KR101797206B1 - Production method for flame-retardant polyethyleneterephthalate having high char yield - Google Patents

Abstract

The present invention relates to a process for producing poly (ethylene terephthalate) and a phosphine-based flame retardant (triphenylphosphate) by using a per sulfate or peroxide reaction catalyst and forming a covalent bond through a radical addition reaction, A method for producing a phosphate-added polyethylene terephthalate polymer resin, and a produced flame retardant polyethylene terephthalate polymer resin.

Description

FIELD OF THE INVENTION The present invention relates to a flame-retardant polyethylene terephthalate having a high carbonization yield,

The present invention relates to a method for producing a flame retardant polyethylene terephthalate resin having excellent carbonization yield and a polyethylene terephthalate resin produced thereby. More specifically, the present invention relates to a flame retardant polyethylene terephthalate resin having a covalent bond of a polyethylene terephthalate resin and a triphenyl phosphate And to a polyethylene terephthalate resin produced thereby.

Polyethylene terephthalate is widely used in many fields such as clothing, interior, padding, non-woven fabric, and industrial materials due to its excellent mechanical properties and easy processability. However, since polyethylene terephthalate is flammable, various additives and methods for imparting flame retardancy to the flame retardant have been studied for application to various applications as described above.

As the flame retardant, halogen-based compounds typified by hexabromocyclododecane (HBCD) have been mainly used. However, in recent years, these compounds have been highly regulated as highly decomposable and highly accumulative substances, It has been desired to develop a flame retardant having high stability because it generates poisonous hydrogen halide gas. In addition, the above-mentioned halogen-based compound is highly likely to leak into the waste liquid for flame-retardant processing and leak, which is likely to lead to environmental problems. Therefore, phosphorus compounds which do not contain a halogen element have been actively studied for imparting flame retardancy to polyethylene terephthalate, and phosphorus compounds are generally used as multifunctional compounds in various fields, and many varieties have been developed.

Phosphoric acid-based compounds are widely used as phosphoric acid-based flame retardants, and they are becoming increasingly important as alternative flame retardants for halogen-based flame retardants, which are subject to environmental regulations due to suffocation and environmental pollution caused by toxic gas generation during combustion. However, in the case of the phosphoric acid-based flame retardant, the amount of the flame retardant to be added to the resin composition is large in order to add sufficient phosphorus to attain the flame retardant effect, and the excessive addition of the monomolecular substance causes the complexity of the process, (DM Ban et al, European Polymer Journal 40 , 1909-1913, 2004).

Triphenylphosphate (TPP), a typical flame retardant of phosphoric acid, is a substance that gives a flame retardant effect by forming a protective film by condensing a combustible material with solid or gas so that it does not come into contact with oxygen. It is volatilized or decomposed, . However, due to the low melting point of triphenylphosphate (TPP) and the volatility in the liquid phase due to the low melting point and sublimation point of the TPP, the additive type manufacturing method by blending with the polymer resin by extrusion and injection process requires additional cooler and independent apparatus, There is a process difficulty (Shinn-Jen Chang et al. Polymer Engineering and Science , 38 , 1471-1481, 1998).

In order to solve this problem, various angles have been studied, and synergistic effects with conventional phenyl phosphoric acid-based flame retardants have been derived by blending with various phenyl-based epoxy resins including novolak type, (K. Lee, et al., Polymer , 43 , 2249-2253, 2002.).

In addition, monomers containing phosphorus are synthesized and then polymerized or reacted with an epoxy resin by using an amine terminal (Shinn-Jen Chang et al. Journal of Applied Polymer Science , 72 , 109-122, 1999.) have also been reported (Park et al., Polymer (Korea), 22, 901, 1998.), but it is difficult to apply it to commercial PET have.

