KR101249577B1 - Flame-retardant polyester resin having high intrinsic viscosity and preparing method thereof - Google Patents

Abstract

The present invention relates to a flame-retardant polyester resin and a method for producing the phosphorus-based compound in the molecular chain of the flame-retardant resin containing 0.1 to 5.0% by weight relative to the flame retardant resin, and has an intrinsic viscosity of 0.70 dl / g or more. .

Flame retardant, polyester, 1,4-cyclohexanedimethanol, ethylene glycol, terephthalic acid, phosphorus compound

Description

Flame-retardant polyester resin having high intrinsic viscosity and preparing method

The present invention relates to a polyester obtained by copolymerizing 1,4-cyclohexanedimethanol or diol containing ethylene glycol as a main component and adding a phosphorus compound. More specifically, the present invention relates to a flame-retardant polyester having a high intrinsic viscosity suitable for injection and extrusion molding, which is not the purpose of a conventional low-viscosity fiber, and a method of manufacturing the same.

Polyethylene terephthalate (PET) is environmentally friendly and contains no harmful substances to humans, so it is widely used in the fields of filling containers and packaging materials for juices, soft drinks, carbonated drinks, molded products, sheets, films, etc. have. In addition, polyesters in which 1,4-cyclohexanedimethanol is copolymerized with ethylene glycol in diols are called PETG or PCTG and likewise contain no harmful substances to humans, and are environmentally friendly, have excellent formability, processability and transparency. It is an important resin widely used in fields such as containers, packaging materials, sheets, and films.

Meanwhile, research on flame retardation through phosphorus-based compounds has been urgently required in polyester fibers, which are widely used in everyday life products such as clothes, bedding, and curtains. In particular, the method of copolymerizing the phosphorus compound in the manufacturing process of the polyester has been actively proposed in that there is no reduction in flame retardancy due to washing, excellent flame retardancy, and low physical property deterioration.

U.S. Patent No. 3,941,752 discloses a flame retardant polyester copolymerized using a specific phosphorus compound, but in order to introduce the phosphorus compound into the molecule, the reactivity of the phosphinic acid group is insufficient among the two reactive functional groups of the phosphinic acid group and the carboxylic acid group. Phosphorus-based compounds have the property of degrading the activity of the catalyst, which makes it difficult to obtain a high molecular weight polyester.

Korean Patent Publication No. 1997-0061931 discloses a method of obtaining a polyester for fiber by carrying out crystallization and solid phase polymerization after melt polymerization to 60 to 80% of the final intrinsic viscosity as a method of increasing the degree of polymerization. This has also been studied for fibers and only a polyester for fibers with an intrinsic viscosity of less than 0.7 dl / g was obtained. In addition, Korean Patent Publication No. 10-1999-0006227 discloses that the mechanical properties are improved by mixing and spinning a polyester copolymerized with an excessive amount of a flame retardant with pure polyethylene terephthalate. Intrinsic viscosity was less than 0.70 dl / g.

Intrinsic viscosity is one of the important qualities of molded articles for the production of films, sheets, injection molded articles, containers, thermoforms by injection and extrusion, not for textile applications. When this intrinsic viscosity is small, the molded article, such as a container and a film, has a small molecular weight, and mechanical property becomes poor, especially a problem in impact resistance. For this reason, PET, PETG, or PCTG resin regards the intrinsic viscosity of molded parts as an important quality control factor. However, until now, no method for producing a flame retardant polyester for non-fibers having an intrinsic viscosity of 0.7 dl / g or more has not been proposed.

In view of the above situation, the present inventors studied flame retardant polyester for non-fibers having an intrinsic viscosity of 0.70 dl / g or more, and found that flame retardancy having an intrinsic viscosity of less than 0.70 dl / g by adding an excessive amount of a phosphorus compound After preparing the polyester, it was successfully melted and mixed with a general polyester having an intrinsic viscosity of 0.70 dl / g or more to obtain a polyester having a high molecular weight of at least 0.70 dl / g while having flame retardancy. Completed on the basis of

Accordingly, it is an object of the present invention to provide a polyester comprising 1,4-cyclohexanedimethanol or ethylene glycol having a flame retardancy of intrinsic viscosity of at least 0.70 dl / g or more as a main component of diol. Underwriter's Laboratory) provides a flame retardant polyester with a V0 as measured by the 94 bar vertical combustion test method.

According to the present invention for achieving the above object,

In a polyester resin produced by copolymerizing an acid component of dicarboxylic acid or ester forming derivative thereof and a diol component of glycol or ester forming derivative thereof,

70 mol% or more of the sum of the 1, 4- cyclohexane dimethanol component and the ethylene glycol component of the diol component is included, and 0.1 to 5.0 wt% of the phosphorus-based compound represented by the formula (1) is included, and the intrinsic viscosity is A flame retardant polyester resin for non-fibers having a rating of V0 of 0.70 dl / g or more and when flame retardancy is measured by the UL 94 bar vertical combustion test method and a method of manufacturing the same are provided.

