TW201414782A - Use of polycyclic organophosphate - Google Patents

Abstract

The invention relates to use of polycyclic organophosphate as a color stabilizer of a polyester resin. The invention also relates to a polyester resin composition with color stability comprising a polyester resin main component and a color stabilizer; wherein the color stabilizer is a polycyclic organophosphate.

Description

Use of polycyclic organic phosphates

The present invention relates to a resin material. In particular, a color stable resin material is provided.

Resin material is a widely used polymer material, which is almost visible in all aspects of daily life, especially polyester resin, which is widely used in automobile door handles, automobile bumpers, motor casings, telephone receivers, Skate bases, iron handles, connectors, electrical outlets, computer fans, transformer coil bobbins and outer casings are an important material in resin materials.

However, in the production process of a polyester resin material, particularly a polycarbonate (polycarbonate, PC)/polybutylene terephthalate (PBT), oxidation and transesterification are also carried out, and metal is also involved. The application of the catalyst, however, the oxidation and transesterification reaction and the residual of the metal catalyst often cause the appearance of the resin material to yellow, resulting in a depreciation of the product. Moreover, the yellowing phenomenon also makes the resin material difficult to dye, resulting in Restrictions on subsequent applications.

In order to solve the yellowing problem of the aforementioned polyester resin material, the color stabilizer has been developed in the industry to be incorporated into a polyester material, and a color stabilizer such as an organometallic phosphate or an organic phosphate ester can be applied, so that the color stabilizer has a metal. The function of chelation can slow down the yellowing caused by the residual metal catalyst. However, these color stabilizers do not have the function of anti-oxidation and cannot improve the yellowing caused by oxidation. Moreover, due to the polyester resin material Transesterification reaction The rate is faster than the chelation reaction of the color stabilizer with the residual metal catalyst, so the addition of such a color stabilizer has limited improvement in the yellowing problem.

Therefore, there is a need in the art to provide a color stabilizer which can comprehensively improve the yellowing phenomenon of polyester resin materials, so as to meet the development requirements of various application fields.

The present invention provides a polycyclic organic phosphate as a color stabilizer, which can comprehensively improve the yellowing phenomenon of the polyester resin material.

The present invention provides a use of a polycyclic organophosphate which is used as a color stabilizer for a polyester resin.

The present invention further provides a color-stable polyester resin composition comprising a material body of a polyester resin and a color stabilizer, wherein the color stabilizer is a polycyclic organophosphate.

The present invention provides a use of a polycyclic organophosphate which is used as a color stabilizer for a polyester resin.

The term "organophosphate" as used in the present invention means an ester compound of phosphoric acid, including but not limited to a product obtained by subjecting phosphoric acid to an esterification reaction.

The term "polycyclic organophosphate" as used in the present invention means an organophosphate having two or more ring structures, and the ring may be a carbocyclic or heterocyclic ring; an aliphatic ring or an aromatic ring; a monocyclic or polycyclic ring; Preferably, the polycyclic ring is a polyphenyl ring.

In one embodiment of the present invention, the polycyclic organic phosphate has a structure represented by the following formula (1):

Wherein: R ₁ and R ₂ independently represents an aromatic-based group; or R ₁ and R ₂ together represent the formula (2) or (3);

R ₃ is selected from the group consisting of OR ₄ and R ₅ ; R ₄ , R ₅ and R ₆ are independently selected from the group consisting of aliphatic and aromatic groups having 1 to 20 carbon atoms; and R ₇ , R ₈ and R ₉ are independently selected from the group consisting of alkyl groups having 1 to 6 carbon atoms.

In a preferred embodiment of the invention, the aryl group is a phenyl group substituted with a tertiary substituent or a phenyl group substituted with a phosphate ester.

In a more preferred embodiment of the invention, the polycyclic organophosphate is tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenylbisphosphite (Tetrakis (2) ,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite), Tris(2,4-di-tert-butylphenyl)phosphite (Tris(2,4-ditert-) Butylphenyl)phosphate), 2,2'-methylene double (4,6-di-tert-butylphenyl)octyl-phosphite (2,6-di-t-butylpnenyl) octyl-phosphite, pentaerythritol tetra[3-(3',5'-di Tert-butyl-4'-hydroxyphenyl)propionate] (Pentaerythritol Tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), bis(2,4-di-tert-butylbenzene) Bis (2,4-di-tert-butylphenyl)pentaerythritol diphosphite or O,O'-Dioctadecylpentaerythritol bis(phosphite) ). These compounds may be used singly or in combination of two or more.

The term "polyester" as used in the present invention refers to a polymer having an ester group functional group in its main chain, which includes, but is not limited to, a polymer obtained by condensation of a polyhydric alcohol and a polybasic acid.

In one embodiment of the invention, the polyester comprises an aliphatic diol moiety having from 2 to 6 carbon atoms and an aromatic dibasic acid hydrazine segment having from 6 to 20 carbon atoms.

