KR20140109619A - Poly(ethersulfone) resin - Google Patents

Abstract

The present invention relates to poly(ether sulfone) resin and, more specifically, to poly(ether sulfone) resin prepared by polymerizing di(halophenyl)sulfone and an aromatic diol of chemical formula 1, and having a repeating unit of chemical formula 2, thereby exhibiting excellent thermostability and being useful for molding materials of optical components. In chemical formulas 1 and 2, each of R1 and R2 is aliphatic hydrocarbon group or phenyl group of 1-6 carbon atoms, or R1 and R2 are rings formed by adjacent carbons connected to each other.

Description

Poly (ether sulfone) resin {POLY (ETHERSULFONE) RESIN}

The present invention relates to a poly (ether sulfone) resin having excellent heat resistance.

Recently, there is a growing demand for engineering plastics having better and reinforced properties all over the world. Among the thermoplastic polymers, poly (ether sulfone) has an excellent position as a thermoplastic polymer in the global market due to its excellent properties in terms of thermal stability, high heat distortion temperature, chemical inertness, electrical characteristics and flame retardancy. The physical properties of such poly (ether sulfone) are due to the diaryl sulfone group having a very stable and high electronegativity including sulfur in the highest oxidation state. Such poly (ether sulfone) is utilized as a coating agent, an adhesive agent, and the like in not only electronic field, aviation industry field, automobile field, medicine field, aerospace industry,

In order to impart specific functionality to such poly (ether sulfone) and improve the processability, studies have been reported for introducing a stable functional group as a substituent, and they have been actively conducted at present.

Silicon-containing polymers, on the other hand, have been used extensively to provide improved material performance and have been actively studied for many years. These polymers have attractive properties such as solubility, low surface tension, good electrical properties, good weatherability, flame retardancy and high gas permeability, as well as stability to heat and chemicals.

A technique for introducing the advantages of such a silicon-containing polymer into poly (ether sulfone) has been proposed (Korean Patent No. 1,214,863). This has the disadvantage that the stability against heat and hydrolysis is improved, but the improvement in thermal stability is insufficient due to introduction of silicon into the branch chain which is not the main chain.

An object of the present invention is to provide a polyarylate resin having a silicone compound introduced into a main chain and having excellent heat resistance.

In order to achieve the above object, the present invention provides a poly (ether sulfone) resin, which is prepared by polymerizing di (halophenyl) sulfone and an aromatic diol represented by the following formula (1) and having a repeating unit represented by the following formula (2).

(In the formulas (1) and (2), R ₁ and R ₂ are each independently an aliphatic hydrocarbon group or a phenyl group having 1 to 6 carbon atoms, or R ₁ and R ₂ are adjacent carbon atoms to form a ring).

Preferably, R ₁ and R ₂ in the general formulas (1) and ( ₂₎ are each independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, or R ₁ and R ₂ may be adjacent carbon atoms to form a ring.

More preferably, the formula (1) may be at least one selected from the following formulas (3) to (6).

,

,

및

로 이루어진 군에서 선택된 1종 이상의 디올을 추가로 함유하여 중합될 수 있다.
The poly (ether sulfone) resin may be bisphenol A,

,

,

And

May be polymerized by further containing at least one diol selected from the group consisting of

The polyarylate resin according to the present invention is excellent in heat resistance and can be advantageously used particularly as a molding material for optical parts.

The present invention relates to a poly (ether sulfone) resin having excellent heat resistance.

Hereinafter, the present invention will be described in detail.

The poly (ether sulfone) resin of the present invention is prepared by polymerizing di (halophenyl) sulfone and an aromatic diol represented by the following formula (1), and is represented by the following formula (2) as a repeating unit.

[Chemical Formula 1]

(2)

(In the formulas (1) and (2), R ₁ and R ₂ are each independently an aliphatic hydrocarbon group or a phenyl group having 1 to 6 carbon atoms, or R ₁ and R ₂ are adjacent carbon atoms to form a ring).

