KR20160007861A - Polyarylene ether sulfone-sulfide compound and method for preparing the same - Google Patents
Polyarylene ether sulfone-sulfide compound and method for preparing the same Download PDFInfo
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims description 9
- 239000000126 substance Substances 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 6
- 229920000642 polymer Polymers 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- -1 sulfone compound Chemical class 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 5
- 238000005580 one pot reaction Methods 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 10
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- RBZMSGOBSOCYHR-UHFFFAOYSA-N 1,4-bis(bromomethyl)benzene Chemical compound BrCC1=CC=C(CBr)C=C1 RBZMSGOBSOCYHR-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/14—Polysulfides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
본 발명의 폴리아릴렌 에테르 설폰-설파이드 화합물은 하기 화학식 1로 표시되는 반복단위를 포함하는 것을 특징으로 한다. 상기 폴리아릴렌 에테르 설폰-설파이드 화합물은 가공성 및 내열성이 우수하다.
[화학식 1]
상기 화학식 1에서, R1, R2, R3 및 R4는 각각 독립적으로 탄소수 1 내지 10의 탄화수소기이고, a, b, c 및 d는 각각 독립적으로 0 내지 4의 정수이며, Z는
[Chemical Formula 1]
In Formula 1, R 1, R 2, R 3 and R 4 are each independently a hydrocarbon group having 1 to 10, a, b, c and d are each independently an integer from 0 to 4, Z is
Description
본 발명은 폴리아릴렌 에테르 설폰-설파이드 화합물 및 이의 제조방법에 관한 것이다. 보다 구체적으로 본 발명은 신규한 구조를 가지며, 가공성 및 내열성이 우수한 폴리아릴렌 에테르 설폰-설파이드 화합물 및 이의 제조방법에 관한 것이다.
The present invention relates to polyarylene ether sulfone-sulfide compounds and processes for their preparation. More specifically, the present invention relates to a polyarylene ether sulfone-sulfide compound having a novel structure and excellent in workability and heat resistance and a method for producing the same.
폴리아릴렌 에테르 설폰-설파이드(polyarylene ether sulfone-sulfide: PES-S)는 고분자 내 유동이 가능한 황 원자(S) 및 산소 원자(O)로 인하여, 극성 유기용매에 용해되기 쉽고 가공성이 우수하다. 통상적으로 폴리아릴렌 에테르 설폰-설파이드는 디클로로디페닐설폰(DCDPS) 등의 디할로게노디아릴술폰 화합물 및 티오디페놀(thiodiphenol, TDP) 등의 디히드록시디아릴설파이드 화합물을 염기 조건 하에서 축중합시켜 얻을 수 있다.Polyarylene ether sulfone-sulfide (PES-S) is easily dissolved in a polar organic solvent and has excellent processability due to sulfur atoms (S) and oxygen atoms (O) that can flow in the polymer. Typically, polyarylene ether sulfone-sulfide is prepared by condensation of a dihalogenenedialyl sulfone compound such as dichlorodiphenyl sulfone (DCDPS) and a dihydroxy diaryl sulfide compound such as thiodiphenol (TDP) .
그러나, 통상적인 폴리아릴렌 에테르 설폰-설파이드는 티오디페놀, 디클로로디페닐설폰 등의 낮은 반응성으로 인해 분자량을 상승시키기 쉽지 않으며, 170℃ 이하의 낮은 유리전이온도를 가질 우려가 있다. 또한, 10,000 g/mol 이하의 수평균분자량을 갖는 폴리아릴렌 에테르 설폰-설파이드의 경우, 기계적 물성 등도 저하될 우려가 있어 상용화하기에는 무리가 있다.However, the conventional polyarylene ether sulfone-sulfide is not easy to increase the molecular weight due to low reactivity of thiodiphenol, dichlorodiphenyl sulfone, etc., and may have a low glass transition temperature of 170 占 폚 or less. In addition, in the case of polyarylene ether sulfone-sulfide having a number average molecular weight of 10,000 g / mol or less, there is a fear that the mechanical properties and the like are also lowered, making commercialization difficult.
따라서, 가공성, 내열성 등이 우수하며, 경제적으로 제조가 가능한 폴리아릴렌 에테르 설폰-설파이드 화합물이 필요한 실정이다.Therefore, there is a need for a polyarylene ether sulfone-sulfide compound which is excellent in workability and heat resistance and can be economically produced.
본 발명의 목적은 신규한 구조를 가지며, 가공성, 내열성 등이 우수한 폴리아릴렌 에테르 설폰-설파이드 화합물을 제공하기 위한 것이다.An object of the present invention is to provide a polyarylene ether sulfone-sulfide compound having a novel structure and excellent in workability and heat resistance.
본 발명의 다른 목적은 상기 폴리아릴렌 에테르 설폰-설파이드 화합물을 경제적으로 제조할 수 있는 제조방법을 제공하기 위한 것이다.Another object of the present invention is to provide a process for producing the polyarylene ether sulfone-sulfide compound economically.
본 발명의 상기 및 기타의 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.
The above and other objects of the present invention can be achieved by the present invention described below.
본 발명의 하나의 관점은 폴리아릴렌 에테르 설폰-설파이드 화합물에 관한 것이다. 상기 폴리아릴렌 에테르 설폰-설파이드 화합물은 하기 화학식 1로 표시되는 반복단위를 포함한다:One aspect of the invention relates to polyarylene ether sulfone-sulfide compounds. The polyarylene ether sulfone-sulfide compound includes a repeating unit represented by the following formula (1): < EMI ID =
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, R1, R2, R3 및 R4는 각각 독립적으로 탄소수 1 내지 10의 탄화수소기이고, a, b, c 및 d는 각각 독립적으로 0 내지 4의 정수이며, Z는
구체예에서, 상기 폴리아릴렌 에테르 설폰-설파이드 화합물의 수평균분자량은 10,000 내지 200,000 g/mol일 수 있다.In embodiments, the number average molecular weight of the polyarylene ether sulfone-sulfide compound may be 10,000 to 200,000 g / mol.
구체예에서, 상기 폴리아릴렌 에테르 설폰-설파이드 화합물의 유리전이온도는 150℃ 이상일 수 있다.In an embodiment, the glass transition temperature of the polyarylene ether sulfone-sulfide compound may be at least 150 < 0 > C.
본 발명의 다른 관점은 상기 폴리아릴렌 에테르 설폰-설파이드 화합물의 제조방법에 관한 것이다. 상기 제조방법은 하기 화학식 2로 표시되는 디히드록시디아릴설파이드 화합물 및 하기 화학식 3으로 표시되는 디할로게노디아릴술폰 화합물을 1.01 : 1 내지 1.10 : 1의 몰비(화학식 2 : 화학식 3)로 반응시켜 하기 화학식 4로 표시되는 중합체를 제조하고; 그리고 제조된 상기 중합체와 하기 화학식 5a로 표시되는 화합물, 하기 화학식 5b로 표시되는 화합물 및 하기 화학식 5c로 표시되는 화합물 중 1종 이상을 포함하는 단량체를 반응시키는 단계를 포함하는 것을 특징으로 한다:Another aspect of the present invention relates to a process for preparing the polyarylene ether sulfone-sulfide compound. The preparation method comprises reacting a dihydroxy diaryl sulfide compound represented by the following formula (2) and a dihalogenenedialyl sulfone compound represented by the following formula (3) in a molar ratio of 1.01: 1 to 1.10: 1 (formula (2) To prepare a polymer represented by the following formula (4); And reacting the produced polymer with a monomer comprising at least one of the compound represented by the following formula (5a), the compound represented by the following formula (5b) and the compound represented by the following formula (5c)
[화학식 2](2)
[화학식 3](3)
[화학식 4][Chemical Formula 4]
[화학식 5a][Chemical Formula 5a]
[화학식 5b][Chemical Formula 5b]
[화학식 5c][Chemical Formula 5c]
상기 화학식 2, 3, 4, 5a, 5b 및 5c에서, R1, R2, R3, R4, R5, R6, R7, a, b, c, d, e, f, g 및 n의 평균값은 상기 화학식 1에서 정의한 바와 같고, X는 할로겐 원자이다.Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , a, b, c, d, e, f, g and The average value of n is as defined in Formula 1, and X is a halogen atom.
구체예에서, 상기 단량체의 투입량은 상기 화학식 4로 표시되는 중합체 100 중량부에 대하여, 0.05 내지 0.5 중량부일 수 있다.In an embodiment, the amount of the monomer may be 0.05 to 0.5 parts by weight based on 100 parts by weight of the polymer represented by the formula (4).
구체예에서, 상기 반응은 염기성 촉매 존재 하에, 150 내지 200℃로 가열하는 것일 수 있다.In embodiments, the reaction may be heating to 150-200 [deg.] C in the presence of a basic catalyst.
구체예에서, 상기 화학식 4로 표시되는 중합체 및 상기 폴리아릴렌 에테르 설폰-설파이드 화합물의 제조는 원 포트(one-pot) 반응일 수 있다.
In embodiments, the preparation of the polymer of Formula 4 and the polyarylene ether sulfone-sulfide compound may be a one-pot reaction.
본 발명은 신규한 구조를 가지며, 가공성, 내열성 등이 우수한 폴리아릴렌 에테르 설폰-설파이드 화합물 및 이를 경제적으로 제조할 수 있는 제조방법을 제공하는 발명의 효과를 갖는다.
The present invention has the effect of providing a polyarylene ether sulfone-sulfide compound having a novel structure and excellent workability and heat resistance, and a process for economically producing the same.
이하, 본 발명을 상세히 설명하면, 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 폴리아릴렌 에테르 설폰-설파이드(polyarylene ether sulfone-sulfide: PES-S) 화합물은 하기 화학식 1로 표시되는 반복단위를 포함하는 것을 특징으로 한다.The polyarylene ether sulfone-sulfide (PES-S) compound according to the present invention is characterized by containing a repeating unit represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, R1, R2, R3 및 R4는 각각 독립적으로 탄소수 1 내지 10의 탄화수소기, 예를 들면, 탄소수 1 내지 10의 알킬기, 탄소수 6 내지 10의 아릴기 등일 수 있다. a, b, c 및 d는 각각 독립적으로 0 내지 4의 정수이며, Z는
In Formula 1, R 1 , R 2 , R 3 and R 4 each independently represent a hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and the like. a, b, c and d are each independently an integer of 0 to 4, and Z is
본 발명의 폴리아릴렌 에테르 설폰-설파이드 화합물은 예를 들면, 하기 화학식 2로 표시되는 디히드록시디아릴설파이드 화합물 및 하기 화학식 3으로 표시되는 디할로게노디아릴술폰 화합물을 1.01 : 1 내지 1.10 : 1의 몰비(화학식 2 : 화학식 3)로 반응시켜 하기 화학식 4로 표시되는 중합체를 제조하고; 그리고 제조된 상기 중합체와 하기 화학식 5a로 표시되는 화합물, 하기 화학식 5b로 표시되는 화합물 및 하기 화학식 5c로 표시되는 화합물 중 1종 이상을 포함하는 단량체를 반응시켜 제조할 수 있다.The polyarylene ether sulfone-sulfide compound of the present invention can be produced, for example, by reacting a dihydroxy diaryl sulfide compound represented by the following formula 2 and a dihalogenenedialyl sulfone compound represented by the following formula 3 in a molar ratio of 1.01: 1 to 1.10: 1 (Formula 2: Formula 3) to prepare a polymer represented by Formula 4 below; And then reacting the produced polymer with a monomer containing at least one of the compound represented by the following formula (5a), the compound represented by the following formula (5b) and the compound represented by the following formula (5c).
[화학식 2](2)
[화학식 3](3)
[화학식 4][Chemical Formula 4]
[화학식 5a][Chemical Formula 5a]
[화학식 5b][Chemical Formula 5b]
[화학식 5c][Chemical Formula 5c]
상기 화학식 2, 3, 4, 5a, 5b 및 5c에서, R1, R2, R3, R4, R5, R6, R7, a, b, c, d, e, f, g 및 n의 평균값은 상기 화학식 1에서 정의한 바와 같고, X는 염소 원자(Cl), 불소 원자(F), 브롬 원자(Br), 요오드 원자(I) 등의 할로겐 원자이다.Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , a, b, c, d, e, f, g and and X is a halogen atom such as chlorine atom (Cl), fluorine atom (F), bromine atom (Br) or iodine atom (I).
구체예에서, 상기 화학식 4로 표시되는 중합체 제조 시의 반응(제1 반응) 및 상기 폴리아릴렌 에테르 설폰-설파이드 화합물 제조 시의 반응(제2 반응)은 각각 염기성 촉매 존재 하에, 150 내지 200℃, 예를 들면 160 내지 190℃의 온도에서 5분 내지 10시간, 예를 들면 10분 내지 7시간 동안 반응시키는 것일 수 있다. 상기 온도 범위에서, 상기 화학식 4로 표시되는 중합체 및 상기 폴리아릴렌 에테르 설폰-설파이드 화합물(상기 화학식 1 반복단위를 포함하는 중합체)을 고수율로 얻을 수 있다. In a specific example, the reaction (first reaction) in the preparation of the polymer represented by Formula 4 and the reaction (second reaction) in the preparation of the polyarylene ether sulfone-sulfide compound are respectively carried out at 150 to 200 ° C , For example, at a temperature of 160 to 190 ° C for 5 minutes to 10 hours, for example, 10 minutes to 7 hours. In the above temperature range, the polymer represented by the formula (4) and the polyarylene ether sulfone-sulfide compound (polymer containing the repeating unit of the formula (1)) can be obtained in high yield.
일 구체예에서, 상기 제1 반응은 반응기에 상기 디히드록시디아릴설파이드 화합물, 상기 염기성 촉매 및 용매를 넣고, 100 내지 150℃로 가열하여 물과 용매를 제거한 후, 상기 디할로게노디아릴술폰 화합물을 넣고, 150 내지 200℃, 예를 들면 160 내지 190℃에서 1 내지 10시간, 예를 들면 4 내지 7시간 동안 반응시켜, 상기 화학식 4로 표시되는 중합체를 제조하는 것일 수 있다.In one embodiment, the first reaction is carried out by adding the dihydroxy diarylsulfide compound, the basic catalyst and a solvent to a reactor, heating the reaction mixture at 100 to 150 ° C to remove water and a solvent, and then adding the dihalogenenedialyl sulfone And the mixture is reacted at 150 to 200 ° C, for example, at 160 to 190 ° C for 1 to 10 hours, for example, for 4 to 7 hours to prepare the polymer represented by the above formula (4).
일 구체예에서, 상기 제2 반응은 반응기에 상기 화학식 4로 표시되는 중합체, 상기 염기성 촉매 및 용매를 넣고, 100 내지 150℃로 가열하여 물과 용매를 제거한 후, 상기 염기성 촉매 및 상기 단량체(화학식 5a, 5b 및/또는 5c)를 넣고, 150 내지 200℃, 예를 들면 160 내지 190℃에서 10 내지 150분 동안 반응시켜, 상기 폴리아릴렌 에테르 설폰-설파이드 화합물을 제조하는 것일 수 있다.In one embodiment, the second reaction is carried out by adding the polymer represented by the formula (4), the basic catalyst and a solvent to a reactor, heating the mixture to 100 to 150 ° C to remove water and a solvent, 5a, 5b and / or 5c), and reacting at 150 to 200 ° C, for example, at 160 to 190 ° C for 10 to 150 minutes to prepare the polyarylene ether sulfone-sulfide compound.
다른 구체예에서, 상기 제1 반응 및 제2 반응은 원 포트(one-pot) 반응일 수 있다. 본 발명에서, 원 포트(one-pot) 반응은 상기와 같이 2단계 이상의 반응 과정에서, 중간 생성물(상기 화학식 4로 표시되는 중합체)을 분리 정제함이 없이, 다음 단계의 반응물을 가하여 반응시키는 방법을 계속적으로 수행함으로써, 목표 화합물인 폴리아릴렌 에테르 설폰-설파이드 화합물을 얻는 반응공정을 의미한다. 예를 들면, 반응기에 상기 디히드록시디아릴설파이드 화합물, 상기 염기성 촉매 및 용매를 넣고, 100 내지 150℃로 가열하여 물을 제거한 후, 상기 디할로게노디아릴술폰 화합물을 넣고, 150 내지 200℃, 예를 들면 160 내지 190℃에서 4 내지 7시간 동안 반응시켜, 상기 화학식 4로 표시되는 중합체를 제조 및 남아있는 용매를 제거한 다음, 반응물에 상기 단량체(화학식 5a, 5b 및/또는 5c, 예를 들면 화학식 5a)를 넣고, 150 내지 200℃, 예를 들면 160 내지 190℃에서 10분 내지 150분 동안 반응시켜, 상기 폴리아릴렌 에테르 설폰-설파이드 화합물을 제조하는 것일 수 있다.In another embodiment, the first reaction and the second reaction may be a one-pot reaction. In the present invention, the one-pot reaction is a method in which the reaction product of the next step is added and reacted without separating and purifying the intermediate product (the polymer represented by the formula 4) To obtain a target compound, polyarylene ether sulfone-sulfide compound. For example, the dihydroxy diarylsulfide compound, the basic catalyst and the solvent are added to the reactor, the water is removed by heating at 100 to 150 ° C, the dihalogenenedialyl sulfone compound is added, , For example, at 160 to 190 ° C for 4 to 7 hours to prepare a polymer represented by the formula (4) and to remove the remaining solvent, and then adding the monomer (5a, 5b and / or 5c, (5a), and reacting at 150 to 200 ° C, for example, at 160 to 190 ° C for 10 minutes to 150 minutes to prepare the polyarylene ether sulfone-sulfide compound.
상기 제1 반응 시, 상기 디히드록시디아릴설파이드 화합물과 상기 디할로게노디아릴술폰 화합물의 몰비(화학식 2 : 화학식 3)는 1.01 : 1 내지 1.10 : 1, 예를 들면 1.01 : 1 내지 1.05 : 1일 수 있다. 상기 범위에서 말단 히드록시기를 갖는 상기 화학식 4로 표시되는 중합체를 고수율로 얻을 수 있다.In the first reaction, the molar ratio of the dihydroxy diaryl sulfide compound and the dihalogenenedialyl sulfone compound (Formula 2) is 1.01: 1 to 1.10: 1, for example, 1.01: 1 to 1.05: 1 < / RTI > The polymer represented by the formula (4) having a terminal hydroxyl group within the above range can be obtained in high yield.
또한, 상기 제2 반응 시, 상기 단량체의 투입량은 상기 화학식 4로 표시되는 중합체 100 몰부에 대하여, 0.05 내지 0.5 몰부, 예를 들면 0.1 내지 0.3 몰부일 수 있다. 상기 범위에서 고분자량의 폴리아릴렌 에테르 설폰-설파이드 화합물을 고수율로 얻을 수 있다.In the second reaction, the amount of the monomer may be 0.05 to 0.5 mol, for example, 0.1 to 0.3 mol, per 100 mol of the polymer represented by the formula (4). In this range, a polyarylene ether sulfone-sulfide compound having a high molecular weight can be obtained in high yield.
구체예에서, 상기 염기성 촉매로는 통상의 알칼리 금속염 또는 알칼리 토금속염을 사용할 수 있으나, 이에 제한되지 않는다. 예를 들면, 탄산칼륨(K2CO3), 탄산나트륨(Na2CO3), 탄산칼슘(CaCO3), 수산화칼륨(KOH), 수산화나트륨(NaOH), 이들의 혼합물 등을 사용할 수 있다. 상기 염기성 촉매는 제1 반응 시, 상기 디히드록시디아릴설파이드 화합물 100 몰부에 대하여, 100 내지 220 몰부, 예를 들면 110 내지 210 몰부로 사용될 수 있다. 구체적으로, 상기 수산화나트륨, 수산화칼슘 등의 경우, 200 내지 210 몰부로 사용할 수도 있다. 상기 범위에서 상기 화학식 4로 표시되는 중합체를 고수율로 얻을 수 있다. 또한, 상기 염기성 촉매는 제2 반응 시, 상기 화학식 4로 표시되는 중합체 100 몰부에 대하여, 0.05 내지 0.5 몰부, 예를 들면 0.1 내지 0.3 몰부로 사용될 수 있다. 상기 범위에서 상기 폴리아릴렌 에테르 설폰-설파이드 화합물을 고수율로 얻을 수 있다.In the specific examples, as the basic catalyst, an ordinary alkali metal salt or alkaline earth metal salt may be used, but is not limited thereto. For example, potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), calcium carbonate (CaCO 3 ), potassium hydroxide (KOH), sodium hydroxide (NaOH) and mixtures thereof can be used. In the first reaction, the basic catalyst may be used in an amount of 100 to 220 moles, for example, 110 to 210 moles, per 100 moles of the dihydroxy diarylsulfide compound. Specifically, in the case of sodium hydroxide and calcium hydroxide, 200 to 210 parts by mol may be used. Within the above range, the polymer represented by the formula (4) can be obtained in high yield. In the second reaction, the basic catalyst may be used in an amount of 0.05 to 0.5 moles, for example, 0.1 to 0.3 moles per 100 moles of the polymer represented by the formula (4). Within the above range, the polyarylene ether sulfone-sulfide compound can be obtained in high yield.
상기 용매로는 당 분야에 사용되는 극성 및/또는 비극성 유기용매를 제한 없이 사용할 수 있으며, 예를 들면, 물(H2O), N-메틸피롤리돈(NMP), 톨루엔(toluene), 디메틸포름아미드(DMF), 디메틸아세트아미드(DMAc), 술포란(sulfolane), 디페닐 술폰(diphenyl sulfone, DPS), 프로필렌 카보네이트(propylene carbonate), 에틸렌 카보네이트(ethylene carbonate), 이들의 혼합물 등을 사용할 수 있다. 구체적으로는, 물, N-메틸피롤리돈, 톨루엔, 이들의 혼합물 등이 사용될 수 있다. 상기 용매는 상기 디히드록시디아릴설파이드 화합물 또는 상기 화학식 4로 표시되는 중합체 100 중량부에 대하여, 120 내지 300 중량부, 예를 들면 190 내지 220 중량부로 사용될 수 있으나, 이에 제한되지 않는다.
As the solvent, polar and / or nonpolar organic solvents used in the art can be used without limitation. Examples of the solvent include water (H 2 O), N-methylpyrrolidone (NMP), toluene, dimethyl (DMF), dimethylacetamide (DMAc), sulfolane, diphenyl sulfone (DPS), propylene carbonate, ethylene carbonate, and mixtures thereof. have. Specifically, water, N-methylpyrrolidone, toluene, a mixture thereof and the like can be used. The solvent may be used in an amount of 120 to 300 parts by weight, for example, 190 to 220 parts by weight, based on 100 parts by weight of the dihydroxy diaryl sulfide compound or the polymer represented by the formula (4), but is not limited thereto.
구체예에서, 상기 화학식 1로 표시되는 반복단위를 포함하는 폴리아릴렌 에테르 설폰-설파이드 화합물은 GPC(gel permeation chromatography)로 측정한 수평균분자량(Mn)이 10,000 내지 200,000 g/mol, 예를 들면 15,000 내지 160,000 g/mol일 수 있으나, 이에 제한되지 않는다.In a specific example, the polyarylene ether sulfone-sulfide compound containing the repeating unit represented by the above formula (1) has a number average molecular weight (Mn) of 10,000 to 200,000 g / mol, as measured by gel permeation chromatography (GPC) But may be, but not limited to, 15,000 to 160,000 g / mol.
상기 폴리아릴렌 에테르 설폰-설파이드 화합물의 유리전이온도는 150℃ 이상, 예를 들면 150 내지 170℃일 수 있다. 상기 범위에서 폴리아릴렌 에테르 설폰-설파이드 화합물의 내열성, 가공성 등이 우수할 수 있다.
The glass transition temperature of the polyarylene ether sulfone-sulfide compound may be 150 ° C or more, for example, 150 to 170 ° C. Within the above range, the polyarylene ether sulfone-sulfide compound may have excellent heat resistance and processability.
본 발명의 폴리아릴렌 에테르 설폰-설파이드 화합물은 내열성 및 가공성이 우수하며, 경제적으로 제조될 수 있다. 또한, 각종 열가소성 수지, 열경화성 수지 등과 함께 다양한 용도의 열가소성 수지 합금, 열경화성 수지 합금 등으로 사용될 수 있다.
The polyarylene ether sulfone-sulfide compound of the present invention is excellent in heat resistance and processability and can be produced economically. In addition, various thermoplastic resins, thermosetting resins and the like can be used for thermoplastic resin alloys and thermosetting resin alloys for various purposes.
이하, 본 발명의 바람직한 실시예를 통해 본 발명의 구성 및 작용을 더욱 상세히 설명하기로 한다. 다만, 이는 본 발명의 바람직한 예시로 제시된 것이며 어떠한 의미로도 이에 의해 본 발명이 제한되는 것으로 해석될 수는 없다.Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
여기에 기재되지 않은 내용은 이 기술 분야에서 숙련된 자이면 충분히 기술적으로 유추할 수 있는 것이므로 그 설명을 생략하기로 한다.
The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.
실시예Example
제조예 1: 화학식 4a로 표시되는 중합체의 제조Preparation Example 1: Preparation of a polymer represented by the formula (4a)
티오디페놀(thiodiphenol, TDP) 22.49 g(101 mmol)을 N-메틸피롤리돈(NMP) 100 mL에 녹인 후, 수산화나트륨(NaOH) 8.162 g(202 mmol), 물 8 mL 및 톨루엔 100 mL를 첨가한 후, 130℃에서 2시간 동안 가열하며 물과 톨루엔을 제거하였다. 다음으로, 디클로로디페닐설폰(DCDPS) 29.27 g(100 mmol)을 넣고, 190℃에서 4시간 가열하였다. 갈색의 중합물을 물에 침전 및 여과하고, 메탄올로 세척 및 여과한 다음, 진공오븐에서 건조하여 하기 화학식 4a로 표시되는 중합체(n의 평균값: 약 42)를 제조하였다{수율: 94%, 수평균분자량(Mn): 18,000 g/mol, 다분산지수(PDI): 1.6, 말단 수산화기(-OH) 함량: 198 meq/kg, (1H-NMR, 300 MHz, DMSO-d6): δ 7.91 (d, J = 8.4 Hz), 7.43-7.36 (m), 7.18-7.09 (m)}.After dissolving 22.49 g (101 mmol) of thiodiphenol (TDP) in 100 mL of N-methylpyrrolidone (NMP), 8.162 g (202 mmol) of sodium hydroxide (NaOH), 8 mL of water and 100 mL of toluene After the addition, the mixture was heated at 130 DEG C for 2 hours to remove water and toluene. Next, 29.27 g (100 mmol) of dichlorodiphenylsulfone (DCDPS) was added and the mixture was heated at 190 占 폚 for 4 hours. The brown polymer was precipitated in water, filtered, washed with methanol and filtered, and then dried in a vacuum oven to obtain a polymer (average value of n: about 42) represented by the following formula 4a {yield: 94% molecular weight (Mn): 18,000 g / mol , polydispersity index (PDI): 1.6, the terminal hydroxyl group (-OH) content: 198 meq / kg, (1 H-NMR, 300 MHz, DMSO-d 6): δ 7.91 ( d, J = 8.4Hz), 7.43-7.36 (m), 7.18-7.09 (m).
[화학식 4a][Chemical Formula 4a]
제조예 2: 화학식 4a로 표시되는 중합체의 제조Production Example 2: Preparation of a polymer represented by the formula (4a)
티오디페놀(thiodiphenol, TDP) 22.718 g(102 mmol)을 N-메틸피롤리돈(NMP) 100 mL에 녹인 후, 수산화나트륨(NaOH) 8.242 g(204 mmol), 물 8 mL 및 톨루엔 100 mL를 첨가한 후, 130℃에서 2시간 동안 가열하며 물과 톨루엔을 제거하였다. 다음으로, 디클로로디페닐설폰(DCDPS) 29.27 g(100 mmol)을 넣고, 180℃에서 5.5시간 가열하였다. 갈색의 중합물을 물에 침전 및 여과하고, 메탄올로 세척 및 여과한 다음, 진공오븐에서 건조하여 상기 화학식 4a로 표시되는 중합체(n의 평균값: 약 37)를 제조하였다{수율: 92%, 수평균분자량(Mn): 16,000 g/mol, 다분산지수(PDI): 1.6, 말단 수산화기(-OH) 함량: 157 meq/kg, (1H-NMR, 300 MHz, DMSO-d6): δ 7.91 (d, J = 8.4 Hz), 7.43-7.36 (m), 7.18-7.09 (m)}.
After dissolving 22.718 g (102 mmol) of thiodiphenol (TMP) in 100 mL of N-methylpyrrolidone (NMP), 8.242 g (204 mmol) of sodium hydroxide (NaOH), 8 mL of water and 100 mL of toluene After the addition, the mixture was heated at 130 DEG C for 2 hours to remove water and toluene. Next, 29.27 g (100 mmol) of dichlorodiphenylsulfone (DCDPS) was added, and the mixture was heated at 180 占 폚 for 5.5 hours. The brown polymer was precipitated in water and filtered, washed with methanol and filtered, and then dried in a vacuum oven to prepare a polymer (average value of n: about 37) represented by the formula 4a {yield: 92% molecular weight (Mn): 16,000 g / mol , polydispersity index (PDI): 1.6, the terminal hydroxyl group (-OH) content: 157 meq / kg, (1 H-NMR, 300 MHz, DMSO-d 6): δ 7.91 ( d, J = 8.4Hz), 7.43-7.36 (m), 7.18-7.09 (m).
제조예 3: 화학식 4a로 표시되는 중합체의 제조Preparation Example 3: Preparation of a polymer represented by the formula (4a)
디플루오로디페닐설폰 (DFDPS) 25.42 g (100 mmol), 티오디페놀(thiodiphenol, TDP) 22.26 g (102 mmol) 및 탄산칼륨(K2CO3) 15.2 g (110 mmol)의 혼합물에 NMP 160 mL 및 톨루엔 80 mL를 첨가한 후, 130℃에서 2시간 동안 가열하며 생성되는 물과 톨루엔을 제거하였다. 다음으로, 150℃에서 5시간 가열 후, 60℃로 냉각하고 여과하였다. 여과된 옅은 노란색 점성의 용액을 물/메탄올 (3:7)에 침전 및 여과하고 진공오븐에서 건조하여 fiber 형태의 상기 화학식 4a로 표시되는 중합체(n의 평균값: 약 186)를 제조하였다{수율: 92%, 수평균분자량(Mn): 80,000 g/mol, 다분산지수(PDI) = 1.7), 말단 수산화기(-OH) 함량: 24 meq/kg, (1H-NMR, 300 MHz, DMSO-d6): δ 7.91 (d, J = 8.4 Hz), 7.43-7.36 (m), 7.18-7.09 (m)}.
Difluoro Lodi sulfone (DFDPS) 25.42 g (100 mmol ), thiodiethylene phenol (thiodiphenol, TDP) 22.26 g ( 102 mmol) and NMP 160 mL To a mixture of potassium carbonate (K 2 CO 3) 15.2 g (110 mmol) And 80 mL of toluene were added, and the mixture was heated at 130 캜 for 2 hours to remove water and toluene. Next, the resultant was heated at 150 DEG C for 5 hours, cooled to 60 DEG C, and filtered. The filtered pale yellow viscous solution was precipitated in water / methanol (3: 7), filtered and dried in a vacuum oven to give the polymer of formula (4a) in the form of fiber (average value of n: about 186) {yield: ( 1 H-NMR, 300 MHz, DMSO-d) was used as the starting material, and the number average molecular weight (Mn): 80,000 g / mol, polydispersity index 6 ): [delta] 7.91 (d, J = 8.4 Hz), 7.43-7.36 (m), 7.18-7.09 (m).
실시예 1: 폴리아릴렌 에테르 설폰-설파이드 화합물의 제조Example 1: Preparation of polyarylene ether sulfone-sulfide compound
상기 제조예 1에서 얻은 중합체 7 g 및 탄산칼륨(K2CO3) 0.417 g(3 mmol)를 NMP 40 mL 및 톨루엔 40 mL에 넣고, 130℃에서 3시간 동안 가열하여 물과 톨루엔을 제거하였다. 다음으로, 1,4-비스(브로모메틸)벤젠(1,4-bis(bromomethyl)benzene) 0.189 g(0.7 mmol)를 투입하고, 160℃에서 20분 동안 가열한 후, 메탄올에 침전 및 세척하고, 여과하였다. 여과물을 진공오븐에서 건조하여 하기 화학식 1a로 표시되는 반복단위를 포함하는 폴리아릴렌 에테르 설폰-설파이드 화합물을 제조하였다{수율: 90%, 수평균분자량(Mn): 36,000 g/mol, 다분산지수(PDI): 2.2, 말단 수산화기(-OH) 함량: 52 meq/kg, (1H-NMR, 300 MHz, DMSO-d6): δ 7.89 (d, J = 8.4 Hz), 7.42-7.34 (m), 7.18-7.09 (m), 5.09 (s)}.7 g of the polymer obtained in Preparation Example 1 and 0.417 g (3 mmol) of potassium carbonate (K 2 CO 3 ) were placed in 40 mL of NMP and 40 mL of toluene and heated at 130 ° C for 3 hours to remove water and toluene. Then, 0.189 g (0.7 mmol) of 1,4-bis (bromomethyl) benzene was added thereto, and the mixture was heated at 160 DEG C for 20 minutes. Then, And filtered. The filtrate was dried in a vacuum oven to prepare a polyarylene ether sulfone-sulfide compound containing a repeating unit represented by the following formula (1a) (yield: 90%, number average molecular weight (Mn): 36,000 g / index (PDI): 2.2, the terminal hydroxyl group (-OH) content: 52 meq / kg, (1 H-NMR, 300 MHz, DMSO-d 6): δ 7.89 (d, J = 8.4 Hz), 7.42-7.34 ( m), 7.18-7.09 (m), 5.09 (s).