In a preferred embodiment of the invention, the polyester comprises the structure shown in the following formula (4):

Wherein: n is an integer of 2 to 6; and R ₁₀ is an aromatic hydroxy group having 6 to 20 carbon atoms.

In a more specific embodiment of the present invention, the polyester resin is polycarbonate, polybutylene terephthalate, polyethylene terephthalate (PET), polyparaphenylene. Propylene dicarboxylate (polytrimethylene terephthalate, PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN) or polycyclohexylene dimethylene terephthalate (PCT). These polymers may be used singly or in combination and copolymerized. More preferably, the polyester resin is polycarbonate, polybutylene terephthalate or a rubber compound thereof.

According to the present invention, the polycyclic organic phosphate acts as a color stabilizer, has an anti-oxidation effect, can also effectively slow down the transesterification reaction, thereby improving the yellowing phenomenon, and making the polyester resin material easy to dye, and application. The products of these materials have a novel and diverse appearance, which is more conducive to industrial applications.

The present invention further provides a color-stable polyester resin composition comprising a material body of a polyester resin and a color stabilizer, wherein the color stabilizer is a polycyclic organophosphate.

The content of each component of the polyester resin composition according to the present invention is determinable by those having ordinary knowledge in the technical field to which the present invention pertains. In a preferred embodiment of the present invention, the polyester resin comprises polycarbonate and is contained in an amount of from about 50% by weight to about 90% by weight; on the other hand, the polyester resin comprises poly(p-phenylene) Butylene formate, and its content is from about 1 wt% to about 50 wt%; the color stabilizer is present in an amount of from about 0.1 phr to about 20 phr; more preferably, the color stabilizer is present in an amount from about 3 phr to about 5 phr. As used herein, "phr" refers to parts per hundred of resin.

The resin composition according to the present invention preferably further comprises at least one auxiliary agent, To enhance the various properties of the composition. The type, composition and content of the auxiliary agent may be determined as needed, such as but not limited to a flame retardant, a modifier, an antioxidant, a photostabilizer, an inorganic filler, a colorant or a dye. These additives may be used singly or in combination of two or more.

In a preferred embodiment of the invention, the adjuvant is a flame retardant. In a preferred embodiment of the invention, the flame retardant is a phosphorus-containing compound or a fluorinated polyolefin. The phosphorus-containing compound is preferably a phosphate ester; the fluorine-containing polyolefin is preferably polytetrafluoroethylene. Preferably, the flame retardant is present in an amount from about 0.2 phr to about 20 phr; more preferably, the flame retardant is present in an amount from about 0.2 phr to about 10 phr.

The color stabilizer of the polycyclic organic phosphate according to the present invention can maintain the fire resistance, heat resistance and impact resistance when applied to a resin composition containing a flame retardant, so that the polyester resin composition can be Both color stability and flame retardant properties are considered.

In another preferred embodiment of the invention, the adjuvant is a modifier. In a preferred embodiment of the invention, the modifier is a graft polymer. Preferably, the modifier is present in an amount from about 0.1 phr to about 10 phr.

The invention is illustrated by the following examples, which are not intended to be limited to the scope of the invention.

Example 1: Polyester resin composition

The polyester resin composition was prepared as shown in Table 1 below, and tested for its properties by a biaxial processing kneading and injection process (ASTM standard test piece injection):

HP-10: 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphate

IR-168: Tris(2,4-di-tert-butylphenyl) phosphite

P-EPQ: tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyldiphosphite

L ^* a ^* b ^* color space (also known as CIELAB) is the most common color space for measuring object colors today. It is widely used in all fields and is one of the uniform color spaces. It was developed by CIE in 1976. Overcoming the original Yxy color space, the equal distance on the x, y chromaticity diagram is not equivalent to the perceived chromatic aberration. In the L ^* a ^* b ^* color space, L ^* is luminance and a ^* b ^* is a chromaticity coordinate.

It can be seen from the test results that after adding the color stabilizer of the polycyclic organic phosphate, the yellowing value (YI) of the example is significantly lower than that of the control group, and the yellowing effect is improved.

Example 2: Flame Retardant Polyester Resin Composition

The flame retardant polyester resin composition was prepared as shown in Table 2 below, and tested for its properties by a biaxial processing kneading and injection process (ASTM standard test piece injection):

HP-10: 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphate

IR-168: Tris(2,4-di-tert-butylphenyl) phosphite

P-EPQ: tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyldiphosphite

M-511: graft modifier (trade name: KANE Ace M-511, manufacturer: KANEKA CORPORATION)

PX-200: Flame retardant (trade name: PX-200, manufacturer: Daihachi Chemical Industry Co., Ltd.)

PTFE: anti-drip agent (trade name: Metablen A-3750, manufacturer: MITSUBISHI RAYON Co., Ltd)

It can be seen from the test results that after adding the color stabilizer of the polycyclic organic phosphate in the example, the yellowing value is significantly lower than that of the control group, and the yellowing effect is improved, and the appropriate fireproof and thermal properties can be maintained. Impact strength.

