431A (en) | Aromatic copolyester composition | |
| US5360900A (en) | Aromatic polyester polyol | |
| WO2004078826A1 (en) | Biodegradable alphatic polyester ionomeric resin and its preparing method | |
| US10106642B2 (en) | Biodegradable copolyesters | |
| EP0711315B1 (en) | A process for preparing hydrolytically stable poly(ethylene-2,6-naphthalene dicarboxylate) polymers | |
| KR20150017797A (en) | Eco-friendly Copolyester Resin and Process of Preparing Same | |
| US6027818A (en) | Thermoplastic copolyester compositions modified with epoxide compounds | |
| KR100849206B1 (en) | Manufacturing method of biodegradable water-based polyester resin | |
| US4309518A (en) | Molding compositions containing high-molecular weight linear polyester | |
| KR20040030813A (en) | Amorphous copolyesters | |
| US6114496A (en) | Biodegradable resin composition and preparation process thereof | |
| CN110914334A (en) | Polyester copolymer | |
| JP2004211008A (en) | Biodegradable copolymer and manufacturing method thereof | |
| JPWO2020004350A1 (en) | Copolymerized polyester composition | |
| KR100349595B1 (en) | Process for producing biodegradable copolyester | |
| JP2848640B2 (en) | Low water absorbing polyester resin composition | |
| JP2006348141A (en) | Polylactic acid resin composition | |
| JP3658479B2 (en) | Polyester resin | |
| JP3284090B2 (en) | Hydrophilic material for film or sheet formation | |
| KR0121996B1 (en) | Biodegrable aliphatic polyester resin composition and method for making thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| 122 | Ep: pct application non-entry in european phase | ||
| NENP | Non-entry into the national phase |
Ref country code: JP |
|
| WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |