KR101404983B1 - biodegradable copolyester resin with flame retardant property and method of manufacturing the same - Google Patents

Abstract

A copolyester resin having flame-retardant properties and biogradability at the same time is manufactured by condensation polymerizing a dicarboxylic acid component consisting of a mixture of (a) aromatic dicarboxylic acid and (b) aliphatic dicarboxylic acid as a first copolymer component; a glycol component selected from a group consisting of (c) aliphatic diol, (d) isosorbide, neopentyl glycol or a mixture thereof and a mixture thereof as a second copolymer component; and (e) a phosphorus reactive flame retardant as a third copolymer component, and has excellent radio-processability, flame-retardant properties and biodegradability.

Description

[0001] The present invention relates to a biodegradable copolyester resin having flame retardancy and a flame retardant property,

The present invention relates to a copolyester resin having both flame retardance and biodegradability and a method for producing the same. More specifically, the present invention relates to a cosolvent having excellent heat resistance, flame retardancy and biodegradability by using at least one of comonomer components of neopentyl glycol and isosorbide derived from biomass which can improve biodegradability based on an aromatic compound Resin and a process for producing the same.

There are many social problems in the world regarding environmental pollution. In the case of various plastics used in the conventional industrial fields, it is difficult to decompose natural materials and it is often treated by landfill and incineration after use. However, It is a harmful substance to cause environmental pollution.

As a countermeasure against the above-mentioned wastes, recently, abandoned PET bottles are greatly contributed to reduce environmental pollution by recycling them as raw materials, but they are not a fundamental solution.

Research on biodegradable resins has been actively pursued as a fundamental solution and has attracted much interest worldwide. Currently available biodegradable resins include starch polymers, polylactide (PLA), polybutylene succinate (PBS), and polybutylene terephthalate-adipate (PBTA).

However, the biodegradable resin is biodegradable and has a limited use due to its low heat resistance. Recently, the application of flame retardant fibers to clothing, wallpaper, and bedding has been increasing rapidly, due to the increasing awareness of safety from the risk of fire, especially in developed countries.

For example, in the United States, the Consumer Product Safety Commission (CPSC) requires that baby sleepwear imported into the United States use permanent flame retardant products. 16CFR 1615 is a special regulation regulating flame retardancy in infant and children's pajamas from 0 to 6 years old and 16CFR 1616 from 7 to 14 years old.

Conventionally, a flame retardant in the form of an inorganic additive was added to exhibit flame retardancy.

Korean Patent No. 4,049,383 discloses a method for producing a flame-retarded fiber by copolymerizing a polyester with an excess amount of a phosphorus-based flame retardant, and shows a technical result that the flame retardancy and the fairness are good. However, the flame retardant in the form of an inorganic additive has a problem that it can be removed during use. In order to secure the flame retardancy required for the recent US pajamas, the content of phosphorus copolymer added is 1 to 4% by weight, ≪ / RTI &

In order to solve these problems, the present inventors have developed a technique for producing a copolyester resin having flame retardancy and biodegradability at the same time by using a reactive type flame retardant in the production of a biodegradable copolyester resin based on an aromatic compound having excellent heat resistance It is as follows.

An object of the present invention is to provide a copolyester resin having excellent flame retardancy and biodegradability both having excellent heat resistance, excellent in spinning processability and a method for producing the same.

Another object of the present invention is to provide a fiber produced from a biodegradable copolyester resin having flame retardancy.

The above and other objects of the present invention can be achieved by the present invention described below.

The copolyester resin having flame retardance and biodegradability at the same time according to the present invention is a dicarboxylic acid component composed of a mixture of (a) an aromatic dicarboxylic acid and (b) an aliphatic dicarboxylic acid as a first copolymerization component; (C) an aliphatic diol, (d) a glycol component comprising isosorbide, neopentyl glycol or a mixture thereof as the second copolymerization component; And (e) a phosphorus-reactive flame retardant as the third copolymerization component.

(a) may be an aromatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof. (b) an aliphatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof.

The dicarboxylic acid component comprises (a) 85 to 95 mol% of an aromatic dicarboxylic acid, and (b) 5 to 15 mol% of an aliphatic dicarboxylic acid.

The glycol component comprises (d) 1 to 10 mol% of biosmooth derived isosorbide or 1 to 10 mol% of neopentyl glycol.

The phosphorus reactive flame retardant (e) includes 3,000 to 20,000 ppm of phosphorus in the resin.

The aliphatic dicarboxylic acid is at least one selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, and sebacic acid.

The glycol component is at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, polyethylene glycol and isosorbide.

The phosphorus reactive flame retardant includes any one of compounds represented by the following formulas (1) to (3).

In the above formulas, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

In embodiments of the present invention, the biodegradable copolyester resin is prepared using at least one catalyst selected from the group consisting of antimony, germanium, manganese acetate, titanium, and mixtures thereof as a reaction catalyst.

Hereinafter, the present invention will be described in detail.

The copolyester resin according to the present invention is excellent in heat resistance, spinnability and biodegradability. Therefore, it is very useful for manufacturing environment-friendly high quality polyester woven fabrics, nonwoven fabrics and industrial textile products. Also, since it has flame retardant property, it can satisfy the flame retardant performance for clothes and bedding, and thus it is possible to provide a product safe against fire.

The present invention relates to a method for producing a copolyester resin having flame retardance and biodegradability at the same time, and it is a method for producing a copolyester resin having both flame retardancy and biodegradability by using at least one of a copolymerization component of biosmale derived isosorbide and neopentyl glycol capable of improving biodegradability based on an aromatic compound And is excellent in heat resistance, flame retardancy and biodegradability.

Biodegradable Copolyester  Suzy

The biodegradable copolyester resin according to the present invention comprises, as a first copolymerization component, a dicarboxylic acid component comprising a mixture of (a) an aromatic dicarboxylic acid and (b) an aliphatic dicarboxylic acid; (C) an aliphatic diol and (d) a glycol component comprising isosorbide, neopentyl glycol or a mixture thereof; And (e) a compound of any one of the following formulas (1) to (3) as a third copolymerization component.

(a) may be an aromatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof. (b) an aliphatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof.

In the above formulas, R1, R2, R3, R4, and R5 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

Wherein the dicarboxylic acid component as the first copolymerization component comprises (a) 85 to 95 mol% of an aromatic dicarboxylic acid; And (b) 5 to 15 mol% of an aliphatic dicarboxylic acid. As the aromatic dicarboxylic acid, terephthalic acid, dimethylterephthalic acid and the like can be used. As the aliphatic dicarboxylic acid, succinic acid, glutaric acid, Dipentaerythritol, pimelic acid, suberic acid, azelaic acid, sebacic acid, and cyclic aliphatic dicarboxylic acid, and glutaric acid is preferably used.

The aromatic dicarboxylic acid, its acid anhydride or a mixture thereof may be contained in an amount of 85 to 95 mol% based on 100 mol% of the total dicarboxylic acid component. When the aromatic dicarboxylic acid, its acid anhydride or a mixture thereof is contained in an amount of less than 85 mol%, the color, heat resistance and spinnability may be lowered and the strength of the fiber produced from the aromatic dicarboxylic acid, When it is contained in an amount exceeding the mol%, the rate of biodegradation is remarkably lowered and the effect of improving the biodegradability may be insufficient.

Wherein the glycol component as the second copolymerization component comprises (c) 80 to 99 mol% of an aliphatic diol; And (d) 1 to 20 mol% of isosorbide, neopentyl glycol or a mixture thereof, wherein the glycol component includes ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, polyethylene glycol , Isosorbide and the like can be used, and ethylene glycol is preferably used.

The isosorbide refers to 1,4: 3,6-dianhydro-D-sorbitol as a glycol derived from biomass and can be easily prepared from a renewable source such as sugars and starches, and the isosorbide Increases the glass transition temperature (Tg) and disturbs the structural regularity of the molecular chains of the copolymerized polyester, thereby improving biodegradability. Therefore, when a certain amount of isosorbide is used, the biodegradable copolyester resin in the present invention can increase the glass transition temperature and further improve the biodegradability.

