KR20150047093A - Phosphorus-containing thermoplastic polyester and phosphorus-containing heat-shrinkable tube made therefrom - Google Patents

Abstract

Disclosed is a thermoplastic polyester containing a flame retardant. The polyester has an inherent viscosity of 0.70 dL/g to 1.10 dL/g. In order to prepare the polyester, a phosphorus-containing flame retardant is combined on a matrix polymer chain by modifying a molecular structure of the matrix polymer. The polyester has phosphorus content of 3,000 to 30,000 ppm based on the weight of the polyester, and is suitable for preparing the phosphorus-containing heat shrinkable tubes which permanently have the characteristics of flame retardance. A flame retardant grade of the prepared phosphorus-containing heat shrinkable sleeve can reach UL94 VTM-2 standard or even UL94 VTM-0 standard.

Description

PHOSPHORUS-CONTAINING THERMOPLASTIC POLYESTER AND PHOSPHORUS-CONTAINING HEAT-SHRINKABLE TUBE MADE THEREFROM < RTI ID = 0.0 >

The present invention relates to copolyesters containing phosphorus flame retardants, and more particularly to copolyesters containing such phosphorus flame retardants which are flame retardant and meet the requirements for the UL94 VTM-2 flammability class and satisfy the requirements for the UL94VTM- Polyester

To a heat-shrinkable tube made of terr.

Heat shrinkable tubes are widely used for packaging various conductive materials for protection and insulation. Japanese Patent Nos. 3169104 and 3329410, as well as U.S. Patent Nos. 3,941,752; 4,157,436; 4,940,772; Some of the given techniques, such as 5,665,801 and 5,859,173, have proposed several polyesters containing flame retardants, which have been widely used for producing flame retardant polyester fibers, textiles, films and circuit boards . However, none of the flame retardant heat shrinkable tubing is applicable in this market.

Since PVC is prohibited, heat-shrinkable tubes for use in electrical insulation are no longer made of PVC. As alternatives, although some of the related polyesters disclosed in the prior art are appropriately used to produce heat shrinkable tubes, none of the given prior art uses polyester containing flame retardants to produce heat shrinkable tubes having flame retardancy I do not mention it.

JP 3169104 B2 JP 3329410 B2 US 3,941,752 US 4,157,436 US 4,940,772 US 5,665,801 A US 5,859,173 A

In view of this, the main purpose of the present invention is to provide a flame retardant effect of a thermoplastic polyester having an intrinsic viscosity of between 0.70 and 1.10 dL / g.

Another object of the present invention is to provide a phosphor-containing heat-shrinkable tube having flame retardancy and heat shrinkability.

The flame retardant effect of thermoplastic polyesters having an intrinsic viscosity of between 0.70 and 1.10 dL / g, which is an important feature of the present invention, is achieved by changing the molecular structure of the polyester to a phosphorus containing flame retardant bonded to the molecular chains of the matrix polymer itself .

The disclosed polyesters have a phosphorus content between 3,000 and 30,000 ppm based on the weight of the polyester and are suitable for preparing phosphorus containing heat shrinkable tubes having permanent flame retardancy. The resulting phosphorous heat-shrinkable tube has a UL94 VTM-2 flammability rating and meets the requirements for the UL94 VTM-0 flammability rating.

The disclosed polyester further comprises between 0.005 and 0.5 wt% inorganic particles based on the weight of the polyester, and the inorganic particles having a particle size between 0.1 and 0.5 탆 are selected from titanium oxide, barium sulfate, calcium carbonate, Silicon.

Other prominent flame retardant, heat-shrinkable, heat-shrinkable, heat-shrinkable tubes of the present invention can be made pure with thermoplastic polyesters containing flame retardants containing phosphorus elements, or with phosphorus containing flame retardants and thermoplastic poly Or a mixture of thermoplastic polyesters having an ester.

Flame-retardant and heat-shrinkable phosphorous heat-shrinkable tubes have a machine-directional shrinkage between 5% and 15%, and transverse-shrinkage greater than 35% when exposed to boiling water. directional shrinkage.

The heat-shrinkable tube of the present invention has a phosphorus content between 3,000 and 12,000 ppm, based on its weight, to provide flame retardancy and insulation to the article to be packaged when used to package the article.

When thermally shrunk and packaging the article, the phosphorus containing heat-shrinkable tube is exposed for 30 minutes at a temperature of 180 ° C or exposed for 180 minutes (or 3 hours) at a temperature of 105 ° C, and then wrinkled, slacking, coming-off, chapping, and warping of the article.

The phosphorus containing heat-shrinkable tube has a UL94 VTM-2 flammability rating and meets the requirements for the UL94 VTM-0 flammability rating. Therefore, phosphorus containing heat-shrinkable tubes are suitable for packaging various conductors and / or electronic devices to provide flame retardancy and insulation to packaged conductors and / or electronic devices.

The thermoplastic polyester of the present invention prepared by linking a phosphorus containing flame retardant to the molecular chains of the matrix polymer is in fact a copolyester polymer (hereinafter referred to as phosphorus containing thermoplastic polyester) as a result of the modification of the molecular structure of the matrix. The disclosed thermoplastic polyesters are permanently flame retardant and are suitable for making flame retardant heat shrinkable tubes. When used to package electronic devices, the heat-shrinkable tube disclosed provides flame retardancy and insulation to the packaged article.

The disclosed phosphorus containing thermoplastic polyesters are made from dioic acid, diol and phosphorus containing flame retardant elements through conventional processes for synthesizing polyesters. For example, a PTA manufacturing process or a DMT manufacturing process can be used to synthesize phosphorus containing thermoplastic polyesters. In this case, the phosphorus-containing flame retardant may be added at any time before the end of the esterification of the dioic acid and the diol, or directly to the plasma of the dioic acid and the diol.

Dioic acid is predominantly pure terephthalic acid (PTA) or an ester thereof, isophthalic acid; 2,6-naphthalene dicarboxylic acid; Or additional secondary components such as their esters can be added. However, these secondary elements are not necessary and, if used, form less than 15 mol% of the co-polyester together.

Diols are mainly ethylene glycol (EG), diethylene glycol; 1,4-cyclohexanedimethanol; Propylene glycol; 2,2-dimethyl-1,3-propylene glycol (NPG); Additional secondary diols such as one selected from the group consisting of 2-ethyl-2-butyl-1,3-propylene glycol (BEPG) and butanediol may be added. However, these secondary diols are not necessary, and if used, less than 15 mol% of the copolyester is formed together. Otherwise, the resulting phosphorus-containing thermoplastic polyester will be in an amorphous state and tend to have aggregation during solid-state polycondensation, which makes it difficult to increase the intrinsic viscosity of the phosphorus containing thermoplastic polyester.

The phosphorus containing flame retardant is one of the phosphorus containing compounds selected from those having the chemical structures of (I), (II), (III), (IV), (V), (VI), (VII) (II), (III), or (IV): < EMI ID =

(I)

;

;

(II)

;

;

(III)

;

;

(IV)

;

;

(V)

;

;

(VI)

;

;

(VII)

;

;

(VIII)

, 여기서 n은 양의 정수이다.

, Where n is a positive integer.

The disclosed phosphorus containing thermoplastic polyester has a phosphorus content between 3,000 and 30,000 ppm based on the weight of the polyester. When the phosphorus containing thermoplastic polyester has a phosphorus content of less than 3,000 ppm, the resulting heat-shrinkable tube does not meet the requirements for the UL94 VTM-2 flammability rating. On the other hand, when the content of phosphorus is higher than 30,000 ppm, it is difficult for the polyester to have an intrinsic viscosity reaching a range of between 0.70 and 1.10 dL / g, and an undesirably low intrinsic viscosity makes the polyester Making it more unstable and can cause severe thickness variations of the produced heat shrinkable tubes.

The disclosed phosphorus containing thermoplastic polyesters have an intrinsic viscosity between 0.70 and 1.10 dL / g, preferably between 0.80 and 1.00 dL / g, and most preferably between 0.80 and 0.90 dL / g. It is possible to directly increase the intrinsic viscosity in the range of between 0.70 and 1.10 dL / g during the melt polymerization process when using the PTA or DMT production process to synthesize the polyester. Instead, it is possible to increase the intrinsic viscosity to between 0.70 and 1.10 dL / g during the solid-state polymerization process. When the phosphorus containing thermoplastic polyester has an intrinsic viscosity lower than 0.70 dL / g, the heat shrinkable tubes produced by melting and extruding the polyester tend to have a non-uniform thickness. On the other hand, if the intrinsic viscosity is higher than 1.10 dL / g, in the process of melting and extruding the polyester to produce the heat shrinkable tubes, the material release tends to be disturbed and the extrusion of the heat shrinkable tubes and the tube- Making the process difficult.

The following description is of an example in which the PTA preparation process is carried out to produce the phosphorus containing thermoplastic polyester disclosed. This PTA manufacturing process consists of the following steps:

1. A process for adding a phosphorus-containing flame retardant to a batch of plasma containing pure terephthalic acid (PTA) and ethylene glycol (EG), wherein the EG / PTA molar ratio is between 1.0 and 2.0;

2. Continuously pumping the plasma into an esterification reactor for the first direct esterification wherein the ethylene glycol and water formed during the direct esterification are led to the distillation column through the vaporization tube for separation and are fed to the bottom of the distillation column The ethylene glycol collected is redirected to the esterification reactor;

Here, the material temperature for the esterification is between 240 and 270 캜, preferably between 250 and 260 캜, and the esterification pressure is between the normal atmosphere and 2.0 Kg / cm 2, preferably between 0.01 and 1.0 Kg / And the esterification time is between 3 and 8 hours, preferably between 4 and 6 hours, and the conversion ratio of the monomer at the outlet of the esterification reactor is at least 92%, preferably higher than 95%.

3. Performing a second polycondensation, wherein the monomers produced by the esterification described above are pumped to the prepolymerization tank for prepolymerization;

Wherein the material temperature for the prepolymerization is between 260 and 280 占 폚, preferably between 250 and 260 占 폚; The prepolymerization pressure is between 10 and 200 mmHg; The prepolymerization time is between 0.5 and 2.0 hours; Wherein the gaseous by-products of the prepolymerization, such as ethylene glycol, are vacuum pumped into the cooler to cool to the liquid;

4. In order to increase its intrinsic viscosity to 0.50 dl / g or more, more preferably 0.60 dl / g or more, and most preferably 0.70 dl / g or more,

For further polycondensation, the oligomer produced by the above-described prepolymerization is subjected to a high vacuum fini-

Continuously purging with a syringe;

Wherein the material temperature in the finisher is between 265 and 290 C, preferably lower than 285 C; Wherein the vacuum pressure in the finisher is less than 2 mm Hg; And

5. Continuously pumping the polymer produced by the finisher to the die head, which is extruded as rods in the die head, which is then cut with a grain cutter with the grains of the disclosed phosphorus containing thermoplastic polyester Said step being rapidly cooled by cold water before becoming.

The following description refers to an example of a DMT production process that is carried out to produce the phosphorus containing thermoplastic polyester disclosed. This DMT manufacturing process includes the following steps:

1. Step of taking the ester of dioic acid as a material for carrying out an ester exchange reaction with a diol and adding an ester exchange catalyst such as manganese acetate before the reaction starts wherein methanol generated in the ester exchange reaction is separated And not introduced into the transesterification tank;

2. adding phosphorus-containing flame retardant at any time before the end of the esterification; And

3. A catalyst selected from antimony catalyst, germanium catalyst, titanium catalyst and any combination thereof is added to effect polymerization in a vacuum environment when the produced amount of methanol reaches 98% theoretical capacity, Upon reaching a viscosity of greater than 0.7 dL / g, immediately removing the copolyester from the polymerization step, rapidly cooling it and cutting it into phosphorus containing thermoplastic polyesters (grains).

Another method of making the disclosed phosphorus containing thermoplastic polyesters is to melt-mix the phosphorus containing flame retardant and the phosphorus-free thermoplastic polyester to obtain a phosphorus containing thermoplastic polyester having an intrinsic viscosity between 0.70 and 1.10 dL / g, Solid-state polymerization to the mixture.

The disclosed phosphorus containing thermoplastic polyester further comprises between 0.005 and 1.0 wt%, preferably between 0.005 and 0.5 wt%, and most preferably between 0.01 and 0.5 wt% inorganic particles, based on the weight of the polyester do. The inorganic particles must be added in the reactor after the end of the esterification reaction but before the polymerization begins.

The inorganic particles are selected from titanium oxide, barium sulfate, calcium carbonate or silicon dioxide and have a particle size of less than 1 탆, preferably between 0.1 and 0.5 탆.

The inorganic particles and the phosphorus-free thermoplastic polyester can together form a masterbatch, and then the masterbatch is subjected to a melt mixing process together with the phosphorus-containing flame retardant to form the disclosed phosphorus-containing thermoplastic polyester.

The heat-shrinkable tube of the present invention is made from the disclosed phosphorus-containing thermoplastic polyester. Based on the weight of the heat shrinkable tube, the tube has a phosphorus content between 3,000 and 12,000 ppm and is a flame retardant heat shrinkable tube (hereinafter referred to as phosphorus containing heat shrinkable tube).

The disclosed phosphorus containing heat-shrinkable tube has a thickness between 20 and 200 [mu]

With a circumference of 300 mm, it has a UL94 VTM-2 flammability rating and meets the requirements for the UL94 VTM-0 flammability rating.

The disclosed phosphorus-containing heat-shrinkable tube is capable of preventing melt-dropping when burned and made of a phosphorus-containing thermoplastic polyester containing inorganic particles, and satisfies the requirements for UL94 VTM-0 flammability rating .

The disclosed phosphorus containing heat-shrinkable tube is produced through the following steps:

1. As the starting material, only the disclosed phosphorus containing thermoplastic polyester or a mixture of phosphorus-containing thermoplastic polyester and phosphorus-free thermoplastic polyester disclosed in a weight ratio of 10 to 40: 60 to 90 (hereinafter collectively referred to as phosphorus containing thermoplastic poly Ester) and drying the phosphorus-containing thermoplastic polyester for 4 to 6 hours in a dehumidified air at 150 to 170 ° C;

2. melting the phosphorus containing thermoplastic polyester in a gel at a temperature between 250 and 270 캜 and extruding the phosphorus containing thermoplastic polyester gel into unstretched hollow tube preforms using an extruder with a die such as a ring;

3. Immediately pass the preforms through a cooling bath for cooling and transfer the preforms to a set of rotational speeds set at 100 rpm to transport the preforms to a hot water bath or an infrared lamp heating apparatus where the preforms are heated to a temperature above their glass transition temperature Passing the preforms between the feed rollers and then introducing compressed air to blow the preforms so that the preforms have a diameter that extends 1.3 times or more, wherein the temperature of the tube- Between 85 DEG C and 105 DEG C; And

4. Taking an expanded tube with a set of nip rollers having a set rotational speed of 105 rpm to obtain the phosphorus containing heat shrinkable tube described.

The unstretched hollow tube preform for the disclosed phosphorus containing heat shrinkable tube expands in the transverse direction (TD) during the tube-blowing process and expands twice in the machine direction (MD) as it passes through the feed and nip rollers. As a result, the disclosed phosphorus containing heat shrinkable tube has a machine direction (MD) tensile ratio equal to the ratio between the tensile speed for the expanded tube and the feed rate for the preform, and the ratio between the diameter of the expanded tube and the diameter of the preform (TD) tensile ratio. ≪ / RTI >

The disclosed phosphorus containing heat shrinkable tube preferably has a machine direction (MD) tensile ratio between 1.0 and 3.0, and a transverse (TD) tensile ratio between 1.3 and 4.5.

The disclosed phosphorus containing heat shrinkable tube is immediately cooled after heat shrinkage in the machine direction (MD) and the transverse direction (TD), and is heat shrinkable. In other words, when heat is applied, the heat-shrinkable tube is contracted in the transverse direction (TD) and the machine direction (MD). Therefore, once the disclosed phosphorus-containing heat-shrinkable tube is heated after being mounted around the article, it causes lateral (TD) shrinkage and machine direction (MD) shrinkage to fit the article tightly.

The disclosed phosphorus containing heat-shrinkable tube further has the following characteristics:

1. After immersing in boiling water at 100 ° C for 30 seconds, the phosphorus containing heat shrinkable tube has a machine direction (MD) heat shrinkage of between 5% and 15% and a transverse (TD) heat shrinkage of greater than 35% .

If the machine direction (MD) heat shrinkage ratio is less than 5%, the phosphorus containing heat shrinkable tube can not fit the article properly. If the machine direction (MD) heat shrinkage ratio is higher than 15%, the phosphorus containing heat shrinkable tube can be deformed and displaced when packaging the article. If the transverse (TD) heat shrinkage is less than 35%, the wrapping closeness of the heat shrinkable tube may be insufficient.