It also relates to blends or alloys of molded articles, such as bottles, containers, films, sheets, etc., made of flame retardant polyester with other polymers.

Flame retardant polyester resin of the present invention for achieving the above object is:

70 mol% or more of terephthalic acid or a derivative component thereof is contained in the dicarboxylic acid component, and 70 mol% or more of the sum of ethylene glycol and 1,4-cyclohexanedimethanol is contained in the diol component, and the following Phosphorus-based compound having the formula (1) is included 0.1 to 5.0% by weight based on the element, characterized in that the intrinsic viscosity is 0.7 ㎗ / g:

Here, R is an alkyl group, an allyl group, a cycloalkyl group or an alkyl group, an allyl group, or a cycloalkyl group which has a substituent, n is an integer of 1-4.

Preferably, the dicarboxylic acid component is (i) 70-100 mol% of terephthalic acid, and (ii) isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, carbon number It is characterized by comprising 0-30 mol% of dicarboxylic acid selected from the group consisting of aromatic dicarboxylic acid having 8 to 14 and aliphatic dicarboxylic acid having 4 to 12 carbon atoms.

Preferably, the diol component is (i) 70-100 mol% of 1,4-cyclohexanedimethanol, or ethylene glycol or mixtures thereof, and (ii) diethylene glycol, triethylene glycol, propanediol, pentanediol, Hexanediol, neopentyl glycol and tetramethylcyclobutanediol is characterized in that it comprises 0 to 30 mol% glycol selected from the group consisting of.

Flame retardant polyester resin production method of the present invention for achieving the above object:

(i) 20-80 weight of the polyester (A) which contains 0.5-6.25 weight% of phosphorus compounds which have the said Formula (1) in the molecular chain of polyester (A) on the basis of a phosphorus element, and has an intrinsic viscosity less than 0.70 dl / g %Wow

(ii) melt-blending 20 to 80% by weight of a polyester (B) having no intrinsic viscosity and a intrinsic viscosity of 0.70 to 1.5 dl / g,

Herein, the polyester (A) and the polyester (B) each contain 70 mol% or more of terephthalic acid or a derivative component thereof in the dicarboxylic acid component, and each of ethylene glycol and 1,4-cyclohexydimethanol in the diol component. Contain at least 70 mole percent,

The flame-retardant polyester resin comprises 0.1 to 5.0% by weight based on the phosphorus compound, characterized in that the intrinsic viscosity is 0.7 ㎗ / g.

Preferably, the dicarboxylic acid component is (i) 70-100 mol% of terephthalic acid, and (ii) isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, carbon number It is characterized by comprising 0-30 mol% of dicarboxylic acid selected from the group consisting of aromatic dicarboxylic acid having 8 to 14 and aliphatic dicarboxylic acid having 4 to 12 carbon atoms.

Preferably, the diol component is (i) 1,4-cyclohexanedimethanol, 70-100 mol% of ethylene glycol or a compound thereof, and (ii) diethylene glycol, triethylene glycol, propanediol, pentanediol, Hexanediol, neopentyl glycol and tetramethylcyclobutanediol is characterized in that it comprises 0 to 30 mol% glycol selected from the group consisting of.

The molded product formed by molding the flame-retardant polyester resin of the present invention is characterized in that the injection molded product, an extruded film, an extruded sheet or an extrusion hollow molded article.

Hereinafter, the present invention will be described in more detail.

In order that the polyester including the phosphorus-based compound having Formula 1 has flame retardancy, it is preferable that the phosphorus-based compound is contained in an amount of 0.1 to 5.0 wt% based on the number of people. The higher the content of phosphorus element, the higher the flame retardancy, but containing more than 5.0% by weight of the polycondensation reaction to increase the intrinsic viscosity of the polyester is difficult, if less than 0.1% by weight it is difficult to express the flame retardancy.

Thus, when polymerizing a polyester containing 1,4-cyclohexanedimethanol or ethylene glycol so that the phosphorus-based compound contains 0.1 to 5.0% by weight of the polyester resin based on the number of people, it is desirable to obtain a high intrinsic viscosity of 0.70 dl / g or more. Very difficult.