[화학식 1a][Formula 1a]
상기 화학식 1a에서, Z는
In the above formula (I), Z is
실시예 2: 폴리아릴렌 에테르 설폰-설파이드 화합물의 제조Example 2: Preparation of polyarylene ether sulfone-sulfide compound
상기 제조예 2에서 얻은 중합체 40 g 및 NaOH 0.570 g(14.2 mmol)를 NMP 200 mL 및 톨루엔 200 mL에 넣고 130℃에서 3시간 동안 가열하여 물과 톨루엔을 제거하였다. 다음으로, 1,4-페닐렌디이소시아네이트(1,4-phenylene diisocyanate) 0.57 g(3.56 mmol)를 투입하고, 130℃에서 1시간 동안 가열한 후, 메탄올에 침전 및 세척하고, 여과하였다. 여과물을 진공오븐에서 건조하여 하기 화학식 1a로 표시되는 반복단위를 포함하는 폴리아릴렌 에테르 설폰-설파이드 화합물을 제조하였다{수율: 90%, 수평균분자량(Mn): 20,000 g/mol, 다분산지수(PDI): 2.0, 말단 수산화기(-OH) 함량: 28 meq/kg, (1H-NMR, 300 MHz, DMSO-d6): δ 7.92 (d, J = 8.4 Hz), 7.43-7.36 (m), 7.18-7.08 (m)}.40 g of the polymer obtained in Preparation Example 2 and 0.570 g (14.2 mmol) of NaOH were added to 200 mL of NMP and 200 mL of toluene, and the mixture was heated at 130 DEG C for 3 hours to remove water and toluene. Next, 0.57 g (3.56 mmol) of 1,4-phenylene diisocyanate was added and the mixture was heated at 130 ° C for 1 hour, then precipitated in methanol, washed, and filtered. The filtrate was dried in a vacuum oven to prepare a polyarylene ether sulfone-sulfide compound containing the repeating unit represented by the following formula (1a) (yield: 90%, number average molecular weight (Mn): 20,000 g / index (PDI): 2.0, the terminal hydroxyl group (-OH) content: 28 meq / kg, (1 H-NMR, 300 MHz, DMSO-d 6): δ 7.92 (d, J = 8.4 Hz), 7.43-7.36 ( m), 7.18-7.08 (m).
[화학식 1a][Formula 1a]
상기 화학식 1a에서, Z는
In the above formula (I), Z is
실시예 3: 폴리아릴렌 에테르 설폰-설파이드 화합물의 제조Example 3: Preparation of polyarylene ether sulfone-sulfide compound
상기 제조예 3에서 얻은 중합체 40 g 및 NaOH 0.570 g(14.2 mmol)를 NMP 200 mL 및 톨루엔 200 mL에 넣고 130℃에서 3시간 동안 가열하여 물과 톨루엔을 제거하였다. 다음으로, 테레프탈로일클로라이드(terephthalolyl chloride) 2.03 g(10 mmol)을 첨가하고 0.57 g(3.56 mmol)를 투입하고, 130℃에서 1시간 동안 가열한 후, 메탄올에 침전 및 세척하고, 여과하였다. 여과물을 진공오븐에서 건조하여 하기 화학식 1a로 표시되는 반복단위를 포함하는 폴리아릴렌 에테르 설폰-설파이드 화합물을 제조하였다{수율: 88%, 수평균분자량(Mn): 150,000 g/mol, 다분산지수(PDI): 2.1, 말단 수산화기(-OH) 함량: 16 meq/kg, (1H-NMR, 300 MHz, DMSO-d6): δ 7.92 (d, J = 8.4 Hz), 7.43-7.36 (m), 7.18-7.08 (m)}.40 g of the polymer obtained in Preparation Example 3 and 0.570 g (14.2 mmol) of NaOH were added to 200 mL of NMP and 200 mL of toluene, and the mixture was heated at 130 DEG C for 3 hours to remove water and toluene. Next, 2.03 g (10 mmol) of terephthalolyl chloride was added, and 0.57 g (3.56 mmol) of terephthaloyl chloride was added. The mixture was heated at 130 캜 for 1 hour, then precipitated in methanol, washed, and filtered. The filtrate was dried in a vacuum oven to prepare a polyarylene ether sulfone-sulfide compound containing a repeating unit represented by the following formula (1a) (yield: 88%, number average molecular weight (Mn): 150,000 g / index (PDI): 2.1, the terminal hydroxyl group (-OH) content: 16 meq / kg, (1 H-NMR, 300 MHz, DMSO-d 6): δ 7.92 (d, J = 8.4 Hz), 7.43-7.36 ( m), 7.18-7.08 (m).
[화학식 1a][Formula 1a]
상기 화학식 1a에서, Z는
In the above formula (I), Z is
실시예 4: 폴리아릴렌 에테르 설폰-설파이드 화합물의 제조Example 4: Preparation of polyarylene ether sulfone-sulfide compound
티오디페놀(TDP) 23.73 g(105 mmol)을 NMP 100 mL에 녹인 용액에 수산화나트륨(NaOH) 8.4 g(210 mmol)를 물 10 mL에 희석해서 첨가한 후, 톨루엔 100 mL를 넣었다. 혼합용액을 130℃에서 4시간 동안 가열하여 물을 제거하고, 디클로로디페닐설폰(DCDPS) 29.27 g, 100 mmol를 첨가한 후, 180℃에서 5시간 가열하면서 남아있는 톨루엔을 제거하였다. 다음으로, 테레프탈로일클로라이드(terephthalolyl chloride) 2.03 g(10 mmol)을 첨가하고, 180℃에서 30분 동안 가열한 뒤 반응온도를 80℃로 냉각하였다. 갈색 점성의 용액을 물/메탄올(3/7, 중량비)에 침전 여과하고 진공오븐에서 건조하여, 원 포트(one-pot) 반응으로 하기 화학식 1a로 표시되는 반복단위를 포함하는 폴리아릴렌 에테르 설폰-설파이드 화합물을 제조하였다{수율: 94%, 수평균분자량(Mn): 34,000 g/mol, 다분산지수(PDI): 1.9, 말단 수산화기(-OH) 함량: 54 meq/kg, (1H-NMR, 300 MHz, DMSO-d6): δ 7.91 (d, J = 8.4 Hz), 7.43-7.36 (m), 7.18-7.09 (m)}.To a solution of 23.73 g (105 mmol) of thiodiphenol (TDP) in 100 mL of NMP was added 8.4 g (210 mmol) of sodium hydroxide (NaOH) diluted in 10 mL of water and then 100 mL of toluene was added. The mixed solution was heated at 130 캜 for 4 hours to remove water, and 29.27 g (100 mmol) of dichlorodiphenylsulfone (DCDPS) was added. The remaining toluene was removed by heating at 180 캜 for 5 hours. Next, 2.03 g (10 mmol) of terephthalolyl chloride was added, and the mixture was heated at 180 占 폚 for 30 minutes and then cooled to 80 占 폚. The brown viscous solution was precipitated in water / methanol (3/7, weight ratio), and dried in a vacuum oven to obtain polyarylene ether sulfone containing repeating units represented by the following formula (1a) in a one- - to prepare a sulfide compound {yield: 94%, number average molecular weight (Mn): 34,000 g / mol , polydispersity index (PDI): 1.9, the terminal hydroxyl group (-OH) content: 54 meq / kg, (1 H- NMR, 300 MHz, DMSO-d 6): δ 7.91 (d, J = 8.4 Hz), 7.43-7.36 (m), 7.18-7.09 (m)}.