The isosorbide is preferably contained in an amount of 1 to 10 mol% based on 100 mol% of the total glycol component. When the isosorbide is contained in an amount of less than 1 mol%, the effect of improving the biodegradability and the glass transition temperature may be insufficient, and when the isosorbide is contained in an amount exceeding 10 mol%, the color, heat resistance and spinnability may be deteriorated .

The neopentyl glycol may be contained in an amount of 1 to 10 mol%, preferably 3 to 10 mol%, based on 100 mol% of the total glycol component. When the neopentyl glycol is contained in an amount exceeding 10 mol%, the spinning processability may be deteriorated.

The phosphorus-containing flame retardant (e) as the third copolymerization component includes 3,000 to 20,000 ppm of phosphorus in the resin based on phosphorus atoms. In case of less than 3,000ppm, the flame retardancy test for Nursery pajamas of USA can not pass 6CFR 1615, and the test result of NFPA 701, which is a flammability test standard of France, shows poor flame retardancy at M2 level. On the other hand, there is a problem that the basic property of the fiber may be lowered due to excessive copolymerization at 20,000 ppm or more, and the process may be deteriorated due to rapid yarn splicing during the spinning process.

Biodegradable Copolyester  Method of producing resin

(1) Step 1: Melting of dicarboxylic acid component and glycol component

The first step of the biodegradable copolyester resin production process comprises (d) a dicarboxylic acid component comprising a mixture of (a) an aromatic dicarboxylic acid and (b) an aliphatic dicarboxylic acid, and (c) Glycerol, isosorbide, neopentyl glycol or a mixture thereof, and then the mixture is melted at a temperature of 220 ° C or higher.

(a) may be an aromatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof. (b) an aliphatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof.

(2) Step 2: Preparation of oligomers having a degree of polymerization of 3 or more

In the second step of the biodegradable copolyester resin production method, a catalyst is added to a mixture in which the dicarboxylic acid component and the glycol component are melted to increase the activity of the aromatic component, and the ester is reacted at a temperature of 220 to 250 ° C. for 1 hour or more Or an ester exchange reaction is carried out to prepare an oligomer having a degree of polymerization of 3 or more and to distill off water, methanol or water as a by-product.

In the embodiment of the present invention, zinc (Zn), cobalt (Co), antimony trioxide (Sb ₂ O ₃ ), titanium (Ti), germanium (Ge), manganese (Mn) A metal compound contained therein or a mixture thereof may be used, and it is preferable to use a metal compound containing sodium, germanium, manganese or titanium, or a mixture thereof, to reduce environmental pollution.

(3) Step 3: Oligomer having a degree of polymerization of 3 or more and phosphorus-containing flame retardant reaction

A phosphorus-based flame retardant is added to an oligomer having a degree of polymerization of 3 or more prepared by Step 2, and an esterification reaction or an ester exchange reaction is further conducted at a temperature of 220 to 250 ° C for 0.5 hour to distill off water or methanol as a by-product.

(4) Step 4: Preparation of high molecular weight copolyester resin

 The oligomer prepared by the three steps is further subjected to condensation polymerization reaction at a temperature of 260 to 290 ° C and a vacuum of 1.0 Torr or less for 60 to 240 minutes to prepare a high molecular weight copolyester resin.

The copolyester resin having flame retardance and biodegradability simultaneously produced by the above-mentioned 4-step resin production method has a melting point of 190 ° C or more and an intrinsic viscosity of 0.6 to 0.8 dL / g.

The catalyst used in step 2 may be used in an amount of 0.05 to 1.0% by weight based on 100% by weight of the total biodegradable copolyester resin at the initial stage or the late stage of the stage 1 or stage 3.

In order to minimize the content of diethylene glycol generated from the aromatic dicarboxylic acid (terephthalic acid), a base may be appropriately added during the production of the biodegradable copolyester resin.

In the embodiment of the present invention, a heat stabilizer may be added at the initial stage or the late stage of the first stage, the second stage, the third stage or the fourth stage, and one or more phosphorus thermal stabilizers such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, .

The features and other advantages of the present invention as described above will become more apparent from the following embodiments. However, the present invention is not limited to the following examples.

Example

The evaluation items shown in the following examples and comparative examples were measured as follows.

Melting point: Measured using a differential scanning calorimeter (Perkin Elmer, DSC).

