TW201725193A - Method for preparing a polymer - Google Patents
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本揭露關於一種聚合物製備方法,更特別關於一種鋶鹽聚合物或聚芳硫醚的製備方法。 The present disclosure relates to a method of preparing a polymer, and more particularly to a process for preparing a phosphonium salt polymer or polyarylene sulfide.
聚芳硫醚是具有出色的物理特性,例如耐熱性、耐化學性、耐火性、及電絕緣特性,因此廣泛用於電腦附件、汽車附件、與腐蝕性化學物質接觸的零件的塗料、以及具有耐化學性的工業纖維。 Polyarylene sulfides are excellent in physical properties such as heat resistance, chemical resistance, fire resistance, and electrical insulation properties, and are therefore widely used in computer accessories, automotive accessories, coatings for parts in contact with corrosive chemicals, and Chemically resistant industrial fibers.
然而,由於傳統聚芳硫醚的製備方法主要係以鹵製程為主,除了低的聚芳硫醚樹脂產率外,還會產生無法回收的含鹵副產物,造成環境汙染。此外,傳統聚芳硫醚樹脂的製備方法所得之聚芳硫醚樹脂純化不易,會有鹵副產物殘留於聚芳硫醚樹脂中。 However, since the preparation method of the conventional polyarylene sulfide is mainly based on a halogen process, in addition to the low polyarylene sulfide resin yield, a halogen-containing by-product which cannot be recovered is generated, which causes environmental pollution. Further, the polyarylene sulfide resin obtained by the method for producing a conventional polyarylene sulfide resin is not easily purified, and a halogen by-product remains in the polyarylene sulfide resin.
因此,業界需要一種新的方法製備聚芳硫醇。 Therefore, the industry needs a new method to prepare polyaryl thiols.
根據本揭露實施例,本揭露提供一種聚合物製備方法,包含將至少一種具有式(I)所示結構的單體在磺酸、二苯胺、及含氧的磷化物(oxygen-containing phosphide)存在下進行反應,得到一鋶鹽聚合物(sulfonium salt polymer)。 According to an embodiment of the present disclosure, the present disclosure provides a method for preparing a polymer comprising the presence of at least one monomer having the structure of the formula (I) in the presence of a sulfonic acid, a diphenylamine, and an oxygen-containing phosphide. The reaction was carried out to obtain a sulfonium salt polymer.
其中x係0、1、或2;R1係C1-6烷基;以及,R2係獨立為氫、或C1-6烷基。 Wherein x is 0, 1, or 2; R 1 is C 1-6 alkyl; and R 2 is independently hydrogen or C 1-6 alkyl.
聚芳硫醚若利用單體(I)(其化學結構可為)在酸性環境下聚合成陽離子聚合物,再進行去甲基化來進行製備,請參照反應式(I),則所得之陽離子聚合物(由單體(I)聚合而成)其轉換率並不高。 Polyarylene sulfide using monomer (I) (its chemical structure can be The polymerization is carried out in an acidic environment to form a cationic polymer, followed by demethylation for preparation. Referring to the reaction formula (I), the conversion rate of the obtained cationic polymer (polymerized from the monomer (I)) is not tall.
此外,若參照反應式(II)製備單體(I),需先將甲基苯基亞碸(methyl phenyl sulfoxide)與茴香硫醚(methyl phenyl sulfide)在酸性環境下合成,在得到陽離子中間體後,再進行去甲基化與氧化反應,才可獲得。,則可能因反應式(II)的製備過程較為繁複,導致聚芳硫醚的產率下降。 In addition, if the monomer (I) is prepared by referring to the reaction formula (II), it is necessary to synthesize methyl phenyl sulfoxide and methyl phenyl sulfide in an acidic environment to obtain a cationic intermediate. After that, demethylation and oxidation are carried out to obtain. However, the preparation process of the reaction formula (II) may be complicated, resulting in a decrease in the yield of the polyarylene sulfide.
基於上述,本揭露實施例提供一種聚合物製備方法,可提昇單體轉換為鋶鹽聚合物的轉換率,且所使用的單體也較容易獲得。根據本揭露實施例,該方法包含將至少一種具有式(I)所示結構的單體在磺酸、二苯胺(diphenyl amine)、及含氧的磷化物(oxygen-containing phosphide)存在下進行聚合反應,得到一鋶鹽聚合物(sulfonium salt polymer)。 Based on the above, the present disclosure provides a method for preparing a polymer, which can increase the conversion rate of a monomer to a phosphonium salt polymer, and the monomer used is also relatively easy to obtain. According to an embodiment of the present disclosure, the method comprises polymerizing at least one monomer having the structure of the formula (I) in the presence of a sulfonic acid, a diphenyl amine, and an oxygen-containing phosphide. The reaction gives a sulfonium salt polymer.
其中x可為0、1、或2;R1可為C1-6烷基;以及,R2可獨立為氫、或C1-6烷基。根據本揭露實施例,該具有式(I)所示結構的單體之亞碸(S=O)官能基可在酸性環境中質子化為具有反應活性之氫氧化鋶(sulfonium hydroxide)官能基,並藉由二苯胺作為電荷穩定試劑,提供電子與氫氧化鋶形成錯體(complex)結構,使芳香環之π電子能夠提升反應性進行聚合反應。此外,在含氧的磷化物(oxygen-containing phosphide)存在下進行聚合反應,可大幅增加具由式(I)所示結構的單體轉換為鋶鹽聚合物(或聚芳硫醚)的轉換率。此外,在得到鋶鹽聚合物之後,可將一親核試劑(nucleophile)進一步 與所得到的鋶鹽聚合物反應,得到一無鹵素殘留之耐高溫聚芳硫醚(polyarylene sulfide)(熔融溫度(Tm)可大於或等於280℃)。根據本揭露實施例,該單體轉換為鋶鹽聚合物(或聚芳硫醚)的轉換率計算方式如下述方程式: Wherein x may be 0, 1, or 2; R 1 may be C 1-6 alkyl; and R 2 may independently be hydrogen or C 1-6 alkyl. According to an embodiment of the present disclosure, the monomeric sulfonium (S=O) functional group of the monomer having the structure of the formula (I) can be protonated into a reactive sulfonium hydroxide functional group in an acidic environment. And by using diphenylamine as a charge stabilizing agent, a complex structure is formed between the electron and the cesium hydroxide, and the π electron of the aromatic ring can enhance the reactivity to carry out the polymerization reaction. Further, the polymerization reaction in the presence of an oxygen-containing phosphide can greatly increase the conversion of a monomer having a structure represented by the formula (I) into a sulfonium salt polymer (or polyarylene sulfide). rate. In addition, after the sulfonium salt polymer is obtained, a nucleophile can be further reacted with the obtained sulfonium salt polymer to obtain a halogen-free residual high temperature polyarylene sulfide (melting temperature ( Tm) can be greater than or equal to 280 ° C). According to an embodiment of the present disclosure, the conversion rate of the monomer to a sulfonium salt polymer (or polyarylene sulfide) is calculated as follows:
根據本揭露實施例,該烷基可為直鏈(linear)或分支鍵(branched)烷基。因此,R1可為甲基(methyl)、乙基(ethyl)、丙基(propyl)、異丙基(isopropyl)、正丁基(n-butyl)、叔丁基(t-butyl)、仲丁基(sec-butyl)、異丁基(isobutyl)、戊基(pentyl)、或己基(hexyl)。此外,R2可各自獨立為氫、氟、甲基、乙基、丙基、異丙基、正丁基、叔丁基、仲丁基、異丁基、戊基、或己基。 According to embodiments of the present disclosure, the alkyl group may be a linear or branched alkyl group. Therefore, R 1 may be methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, or Sec-butyl, isobutyl, pentyl, or hexyl. Further, R 2 may each independently be hydrogen, fluorine, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, sec-butyl, isobutyl, pentyl, or hexyl.