Due to the poor solubility and chemical resistance properties of polyethylene terephthalate, the chemical processing of conventional polyethylene terephthalate can be carried out either on the surface of the polyethylene terephthalate pellets or on the surface of a swelled form of fibers (Hae-Ryong Lee, Surface and Coatings Technology 142, 468-473, 2001., Xiang Ping, Radiation Physics and Chemistry 79, 941-946, 2010), it is known that it is difficult to achieve sufficient molecular chain bonding. As a result, it is very difficult to achieve flame retardancy to a required level even when the phosphorus compound is used as the flame retardant or when the content is increased to increase the flame retardancy.

Accordingly, there is a technology capable of easily producing a fire retardant polyethylene terephthalate, which can easily induce the formation of charcoal (char) by application of a phosphorus / nitrogen type or inorganic flame retardant which does not generate a toxic gas to the human body .

In order to solve the above-mentioned problems, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a process for producing poly (ethylene terephthalate), which comprises reacting polyethylene terephthalate with phenol, chlorophenol, isopropanol, dimethyl formamide, dimethyl sulphoxide ), Phenol / 1,1,1-trichloroethane co-solvent, nitrobenzene, bis (hydroxyethyl) terephthalate, etc. After dissolving in an organic solvent, a peroxide-based or peroxide-based reaction catalyst is added to form a functional group on polyethylene terephthalate and triphenylphosphate, which is a phosphoric acid-based flame retardant, followed by forming a covalent bond by radical addition reaction to form a polyethylene terephthalate Reactive flame retardant polyethylene terephthalate in which triphenylphosphate as a flame retardant is bonded by an intermolecular covalent bond And to provide a method for manufacturing the same.

By increasing the content of the phosphoric acid-based flame retardant in the flame-retardant polyethylene terephthalate polymer produced by the conventional addition type method through such a manufacturing method, it is possible to simplify the complexity of the process caused between the extrusion and the injection, It is intended to provide a flame retardant polyethylene terephthalate resin having a char yield.

In order to solve the above-mentioned problems, the present invention provides a process for producing a polyethyleneterephthalate polymer resin, which comprises dissolving a polyethylene terephthalate polymer resin and triphenylphosphate as a phosphoric acid flame retardant in an organic solvent, introducing a radical reaction catalyst into the organic solvent, And then causing triphenylphosphine to be covalently bonded by a radical addition reaction. The present invention also provides a method for producing a flame retardant polyethylene terephthalate polymer resin.

The present invention is also directed to a process for the preparation of a compound of formula I wherein the organic solvent is selected from the group consisting of Phenol, Chlorophenol, Isopropanol, Dimethyl formamide, Dimethyl sulphoxide, Phenol / 1,1 , 1,1,1-trichloroethane co-solvent, Nitrobenzene, and bis (hydroxyethyl) terephthalate). A method for producing a flame retardant polyethylene terephthalate polymer resin is provided.

The present invention also provides a method for producing a flame retardant polyethylene terephthalate polymer resin, wherein the radical-based reaction catalyst is a peroxide-based or peroxide-based catalyst.

The present invention also relates to a flame retardant polyethylene terephthalate polymer resin characterized in that the radical type reaction catalyst is ammonia persulfate (APS) or potassium persulfate (KPS) or benzoyl peroxide (BPO) And a manufacturing method thereof.

The present invention also provides a method for producing a flame retardant polyethylene terephthalate polymer resin, wherein the radical addition reaction is carried out at a temperature of 70 ° C or more and 120 ° C or less.

The present invention also provides a method for producing a flame retardant polyethylene terephthalate polymer resin, wherein the radical addition reaction is carried out for 2 to 12 hours.

The present invention also provides a polyethylene terephthalate polymer resin having excellent flame retardancy with a carbonization yield of 25% or more.

The flame-retardant polyethylene terephthalate polymer resin of the present invention is prepared by dissolving polyethylene terephthalate (PET), which is difficult to dissolve in an appropriate organic solvent, and then adding a persulfate or peroxide reaction catalyst to introduce triphenylphosphate Is bonded to activated polyethylene terephthalate, and it is possible to solve the difficulty of the chemical treatment due to the complexity of the process caused by the existing triphenyl phosphate and the chemical resistance of the polyethylene terephthalate, It is possible to produce polyethylene terephthalate having a carbonization yield.