[화학식 1a][Formula 1a]
상기 화학식 1a에서, Z는
In the above formula (I), Z is
물성 평가 방법Property evaluation method
(1) 유리전이온도(Tg)(단위: ℃): Different Scanning Calorimeter(DSC)를 사용하여 측정하였다. DSC는 TA Instrument사의 Q20 측정기를 이용하였고, 질소 분위기, 30 내지 400℃의 온도 범위에서 승온 속도 10℃/min, 냉각 속도 10℃/min의 조건으로 측정하였다.(1) Glass transition temperature (Tg) (unit: 占 폚): Measured using a differential scanning calorimeter (DSC). DSC was measured using a Q20 measuring instrument manufactured by TA Instrument under the conditions of a nitrogen atmosphere, a temperature range of 30 to 400 占 폚 at a heating rate of 10 占 폚 / min and a cooling rate of 10 占 폚 / min.
(2) 5% 중량감소온도(Td(5%))(단위: ℃): TGA(장치명: Discovery, 제조사: TA Instrument)를 사용하여, 승온 속도 20 ℃/min, 온도구간 30 내지 700℃, 질소 분위기 및 Pt 팬(pan) 사용 조건에서, 화합물의 중량이 5% 감소할 때의 온도를 측정하였다.
(2) 5% weight reduction temperature (Td (5%)) (unit: 占 폚): temperature rise rate 20 占 폚 / min, temperature range 30 to 700 占 폚, TGA (apparatus name: Discovery, Under a nitrogen atmosphere and using a Pt pan, the temperature at which the weight of the compound decreased by 5% was measured.
상기 결과로부터, 본 발명의 폴리아릴렌 에테르 설폰-설파이드 화합물은 가공성, 내열성 등이 우수하며, 경제적으로 제조할 수 있음을 알 수 있다.
From the above results, it can be seen that the polyarylene ether sulfone-sulfide compound of the present invention has excellent processability and heat resistance, and can be produced economically.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
[화학식 1]
상기 화학식 1에서, R1, R2, R3 및 R4는 각각 독립적으로 탄소수 1 내지 10의 탄화수소기이고, a, b, c 및 d는 각각 독립적으로 0 내지 4의 정수이며, Z는
A polyarylene ether sulfone-sulfide compound comprising a repeating unit represented by the following formula (1):
[Chemical Formula 1]
In Formula 1, R 1, R 2, R 3 and R 4 are each independently a hydrocarbon group having 1 to 10, a, b, c and d are each independently an integer from 0 to 4, Z is
The polyarylene ether sulfone-sulfide compound according to claim 1, wherein the polyarylene ether sulfone-sulfide compound has a number average molecular weight of 10,000 to 200,000 g / mol.
The polyarylene ether sulfone-sulfide compound according to claim 1, wherein the polyarylene ether sulfone-sulfide compound has a glass transition temperature of 150 ° C or higher.
제조된 상기 중합체와 하기 화학식 5a로 표시되는 화합물, 하기 화학식 5b로 표시되는 화합물 및 하기 화학식 5c로 표시되는 화합물 중 1종 이상을 포함하는 단량체를 반응시키는 단계를 포함하는 것을 특징으로 하는 하기 화학식 1로 표시되는 반복단위를 포함하는 폴리아릴렌 에테르 설폰-설파이드 화합물의 제조방법:
[화학식 1]
상기 화학식 1에서, R1, R2, R3 및 R4는 각각 독립적으로 탄소수 1 내지 10의 탄화수소기이고, a, b, c 및 d는 각각 독립적으로 0 내지 4의 정수이며, Z는
[화학식 2]
[화학식 3]
[화학식 4]
[화학식 5a]
[화학식 5b]
[화학식 5c]
상기 화학식 2, 3, 4, 5a, 5b 및 5c에서, R1, R2, R3, R4, R5, R6, R7, a, b, c, d, e, f, g 및 n의 평균값은 상기 화학식 1에서 정의한 바와 같고, X는 할로겐 원자이다.
Reacting a dihydroxy diarylsulfide compound represented by the following formula (2) and a dihalogenenedialyl sulfone compound represented by the following formula (3) with a molar ratio of 1.01: 1 to 1.10: 1 (formula (2) ≪ / RTI > And
Reacting the produced polymer with a monomer comprising at least one member selected from the group consisting of a compound represented by the following formula (5a), a compound represented by the following formula (5b) and a compound represented by the following formula (5c) A process for producing a polyarylene ether sulfone-sulfide compound containing a repeating unit represented by the formula:
[Chemical Formula 1]
In Formula 1, R 1, R 2, R 3 and R 4 are each independently a hydrocarbon group having 1 to 10, a, b, c and d are each independently an integer from 0 to 4, Z is
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5a]
[Chemical Formula 5b]
[Chemical Formula 5c]
Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , a, b, c, d, e, f, g and The average value of n is as defined in Formula 1, and X is a halogen atom.
5. The process for producing a polyarylene ether sulfone-sulfide compound according to claim 4, wherein the amount of the monomer is 0.05 to 0.5 parts by weight based on 100 parts by weight of the polymer represented by the formula (4).
5. The process according to claim 4, wherein the reaction is carried out in the presence of a basic catalyst at a temperature of from 150 to 200 占 폚.
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| KR20100040965A (en) | 2007-08-10 | 2010-04-21 | 도레이 카부시키가이샤 | Aromatic polyether sulfone having hydroxyphenyl end group and method for producing the same |
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