Therefore, in the present invention, the phosphorus-based compound does not include 20 to 80% by weight of the polyester (A) having an intrinsic viscosity of less than 0.70 dl / g and an flame retardant component in excess of 0.5 to 6.25% by weight based on the number of people. 20 to 80% by weight of polyester (B) having an intrinsic viscosity of 0.70 ㎗ / g or more is melt-mixed, resulting in an intrinsic viscosity of 0.70 ㎗ / g or more having excellent flame retardancy and excellent mechanical properties and impact resistance. When flame retardancy is measured by the test method, flame retardant polyester having a grade of V0 can be obtained. In particular, mechanical properties and impact resistance are superior to polyesters of the same component having an intrinsic viscosity of less than 0.70 dl / g used for textiles.

It also relates to molded articles, such as bottles, containers, films, sheets, etc., made of flame retardant polyester, and blends or alloys with other polymers.

The phosphorus compound may be, for example, (2-carboxyethyl) methylphosphinic acid, (2-methoxycarbonylethyl) methylphosphinic acid, (2-methoxycarbonylethyl) phenylphosphinic acid, or a cyclic anhydride thereof. However, the present invention is not limited thereto.

On the other hand, the acid component used in the present invention is preferably terephthalic acid or a derivative component thereof, and isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and 8 to 14 carbon atoms. Aromatic dicarboxylic acid, aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and the like can be used.

It is preferable that the said acid component contains 80-100 mol% of terephthalic-acid components, and 0-20 mol% of dicarboxylic acid.

The diol component used in the present invention is (i) 70 to 100 mol% of 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof and (ii) diethylene glycol, triethylene glycol, propanediol, pentanediol, hexane It is preferable to include 0 to 30 mol% of a glycol selected from the group consisting of diol, neopentyl glycol and tetramethylcyclobutanediol.

In addition, it is possible to easily control the flame retardant grade of the molded article, such as injection molded or extruded by adjusting the melt mixing ratio.

The method of melt mixing may vary depending on the mixing efficiency of the screw of the molding machine, but the flame-retardant polyester and the general polyester are mixed in a pellet in proportion to the ratio, and injection or extrusion molding is performed in the barrel. It is possible to simultaneously mold while melt mixing. In the case where the melt mixing efficiency is insufficient, a method of extruding a general polyester and a flame retardant polyester and cutting the pellets in a pellet state before molding may be used for molding again.

Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited thereto.

⊙ Intrinsic Viscosity (IV): dissolved in 150 ° C ortho-chlorophenol at a concentration of 0.12% and measured using a Ubelrod viscometer in a 35 ° C thermostat.

⊙ Polyester composition analysis: Analyze the content of dicarboxylic acid, glycol component and flame retardant component using 300MHz 1H-NMR.

⊙ The flame retardant polyester used in the example was SK Chemicals' EH-100F product, which has an intrinsic viscosity of 0.66 and is a 2-carboxyl-ethyl-phenyl- as a phosphorus compound for imparting flame retardancy. Phosphonic acid copolymerized, containing 0.8% by weight phosphorus relative to polymer.

Flame retardant measurement: measured by UL (Underwriter's Laboratory) 94 bar vertical combustion test method.

⊙ Impact strength test method: Izod impact strength test method according to ASTM D256 method measured by notch at room temperature.

Unless stated otherwise in the following Examples and Comparative Examples, the unit "parts" means "parts by weight". In addition, the physical properties shown in the following Examples and Comparative Examples were measured by the following method.

Example 1

SK Chemical's EH-100F product pellets were mixed with 50 wt% chips on polyethylene terephthalate pellets having an intrinsic viscosity of 0.80, containing no flame retardant, 100 mol% terephthalic acid in dicarboxylic acid and 100% ethylene glycol in glycol, It is dried for 12 hours at 160 ℃ vacuum dryer. Since the barrel temperature was maintained at 275 ℃ a single screw (single screw) injection machine was injected with a 3.2 mm thick UV 94 test specimen. The intrinsic viscosity, impact strength, flame retardancy, and flame retardant content of this specimen were analyzed and measured and summarized in Table 1.

Example 2

SK Chemical's EH-100F product pellets are dried in a 160 ° C. vacuum dryer for 12 hours. This was intrinsic viscosity 0.78 dl / g, dried for 12 hours in a 65 ℃ vacuum dryer, containing no flame retardant, 100 mol% of terephthalic acid in dicarboxylic acid, 32 mol% of 1,4-cyclohexanedimethanol in glycol, It is mixed in 50 weight% chip | tip into polyester pellet which is 64 mol% of ethylene glycol and 4 mol% of diethylene glycol. Thereafter, 3.2 mm thick UV 94 test specimens were ejected by a single screw injector maintained at a barrel temperature of 270 ° C. The intrinsic viscosity, impact strength, flame retardancy, and flame retardant content of this specimen were analyzed and measured and summarized in Table 1.

