KR101855858B1 - Polyester Resin having High Viscosity for Foaming, and Preparation Method of Polyester Resin Foam Using the Same - Google Patents
Polyester Resin having High Viscosity for Foaming, and Preparation Method of Polyester Resin Foam Using the Same Download PDFInfo
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- KR101855858B1 KR101855858B1 KR1020150191469A KR20150191469A KR101855858B1 KR 101855858 B1 KR101855858 B1 KR 101855858B1 KR 1020150191469 A KR1020150191469 A KR 1020150191469A KR 20150191469 A KR20150191469 A KR 20150191469A KR 101855858 B1 KR101855858 B1 KR 101855858B1
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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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
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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
- C08G2101/00—Manufacture of cellular products
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- C08G2101/0066—
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
Abstract
The present invention relates to a polyester resin foam having a peak in the range of 6.75 to 7.15 ppm when measured by 1 H-NMR, and a resin produced by using maleic anhydride is introduced into a foaming step to reduce the amount of the thickener introduced, And it is possible to provide a high-quality foam.
Description
The present invention relates to a polyester resin for foaming having a high melt viscosity and a method for producing a polyester resin foam using the same.
Polyester is an eco-friendly material and has excellent mechanical properties, excellent heat resistance and chemical resistance, and can be used in various fields requiring light weight and high physical properties. Since the polyester is a crystalline resin, it has been difficult to mold it into a desired shape by extrusion foaming after melting. However, with the development of technology, it has become possible to manufacture an expanded molded article through a foaming process.
As one example,
In the case of producing a foam using a polyester resin, viscosity is controlled by adding a thickener. However, when the amount of the thickener is excessive, the physical properties of the foam are lowered and the quality uniformity of the foam is lowered.
In order to solve such a problem, the present invention provides a polyester resin by adding maleic anhydride and providing a foam by using the resin.
In order to achieve the above object,
The present invention, as one embodiment,
A polyester resin foam which satisfies the following
[Condition 1]
1 H-NMR measurement has a peak in the range of 6.75 to 7.15 ppm.
As yet another embodiment, the present invention provides a polyester resin for foaming satisfying the following
[Condition 2]
The melt viscosity (MV) of the resin is preferably 3,000 to 15,000 poise
[Condition 3]
The intrinsic viscosity (IV) of the resin ranges from 0.4 to 0.7 dl / g.
As yet another embodiment,
A method for producing a foam comprising a step of introducing a polyester resin having a melt viscosity (MV) of 3,000 to 15,000 poise at 280 ° C and an intrinsic viscosity (IV) of 0.4 to 0.7 dl / g into a foaming process and foaming to provide.
By using the resin according to the present invention, it is possible to produce a foam having an excellent process stability by reducing the amount of the thickener added.
1 and 2 show the 1 H-NMR measurement results of the foam according to Examples 1 and 2, respectively.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail.
It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
In the present invention, the terms "comprising" or "having ", and the like, specify that the presence of a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.
In the present invention, "weight part" means the weight ratio between the components.
The term "main component " in the present invention means that at least 95 parts by weight, at least 96 parts by weight, at least 97 parts by weight, at least 98 parts by weight or at least 99 parts by weight based on the total weight of the composition or mixture.
In addition, in the present invention, the term "cell" means a microstructure expanded by foaming in a polymer.
Further, in the present invention, the "melting point" means a temperature at which the solid polymer resin starts to melt in a liquid phase.
In the present invention, the "expansion ratio" means the volume ratio of the polymer resin before foaming to the polymer resin after foaming.
Hereinafter, the present invention will be described in more detail.
The present invention, in one embodiment,
A polyester resin foam which satisfies the following
[Condition 1]
1 H-NMR measurement has a peak in the range of 6.75 to 7.15 ppm.
The foam according to the present invention is characterized by foaming using a resin prepared by adding maleic anhydride (MA, maleic anhydride). Specifically, the foam can be confirmed whether or not the maleic anhydride (MA) is used through 1 H-NMR measurement.
The results of the 1 H-NMR measurement according to the above-mentioned
[Chemical Formula 1]
In the general formula (1), n means an integer of 1 or more, and is not particularly limited, but may range from 1 to 100,000.