2. When thermally shrinking and packing the article, the phosphorus-containing heat-shrinkable tube is exposed to a temperature of 180 ° C for 30 minutes or exposed to a temperature of 105 ° C for 180 minutes, thereby causing wrinkles, bumps, loosening, peeling, And the article is completely wrapped without defects of warpage.

3. The phosphorous heat-shrinkable tube is applicable for packaging aluminum capacitors, lithium batteries and motor coils to impart flame retardancy and insulation to packaged aluminum capacitors, lithium batteries and motor coils.

4. The phosphorus containing heat-shrinkable tube, when containing inorganic particles, can be more relaxed after rolling up.

5. Phosphorus-containing heat-shrinkable tubes printed in patterns remain crisp and clear, even after being cleaned by acetone.

Other methods of making the disclosed phosphorus containing heat shrinkable tubing are accomplished using a double bubble tubular film extrusion process.

Several examples and comparative examples are given below to further illustrate the physical properties and properties of the heat-shrinkable tube disclosed.

1. Test for flammability rating :

UL94-VTM thin material run according to vertical combustion test.

2. Test for stability during tube blowing :

Observe whether the heat-shrinkable tube has a uniform thickness.

3. Testing for packaging appearance :

When the phosphorus containing heat-shrinkable tube is thermally shrunk to package the article, after it is placed in the oven for 30 minutes to be exposed to a temperature of 180 ° C or to be exposed to a temperature of 105 ° C for 180 minutes, Observe whether it fits perfectly on the surface of the article without shattering, peeling, bursting and twisting.

[Preformed "phosphorless grains"]

Sample PET-A Polyester Grain: Copolyester containing about 2.5 mole% IPA

Sample PET-C Polyester Grain: Copolyester containing about 10 mole% IPA

 [Preformed "phosphorus polyester grains"]

< PET- F1 polyester grain>: Using flame retardant (I)

(I) (i.e., propionic acid 3- (hydroxyphenylphosphinyl)) and 3.243 parts by weight of ethylene glycol (EG) were added to a mixture of 10.81 parts by weight of bis-hydroxyethyl terephthalate monomer (abbreviated here as BHET), 0.4478 parts by weight of flame retardant And then these materials are put into the reactor for the melt polymerization process reaction.

According to the process described above for producing the disclosed phosphorus containing thermoplastic polyester, the arrangement of phosphorus containing polyester grains having a phosphorus content of 6,000 ppm and an intrinsic viscosity for melt polycondensation of 0.65 dL / g was synthesized. After solid-state polymerization, the resulting PET-F1 polyester grains had an intrinsic viscosity of 0.80 dL / g.

< PET- F2 polyester grain>: Using flame retardant (Ⅱ)

10.81 parts by weight of BHET, 0.522 parts by weight of flame retardant (II) (i.e., oxaphosphorane glycol ester) and 3.243 parts by weight of ethylene glycol (EG) were measured and then the materials were fed into the reactor for the melt polymerization reaction.

According to the process described above for producing the disclosed phosphorus containing thermoplastic polyester, the arrangement of phosphorus containing polyester grains having a phosphorus content of 6,000 ppm and an intrinsic viscosity for molten polycondensation of 0.65 dL / g was synthesized. After solid-state polymerization, the resulting PET-F2 polyester grains had an intrinsic viscosity of 1.10 dL / g.

< PET- F3 polyester grain>: Using flame retardant (Ⅲ)

10.81 parts by weight of BHET, 0.84 parts by weight of flame retardant (III) (i.e., butanedioic acid, bis (2-hydroxyethyl) (6H-dibenz [c, e] [1,2] oxaphosphorin- ) Ester) and 3.243 parts by weight of ethylene glycol (EG) were measured, and then these materials were charged to the reactor for the melt polymerization reaction.

According to the process described above for producing the disclosed phosphorus containing thermoplastic polyester, the arrangement of phosphorus containing polyester grains having a phosphorus content of 6,000 ppm and an intrinsic viscosity for molten polycondensation of 0.65 dL / g was synthesized. After solid-state polymerization, PET-F3 polyester grains have an intrinsic viscosity of 0.9 dL / g.

< PET- F4 polyester grain>: Using flame retardant (IV)

10.81 parts by weight of BHET, 0.8695 parts by weight of a flame retardant (IV) (i.e., 2- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Phenoxy) phenylene ester) and 3.243 parts by weight of ethylene glycol (EG) were measured, and then these materials were fed into the reactor for the melt polymerization reaction.