Preferably, R ₁ and R ₂ in the general formulas (1) and ( ₂₎ are each independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, or R ₁ and R ₂ may be adjacent carbon atoms to form a ring.

More preferably, the formula (1) may be at least one selected from the following formulas (3) to (6).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The above formula (1) is a method commonly used in the art, for example, 1) Bioorganic and Medicinal Chemistry Letters; vol. 19; nb. 12; (2009); p. 3157-3161: 2) Phosphorus, Sulfur and Silicon and the Related Elements; vol. 181; nb. 2; (2006); p. 239-248: 3) Journal of Organometallic Chemistry; vol. 36; (1972); p. 283-291: 4) Journal of the American Chemical Society; vol. 74; (1952); p. 1003, 1005: 5) Macromolecules; vol. 45; nb. One; (2012); p. 211-220: 6) Russian Journal of General Chemistry; vol. 70; nb. 11; (2000); p. 1749-1751: 7) Journal of Organometallic Chemistry; vol. 36; (1972); p. 283-291, and the like.

In the present invention, the compound of formula (I) is prepared by the reaction shown in Reaction Scheme 1 below, but the present invention is not limited thereto.

[Reaction Scheme 1]

(Wherein R ₁ and R ₂ are each independently an aliphatic hydrocarbon group or a phenyl group having 1 to 6 carbon atoms, or R ₁ and R ₂ are adjacent carbon atoms to form a ring).

,

,

및

등과 같은 디올을 혼합 사용할 수 있다. 이때, 상기 화학식 1의 방향족 디올에 혼합되는 디올은 내열성과 투과율을 고려하여 상기 화학식 1 100중량부에 대하여 100중량부 이하로 함유하는 것이 바람직하다.In addition to the aromatic diols of the above formula (1), bisphenol A,

,

,

And

And the like. In this case, the diol mixed in the aromatic diol represented by the formula (1) is preferably contained in an amount of 100 parts by weight or less based on 100 parts by weight of the formula (1) in consideration of heat resistance and transmittance.

Di (halophenyl) sulfone, which is polymerized with the aromatic diol of Formula 1, may be di (4-fluorophenyl) sulfone or di (4-chlorophenyl) sulfone. Considering the reactivity of the nucleophilic substitution reaction, di (4-fluorophenyl) sulfone is preferred.

These di (halophenyl) sulfone may be used alone or in combination of two or more.

The present invention is produced by condensation of an aromatic diol of the formula (1) with di (halophenyl) sulfone. The polycondensation reaction is generally used in the art and is preferably carried out in a solution phase using an organic solvent.

The organic solvent is preferably one having a high boiling point (for example, 140 占 폚 or higher), for example, dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO) And the like.

At this time, the condensation polymerization reaction is preferably carried out under stirring at 100 to 200 ° C, preferably 130 to 160 ° C.

It is preferable that the above-mentioned condensation polymerization reaction is carried out by using at least one catalyst for polymerization reaction selected from a protonic acid, a tin compound, a titanium compound and an antimony compound. The catalyst for the polymerization reaction is preferably used in an amount of 0.02% by weight or less based on the reaction mixture.

The poly (ether sulfone) resin thus prepared has a glass transition temperature of 200 to 220 캜 and is easily dissolved in an organic solvent such as dimethyl sulfoxide (DMSO) or dimethylacetamide (DMAc) at room temperature.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Synthetic example  1: Formula 3

)의 방향족 디올을 얻었다.After dissolving P-bromophenol (172 g, 1 mol) and benzyl bromide (178.5 g, 1.05 mol) in acetonitrile (1 L), K ₂ CO ₃ (176 g, 2 mol) was added and reacted at 50 ° C for 24 hours, After filtering with a glass filter, the solvent was removed by distillation under reduced pressure. The reaction mixture was dissolved in anhydrous THF, the temperature was lowered to -78 ° C, and a 2.2M n-BuLi hexane solution was slowly added dropwise so that n-BuLi became 1.15mol. Dimethyldichlorosilane (64 g, 0.5 mol) was then slowly added dropwise, the temperature was raised to room temperature, stirred for 24 hours, filtered through a glass filter, and then the solvent was distilled off under reduced pressure. The reaction mixture was again dissolved in THF (500 mL) and EtOH (500 mL), and 10% Pd / C was added thereto so that the concentration of Pd became 0.05 mol, 200 g of ammonium formate was added and the mixture was refluxed for 2 hours. Thereafter, the reaction mixture was filtered with a glass filter, and the solvent was distilled off under reduced pressure to obtain the compound represented by Formula 3 (

) Of an aromatic diol.