The 1 H-NMR measurement can be performed using a mixed solvent of TFA (Trifluoroacetic Acid-d) / CDCl 3 (Chloroform-d). For example, the foam can be measured by dissolving the foam in a mixed solvent in which a small amount of TFA is added to CDCl 3 . As a result of the measurement, it was confirmed that the intrinsic peak appeared in the corresponding range, and the area of the intrinsic peak may be, for example, 2.5 to 30 integral, or 3.5 to 25 integral, or 3 to 13 integral range. The area of the inherent peak is a relative value. Specifically, when the polyethylene terephthalate (PET) is used as the main resin, the area of the peak has a peak area in the range of 7.5 to 8.5 ppm corresponding to hydrogen of the terephthalic acid (TPA) benzene ring is 100 It is based on integral.
The polyester resin foam according to the present invention is prepared by adding a maleic anhydride to a resin and providing a foam through a foaming process.
As an example, the density of the polyester foam according to the invention may range from 30 to 200 kg / m < 3 >. Specifically, the density of the foam may be in the range of 50 to 100 kg / m 3 , 100 to 200 kg / m 3, or 70 to 150 kg / m 3 . By controlling the density of the foam in the above range, the weight per unit volume of the polyester foam is prevented from increasing excessively and the elasticity is improved.
As an example, the flexural strength (KS M ISO 844) of the polyester foam according to the present invention may range from 70 to 110 N / cm 2 . Specifically, the flexural strength may be in the range of 75 to 110 N / cm 2 , 80 to 110 N / cm 2, or 80 to 100 N / cm 2 .
As one example, the flexural strength ratio of density of the polyester foam may satisfy the following general formula (1).
[Formula 1]
Z / Y = 1.2
In the above
For example, the density to flexural strength ratio of the polyester foam may range from 1.2 or more, 1.2 to 2, 1.3 to 1.8 or 1.4 to 1.6. The polyester foam according to the present invention satisfies the density to bending strength ratio in the above range, thereby realizing weight reduction and preventing deformation. This means that in the polyester foam according to the present invention, the pores may not be bonded to each other but the closed cells may be formed independently, and thus excellent heat insulation can be expected.
In the
As an example, the polyester foam according to the present invention may have a tensile strength (ASTM C 297) in the range of 1.5 to 2.5 N / mm < 2 >. Specifically, the tensile strength may be in the range of 1.6 to 2.3 N / mm 2 or 1.7 to 2.1 N / mm 2 . When the tensile strength is in the above range, the polyester foam achieves improved elasticity and strength performance.
The present invention also provides a polyester resin for foaming. The resin is suitable for a foaming process for producing a foam, and is characterized in that it is produced by adding maleic anhydride (MA).
In one embodiment of the present invention, the polyester resin for foaming satisfies the following
[Condition 2]
The melt viscosity (MV) of the resin is preferably 3,000 to 15,000 poise
[Condition 3]
The intrinsic viscosity (IV) of the resin ranges from 0.4 to 0.7 dl / g.
The polyester resin for foaming according to the present invention is characterized by exhibiting a high melt viscosity while maintaining the intrinsic viscosity of the resin. The present invention can produce foam of high quality by lowering the amount of the thickener input by performing a foaming process using a polyester resin having a high melt viscosity.
More specifically, the melt viscosity (MV) of the resin can range from 3,000 to 10,000 poise, from 3,000 to 7,000 poise, from 5,000 to 8,000 poise, or from 3,500 to 6,700 poise. In addition, the intrinsic viscosity (IV) of the resin may range from 0.4 to 0.6 dl / g, from 0.6 to 0.65 dl / g, from 0.5 to 0.7 dl / g, or from 0.62 to 0.65 dl / g.
The polyester resin for foaming according to the present invention satisfies any one of the following
[Condition 4]
The glass transition temperature (Tg) of the resin is 60 ° C or higher.
Specifically, the glass transition temperature of the foamable polyester resin may be in the range of 60 to 85 캜, 60 to 80 캜, 62 to 80 캜, 65 to 80 캜, or 70 to 80 캜. That is, the polyester resin for foaming according to the present invention can maintain a high glass transition temperature while preventing the intrinsic viscosity of the resin from being lowered. The glass transition temperature of the resin is too low, the strength of the foam may be lowered, and the rate of change with time in the course of extrusion or foaming may be lowered, which may cause a decrease in productivity.