Accordingly, the present invention relates to a method of blending triphenylphosphate, which is a phosphoric acid-based flame retardant, into a polymer resin, in comparison with a conventional method of blending a flame retardant into one component of a polyethylene terephthalate polymer resin, , It is chemically bonded to the polymer chain, and thus it is possible to provide more excellent flame retardancy. Also, the problem of decomposition of the polymer resin due to the volatilization loss and destruction of the flame retardant due to heat and pressure generated during extrusion or injection after the blending, and the role of the phosphoric acid flame retardant as a plasticizer can be solved. This process advantage also has the advantage of simplifying the complexity of existing blending processes.

Also, since the polyethylene terephthalate polymer resin produced in the present invention has a carbonization yield of 25% or more, it plays a role of forming a strong carbon shielding layer on the burning surface of the polymer upon combustion, and thus it is possible to obtain excellent flame retardancy.

1 shows FT-IR absorption spectra of polyethylene terephthalate and pure polyethylene terephthalate (pPET) of Example 1 in which triphenyl phosphate (TPP) is additionally bonded.
2 shows a solid-state ³¹ P-NMR spectrum of polyethylene terephthalate and pure polyethylene terephthalate (pPET) of Example 1 to which triphenylphosphate (TPP) is additionally bonded.
3 shows a TGA thermogravimetric curve of polyethylene terephthalate and pure polyethylene terephthalate (pPET) of Example 1 to which triphenyl phosphate (TPP) is additionally bonded.
FIG. 4 is a graph showing the results of a comparison between the polyethylene terephthalate of Example 1 in which triphenylphosphate (TPP) is additionally bonded and polyethylene terephthalate (Comparative Example 1) to which bisphenol bisdiphenyl phosphate (BDP) is added, lysineol bisphosphate (RDP) (Comparative Example 2) and pure polyethylene terephthalate (pPET).

The inventors of the present invention have conducted studies to solve the difficulty of the process with low persistence of flame retardancy in the case of a polyethylene terephthalate polymer resin produced by blending a conventional flame retardant with a polyethylene terephthalate polymer resin.

TECHNICAL FIELD The present invention relates to a process for producing a reaction-type flame-retardant polymer resin in which triphenylphosphate as a phosphoric acid-based flame retardant is linked to polyethylene terephthalate by an intermolecular covalent bond, and a polymer resin produced thereby, and a peroxide- or peroxide- A catalyst is added to produce an active functional group in polyethylene terephthalate and triphenyl phosphate, and a flame-retardant polymer in which triphenylphosphate, a phosphate-based flame retardant, is chemically bonded to polyethylene terephthalate by covalent bond formation by radical addition reaction.

According to the production method of the present invention, it is possible to provide a flame retardant polyethylene terephthalate having a carbonization yield of 25% or more by reducing the complexity of the process through the production of a polymer resin in which a flame retardant is present in the molecule in a reactive system, Phthalate polymer resin can be provided.

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

The method for producing a flame retardant polyethylene terephthalate polymer according to the present invention comprises the steps of dissolving polyethylene terephthalate and triphenyl phosphate in an organic solvent and then introducing a radical reaction catalyst into the organic solvent to prepare polyethylene terephthalate with triphenylphosphate Is covalently bonded by a radical addition reaction.

Polyethylene terephthalate and triphenyl phosphate are commonly used in this field and can be used without any particular limitation.

Polyethylene terephthalate and triphenyl phosphate are preferably used in a weight ratio of 1.4: 1 to 10: 1. This is a range that can satisfy the inherent physical properties and flame retardancy of polyethylene terephthalate.