Comparative Example 1

SK Chemical's EH-100F product pellets are dried in a 160 ° C. vacuum dryer for 12 hours. Thereafter, 3.2 mm thick UV 94 test specimens were injected into a single screw injector maintained at a barrel temperature of 275 ° C. The intrinsic viscosity, impact strength, flame retardancy, and flame retardant content of this specimen were analyzed and measured and summarized in Table 1.

Comparative Example 2

SK Chemical's EH-100F product pellets are 50% by weight in polyethylene terephthalate pellets having an intrinsic viscosity of 0.65, no flame retardant, 100 mol% terephthalic acid in dicarboxylic acid and 100 mol% ethylene glycol in glycol. After mixing, and dried for 12 hours at 160 ℃ vacuum dryer. Thereafter, 3.2 mm thick UV 94 test specimens were injected into a single screw injector maintained at a barrel temperature of 275 ° C. The intrinsic viscosity, impact strength, flame retardancy, and flame retardant content of this specimen were analyzed and measured and summarized in Table 1.

Comparative Example 3

SK Chemical's EH-100F product pellets are dried in a 160 ° C. vacuum dryer for 12 hours. The intrinsic viscosity was 0.65 dried in a vacuum dryer at 65 DEG C for 12 hours, 100 mol% of terephthalic acid in dicarboxylic acid, 32 mol% of 1,4-cyclohexanedimethanol in glycol, 65 mol% of ethylene glycol, diethylene The glycol is mixed in 3 mol% polyester pellets in 50 wt% chips. Thereafter, 3.2 mm thick UV 94 test specimens were injected into a single screw injector maintained at a barrel temperature of 270 ° C. The intrinsic viscosity, impact strength, flame retardancy, and flame retardant content of this specimen were analyzed and measured and summarized in Table 1.

division Injection specimen
Phosphorus content
(weight%) Intrinsic Viscosity of Injection Specimen
(㎗ / g) Injection specimen
Impact strength
(Kgcm / cm) Flammability
(UL94 flame retardant grade) Example 1 0.3 0.74 4.4 V0 Example 2 0.3 0.73 4.3 V0 Comparative Example 1 0.3 0.62 3.0 V0 Comparative Example 2 0.3 0.64 2.9 V0 Comparative Example 3 0.3 0.63 3.1 V0

As can be seen from the above examples and comparative examples, according to the present invention, flame retardant polyesters having an intrinsic viscosity of 0.70 dl / g or more can be obtained from flame retardant polyesters copolymerized with 1,4-cyclohexanedimethanol or ethylene glycol. In addition, it is suitable for injection and extrusion molding according to high intrinsic viscosity, and has the advantage of having mechanical properties such as good impact strength.

It will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention. Accordingly, all the simple modifications and variations of the present invention fall within the scope of the present invention, and the specific scope of the present invention will be apparent from the appended claims and their equivalents.

Claims (8)

delete delete delete (i) a polyester having a phosphorus compound having the following formula (1) in the molecular chain of the polyester (A) in an amount of 0.5 to 6.25% by weight relative to the polyester (A), and having an intrinsic viscosity of less than 0.70 dl / g A) 20 ~ 80% by weight (ii) melt-blending 20 to 80% by weight of polyester (B) having no intrinsic viscosity and 0.70 to 1.5 dl / g, Herein, the polyester (A) and the polyester (B) each contain 70 mol% or more of terephthalic acid or a derivative component thereof in the dicarboxylic acid component, and the ethylene glycol and 1,4-cyclohexanedimethanol in the diol component. Contain at least 70 mole percent, Flame-retardant polyester resin production method comprising a 0.1 to 5.0% by weight of the phosphorus-based compound based on the number of people, intrinsic viscosity of 0.7 ㎗ / g or more: Formula 1

Here, R is an alkyl group, an allyl group, a cycloalkyl group or an alkyl group, an allyl group, or a cycloalkyl group which has a substituent, n is an integer of 1-4. The dicarboxylic acid component according to claim 4, wherein the dicarboxylic acid component comprises (i) 70-100 mol% of terephthalic acid, and (ii) isophthalic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, Flame retardant polyester resin manufacturing method comprising 0 to 30 mol% of dicarboxylic acid selected from the group consisting of aromatic dicarboxylic acid having 8 to 14 carbon atoms and aliphatic dicarboxylic acid having 4 to 12 carbon atoms . The diol component according to claim 4, wherein the diol component comprises (i) 70-100 mol% of 1,4-cyclohexanedimethanol, or ethylene glycol or mixtures thereof, and (ii) diethylene glycol, triethylene glycol, propanediol, pentane. A flame retardant polyester resin manufacturing method comprising 0 to 30 mol% of a glycol selected from the group consisting of diol, hexanediol, neopentyl glycol and tetramethylcyclobutanediol. delete delete