(Chemical Formula 3) NMR / Acetone-d ₆ ; 8.42 (2H), 7.35 (4H), 6.84 (4H), 0.45 (6H).

Synthetic example  2: Formula 4

대신에

를 사용하여 화학식 4(

)의 방향족 디올을 얻었다.The reaction was carried out in the same manner as in Synthesis Example 1,

Instead of

(4 < RTI ID = 0.0 >

) Of an aromatic diol.

(Chemical Formula 4) NMR / Acetone-d ₆ ; 8.43 (2H), 7.34 (4H), 6.83 (4H), 0.98 (6H), 0.80 (4H).

Synthetic example  3: 5

대신에

를 사용하여 화학식 5(

)의 방향족 디올을 얻었다.The reaction was carried out in the same manner as in Synthesis Example 1,

Instead of

(5 < RTI ID = 0.0 >

) Of an aromatic diol.

(Chemical Formula 5) NMR / Acetone-d ₆ ; 7.53 (3H), 7.35 (4H), 6.87 (2H), 6.84 (4H), 0.55 (3H).

Synthetic example  4: 6

대신에

를 사용하여 화학식 6(

)의 방향족 디올을 얻었다.The reaction was carried out in the same manner as in Synthesis Example 1,

Instead of

(6 < RTI ID = 0.0 >

) Of an aromatic diol.

(Chemical Formula 6) NMR / Acetone-d ₆ ; 8.43 (2H), 7.34 (4H), 6.86 (4H), 1.61 (4H), 0.78 (4H).

Example  One

(24.4 g, 0.1 mol) and di (4-fluorophenyl) sulfone (25.4 g, 0.1 mol) were added to a 500 mL three-round round Bottom flask. After dissolving the solid in dimethylacetamide (DMAC) / toluene, anhydrous potassium carbonate was added. The dark green mixture thus obtained was stirred vigorously at 140 < 0 > C until water was formed by azeotropic distillation. The reaction mixture was then slowly heated to 160 < 0 > C to remove toluene. The reaction temperature was maintained at 160 to 165 占 폚 for 12 hours and then cooled to room temperature. The mixture was precipitated in methanol / water (2.5 ml / 250 ml) containing a few drops of hydrochloric acid, and the solvent was removed under heating vacuum conditions to obtain a white powder polymer.

The obtained polymer was C = 67.88 obtained by elemental analysis using an element analyzer; H = 5.02; S = 6.91 to be a poly (ether sulfone) resin represented by the following formula (7).

(7)

Example  2

(11.4g, 0.05mol)의 혼합물을 사용하여 폴리(에테르설폰) 수지를 제조하였다. 원소분석기를 이용한 원소분석으로 얻어진 C=70.56; H=5.03; S=7.11로부터 하기의 화학식 8로 대표되는 폴리(에테르설폰) 수지임을 확인하였다.The aromatic diol (12.2 g, 0.05 mol) of the formula (3) was reacted with the aromatic diol of the formula (3) in place of the aromatic diol (24.4 g,

(11.4 g, 0.05 mol) was used to prepare a poly (ether sulfone) resin. C = 70.56 obtained by elemental analysis using elemental analyzer; H = 5.03; (Ether sulfone) resin represented by the following formula (8) from S = 7.11.