The organic solvent is selected from the group consisting of phenol, chlorophenol, isopropanol, dimethyl formamide, dimethyl sulphoxide, phenol / 1,1,1-trichloro (1,1,1-trichloroethane) co-solvent, nitrobenzene, and bis (hydroxyethyl) terephthalate.

The radical-type reaction catalyst causes the polyethylene terephthalate and triphenyl phosphate to have a new active site by migration during the reaction, and by this chain reaction, a flame retardant polyethylene terephthalate resin in which triphenyl phosphate is chemically additionally bonded is obtained.

As the radical type reaction catalyst, a persulfate type or peroxide type reaction catalyst can be preferably used. Examples of the persulfate-based reaction catalyst include ammonia persulfate (APS), potassium persulfate (KPS), sodium persulfate (SPS) hydroxymethanesulfinic acid monosodium salt dehydrate, HSNa) is preferably used. As the peroxide reaction catalyst, benzoyl peroxide (BPO) and dicumylperoxide (DCP) are preferably used. In order to obtain a higher addition rate of the flame retardant, it is preferable to use a persulfate-based reaction catalyst, in particular, ammonia sulfur sulfate.

The addition reaction by the catalyst is preferably carried out at a temperature of 70 ° C to 120 ° C, and it is not preferable because the addition reaction does not occur at a temperature lower than 70 ° C. When the temperature is higher than 120 ° C, the volatilization of the solvent and the radical chain reaction Destabilization is undesirable.

The reaction time is preferably 2 to 12 hours under stable reaction conditions.

The polymer solution in which the addition reaction has been completed is immersed in a suitable solvent capable of stopping the activity of the radical catalyst such as cooled methanol or distilled water to obtain a precipitate and then filtered. As a suitable organic solvent, a co-solvent having a volume ratio of methanol and distilled water of 1: 1 can be preferably used.

Then, the resulting white light colored polymer powder is dissolved in an appropriate organic solvent and the immersing process is repeated to purify the polymer, and then the obtained polymer is dried under vacuum. As a suitable organic solvent, a 1: 1 co-solvent of phenol / 1,1,1-trichloroethane in a volume ratio can be preferably used.

Poly (ethylene terephthalate) to which triphenyl phosphate is additionally bonded has a characteristic of having a carbonization yield of 25% or more. Therefore, when used in combination with polycarbonate and commercial polyethylene terephthalate to which triphenyl phosphate is not added, it can be used as an excellent char carbon protective film formation promoter, and it can be used in combination with other general-purpose polymer resins.

The present invention will now be described in detail with reference to the following embodiments. However, it is to be understood that the technical idea of the present invention is not limited thereto, but can be modified by those skilled in the art.

Example

[Example 1]

2.5 g of polyethylene terephthalate (PET) resin and 1.8 g of triphenyl phosphate (TPP) were mixed in a three-necked flask equipped with a stirrer, a nitrogen inlet tube, a reflux condenser, an anchor type Teflon stirrer and a mechanical stirrer, (Phenol) / 1,1,1-trichloroethane (1: 1 by volume) was put in a 100-ml aliquot, and the mixture was passed through a fatigue roll and a water removal filter to remove oxygen and moisture And the mixture was stirred at 70 DEG C for 2 hours in a nitrogen stream to completely dissolve it.

Thereafter, 5.0 x 10 ^-3 mol of ammonium persulfate (APS) as a persulfate-based reaction catalyst was added to the solution, and the reaction was carried out for 4 hours. When the reaction was completed, the reaction mixture was gradually added dropwise to the co- The resulting precipitate was filtered and dissolved in a 1: 1 volume ratio phenol / 1,1,1-trichloroethane co-solvent and precipitated in a methanol / distilled water co-solvent. Which was repeated three times.

Thereafter, it was dried under vacuum at 55 캜 for 2 days to obtain 2.8 g of an off-white resin powder. The chemical properties of the obtained resin powder were analyzed, and the results are shown in Figs. 1 to 4. Fig.