Intrinsic Viscosity (IV): Copolymer polyester was dissolved in phenol / tetrachloroethane (weight ratio 50/50) to make a 0.5 wt% solution and measured at 35 DEG C with a Ubbelohde viscometer.

Color: Color-b value was measured using CR-100 colorimeter manufactured by Minolta Co.

* Radiation fairness: Radiation was carried out at 290 ℃ for more than 24 hours, and the number of cuts and single yarns were evaluated for 24 hours according to the following criteria.

?: 0 times,?: 1 to 2 times,?: 3 times to 5 times, X: 6 times or more

* Strength: Strength was measured using a strength meter of INSTRON.

* Biodegradability: After the obtained co-polyester chips are frozen and pulverized, they are buried in a compost kept under constant conditions (52 to 58 ° C, 80 to 90% in humidity) for biodegradation under composting conditions. Respectively. Standard soil and landfill conditions used here were in accordance with ASTM D 5338-92.

* Flame retardancy: It was evaluated by NFP 92-503, 504, 505 of French flame retardancy test method which is the most widely used flame retardancy authentication method in the world.

Example  One

In an ester reaction tank containing a polyethylene terephthalate oligomer obtained by direct esterification reaction of terephthalic acid and ethylene glycol, a dicarboxylic acid as a first copolymerization component was added in an amount of 90 mol% of terephthalic acid and 10 mol% of glutaric acid , 99 mol% of ethylene glycol and 1 mol% of isosorbide were added as a second copolymerization component to the total amount of the dicarboxylic acid component, and then the mixture was reacted at 245 ° C in the presence of manganese acetate as a typical transesterification catalyst The transesterification reaction was completed for 1 hour. Then, 3-hydroxyphenylphosphinylpropyne acid flame retardant, which is a phosphorus reactive flame retardant, was added so that the phosphorus content in the resin was 6,500 ppm based on phosphorus, the esterification reaction was carried out at a temperature of 245 DEG C for 0.5 hour, After adding antimony trioxide, which is a polymerization reaction catalyst, the temperature was raised to 285 ° C while reducing the pressure so that the final degree of vacuum was 1 mmHg or less, and the condensation polymerization reaction was carried out.

The physical properties and fiberizing radiation properties of the copolyester resin thus condensed were evaluated, and the measurement results of the weight loss due to biodegradation and the flame retardancy characteristics are shown in Table 1. [

Example  2 to 5 and Comparative Example  1 to 4

The same procedure as in Example 1 was repeated except that the copolymerization ratio of terephthalic acid, glutaric acid, ethylene glycol, isosorbide, and neopentyl glycol was changed as shown in Table 1 below.

As can be seen from the results of Table 1, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, ethylene glycol, isosorbide, neopentyl glycol, and flame retardant were added in amounts specified in Table 1 for the purpose of imparting biodegradability and flame- The copolyester resin was stable in physical properties such as color, melting point and glass transition temperature, and had excellent processability and strength in terms of radiation properties as compared with Comparative Examples 2 to 4. Comparative Examples 2 to 4 showed an increase in copolymerization composition It was found that the melting point and thermal stability were lowered, the processability was poor, and the color of the resin was poor.

Claims (13)

A dicarboxylic acid component comprising a mixture of (a) an aromatic dicarboxylic acid and (b) an aliphatic dicarboxylic acid as the first copolymerization component;
(C) an aliphatic diol and (d) a glycol component comprising isosorbide, neopentyl glycol or a mixture thereof; And
(E) a phosphorus-containing reaction-type flame retardant component comprising at least one compound of the following general formulas (1) to (3) as a third copolymerization component;
Lt; / RTI >
Wherein the dicarboxylic acid component (a) is 85 to 95 mol% of an aromatic dicarboxylic acid, an acid anhydride thereof or a mixture thereof, and the component (b) is an aliphatic dicarboxylic acid, an acid anhydride or a mixture thereof Wherein the glycol component comprises 80 to 99 mol% of the component (c) and 1 to 20 mol% of the component (d). The flame retardant biodegradable copolyester resin according to claim 1,

