KR20120076149A - Self-recovering polyester resin having excellent suppleness and elasticity, and its preparation - Google Patents
Self-recovering polyester resin having excellent suppleness and elasticity, and its preparation Download PDFInfo
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- KR20120076149A KR20120076149A KR1020100138178A KR20100138178A KR20120076149A KR 20120076149 A KR20120076149 A KR 20120076149A KR 1020100138178 A KR1020100138178 A KR 1020100138178A KR 20100138178 A KR20100138178 A KR 20100138178A KR 20120076149 A KR20120076149 A KR 20120076149A
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- South Korea
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- polyester resin
- weight
- cyclohexanediol
- polycarbonate diol
- reaction
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- 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
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
The present invention relates to a polyester resin and a method for producing the same, and more particularly, to a polyester resin containing cyclohexanediol and polycarbonate diol and a method for producing the same.
In general, polyester resins are inexpensive and have excellent mechanical and chemical properties. They are widely used in construction and industrial resins. They are often used in interior materials such as automotive air cleaners, oil filters, wheels, and bumpers, as well as in primers, intermediates and top coats. It is widely used in the same automotive paints. When polyester is used in various industrial interior materials or paints, properties required include durability, scratch resistance, chipping resistance, acid resistance, and flexibility.
Durability and scratch resistance means resistance to scratches on the surface of the coating film, and the chipping resistance means durability against coating damage that the film is peeled off by external impact or reaches the steel sheet. The acid resistance is due to the effects of wild bird droppings or acid rain due to the recent severe air pollution, the surface of the coating film is damaged, stains and irregularities are often generated on the surface of the coating, which means resistance to this. Flexibility means the property of improving the moldability of a coating film by appropriate paint viscosity. Accordingly, research for improving the quality of the polyester resins used in industrial interior materials and various paints has been steadily progressed.
As a related art relating to a method for producing a polyester resin for coating, Korean Patent Application No. 1991-18269 is known for a method for producing a polyester resin for coating by modifying two kinds of polyesters with aliphatic diisocyanate. If it is used as an industrial paint has the advantage of excellent cold resistance adhesion. However, when it is used as an industrial paint, the adhesion is improved, but there is a problem that the hardness and smoothness worsens.
In addition, Korean Patent No. 456970 is known for a coating composition using a urethane-modified polyester resin. However, in this case, the durability of the coating film is reduced, and it is still necessary to use a solvent for viscosity adjustment in order to adjust the viscosity of the paint.
Existing polyester resins as described above have the disadvantage of low flexibility and formability due to the limitation of molecular structure and chain length of the dihydroxy compound and the dicarboxylic acid compound as a basic raw material, and the high viscosity of the synthesized resin In addition, there was a non-environmental problem in that a viscosity adjusting solvent should be used.
An object of the present invention is to provide a polycarbonate diol-containing polyester resin with improved elasticity and flexibility by adding cyclohexanediol and polycarbonate diol to the polyester resin.
According to a preferred embodiment of the present invention to solve the above problems, a first step of esterifying a dicarboxylic acid compound and a dihydroxy compound including cyclohexanediol in 1: 0.7 to 1: 0.9 equivalent ratio; And a second step of adding 15 wt% to 50 wt% of the polycarbonate diol to the product of the reaction, wherein the cyclohexanediol is 5 wt% to 25 wt% of the total resin weight. The manufacturing method of this containing polyester resin is provided.
According to another suitable embodiment of the present invention, the first step is a step heating step in a section 150 ~ 200 ℃, the second step is a step temperature up to 180 ℃ or more after adding polycarbonate diol at a temperature less than 180 ℃ It is characterized by going through the process.
According to another suitable embodiment of the present invention, there is provided a polyester resin containing a polycarbonate diol according to the above production method having a number average molecular weight of 3,000 to 5,000 and the following formula.
The polyester resin of the present invention exhibits superior properties in flexibility and elasticity than conventional polyester resins. Through this, it can be usefully used for automotive paints and various other applications such as various industrial coatings that require flexibility and elasticity. In addition, since the viscosity is lower than the same molecular weight of the existing polyester resin can reduce the amount of solvents used for the purpose of viscosity dilution can exhibit an environmentally friendly effect.
Polycarbonate diol is a compound containing a carbonate structure and has excellent physical properties such as flexibility and surface hardness and durability, and is mainly used as a raw material for high-quality polyurethane resins. It has a hydroxyl group at both ends of the molecular chain and can react with the dicarboxylic acid compound to produce an ester bond, which is applicable to polyester resins. In addition, unlike the basic raw materials of the conventional polyester resin has a long chain structure in the molecular chain can be expected excellent properties in terms of flexibility. However, the problem of deterioration of the inherent elasticity of the coating due to the low glass transition temperature and maximization of the flexibility may be caused. In order to compensate for this, the present invention adds cyclohexanediol having a cyclic structure to satisfy flexibility and elasticity at the same time. The present invention aims to provide a polyester resin having excellent self-recovery from physical damage.
In order to provide a polyester resin with improved flexibility and elasticity, the present invention synthesizes a polyester resin including cyclohexanediol primarily and composed of carboxylic acid at both ends thereof, and secondarily changes the temperature conditions of the polycarbonate. Diol is further added to prepare a polyester resin containing polycarbonate diol.
The present invention comprises a first step of esterifying a dicarboxylic acid compound and a dihydroxy compound including cyclohexanediol in a ratio of 1: 0.7 to 1: 0.9 equivalents; And a second step of adding 15 wt% to 50 wt% of the polycarbonate diol to the total weight of the resin in the product of the reaction, wherein the cyclohexanediol is 5 wt% to 25 wt% of the total weight of the resin. The manufacturing method of this containing polyester resin is provided.
The polyester resin of the present invention primarily reacts a dihydroxy compound including a dicarboxylic acid compound and a cyclohexanediol to form an ester bond. At this time, by reacting 1: 0.7 ~ 1: 0.9 in the equivalent ratio of the dicarboxylic acid compound and the dihydroxy compound to prepare a resin having a carboxyl group.
When the equivalent weight of the dihydroxy compound compared to the dicarboxylic acid compound is less than 0.7, the ester coupling reaction does not sufficiently occur. When the equivalent weight of the dihydroxy compound is greater than 0.9, the chain structure in the polyester molecule is reduced, and the elongation of the resin is lowered.
As the dicarboxylic acid compound constituting the polyester resin of the present invention, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenylcarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid, cyclo One or more compounds selected from the group consisting of dicarboxylic acids such as hexanedicarboxylic acid, adipic acid and sebacic acid and alkyl, alkoxy and haloken-substituted derivatives thereof, and ester forming derivatives such as respective dimethyl esters, may be used. Can be.
Examples of the dihydroxy compound constituting the polyester resin of the present invention include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hydroquinone, resorcinol, hydroxyphenyl, naphthalenediol, dihydroxydiphenyl ether, and cyclohexanediol. , Dihydroxy compounds such as 2,2-bis (4-hydroxyphenyl) propane, polycarbonatediol and diethoxylated bisphenol A themselves: the group consisting of polyoxyalkylene glycols and alkyl, alkoxy or halogen-substituted derivatives thereof One or more compounds selected from can be used.
In addition, polyesters having a branched or crosslinkable structure made using a small amount of trifunctional or higher monomers may also be used in the present invention, and the trifunctional monomers are for example trimellitic acid, trimesic acid and pyromelli Triacid, pentaerythritol, trimethylolpropane and the like.
The content of the cyclohexanediol is 5 to 25% by weight based on the total weight of the polyester resin, the content of the polycarbonate diol can be adjusted to 15 to 50% by weight relative to the total weight of the polyester resin. The content of the cyclohexanediol is preferably 5 to 25% by weight based on the total weight, more preferably 10 to 20% by weight relative to the total weight. When the content of cyclohexanediol is less than 5% by weight, the degree of scratch recovery is insufficient, and when the content of cyclohexanediol is more than 25% by weight, the flexibility is inferior. On the other hand, the content of the polycarbonate diol is preferably 15 to 50% by weight based on the total weight, more preferably 25 to 35% by weight relative to the total weight. When the polycarbonate diol is less than 15% by weight, the effect of improving the elongation is small, and when it is more than 50% by weight, the tensile strength is lowered.
In another aspect, the present invention is characterized in that the first step is subjected to a step temperature rising process in the 150 ~ 200 ℃ section, the second step is a step temperature rising process to more than 180 ℃ after adding the polycarbonate diol at a temperature less than 180 ℃ There is this. Since the pyrolysis temperature of the polycarbonate diol starts at 220 ° C. or more, the compound having much of the dicarboxyl group is reacted at a high temperature, and when the reaction is stabilized, the polycarbonate diol is introduced by lowering the temperature. Thereafter, the temperature was raised to 180 ° C. in a step temperature raising method for a stable reaction, and the reaction was terminated at a point of 5 or less.
The polymerization reaction temperature of the ester bond is 150 ° C. or more, and condensation water is generated while the condensation reaction of the carboxyl group and the hydroxyl group proceeds. When the reaction temperature is lower than 150 ℃, the reaction does not occur smoothly. Especially when using a material with high melting point such as terephthalic acid or isophthalic acid, the reaction must proceed at a temperature higher than the melting point of the raw material. Problems arise in terms of the stability of the polycarbonate diol which starts to decompose. Therefore, when using a raw material with a melting point of 180 ° C. or higher, a primary polyester resin having a carboxyl group except for polycarbonate diol is prepared, and then polycarbonate diol is added at a temperature below 180 ° C. Polyester resin is prepared.
In another aspect, the present invention provides a polyester resin containing a cyclohexanediol and polycarbonate diol according to the manufacturing method number average molecular weight of 3,000 ~ 50,000. Since the polyester resin according to the present invention contains a large amount of hydroxyl groups, it can be cured using a melamine curing agent, an isocyanate series curing agent, or the like.
Hereinafter, the present invention will be described in detail with reference to Examples. However, the scope of the present invention is not limited by the following examples.
≪ Example 1 >
Preparation of polyester resin containing 3% by weight of cyclohexanediol and 32% by weight of polycarbonate diol
(In the above structural formula, n is a positive integer.)
The reaction scheme briefly illustrates a process for preparing a polyester resin containing cyclohexanediol and polycarbonate diol according to an embodiment of the present invention. A four-necked flask of 500 mL was attached with a thermometer, condenser, stirrer and heater. 18% by weight of phthalic anhydride, 22% by weight of isophthalic acid as dicarboxylic acid compound, 3% by weight of 1,4 cyclohexanediol as dihydroxy compound, 3% by weight of ethylene glycol, 10% by weight of trimethylol propane, 1,6 12 wt% hexanediol and 32 wt% polycarbonatediol were used. Then, the temperature is raised to about 150 ° C. under a nitrogen atmosphere, and the temperature is increased to 200 ° C. in a step to carry out the polymerization reaction of the dicarboxylic acid compound and the dihydroxy compound. As a result of the reaction, a polymer having an equivalence ratio of dicarboxylic acid compound and dihydroxy compound of 1: 0.9 was formed, and after removing the condensed water generated in the reaction, the reaction temperature was lowered to 100 ° C. and 32 wt% of polycarbonate diol was added thereto. After that, the temperature was raised to 180 ° C. for the ester coupling reaction. The reaction progress was observed by measuring the acid value using 0.1 N KOH solution. When the acid value of the compound drops below 5, the reaction is terminated to obtain a polyester resin containing cyclohexanediol and polycarbonate diol having a solid content of 100%.
<Example 2>
Preparation of polyester resin containing 5% by weight of cyclohexanediol and 32% by weight of polycarbonate diol
A four-necked flask of 500 mL was attached with a thermometer, condenser, stirrer and heater. 18% by weight of phthalic anhydride, 22% by weight of isophthalic acid as dicarboxylic acid compound, 5% by weight of 1,4 cyclohexanediol as dihydroxy compound, 3% by weight of ethylene glycol, 10% by weight of trimethylol propane, 1,6 10 wt% hexanediol and 32 wt% polycarbonatediol were used. Then, the temperature is raised to about 150 ° C. under a nitrogen atmosphere, and the temperature is increased to 200 ° C. in a step to carry out the polymerization reaction of the dicarboxylic acid compound and the dihydroxy compound. As a result of the reaction, a polymer having an equivalence ratio of 1: 0.9 of the dicarboxylic acid compound and the dihydroxy compound was formed, and after removing the condensation water generated in the reaction, the reaction temperature was lowered to 100 ° C. and 32 wt% of polycarbonate diol was added thereto. Thereafter, the temperature is raised to 180 ° C. to effect ester bonding. The reaction progress was observed by measuring the acid value using 0.1 N KOH solution. When the acid value of the composite drops to 5 or less, the reaction is terminated to obtain a polyester resin containing cyclohexanediol and polycarbonate diol having a solid content of 100%.
<Example 3>
Preparation of polyester resin containing 8% by weight of cyclohexanediol and 32% by weight of polycarbonatediol
A four-necked flask of 500 mL was attached with a thermometer, condenser, stirrer and heater. 18% by weight of phthalic anhydride, 22% by weight of isophthalic acid as dicarboxylic acid compound, 8% by weight of 1,4 cyclohexanediol as dihydroxy compound, 3% by weight of ethylene glycol, 10% by weight of trimethylol propane, 1,6 7 wt% hexanediol and 32 wt% polycarbonatediol were used. Then, the temperature is raised to about 150 ° C. under a nitrogen atmosphere, and the temperature is increased to 200 ° C. in a step to carry out the polymerization reaction of the dicarboxylic acid compound and the dihydroxy compound. As a result of the reaction, a polymer having an equivalence ratio of dicarboxylic acid compound and dihydroxy compound of 1: 0.9 was formed, and after the condensation water generated in the reaction was removed, the reaction temperature was lowered to 100 ° C., and 32 wt% of polycarbonate diol was added thereto. Thereafter, the temperature is raised to 180 ° C. to effect ester bonding. The reaction progress was observed by measuring the acid value using 0.1 N KOH solution. When the acid value of the composite drops to 5 or less, the reaction is terminated to obtain a polyester resin containing cyclohexanediol and polycarbonate diol having a solid content of 100%.
Comparative Example
Top coat for general automotive
The physical properties were compared by acquiring the acryl-melamine cured top coats commonly used by Fiji, an automobile paint manufacturer.
Car Wash Test Results (AMTEC KISTLER LABORATORY CAR WASH)
After forming the cured coating film of the polyester resin obtained in the Example, the physical properties were evaluated. In order to measure the scratch resistance of the cured coating film, we used DIN 55668, AMTEC KISTLER LABORATORY CAR WASH, a pre-washing test for automotive topcoat. The extent of restoration was evaluated. The glossiness of the coating film was measured at 20 ° angle according to the ASTM D 2457 method. The thickness of the cured coating film was about 50 μm, and the curing agent used was Cymel 303 manufactured by methylated melamine-based Cytec Co., Ltd., and curing was performed under curing conditions at 150 ° C. for 1 hour. Heat treatment for self-restoration was carried out using a hot air drying oven at 100 ℃, 10 minutes conditions.
Car wash results are shown in Table 1 below.