According to the FT-IR absorption spectrum shown in Fig. 1, the CP peak indicating the bond of carbon and phosphorus not present in pure polyethylene terephthalate (pPET) was observed at 530 cm ^-1 and 600 cm ^-1 in Example 1 . From this, it can be confirmed that triphenylphosphate is chemically bonded to polyethylene terephthalate by radical addition reaction.

FIG. 2 shows the presence or absence of phosphorus through comparison of a ³¹ P-NMR spectrum of a solid sample of the dried sample of Example 1 with pure polyethylene terephthalate (pPET). From this, it was confirmed that triphenylphosphine was converted into polyethylene terephthalate It can be confirmed that the phthalate is chemically additionally bonded.

Analysis of the TGA thermogravimetric curve shown in FIG. 3 confirmed that the poly (ethylene terephthalate) added with triphenyl phosphate had a carbonization yield of 47.2%.

[Example 2]

100 ml of phenol was added to a mixture of polyethylene terephthalate resin and triphenyl phosphate prepared in the same manner as in Example 1, and the mixture was heated at 70 ° C for 2 hours in a nitrogen stream in which oxygen and moisture were removed through a fatigue roll and a water- And completely dissolved by stirring.

5.0 x ^10-3 mol of ammonium ammonia sulfate (APS) was added to the solution, and the mixture was reacted for 2 hours, then immersed in hot methanol and purified three times.

The purified product was dried under vacuum at 55 캜 for 2 days to obtain 2.7 g of an off-white resin powder.

FT-IR and solid phase ³¹ P-NMR measurement of the dried sample confirmed that triphenylphosphate was added to the polyethylene terephthalate.

The TGA thermal weight loss curve of the dried sample was found to have a carbonization yield of 35.2%.

[Example 3]

100 ml of chlorophenol was added to a mixture of polyethylene terephthalate resin and triphenyl phosphate prepared in the same manner as in Example 1, and the mixture was passed through a fatigue roll and a water removal filter to remove oxygen Lt; / RTI > for 1 hour.

2.0 x 10 ^-4 mol of ammonium ammonia sulfate (APS) is added to the solution, reacted for 4 hours, and precipitated in a co-solvent of cold methanol and distilled water. Thereafter, the precipitate was separated by filtration, and then dissolved in phenol / 1,1,1-trichloroethane (co-solvent) of 1: 1 by volume ratio and precipitated three times Lt; / RTI >

The purified product was dried under vacuum at 55 캜 for 2 days to obtain 2.7 g of an off-white resin powder.

From the FT-IR and solid phase ³¹ P-NMR measurements of the dried sample, it was confirmed that the triphenyl phosphate was chemically bonded to the polyethylene terephthalate.

The TGA thermal weight loss curve of the dried sample was found to have a carbonization yield of 29.8%.

[Example 4]

100 ml of nitrobenzene was added to a mixture of polyethylene terephthalate resin and triphenyl phosphate prepared in the same manner as in Example 1, and the mixture was passed through a fatigue roll and a water removal filter, Lt; / RTI > and completely dissolved by stirring.

2.0 x 10 ^-3 mol of benzoyl peroxide (BPO) was added to the solution and the reaction was carried out for 4 hours. Then, the precipitate was separated by filtration and then purified by washing with hot methanol three times.

Thereafter, the purified product was dried under vacuum at 55 캜 for 2 days to obtain 2.8 g of an off-white resin powder.

FT-IR and solid phase ³¹ P-NMR measurement of the dried sample confirmed that triphenylphosphate was added to the polyethylene terephthalate.

The TGA thermogravimetric curve analysis showed that the carbonization yield was 26.0%.

[Example 5]

2.5 g of a polyethylene terephthalate (PET) resin and 1.8 g of triphenyl phosphate (TPP) were mixed with a radical reaction apparatus prepared in the same manner as in Example 1, and phenol / 1,1,1-trichloroethane (1 , 1,1-Trichloroethane) in a volume ratio of 6: 4, and the mixture was thoroughly dissolved by stirring at 110 ° C for 2 hours in a nitrogen stream in which oxygen and moisture were removed through a fatigue roll and a moisture removing filter.