The above-described embodiments are merely illustrative of the principles and effects of the invention, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

Claims (19)

A use of a polycyclic organophosphate which is used as a color stabilizer for polyester resins. The use according to claim 1, wherein the polycyclic organic phosphate has a structure represented by the following formula (1): Wherein: R ₁ and R ₂ independently represent an aromatic group; or R ₁ and R ₂ together represent formula (2) or formula (3); R ₃ is selected from the group consisting of OR ₄ and R ₅ ; R ₄ , R ₅ and R ₆ are independently selected from the group consisting of aliphatic and aromatic groups having 1 to 20 carbon atoms; and R ₇ , R ₈ and R ₉ are independently selected from the group consisting of alkyl groups having 1 to 6 carbon atoms. The use according to claim 2, wherein the aromatic group is a phenyl group substituted with a tertiary substituent or a phenyl group substituted with a phosphate. The use according to any one of claims 1 to 3, wherein the polycyclic organophosphate is selected from the group consisting of tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyldiphosphite (Tetrakis) (2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite), Tris(2,4-di-tert-butylphenyl)phosphite (Tris(2,4-) Ditert-butylphenyl)phosphate), 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphate (2,2-methylenebis(4,6-di-t-butylpnenyl)octyl- Phosphine), pentaerythritol tetra [3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate] (Pentaerythritol Tetrakis [3-(3,5-di-tert-butyl-4- Hydroxyphenyl)propionate), Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite and O,O'-dioctadecyl a group consisting of O, O'-Dioctadecylpentaerythritol bis (phosphite). The use according to any one of claims 1 to 3, wherein the polyester comprises an aliphatic diol group having 2 to 6 carbon atoms and an aromatic dibasic acid group having 6 to 20 carbon atoms. . The use according to any one of claims 1 to 3, wherein the polyester comprises a structure represented by the following formula (4): Wherein: n is an integer of 2 to 6; and R ₁₀ is an aromatic hydroxy group having 6 to 20 carbon atoms. The use of any one of claims 1 to 3, wherein the polyester resin is Polycarbonate (PC), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polytrimethylene terephthalate (polybutylene terephthalate) Polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN) and polycyclohexylene dimethylene terephthalate (PCT) Group. A color-stable polyester resin composition comprising a material body of a polyester resin and a color stabilizer, wherein the color stabilizer is a polycyclic organic phosphate. The composition according to claim 8, wherein the polycyclic organophosphate has a structure represented by the following formula (1): Wherein: R ₁ and R ₂ independently represent an aromatic group; or R ₁ and R ₂ together represent formula (2) or formula (3); R ₃ is selected from the group consisting of OR ₄ and R ₅ ; R ₄ , R ₅ and R ₆ are independently selected from the group consisting of aliphatic and aromatic groups having 1 to 20 carbon atoms; and R ₇ , R ₈ and R ₉ are independently selected from the group consisting of alkyl groups having 1 to 6 carbon atoms. The composition according to claim 8, wherein the aryl group is a phenyl group substituted with a tertiary substituent or a phenyl group substituted with a phosphate. The composition according to any one of claims 8 to 10, wherein the polycyclic organophosphate is selected from the group consisting of tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyldiphosphite, Tris(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octylphosphine, pentaerythritol tetra[3-(3' , 5'-di-tert-butyl-4'-hydroxyphenyl)propionate], bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite and O,O'-dioctadecyl a group consisting of pentaerythritol bisphosphite. The composition according to any one of claims 8 to 10, wherein the polyester comprises an aliphatic diol group having 2 to 6 carbon atoms and an aromatic dibasic acid having 6 to 20 carbon atoms. segment. The composition according to any one of claims 8 to 10, wherein the polyester comprises a structure represented by the following formula (4): Wherein: n is an integer of 2 to 6; and R ₁₀ is an aromatic hydroxy group having 6 to 20 carbon atoms. The composition according to any one of claims 8 to 10, wherein the polyester resin is selected from the group consisting of polycarbonate, polybutylene terephthalate, polyethylene terephthalate, and polytrimethylene terephthalate. A group consisting of a diester, polyethylene naphthalate, polybutylene naphthalate, and polyethylene terephthalate. The composition according to any one of claims 8 to 10, further comprising at least one auxiliary agent, wherein the auxiliary agent is selected from the group consisting of a flame retardant, a modifier, an antioxidant, a light stabilizer, an inorganic filler, a colorant and a dye. a group of people. The composition of claim 15 wherein the flame retardant is selected from the group consisting of phosphorus-containing compounds and fluorinated polyolefins. The composition of claim 16, wherein the phosphorus-containing compound is a phosphate. The composition of claim 16, wherein the fluoropolyolefin is polytetrafluoroethylene. The composition of claim 15 wherein the modifying agent is a graft polymer.