[Condition 5]
The content of the cyclic compound contained in the resin is 0.1 wt% or less.
Specifically, the content of the cyclic compound contained in the resin may be 0.5 wt% or less, 0.1 wt% or less, or 0.05 wt% or less. The polyester resin for foaming according to the present invention contains substantially no cyclic compound, and the lower limit thereof is not particularly limited, and may be, for example, 0.01 wt% or more, or 0.001 wt% or more.
Since the polyester resin for foaming according to the present invention does not substantially contain a cyclic compound acting as a foreign substance, the efficiency of the foaming process is high and uniform foaming is possible.
In the present invention, the cyclic compound refers to a foreign component contained in the resin, and specifically refers to a cyclic compound having a degree of polymerization of 2 to 3 produced in the synthesis of a resin. These cyclic compounds appear to be formed during the synthesis of resins using mainly isophthalic acid. The measurement of the content of the cyclic compound means, for example, a cyclic compound having a degree of polymerization of 2 to 3 produced in the synthesis of a resin. These cyclic compounds appear to be formed during the synthesis of resins using mainly isophthalic acid. The content of the cyclic compound can be measured by, for example, dissolving the polyester in trifluoroacetic acid and using a DRX-300 proton nuclear magnetic resonance apparatus (1 H NMR) of Bruker.
Examples of such a polyester resin include an aromatic or aliphatic polyester resin synthesized from a dicarboxylic acid component and a glycol component or a hydroxycarboxylic acid. The polyester resin may be, for example, polyethylene terephthalate (PET), polystyrene (PS), polybutylene terephthalate (PBT), polylactic acid (PLA), polyglycolic acid Polyglycolic acid (PGA), Polypropylene (PP), Polyethylene (PE), Polyethylene adipate (PEA), Polyhydroxyalkanoate (PHA), Polytrimethylene Terephthalate , PTT), and polyethylene naphthalate (PEN). Specifically, polyethylene terephthalate (PET) may be used in the present invention.
Further, the present invention provides a method for producing a foam using the above-mentioned polyester resin for foaming.
In one embodiment, the method of producing a foam according to the present invention comprises introducing a polyester resin having a melt viscosity (MV) of 3,000 to 15,000 poise and an intrinsic viscosity (IV) of 0.4 to 0.7 dl / g into a foaming process, . The melt viscosity (MV) is a value measured at 280 ° C.
More specifically, in the method for producing a foam according to the present invention, the polyester resin to be introduced into the foaming step can be selectively applied to a batch type or a continuous type polymerization type in the production of a polyester resin.
As one example, the polyester resin to be introduced into the foaming step may be,
(1) an acidic component comprising 50 to 95 mol% of terephthalic acid and 5 to 50 mol% of maleic anhydride (MA); And
(2) a diol component comprising 70 to 100 mol% of ethylene glycol and 0 to 30 mol% of a diol having a boiling point of less than 300 DEG C
To prepare a copolymer polyester through an esterification reaction and a polycondensation reaction.
In the process of producing the copolymer polyester, the acid component may include terephthalic acid and maleic anhydride. Specifically, the acid component may further include isophthalic acid or a derivative thereof. The derivative means an ester-forming derivative of isophthalic acid. The isophthalic acid or its derivative may be added in an amount of 20 mol% or less based on the acid component.
As the diol component, it is also possible to use ethylene glycol alone, or to use a diol having a boiling point of less than 300 캜 with ethylene glycol.
In the present invention, the content of the acid component and the diol component added during the production of the polyester resin can be controlled at a ratio (molar ratio) of 1: 0.9 to 1: 2, or 1: 1 to 1: 1.5. For example, the resin can be prepared by adding an excessive amount of a diol component to the content of the acid component.
In the present invention, by producing a resin using maleic anhydride (MA), production of a cyclic compound as a side reaction product is suppressed, productivity can be enhanced, and a foam of uniform quality can be produced. When the content of the maleic anhydride is too small, the melt viscosity is not sufficiently increased, so that a low-density polyester foam can not be obtained, and in the opposite case, an excessive increase in melt viscosity may adversely affect the fairness.
In particular, the resin according to the present invention can reduce the amount of the polyfunctional component used as the thickener by increasing the melt viscosity, thereby producing a polyester foam of uniform quality and reducing the production cost.