Thereafter, 1.651 × 10 ^-4 mol of ammonium persulfate (APS) as a persulfate-based reaction catalyst was added to the solution, followed by reaction for 4 hours. After the reaction was completed, the precipitate was slowly added dropwise to the co-solvent consisting of cooled methanol and distilled water to obtain a precipitate. The precipitate was filtered to obtain a 6: 4 volume ratio phenol / 1,1,1-trichloroethane (1,1,1- Trichloroethane) co-solvent and precipitated in a methanol / distilled water co-solvent were repeatedly refined three times.

Thereafter, the purified product was dried under vacuum at 55 캜 for 2 days to obtain 3.0 g of an off-white resin powder.

The TGA thermogravimetric curve analysis of the dried sample showed that it had a carbonization yield of 45.2%.

[Example 6]

100 ml of phenol was added to a mixture of polyethylene terephthalate resin and triphenyl phosphate prepared as in Example 5, and the mixture was heated at 110 ° C for 2 hours in a nitrogen stream in which oxygen and moisture were removed through a fatigue roll and moisture removing filter And completely dissolved by stirring.

Then, 1.651 × 10 ^-4 mol of ammonium persulfate (APS) as a persulfate-based reaction catalyst was dissolved in about 10 ml of N, N-dimethylformamide, After the completion of the reaction, the reaction mixture was slowly added dropwise to a co-solvent composed of cooled methanol and distilled water to obtain a precipitate. The precipitate was filtered, and a phenol / 1,1,1-trichloroethane 1,1,1-Trichloroethane) co-solvent. Thereafter, the method of precipitating in a methanol / distilled water co-solvent was repeated three times and purified.

Thereafter, the purified product was dried under vacuum at 55 캜 for 2 days to obtain 2.7 g of an off-white resin powder.

The TGA thermogravimetric curve analysis of the dried samples showed that the carbonization yield was 48.3%.

[Examples 7 to 13]

The remaining conditions were the same as in Example 5 except for the conditions shown in Table 1 below. After that, the purified product was dried under vacuum at 55 ° C for 2 days to obtain an off-white resin powder. Respectively.

Table 1 shows the carbonization yields obtained from the TGA thermal weight reduction curve analysis results of the dried samples obtained in the respective Examples.

Example Radical  catalyst Radical
Amount of catalyst
( mol ) Phosphate flame retardant Organic solvent reaction
Temperature
(° C) reaction
time
( hr ) Yield
(g) carbonization
Yield
(%) Example 7 APS 2.0 x 10 ^-3 TPP Chlorophenol 70 4 2.7 25.1 Example 8 BPO 1.0 x 10 ^-4 TPP Nitrobenzene 70 8 2.8 28.9 Example 9 APS 1.0 x 10 ^-3 TPP phenol 80 4 2.7 22.4 Example 10 APS 2.0 x 10 ^-3 TPP phenol 90 2 2.8 29.8 Example 11 KPS 5.0 x 10 ^-3 TPP Phenol & TCE 80 4 2.9 31.8 Example 12 BPO 5.0 x 10 ^-3 TPP Dimethyl sulfoxide 75 4 2.8 32.6 Example 13 APS 5.0 x 10 ^-3 TPP Phenol & TCE 90 8 2.0 52.1

* TCE: trichlorethylene

[Comparative Example 1]

(Phenol) and 1,1,1-trichloroethane (TCE) were mixed at a ratio of 1: 1 by volume in a mixture of polyethylene terephthalate resin prepared as in Example 1 and bisphenol Avis Diphenyl phosphate (BDP) And the fatigue was completely dissolved by stirring at 70 ° C for 4 hours in a nitrogen stream in which oxygen and moisture were removed through a roll and a moisture removing filter.