根據本揭露實施例,該磺酸可為具有式(II)所示結構的化合物,
根據本揭露實施例,在本揭露所述聚合物製備方法中添加該含氧的磷化物,可大幅增加具有式(I)所示結構的單體轉換為鋶鹽聚合物的轉換率。該含氧的磷化物可為由氧及磷所構成的化合物,例如磷酸酐(P2O5)。此外,該含氧的磷化物可為由氧、氫及磷所構成的化合物,例如多聚磷酸(H(n+2)PnO(3n+1),其中n大於1)。根據本揭露實施例,該含氧的磷化物與該單體的莫耳比可為約0.5至2,例如約0.5至1.5。 According to the embodiments of the present disclosure, the oxygen-containing phosphide is added to the polymer preparation method of the present disclosure, and the conversion ratio of the monomer having the structure represented by the formula (I) to the onium salt polymer can be greatly increased. The oxygen-containing phosphide may be a compound composed of oxygen and phosphorus, such as phosphoric anhydride (P 2 O 5 ). Further, the oxygen-containing phosphide may be a compound composed of oxygen, hydrogen, and phosphorus, such as polyphosphoric acid (H (n+2) P n O (3n+1) , wherein n is greater than 1). According to embodiments of the present disclosure, the molar ratio of the oxygen-containing phosphide to the monomer may be from about 0.5 to 2, such as from about 0.5 to 1.5.
根據本揭露實施例,該二苯胺與該單體的莫耳比可為約0.5至2,例如約0.5至1.5。上述二苯胺以及含氧的磷化物係促進該具有式(I)所示結構的單體進行聚合反應,二苯胺以及含氧的磷化物並非反應物。 According to embodiments of the present disclosure, the molar ratio of the diphenylamine to the monomer may be from about 0.5 to 2, such as from about 0.5 to 1.5. The diphenylamine and the oxygen-containing phosphide promote polymerization of the monomer having the structure represented by the formula (I), and the diphenylamine and the oxygen-containing phosphide are not reactants.
根據本揭露實施例,本揭露所述聚合物製備方法可將一種具有式(I)所示結構的單體在磺酸、二苯胺、及含氧的磷化物存在下進行聚合反應,其中該具有式(I)所示結構的單體可例如為
根據本揭露實施例,以本揭露所述聚合物製備方法所得之鋶鹽聚合物可具有至少一種具有式(III)所示結構的重複單元,
其中x可為0、1、或2;R1可為C1-6烷基;R2可獨立為氫、或C1-6烷基;以及,R3可為氫、C1-6烷基、或C1-6氟烷基。根據本揭露某些實施例,該具有式(III)所示結構的重複單元可為
根據本揭露實施例,該聚合物製備方法,在獲得該鋶 鹽聚合物之後,可更包含將一親核試劑(nucleophile)與該鋶鹽聚合物反應,得到一聚芳硫醚(polyarylene sulfide)。其中,該親核試劑(nucleophile)可例如為具有取代/非取代基的吡啶或其衍生物(例如:吡啶、4-甲基吡啶)、胺類(如:三乙胺)、鹵化鹽類(例如:氯化鉀)、醇類(例如:甲醇、乙醇)、或醯胺類(例如:二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯酮),且該親核試劑與具有式(I)所示結構的單體(用來合成該鋶鹽聚合物)的莫耳比可為約1至100,即亦可加入過量親核試劑作為溶劑。該聚芳硫醚可具有至少一種具有式(IV)所示結構的重複單元。 According to an embodiment of the present disclosure, the method for preparing a polymer, in obtaining the crucible After the salt polymer, the nucleophile may be further reacted with the sulfonium salt polymer to obtain a polyarylene sulfide. Wherein, the nucleophile may be, for example, a pyridine having a substituted/unsubstituted group or a derivative thereof (for example, pyridine, 4-methylpyridine), an amine (such as triethylamine), or a halogenated salt ( For example: potassium chloride), alcohols (eg methanol, ethanol), or guanamines (eg dimethylformamide, dimethylacetamide, N-methylpyrrolidone), and the nucleophile The molar ratio of the reagent to the monomer having the structure of the formula (I) for synthesizing the phosphonium salt polymer may be from about 1 to 100, that is, an excess of a nucleophile may also be added as a solvent. The polyarylene sulfide may have at least one repeating unit having the structure represented by the formula (IV).