In the present invention, the viscosity of the resin is controlled by injecting a thickening component. The thickening component can be classified into reaction type and additive type depending on the input method. In the present invention, the reactive type thickening component is added during the synthesis of the resin, and for example, a polyfunctional component can be used. Further, the addition type thickening component is added to the foaming step. In the present invention, either one or both of the above reaction type and addition type thickening components can be used in order to realize a viscosity suitable for foaming.
The multifunctional component used as the reactive type thickening component may include, for example, at least one selected from the group consisting of a polycarboxylic acid, a polyol and a polyoxycarboxylic acid. For example, the polyfunctional component may be selected from the group consisting of trimellitic acid, trimesic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid and their acid esters , Derivatives of acid anhydrides and the like, glycerin, pentaerythritol and sorbitol. The multifunctional component lowers the reaction temperature during the condensation polymerization, shortens the reaction time, improves color defects, and increases the viscosity of the resin. The content of the polyfunctional component may be in the range of 50 to 10,000 ppm, 50 to 1,000 ppm, or 500 to 2,000 ppm. If the added amount of the polyfunctional component is too small, the desired crosslinking agent can not be attained. If the added amount is too large, a problem is caused by a sudden crosslinking phenomenon.
In the present invention, by using a resin having a high melt viscosity, the addition amount of the polyfunctional component can be remarkably reduced, or an excellent foam performance can be realized in spite of the same addition amount.
As one example, in the present invention, an additive type thickening component can be added in the foaming step. The content of the additive type thickening component may be in the range of 0.01 to 10 wt%, 0.01 to 10 wt%, 0.01 to 1 wt%, 0.1 to 10 wt%, or 0.01 to 5 wt%, based on 100 wt% have. The addition type thickening component is not particularly limited, but for example, pyromellitic dianhydride (PMDA) may be used, and the above-described polyfunctional component may be used.
Further, in the step of introducing the produced resin into the foaming process and foaming, various additives can be added. Such additives can be added not only in the foaming step but also in the resin synthesis process, as the case may be.
In the foaming process, additives such as heat stabilizers and nucleating agents may be included.
Examples of the nucleophilic agent include talc, mica, silica, diatomaceous earth, alumina, titanium oxide, zinc oxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, potassium carbonate, calcium carbonate, magnesium carbonate, , Inorganic compounds such as glass beads; Organic compounds such as polytetrafluoroethylene and polytetrafluoroethylene azodicarbone amide; A mixture of sodium hydrogencarbonate and citric acid; And an inert gas such as nitrogen.
The thermal stabilizer may include a pentavalent and / or trivalent phosphorus compound or a phenolic compound having a large chemical structural steric hindrance. Specifically, the pentavalent and / or trivalent phosphorus compounds may include trimethylphosphite, phosphoric acid, phosphorous acid, tris (2,4-di-tert-butylphenyl) phosphite, The compound was a pentaerythritol tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Pentaerythritol tetrakis propionate, Irganox 1010), 1,1,3-tris (2-methyl-4-hydroxy-5-tert- tert-butylphenyl) butane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ) propionate, N, N'-hexamethylenebis (3,5-tert-butyl-4-hydroxyhydrocinnamamide) ), Ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] N, N '- (hexane-1,6-diyl) bis (3- (3,5 di-tert-butyl-4-hydroxyphenyl) ) Propionamide (N, N '- (Hexane-1,6-diyl) bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide).
Further, the foam may further include additives for realizing various functions such as adiabatic function, flame retardant function, VOC abatement function, hydrophilization function, waterproof function, antibacterial function, deodorizing function and / or ultraviolet ray shielding. Specifically, the additive may be at least one kind of an insulating agent, a hydrophilizing agent, a waterproofing agent, a flame retardant, an antibacterial agent, a deodorant, and an ultraviolet screening agent.
At this time, the heat insulating material may be graphite containing carbonaceous component, carbon black, graphene and the like, and may be graphite in detail.
The flame retardant may be a bromine compound such as tetrabromobisphenol A and / or decabromodiphenyl ether; Phosphorus compounds such as aromatic phosphoric acid esters, aromatic condensed phosphoric acid esters, halogenated phosphoric acid esters, and the like; Antimony compounds such as antimony trioxide, and antimony pentoxide; (Al), magnesium (Mg), calcium (Ca), nickel (Ni), cobalt (Co), tin (Sn), zinc (Zn), copper (Cu), iron (Fe) And boron (B). ≪ / RTI > When a metal hydroxide is included as the flame retardant, the metal hydroxide may include at least one of aluminum hydroxide and magnesium hydroxide, but is not limited thereto.