In the above formulas, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.
delete The flame retardant biodegradable copolyester resin according to claim 1, wherein the phosphorus reactive flame retardant has a phosphorus content in the resin of 3,000 to 20,000 ppm based on phosphorus atoms.
The aromatic dicarboxylic acid according to claim 1, wherein the aromatic dicarboxylic acid is selected from terephthalic acid or dimethyl terephthalic acid, and the aliphatic dicarboxylic acid is selected from the group consisting of a succinic acid, glutaric acid, adipic acid, pimeric acid, Wherein the biodegradable copolyester resin having flame retardancy is characterized in that at least one member selected from the group consisting of stearic acid, sebacic acid, cyclic aliphatic dicarboxylic acid is selected.
The method according to claim 1, wherein the glycol component is selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, polyethylene glycol and isosorbide. Containing biodegradable copolyester resin.
The method according to claim 1, wherein at least one selected from the group consisting of the isosorbide, the neopentyl glycol, and the mixture thereof, which is 1,4: 3,6-dianhydro-D-sorbitol as the glycol derived from the biomass, Is 1 to 20 mol% based on the total glycol component.
a dicarboxylic acid component comprising a mixture of (a) an aromatic dicarboxylic acid and (b) an aliphatic dicarboxylic acid, and (c) an aliphatic diol and (d) isosorbide, neopentyl glycol, Mixing the glycol components and melting the mixture at a temperature of 220 캜 or higher;
A catalyst is added to a mixture of the dicarboxylic acid component and the glycol component melted and an esterification reaction or transesterification reaction is carried out at a temperature of 220 to 250 ° C for 1 hour or more to prepare an oligomer having a polymerization degree of 3 or more, Water and methanol or water;
A phosphorus-based flame retardant containing at least one compound of the following formulas (1) to (3) is added to the prepared oligomer having a degree of polymerization of 3 or more, and the esterification reaction or transesterification reaction is further carried out at a temperature of 220 to 250 ° C for 0.5 hour , Three steps of distilling water or methanol as a by-product; And
The oligomer is further subjected to condensation polymerization at a temperature of 260 to 290 ° C and a vacuum of 1.0 Torr or less for 60 to 240 minutes to produce a high molecular weight copolyester resin;
By weight based on the total weight of the biodegradable copolyester resin.

In the above formulas, R1, R2, R3, R4, and R5 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.
The method according to claim 7, wherein the catalyst is selected from the group consisting of Zn, Co, Sb ₂ O ₃ , Ti, Ge, Mn, , Or a metal compound or mixture of at least one selected from the group consisting of sodium, germanium, manganese, and titanium is used as the flame retardant. The flame retardant biodegradable copolyester resin according to claim 1,
[8] The composition according to claim 7, wherein the dicarboxylic acid component (a) is 85 to 95 mol% of an aromatic dicarboxylic acid, an acid anhydride or a mixture thereof, and the component (b) is an aliphatic dicarboxylic acid, Wherein the glycol component is 80 to 99 mol% of the component (c) and 1 to 20 mol% of the component (d), and the glycol component is a biodegradable nose having a flame retardancy A method for producing a polyester resin.
The flame retardant biodegradable copolyester resin according to claim 7, wherein the phosphorus-containing flame retardant has a phosphorus content in the resin of 3,000 to 20,000 ppm based on phosphorus atoms.
8. The method of claim 7, wherein the aromatic dicarboxylic acid is selected from terephthalic acid or dimethyl terephthalic acid, and the aliphatic dicarboxylic acid is selected from the group consisting of a succinic acid, glutaric acid, adipic acid, pimeric acid, , Sebacic acid, and cyclic aliphatic dicarboxylic acid. The method for producing a biodegradable copolyester resin according to claim 1,
The flame retardant composition according to claim 7, wherein the glycol component is selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, polyethylene glycol and isosorbide. Of the biodegradable copolyester resin.
[Claim 7] The method according to claim 7, wherein at least one selected from the group consisting of isosorbide, neopentyl glycol and mixtures thereof as the glycol derived from the biomass, which is 1,4: 3,6-dianhydro-D-sorbitol, Is 1 to 20 mol% based on the total glycol component. The method for producing a biodegradable copolyester resin having flame retardancy.