其中x可為0、1、或2;以及,R2可獨立為氫、或C1-6
烷基。該具有式(IV)所示結構的重複單元可例如為、
為了讓本揭露之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉數實施例及比較實施例,作詳細說明如下: The above and other objects, features and advantages of the present invention will become more apparent and understood.
實施例1: Example 1:
將0.5g之甲基苯基亞碸(methyl phenyl sulfide)、0.25g之五氧化二磷(phosphorus pentoxide、P2O5)與0.3g之二苯胺(diphenyl amine),加入一反應瓶中。接著,在0℃冰浴下,緩慢加入3ml之三氟甲基磺酸(trifluoromethanesulfonic acid)於反應瓶中。在室溫下反應1小時後,將反應瓶緩慢回到室溫。反應20小時後,將所得物倒入100ml之乙醚中並劇烈攪拌,再用少量丙酮清洗。乾燥後得到鋶鹽聚合物(I)(白色固體)。 0.5 g of methyl phenyl sulfide, 0.25 g of phosphorus pentoxide (P 2 O 5 ) and 0.3 g of diphenyl amine were placed in a reaction flask. Next, 3 ml of trifluoromethanesulfonic acid was slowly added to the reaction flask under an ice bath at 0 °C. After reacting for 1 hour at room temperature, the reaction flask was slowly returned to room temperature. After reacting for 20 hours, the resultant was poured into 100 ml of diethyl ether and vigorously stirred, and then washed with a small amount of acetone. After drying, the onium salt polymer (I) (white solid) was obtained.
接著,將所得鋶鹽聚合物(I)溶於15ml之4-甲基吡啶(4-methylpyridine)中,並加熱至迴流(約100℃)。反應6小時後,將所得產物倒入30ml之鹽酸水溶液(濃度為10%),再用少量丙酮清洗,得到聚芳硫醚(I)(白色固體),轉換率約為88%。上述反應之反應式如下所示:
接著,使用示差掃描量熱儀(differential scanning calorimetry、DSC)量測所得聚芳硫醚(I),得知其熔融溫度(Tm)達281℃以及其再結晶溫度(Tc)達210℃。接著,以紅外線光譜儀(FT-IR)量測聚芳硫醚(I),結果如下:IR(cm-1):3065,1573,1471,1387,1092,1009,998,815,742。 Next, the obtained polyarylene sulfide (I) was measured by differential scanning calorimetry (DSC), and it was found that the melting temperature (Tm) thereof was 281 ° C and the recrystallization temperature (Tc) thereof was 210 ° C. Next, the polyarylene sulfide (I) was measured by an infrared spectrometer (FT-IR), and the results were as follows: IR (cm -1 ): 3065, 1573, 1471, 1387, 1092, 1009, 998, 815, 742.
實施例2: Example 2:
將3g之苯基硼酸(phenylboronic acid)、3.45g之4-溴硫代苯甲醚(4-bromothioanisole)、0.1g之Pd(PPh3)4、與1.5g之氫氧化鈉(Na2CO3)加入一反應瓶中。接著,在氮氣下緩慢將50ml之甲苯、60ml
之去離子水、與10ml之甲醇加入該反應瓶。接著,在100℃下反應24小時後,用乙酸乙酯與水對所得溶液萃取三次,並取有機層抽乾,得到化合物(I)(1-methylsulfanyl-4-phenylbenzene),產率約為99%。上述反應之反應式如下所示:
利用核磁共振光譜分析化合物(I),所得之光譜資訊如下:1H NMR(500MHz,ppm,CDCl3):2.55(-CH3,s),7.33-7.37(phenyl,3H,m),7.43-7.45(phenyl,2H,m),7.54-7.6(phenyl,4H,m)。 The compound (I) was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: 1 H NMR (500 MHz, ppm, CDCl 3 ): 2.55 (-CH 3 , s), 7.33 - 7.37 (phenyl, 3H, m), 7.43 7.45 (phenyl, 2H, m), 7.54-7.6 (phenyl, 4H, m).