5.0 x ^10-3 mol of ammonium ammonia sulfate (APS) was added to the solution, allowed to react for 4 hours, and precipitated in a co-solvent of cold methanol and distilled water. Thereafter, the precipitate was separated by filtration, and then dissolved in a phenol / 1,1,1-trichloroethane co-solvent having a volume ratio of 1: 1 and precipitated three times Lt; / RTI >

Thereafter, it was dried under vacuum at 55 캜 for 2 days to obtain 3.0 g of an off-white resin powder.

From the FT-IR and solid phase ³¹ P-NMR measurements of the dried sample, it can be confirmed that bisphenol Avisid diphenyl phosphate was added to the polyethylene terephthalate, but according to the TGA thermogravimetric curve analysis shown in FIG. 4, Yield. ≪ / RTI >

[Comparative Example 2]

(Phenol) and 1,1,1-trichloroethane (TCE) were added to a mixture of polyethylene terephthalate resin prepared as in Example 1 and a phosphoric acid-based flame retardant, lyscinol bisdiphenyl phosphate (RDP) : 1, and the fatigue was completely dissolved by stirring at 70 ° C for 4 hours in a nitrogen stream in which oxygen and moisture were removed through a roll and a water removal filter.

5.0 x ^10-3 mol of ammonium ammonia sulfate (APS) was added to the solution, allowed to react for 4 hours, and precipitated in a co-solvent of cold methanol and distilled water. Thereafter, the precipitate was separated by filtration, and then dissolved in a phenol / 1,1,1-trichloroethane co-solvent having a volume ratio of 1: 1 and precipitated three times Lt; / RTI >

Thereafter, it was dried under vacuum at 55 캜 for 2 days to obtain 2.9 g of an off-white resin powder.

From the FT-IR and solid phase ³¹ P-NMR measurements on the dried samples, it can be seen that the lyscinol bisdiphenyl phosphate was added to the polyethylene terephthalate, but according to the TGA thermogravimetric curve analysis shown in FIG. 4, It can be confirmed that the carbonization yield is low.

In the case of Comparative Example 1 and Comparative Example 2, intramolecular addition bonding was judged to be more difficult due to steric hindrance as compared with the triphenyl phosphate used in the Examples.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

The polyethylene terephthalate polymer resin and triphenyl phosphate are dissolved in an organic solvent and then a radical reaction catalyst is added to the organic solvent so that the polyethylene terephthalate polymer resin is covalently bound to the triphenylphosphate by a radical addition reaction By weight based on the total weight of the flame retardant polyethyleneterephthalate polymer resin. The method according to claim 1,
The organic solvent may be at least one selected from the group consisting of Phenol, Chlorophenol, Isopropanol, Dimethyl formamide, Dimethyl sulphoxide, Phenol / 1,1,1- (1, 1, 1-trichloroethane) co-solvent, nitrobenzene, and bis (hydroxyethyl) terephthalate. The flame retardant polyethylene terephthalate Method for producing phthalate polymer resin. The method according to claim 1,
Wherein the radical-based reaction catalyst is a peroxide-based or peroxide-based catalyst. The method of claim 3,
Wherein the radical reaction catalyst is ammonia sulfur (APS) or potassium persulfate (KPS) or benzoyl peroxide (BPO). 2. The method according to claim 1, wherein the radical reaction catalyst is ammonium persulfate (APS) or potassium persulfate (KPS) or benzoyl peroxide (BPO). The method according to claim 1,
Wherein the radical addition reaction is carried out at a temperature of 70 ° C or more and 120 ° C or less. The method according to claim 1,
Wherein the radical addition reaction is carried out for 2 to 12 hours. ≪ RTI ID = 0.0 > 11. < / RTI > A polyethylene terephthalate polymer resin produced by the method according to any one of claims 1 to 6, characterized in that the carbonization yield is 25% or more.

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