[Chemical Formula 8]

Example  3

(10.1g, 0.05mol)의 혼합물을 사용하여 폴리(에테르설폰) 수지를 제조하였다. 원소분석기를 이용한 원소분석으로 얻어진 C=68.55; H=4.49; S=7.32로부터 하기의 화학식 9로 대표되는 폴리(에테르설폰) 수지임을 확인하였다.The aromatic diol (12.2 g, 0.05 mol) of the formula (3) was reacted with the aromatic diol of the formula (3) in place of the aromatic diol (24.4 g,

(10.1 g, 0.05 mol) was used to prepare a poly (ether sulfone) resin. C = 68.55 obtained by elemental analysis using elemental analyzer; H = 4.49; (Ether sulfone) resin represented by the following formula (9) from S = 7.32.

[Chemical Formula 9]

Example  4

(10.0g, 0.05mol)의 혼합물을 사용하여 폴리(에테르설폰) 수지를 제조하였다. 원소분석기를 이용한 원소분석으로 얻어진 C=70.08; H=4.73; S=7.34로부터 하기의 화학식 10으로 대표되는 폴리(에테르설폰) 수지임을 확인하였다.The aromatic diol (12.2 g, 0.05 mol) of the formula (3) was reacted with the aromatic diol of the formula (3) in place of the aromatic diol (24.4 g,

(10.0 g, 0.05 mol) was used to prepare a poly (ether sulfone) resin. C = 70.08 obtained by elemental analysis using elemental analyzer; H = 4.73; (Ether sulfone) resin represented by the following chemical formula 10 from S = 7.34.

[Chemical formula 10]

Example  5

(16.8g, 0.05mol)의 혼합물을 사용하여 폴리(에테르설폰) 수지를 제조하였다. 원소분석기를 이용한 원소분석으로 얻어진 C=63.02; H=3.89; S=6.35 로부터 하기의 화학식 11로 대표되는 폴리(에테르설폰) 수지임을 확인하였다.The aromatic diol (12.2 g, 0.05 mol) of the formula (3) was reacted with the aromatic diol of the formula (3) in place of the aromatic diol (24.4 g,

(16.8 g, 0.05 mol) was used to prepare a poly (ether sulfone) resin. C = 63.02 obtained by elemental analysis using elemental analyzer; H = 3.89; S = 6.35, it was confirmed to be a poly (ether sulfone) resin represented by the following formula (11).

(11)

Example  6

(Ether sulfone) resin was prepared by using the aromatic diol (27.2 g, 0.1 mol) of the formula (4) in place of the aromatic diol (24.4 g, 0.1 mol) of the formula (3). C = 68.96 obtained by elemental analysis using elemental analyzer; H = 5.58; (Ether sulfone) resin represented by the following formula (12) from S = 6.58.

[Chemical Formula 12]

Example  7

(Ether sulfone) resin was prepared by using the aromatic diol (30.6 g, 0.1 mol) of the formula (5) in place of the aromatic diol (24.4 g, 0.1 mol) of the formula (3). C = 71.37 obtained by elemental analysis using elemental analyzer; H = 4.83; (Ether sulfone) resin represented by the following formula 13 from S = 6.15.

[Chemical Formula 13]

Example  8

(Ether sulfone) resin was prepared by using the aromatic diol (27.0 g, 0.1 mol) of the formula (6) in place of the aromatic diol (24.4 g, 0.1 mol) of the formula (3). C = 69.25 obtained by elemental analysis using elemental analyzer; H = 5.19; (Ether sulfone) resin represented by the following chemical formula 14 from S = 6.60.

[Chemical Formula 14]

Comparative Example  One

(22.8g, 0.1mol)을 사용하여 폴리(에테르설폰) 수지를 제조하였다. 원소분석기를 이용한 원소분석으로 얻어진 C=73.11; H=5.23; S=7.23로부터 하기의 화학식 15로 대표되는 폴리(에테르설폰) 수지임을 확인하였다.The procedure of Example 1 was repeated, except that the aromatic diol (24.4 g, 0.1 mol) of the formula (3)

(22.8 g, 0.1 mol) was used to prepare a poly (ether sulfone) resin. C = 73.11 obtained by elemental analysis using elemental analyzer; H = 5.23; (Ether sulfone) resin represented by the following chemical formula 15 from S = 7.23.