接著,將1g之化合物(I),加入一反應瓶中,並緩慢加入10ml之冰醋酸與2ml之雙氧水(濃度為30%)。在室溫下反應20分鐘後,將所得溶液過濾,得到橘色固體。將橘色固體以二氯甲烷與水進行萃取三次,並收集有機層。接著,對有機層進行除水、過濾、及濃縮後,得到化合物(II)。上述反應之反應式如下所示:
利用核磁共振光譜分析化合物(II),所得之光譜資訊如下:1H NMR(500MHz,ppm,CDCl3):2.80(-CH3,s),7.42-7.51(biphenyl,3H,m),7.62-7.63(biphenyl,2H,m),7.73-7.78(biphenyl,4H,m)。 The compound (II) was analyzed by nuclear magnetic resonance spectroscopy, and the obtained spectral information was as follows: 1 H NMR (500 MHz, ppm, CDCl 3 ): 2.80 (-CH 3 , s), 7.42 - 7.51 (biphenyl, 3H, m), 7.62 7.63 (biphenyl, 2H, m), 7.73-7.78 (biphenyl, 4H, m).
接著,將0.5g之化合物(II)、0.39g之二苯胺、及0.16g之五氧化二磷(phosphorus pentoxide、P2O5)加入一反應瓶中。接著,在0℃冰浴下緩慢加入5ml之三氟甲基磺酸。在冰浴下反應1小時後,緩慢回到室溫。接著,反應20小時後,將所得物倒入100ml之乙醚中並劇烈攪拌,再用少量丙酮清洗。乾燥後得到鋶鹽聚合物(II)。接著,將所得鋶鹽聚合物(II)溶於6ml之4-甲基吡啶(4-methylpyridine)中並在室溫下攪拌1小時,接著加熱至迴流(約120℃)。反應20小時後,將所得產物倒入30ml之鹽酸水溶液(濃度為10%),再用少量丙酮清洗,得到聚芳硫醚(II)(白色固體),轉換率約為90%,如表1所示。上述反應之反應式如下所示:
接著,使用示差掃描量熱儀(differential scanning calorimetry、DSC)量測所得聚芳硫醚(II),得知其熔融溫度(Tm)達404℃以及其再結晶溫度(Tc)達369℃。接著,以紅外線光譜儀(FT-IR)量測聚芳硫醚(II),結果如下:IR(cm-1):3026,1590,1474,1391,1313,1152,1137,1090,1045,998,952,811,758,690。 Next, the obtained polyarylene sulfide (II) was measured by differential scanning calorimetry (DSC), and it was found that the melting temperature (Tm) thereof was 404 ° C and the recrystallization temperature (Tc) thereof was 369 ° C. Next, the polyarylene sulfide (II) was measured by an infrared spectrometer (FT-IR), and the results were as follows: IR (cm -1 ): 3026, 1590, 1474, 1391, 1313, 1152, 1137, 1090, 1045, 998, 952, 811, 758, 690.