According to the process described above for producing the disclosed phosphorus containing thermoplastic polyester, the arrangement of phosphorus containing polyester grains having a phosphorus content of 6,000 ppm and an intrinsic viscosity for molten polycondensation of 0.65 dL / g was synthesized. After solid-state polymerization, PET-F4 polyester grains have an intrinsic viscosity of 0.9 dL / g.

< PET- F5 polyester grain>: Using flame retardant (I)

The obtained PET-F5 polyester grain was produced by the same synthetic process as that for producing PET-F1 polyester, in addition to having a phosphorus content of 30,000 ppm and an intrinsic viscosity for melt polycondensation of 0.60 dL / g. After solid-state polymerization, PET-F5 polyester grains have an intrinsic viscosity of 0.80 dL / g.

< PET- F6 polyester grain>: Using flame retardant (I)

The obtained PET-F6 polyester grain had the same content as that of PET-F1 polyester, in addition to having a phosphorus content of 6,000 ppm, a calcium carbonate content of 3,000 ppm and an intrinsic viscosity for melt polycondensation of 0.65 dL / g. It is produced by a synthetic process. After solid-state polymerization, PET-F6 polyester grains have an intrinsic viscosity of 0.8 dL / g.

< PET- F7 polyester grain>: Using flame retardant (I)

To synthesize phosphorus-containing polyester grains containing 6,000 ppm of phosphorus, a twin-screw extruder was used to melt and mix the PET-A polyester grain and flame retardant (I) Wherein the phosphorus-containing thermoplastic polyester is produced using a process for producing the disclosed phosphorus-containing thermoplastic polyester. After solid-state polymerization, PET-F7 polyester grains have an intrinsic viscosity of 0.8 dL / g.

[Example 1]

Heat shrinkable tubes were made of PET-F1 polyester grains. The formulas and test results of the polyester grains are listed in Table 1.

[Example 2]

Heat shrinkable tubes were made of PET-F2 polyester grains. The formulas and test results of the polyester grains are listed in Table 1.

 [Example 3]

Heat-shrinkable tubes were made of PET-F3 polyester grains. The formulas and test results of the polyester grains are listed in Table 1.

 [Example 4]

Heat shrinkable tubes were made of PET-F4 polyester grains. The formulas and test results of the polyester grains are listed in Table 1.

 [Example 5]

The heat-shrinkable tube was made of PET-A polyester grain and PET-F5 polyester grain premixed at a weight ratio of 60:40. The formulas and test results of the polyester grains are listed in Table 1.

[Example 6]

The heat-shrinkable tube was made of PET-A polyester grain and PET-F5 polyester grain premixed at a weight ratio of 80:20. The formulas and test results of the polyester grains are listed in Table 1.

[Example 7]

The heat-shrinkable tube was made of PET-A polyester grain and PET-F5 polyester grain premixed at a weight ratio of 90:10. The formulas and test results of the polyester grains are listed in Table 1.

[Example 8]

Heat shrinkable tubes were made of PET-F6 polyester grains. The formulas and test results of the polyester grains are listed in Table 1.

[Example 9]

Heat shrinkable tubes were made of PET-F7 polyester grain. The formulas and test results of the polyester grains are listed in Table 1.

[Comparative Example 1]

The heat-shrinkable tube was made of PET-C polyester grain. The formulas and test results of the polyester grains are listed in Table 1.

[Comparative Example 2]

The heat-shrinkable tube was made of PET-C polyester grain and PET-F5 polyester grain premixed at a weight ratio of 92: 8. The formulas and test results of the polyester grains are listed in Table 1.

[Comparative Example 3]

The heat-shrinkable tube was made into PET-F1 polyester grain before solid-state polymerization (IV = 0.65 dL / g). The formulas and test results of the polyester grains are listed in Table 1.