(20 °)
(20 °)
※ Restoration rate (%) = Gloss before washing / Gloss after heat treatment x 100
Comparative Example 1 is an acryl-melamine cured product, which is generally used as a top coat for automobiles, in order to distinguish it from the examples. As a result of washing, constant gloss deterioration occurred, and self-restore was hardly performed even after heat treatment. Able to know. Examples 1 to 3 are properties of the cured coating film prepared by fixing the content of polycarbonate diol and adjusting the content of cyclohexanediol. As the content of cyclohexanediol increased, the elasticity of the coating film increased, resulting in a decrease in gloss after washing, but the self-recovery rate after heat treatment under 100 ° C. for 10 minutes was reversed. The scratch resilience for use as an automotive top coat was found to be the best polyester resin containing 8% by weight of cyclohexanediol of Example 3, 32% by weight of polycarbonatediol.
Claims (3)
A second step of adding 15 to 50% by weight of the polycarbonate diol to the total weight of the resin to the product of the reaction,
Method for producing a polyester resin containing polycarbonate diol, wherein the cyclohexanediol is 5 to 25% by weight relative to the total weight of the resin.
(n is a positive integer)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100138178A KR20120076149A (en) | 2010-12-29 | 2010-12-29 | Self-recovering polyester resin having excellent suppleness and elasticity, and its preparation |
| PCT/KR2011/001501 WO2012091218A1 (en) | 2010-12-29 | 2011-03-04 | Self-recovery polyester resin containing highly flexible polycarbonate diol and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100138178A KR20120076149A (en) | 2010-12-29 | 2010-12-29 | Self-recovering polyester resin having excellent suppleness and elasticity, and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20120076149A true KR20120076149A (en) | 2012-07-09 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020100138178A KR20120076149A (en) | 2010-12-29 | 2010-12-29 | Self-recovering polyester resin having excellent suppleness and elasticity, and its preparation |
Country Status (2)
| Country | Link |
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| KR (1) | KR20120076149A (en) |
| WO (1) | WO2012091218A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150097902A (en) | 2014-02-18 | 2015-08-27 | 경북대학교 산학협력단 | self-healing Polyurethane Coatings |
| WO2018190647A2 (en) | 2017-04-13 | 2018-10-18 | 주식회사 쎄코 | Self-healing functional polyvinyl-based compound and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207901A (en) * | 2015-02-06 | 2017-09-26 | 东曹株式会社 | Coating urethane resin compositions and the feel coating using said composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04222822A (en) * | 1990-12-21 | 1992-08-12 | Sekisui Chem Co Ltd | Polyester carbonate copolymer |
| JPH05295094A (en) * | 1992-04-16 | 1993-11-09 | Teijin Ltd | Polycabonate-ester block copolymer and its production |
| JPH061837A (en) * | 1992-06-19 | 1994-01-11 | Chisso Corp | Polyester carbonate resin having cyclohexane ring |
| JPH10139986A (en) * | 1996-11-12 | 1998-05-26 | Toyobo Co Ltd | Resin composition |
| JP2001206939A (en) * | 2000-01-24 | 2001-07-31 | Toyobo Co Ltd | Thermoplastic polyester elastomer |
| WO2008093574A1 (en) * | 2007-01-29 | 2008-08-07 | Toyo Boseki Kabushiki Kaisha | Method for producing polyester-polycarbonate type thermoplastic polyester elastomer and polyester-polycarbonate type thermoplastic polyester elastomer |
-
2010
- 2010-12-29 KR KR1020100138178A patent/KR20120076149A/en not_active Application Discontinuation
-
2011
- 2011-03-04 WO PCT/KR2011/001501 patent/WO2012091218A1/en active Application Filing
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150097902A (en) | 2014-02-18 | 2015-08-27 | 경북대학교 산학협력단 | self-healing Polyurethane Coatings |
| WO2018190647A2 (en) | 2017-04-13 | 2018-10-18 | 주식회사 쎄코 | Self-healing functional polyvinyl-based compound and preparation method thereof |
| US11136470B2 (en) | 2017-04-13 | 2021-10-05 | Ceko Co., Ltd. | Self-healing functional polyvinvyl-based compound and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| WO2012091218A1 (en) | 2012-07-05 |
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