In addition, the VOC reducing agent may include Graf and / or Bactoster Alexin. At this time, the toast alecine is a natural sterilizing material extracted from propolis.
In addition, the hydrophilic agent is not particularly limited, but specifically includes anionic surface active agents (for example, fatty acid salts, alkylsulfuric acid ester salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylsulfosuccinic acid salts, (For example, polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, Polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene alkylamines, alkylalkanolamides), cationic and amphoteric surfactants (for example, alkylamine salts, quaternary ammonium salts, alkyl betaines, Amine oxides, etc.) and water-soluble polymers or protective colloids (e.g., gelatin, methylcellulose, Polyoxyethylene-polyoxypropylene block copolymer, polyacrylamide, polyacrylic acid, polyacrylic acid salt, sodium alginate, polyvinyl alcohol partial saponification, etc.), such as hydroxyethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, polyethylene glycol, And may include one or more species.
Further, the waterproofing agent may be a silicone-based, epoxy-based, cyanoacrylic acid-based, polyvinyl acrylate-based, ethylene vinyl acetate-based, acrylate-based, polychloroprene-based, polyimide-based, copolymer of a polyurethane resin and a polyester resin Series, a copolymer series of a polyol and a polyurethane resin, a copolymer series of a polyacrylic resin and a polyurethane resin, and a copolymer series of a cyanoacrylate and a urethane.
Examples of the antimicrobial agent include a composite obtained by adding at least one metal selected from the group consisting of silver, zinc, copper and iron to at least one carrier selected from the group consisting of hydroxyapatite, alumina, silica, titania, zeolite, zirconium phosphate and aluminum polyphosphate . ≪ / RTI >
The deodorant may be a porous material. Since the porous material has a strong tendency to physically adsorb a fluid flowing around the porous material, it is possible to adsorb a volatile organic compound (VOC). The deodorant may be selected from, for example, silica, zeolite and calcium (Ca), sodium (Na), aluminum (Al), silver (Ag), copper (Cu), tin (Zn), iron (Fe), cobalt ) And nickel (Ni), or a mixture of two or more thereof. The average particle size of the deodorant can be from 1 to 20 microns, for example, from 1 to 10 microns or less. If the average size of the deodorant particles exceeds 20 탆, pinholes are generated on the surface of the foam during the production of the foam to deteriorate the quality of the product. If the numerical range is satisfied, The attraction force is increased.
Further, sunscreen agents may include, but are not limited to, organic or inorganic sunscreens. Examples of the organic ultraviolet screening agent include p-aminobenzoic acid derivatives, benzylidene campo derivatives, cinnamic acid derivatives, benzophenone derivatives, benzotriazole derivatives, and mixtures thereof. Examples of the inorganic ultraviolet screening agents include titanium dioxide, Zinc, manganese oxide, zirconium dioxide, cerium dioxide, or mixtures thereof.
At this time, it can be performed by forming a resin melt during the foaming process and mixing the foaming agent with the resin melt. The foaming agent may include a thermally decomposing foaming agent, a volatile foaming agent, or a mixture thereof. As the pyrolytic foaming agent, for example, an inorganic foaming agent containing sodium hydrogencarbonate; Azo compounds including azodicarbonamide and the like; Nitroso compounds including N, N'-dinitroso pentamethylene tetramine and the like; p, p'-oxybis (benzene sulfonyl hydrazide)], and the like, and the like. As the volatile foaming agent, for example, an inert gas such as carbon dioxide gas (CO 2 ) or nitrogen gas (N 2 ), or an organic foaming agent such as methane, propane, butane, hexane and the like. At this time, when a pyrolytic foaming agent or a volatile foaming agent is used, there is an advantage that a foamed molded article of high magnification can be obtained.
Further, the foaming step may be performed by cooling the foamable melt through an extruder at 220 to 260 ° C so as to facilitate foaming, and then passing the cooled foamed melt through a die (Dei). At this time, the eutectic flux of the expandable melt may be in the range of 1.2 dl / g or more and 1.2 to 1.5 dl / g. By controlling the intrinsic viscosity of the resin to be suitable for foaming, a foam having a high expansion ratio can be effectively produced. In addition, the formed foam may be maintained in a form using a calibrator.
Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples.
However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited to the following Examples and Experimental Examples.
Example One
Terephthalic acid and ethylene glycol were added to the ester reaction tank and reacted at a temperature of 258 ° C by a conventional method to prepare an oligomer having a 96% reaction rate. Maleic anhydride (MA) was added to the obtained oligomer in an amount of 25 mol% of the total acid components, trimethylol propane (hereinafter referred to as 'TMP') as one of the multifunctional components and 1,000 ppm of a common ester exchange catalyst Lt; RTI ID = 0.0 > 250 C. < / RTI > The esterification oligomer thus obtained was charged with a conventional polycondensation catalyst, and the polycondensation reaction was carried out by raising the temperature to 280 DEG C while gradually reducing the pressure to 0.1 mmHg.
The performance of the produced polyester resin was evaluated as described above, and the results are shown in Table 1 below.
The polyester resin thus prepared was dried in a dryer at 130 ° C for 8 hours so that the water content was 50 ppm or less.
0.15 parts by weight of talc was heated to 280 DEG C on the basis of 100 parts by weight of the PET resin from which the moisture had been removed in the first extruder to prepare a resin melt.
Then, 5 parts by weight of carbon dioxide gas as a blowing agent was added to the first extruder based on 100 parts by weight of the PET resin, followed by extrusion foaming to produce an expanded molded article.
Example 2
The same procedure as in Example 1 was carried out except that the amount of maleic anhydride (MA) charged into the PET resin was 10 mol% of the total acid component in the preparation of the PET resin, and 0.1 part by weight of PMDA was used in the foaming step .
The performance of the produced polyester resin was evaluated as described above, and the results are shown in Table 1 below.
Comparative Example One
Terephthalic acid and ethylene glycol were added to the ester reaction tank and reacted at a temperature of 258 ° C by a conventional method to prepare an oligomer having a 96% reaction rate. The esterification oligomer thus obtained was charged with a conventional polycondensation catalyst, and the polycondensation reaction was carried out by raising the temperature to 280 DEG C while gradually reducing the pressure to 0.1 mmHg.
After the polymerization, the foaming process is the same as in Example 1.
The polyester resin thus prepared was dried at 150 ° C. for 8 hours in a dryer so that the water content was 50 ppm or less.
0.15 parts by weight of talc was heated to 280 DEG C on the basis of 100 parts by weight of the PET resin from which the moisture had been removed in the first extruder to prepare a resin melt.
Then, 5 parts by weight of carbon dioxide gas as a blowing agent was added to the first extruder based on 100 parts by weight of the PET resin, followed by extrusion foaming to produce an expanded molded article.
Comparative Example 2
Except that 0.3 parts by weight of pyromellitic diahydride (PMDA) was added during the foaming step.
Experimental Example One
The physical properties of the resins prepared in Examples 1 and 2 and Comparative Example 1 were measured. The specific physical properties are measured as follows.
(1) Measurement of intrinsic viscosity (IV)
The copolymerized polyester was dissolved in phenol / tetrachloroethane (weight ratio 50/50) to make a 0.5 wt.% Solution, and then measured at 35 DEG C with a Ubbelohde viscometer.
(2) Measurement of glass transition temperature (Tg)
Were measured using a thermal differential scanning calorimeter (Perkin Elmer, DSC-7).
(3) Measurement of melt viscosity (MV)
The melt viscosity of the prepared resin was measured at 280 占 폚 using RDA-III of Rheometric Scientific. Specifically, the melt viscosity was measured at 280 ° C., and when the initial frequency was set from 1.0 rad / s to the final frequency = 500.0 rad / s under the frequency sweep condition at the set temperature, it was measured at 100 rad / s Was calculated as a melting point.
(4) Measurement of foreign matter (cyclic compound) content
The molar percentage of the additive of the copolymerized polyester was measured by dissolving the copolymer polyester in trifluoroacetic acid and using a DRX-300 proton nuclear magnetic resonance apparatus (1 H NMR) of Bruker.
Referring to Table 1, when Examples 1 and 2 are compared with Comparative Example 1, the intrinsic viscosity is equivalent, but the melt viscosity of Examples 1 and 2 ranges from 3,780 to 6,548 poise, which is significantly higher than Comparative Example 1 .