Table 1: Weight-based formulas of polyester grains and measurements of heat-shrinkable tubes made therefrom

week:

1. PET-A contains 2.5 mole% of IPA; IV = 0.72 dl / g;

2. PET-C contains 10 mole% of IPA; IV = 0.85 dl / g;

3. PET-F1 uses flame retardant (I) and has a phosphorus content of 6,000 ppm; IV = 0.80 dl / g;

4. PET-F2 uses flame retardant (II) and has a phosphorus content of 6,000 ppm; IV = 1.10 dl / g;

5. PET-F3 uses flame retardant (III) and has a phosphorus content of 6,000 ppm; IV = 0.90 dl / g;

6. PET-F4 uses flame retardant (IV) and has a phosphorus content of 6,000 ppm; IV 0.90 dl / g;

7. PET-F5 uses flame retardant (I) and has a phosphorus content of 30,000 ppm; IV = 0.80 dl / g;

8. PET-F6 uses flame retardant (I) and has a phosphorus content of 6,000 ppm and a calcium carbonate content of 3,000 ppm; IV = 0.80 dl / g;

9. PET-F7 is prepared using a twin-screw extruder, using flame retardant (II) and having a phosphorus content of 6,000 ppm; IV = 0.80 dl / g.

Results :

According to Table 1, phosphorus containing heat-shrinkable tubes made from the polyesters of Examples 1 to 9 were found to have flame retardancy and heat shrinkability, and the flame retardancy ability satisfied at least the requirements for UL94 VTM-0 flammability rating . In addition, all of the resulting phosphorus containing heat-shrinkable tubes exhibited pavement integrity after 180 ° C-heating for 30 minutes and after heating at 105 ° C for 3 hours, thereby meeting industry specifications.

Claims (7)

A phosphorus-containing thermoplastic polyester for use in the manufacture of phosphorus containing heat-shrinkable tubes having a UL94 VTM-2 flammability rating,
Said polyester having an intrinsic viscosity between 0.70 and 1.10 dL / g and a phosphorus content between 3000 and 30,000 ppm, based on the weight of said polyester, in the presence of the phosphorus containing flame retardant added prior to termination of the esterification, (PTA) or its ester reacts with ethylene glycol (EG) with a molar ratio (EG / PTA) of EG to PTA in the range of between 1.0 and 2.0 to continuously undergo the polymerization and polycondensation processes ; The phosphorus containing flame retardant is selected from phosphorus containing compounds selected from those having the following chemical formulas (I), (II), (III), (IV), (V), (VI), (VII) Or a combination thereof. The phosphorus-containing thermoplastic polyester according to claim 1,
(I)

;
(II)

;
(III)

;
(IV)

;
(V)

;
(VI)

;
(VII)

;
(VIII)

. The method according to claim 1,
Based on the weight of the polyester, the polyester further comprises between 0.005 and 0.5 wt% inorganic particles, and the inorganic particles having a particle size between 0.1 and 0.5 탆 are selected from the group consisting of titanium oxide, barium sulfate, calcium carbonate Or silicon dioxide. &Lt; Desc / Clms Page number 24 &gt; 3. The method according to claim 1 or 2,
The intrinsic viscosity of the polyester is between 0.80 and 1.00 dL / g
Containing thermoplastic polyester. A phosphorus-containing heat-shrinkable tube made of the phosphorus-containing thermoplastic polyester of claim 1,
Having a phosphorus content between 3,000 and 12,000 ppm based on the weight of the heat-shrinkable tube and having machine directional shrinkage between 5% and 15% and transverse shrinkage greater than 35% when exposed to boiling water, -2 &lt; / RTI &gt; flammability rating. 5. The method of claim 4,
The phosphorous-containing heat-shrinkable tube is thermally shrunk to package the article and then heated at a temperature of 180 ° C for 30 minutes or at 105 ° C for 3 hours, followed by creases, bumps, loosening, peeling, Lt; RTI ID = 0.0 &gt; and / or &lt; / RTI &gt; torsion and without defects of warping. A phosphorus-containing heat-shrinkable tube made of the phosphorus-containing thermoplastic polyester of claim 2,
Based on the weight of the heat-shrinkable tube, a phosphorus content between 3,000 and 12,000 ppm and between 0.01 and 0.5 wt% inorganic particles, mechanical-directional shrinkage between 5% and 15% when exposed to boiling water and 35 % &Lt; / RTI &gt; and has a UL94 VTM-0 flammability rating. The method according to claim 6,
The phosphorous-containing heat-shrinkable tube is thermally shrunk to package the article and then heated at a temperature of 180 ° C for 30 minutes or at 105 ° C for 3 hours, followed by creases, bumps, loosening, peeling, Lt; RTI ID = 0.0 &gt; and / or &lt; / RTI &gt; twist, and still maintain complete packaging conditions without defects of warpage.