 [Chemical Formula 15]

Comparative Example  2

(20.2g, 0.1mol)을 사용하여 폴리(에테르설폰) 수지를 제조하였다. The procedure of Example 1 was repeated, except that the aromatic diol (24.4 g, 0.1 mol) of the formula (3)

(20.2 g, 0.1 mol) was used to prepare a poly (ether sulfone) resin.

C = 69.05 obtained by elemental analysis using elemental analyzer; H = 4.10; (Ether sulfone) resin represented by the following chemical formula 16 from S = 7.68.

[Chemical Formula 16]

Comparative Example  3

(20.0g, 0.1mol)을 사용하여 폴리(에테르설폰) 수지를 제조하였다. 원소분석기를 이용한 원소분석으로 얻어진 C=72.27; H=4.61; S=7.72로부터 하기의 화학식 17로 대표되는 폴리(에테르설폰) 수지임을 확인하였다.The procedure of Example 1 was repeated, except that the aromatic diol (24.4 g, 0.1 mol) of the formula (3)

(20.0 g, 0.1 mol) was used to prepare a poly (ether sulfone) resin. C = 72.27 obtained by elemental analysis using elemental analyzer; H = 4.61; (Ether sulfone) resin represented by the following chemical formula 17 from S = 7.72.

[Chemical Formula 17]

Comparative Example  4

(33.6g, 0.1mol)을 사용하여 폴리(에테르설폰) 수지를 제조하였다. 원소분석기를 이용한 원소분석으로 얻어진 C=58.80; H=3.11; S=5.81로부터 하기의 화학식 18로 대표되는 폴리(에테르설폰) 수지임을 확인하였다.The procedure of Example 1 was repeated, except that the aromatic diol (24.4 g, 0.1 mol) of the formula (3)

(33.6 g, 0.1 mol) was used to prepare a poly (ether sulfone) resin. C = 58.80 obtained by elemental analysis using elemental analyzer; H = 3.11; (Ether sulfone) resin represented by the following chemical formula 18 from S = 5.81.

[Chemical Formula 18]

Test Example

The physical properties of the poly (ether sulfone) resin prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.

Heat resistance

Tg was measured using a Q1000 instrument manufactured by TA instruments, and classified as follows.

[Evaluation standard]

?: Tg of 200 占 폚 or more

占 Tg less than 200 占 폚

division Heat resistance Example 1 ○ Example 2 ○ Example 3 ○ Example 4 ○ Example 5 ○ Example 6 ○ Example 7 ○ Example 8 ○ Comparative Example 1 × Comparative Example 2 × Comparative Example 3 × Comparative Example 4 ×

As shown in Table 1, it was confirmed that the poly (ether sulfone) resins of Examples 1 to 8 according to the present invention were superior in heat resistance to those of Comparative Examples 1 to 4.

Claims (4)

(Ether sulfone) resin which is prepared by polymerizing di (halophenyl) sulfone and an aromatic diol represented by the following formula (1) and having a repeating unit represented by the following formula (2):
[Chemical Formula 1]

(2)

(In the formulas (1) and (2), R ₁ and R ₂ are each independently an aliphatic hydrocarbon group or a phenyl group having 1 to 6 carbon atoms, or R ₁ and R ₂ are adjacent carbon atoms to form a ring).
[2] The method of claim 1, wherein R ₁ and R ₂ in formulas (1) and ( ₂₎ are each independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, or R ₁ and R ₂ are poly Ether sulfone) resin.
The poly (ether sulfone) resin according to claim 2, wherein the formula (1) is at least one selected from the following formulas (3) to (6)
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The poly (ether sulfone) resin according to claim 1, wherein the poly (ether sulfone) resin is bisphenol A,

,

,

And

Wherein the poly (ether sulfone) resin further comprises at least one diol selected from the group consisting of poly (ether sulfone) resins.