Experimental Example 2.
The foams prepared in Examples 1 and 2 were dissolved in a mixed solvent of TFA / CDCl 3 (Trifluoroacetic Acid-d / Chloroform-d, where d is replaced with deuterium (D) NMR was measured. The NMR measurement was carried out using a mixed solvent of TFA: CDCl 3 mixed at a volume ratio of 1:20. Specifically, the chemical shift is confirmed, and TFA shows a peak near 11.50 ppm (singlet, single peak), and CDCl 3 shows a peak near 7.24 ppm (singlet, single peak). The measured results are shown in FIGS. 1 and 2.
1 is a 1 H-NMR data of a foam prepared using the resin according to Example 1. Fig. Referring to FIG. 1, it can be seen that a peak appears in the range of 6.75 to 7.15 ppm, and specifically, a peak exists in an area of 12.872 integral in the corresponding range. Through this, it was confirmed that the foam according to the present invention was a foam of a resin prepared by adding maleic anhydride (MA).
2 is a 1 H-NMR data of a foam produced using the resin according to Example 2. Fig. Referring to FIG. 2, it can be seen that a peak appears in the range of 6.75 to 7.15 ppm, and specifically, a peak exists in the area of 3.833 integral in the corresponding range. Through this, it was confirmed that the foam according to the present invention was a foam of a resin prepared by adding maleic anhydride (MA).
1 and 2, even if the amount of maleic anhydride MA to be added is varied, the range in which the intrinsic peak is exhibited is constant. Through this, it can be confirmed that the foam according to the present invention is a foam of a resin prepared by injecting maleic anhydride (MA).
Claims (7)
The density according to KS M ISO 845 ranges from 70 to 150 kg / m 3 ,
Foam of an aromatic polyester resin satisfying the flexural strength according to KS M ISO 844 of 80 to 100 N / cm 2 :
[Condition 1]
1 H-NMR measurement has a peak in the range of 6.75 to 7.15 ppm.
Wherein the aromatic polyester resin comprises 50 to 95 mol% of terephthalic acid and 5 to 50 mol% of maleic anhydride (MA) as acid components and satisfies the following conditions 2 to 4:
[Condition 2]
The melt viscosity (MV) of the resin is preferably 3,000 to 15,000 poise
[Condition 3]
The intrinsic viscosity (IV) of the resin is 0.4 to 0.7 dl / g
[Condition 4]
The glass transition temperature (Tg) of the resin is 60 ° C or higher.
The aromatic polyester resin to be introduced into the foaming step,
From 50 to 95 mol% of terephthalic acid, and from 5 to 50 mol% of maleic anhydride (MA); And
And a diol component comprising 70 to 100 mol% of ethylene glycol and 0 to 30 mol% of a diol having a boiling point of less than 300 DEG C through esterification and condensation polymerization to produce a copolymer polyester Method of manufacturing foam.
The foam manufacturing method
A step of further adding a polyfunctional component in the step of producing an aromatic polyester resin; And
And introducing the produced resin into a foaming step and further adding a thickening agent at the foaming step.
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| KR1020150191469A KR101855858B1 (en) | 2015-12-31 | 2015-12-31 | Polyester Resin having High Viscosity for Foaming, and Preparation Method of Polyester Resin Foam Using the Same |
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| KR101855858B1 true KR101855858B1 (en) | 2018-06-12 |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2004300C (en) | 1988-12-01 | 1999-05-11 | Motoshige Hayashi | Process for producing polyester resin foam and polyester resin foam sheet |
| KR20000059815A (en) * | 1999-03-09 | 2000-10-05 | 한형수 | Method for the preparation of the aliphatic polyester |
| KR20090012684A (en) * | 2007-07-31 | 2009-02-04 | 주식회사 닉시안 | Pseudomonas sp. nix-36 for removing xenobiotic substance in dye wastewater and its use |
| KR100918292B1 (en) * | 2007-08-20 | 2009-09-18 | 오씨아이 주식회사 | A method for preparing polyester polyol by using by-product of maleic anhydride |
| KR20130100979A (en) * | 2010-07-13 | 2013-09-12 | 인비스타 테크놀러지스 에스.에이.알.엘. | High dimensional stability polyester compositions |
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