比較例1: Comparative Example 1:
將0.5g之化合物(II)與0.39g之二苯胺加入一反應瓶中。接著,在0℃冰浴下緩慢加入5ml之三氟甲基磺酸。在冰浴下反應1小時後,緩慢回到室溫。接著,反應20小時後,將所得物倒入100ml之乙醚中並劇烈攪拌,再用少量丙酮清洗。乾燥後得到鋶鹽 聚合物(II)。接著,將所得鋶鹽聚合物(II)溶於6ml之4-甲基吡啶(4-methylpyridine)中並在室溫下攪拌1小時,接著加熱至迴流(約120℃)。反應20小時後,將所得產物倒入30ml之鹽酸水溶液(濃度為10%),再用少量丙酮清洗,得到聚芳硫醚(II)(白色固體),轉換率約為57%,如表1所示。 0.5 g of the compound (II) and 0.39 g of diphenylamine were placed in a reaction flask. Next, 5 ml of trifluoromethanesulfonic acid was slowly added under an ice bath at 0 °C. After reacting for 1 hour in an ice bath, it was slowly returned to room temperature. Then, after reacting for 20 hours, the resultant was poured into 100 ml of diethyl ether and vigorously stirred, and then washed with a small amount of acetone. After drying, get strontium salt Polymer (II). Next, the obtained onium salt polymer (II) was dissolved in 6 ml of 4-methylpyridine and stirred at room temperature for 1 hour, followed by heating to reflux (about 120 ° C). After reacting for 20 hours, the obtained product was poured into a 30 ml aqueous hydrochloric acid solution (concentration: 10%), and washed with a small amount of acetone to obtain a polyarylene sulfide (II) (white solid), and the conversion rate was about 57%, as shown in Table 1. Shown.
與比較例1相比,實施例2在將化合物(II)進行聚合時,除了加入三氟甲基磺酸及二苯胺外,還進一步加入五氧化二磷。請參照表1,與比較例1相比,以實施例2所述方式製備聚芳硫醚(II),所得之轉換率明顯提高。 In Comparative Example 1, in the case of polymerizing the compound (II), in addition to the addition of trifluoromethanesulfonic acid and diphenylamine, phosphorus pentoxide was further added. Referring to Table 1, the polyarylene sulfide (II) was prepared in the manner described in Example 2 as compared with Comparative Example 1, and the conversion ratio obtained was remarkably improved.
實施例3: Example 3:
將0.19g之甲基苯基亞碸、0.3g之化合物(II)、0.2g之五氧化二磷、與0.23g二苯胺加入一反應瓶中。接著,在0℃冰浴下緩慢加入3ml之三氟甲基磺酸。在冰浴下反應1小時後,緩慢回到室溫。接著,反應20小時後,將所得物倒入100ml之乙醚中並劇烈攪拌,再用少量丙酮清洗。乾燥後得到鋶鹽聚合物(III)。接著,將所得鋶鹽聚合物(III)溶於15ml之4-甲基吡啶(4-methylpyridine)中並在室溫下攪拌1小時,接著加熱至迴流(約100℃)。反應6小時後,將所得產物倒入30ml之鹽酸水溶液(濃度為10%),再用少量丙酮清洗,得到聚芳硫醚(III)(白色固體),轉換率約為35%,如表2所示。上述反應之反應式
如下所示:
接著,使用示差掃描量熱儀(differential scanning calorimetry、DSC)量測所得聚芳硫醚(III),得知其玻璃轉換溫度(Tg)達113℃。接著,以紅外線光譜儀(FT-IR)量測聚芳硫醚(III),結果如下:IR(cm-1):3024,1584,1474,1389,1319,1178,1155,1090,1001,810,759,694。 Next, the obtained polyarylene sulfide (III) was measured by differential scanning calorimetry (DSC), and the glass transition temperature (Tg) thereof was found to be 113 °C. Next, the polyarylene sulfide (III) was measured by an infrared spectrometer (FT-IR), and the results were as follows: IR (cm -1 ): 3024, 1584, 1474, 1389, 1319, 1178, 1155, 1090, 1001, 810, 759, 694.
比較例2: Comparative Example 2:
如實施例3所述方式進行,除了不添加五氧化二磷,所得之聚芳硫醚(III)轉換率約為5%,如表2所示。 The conversion rate of the obtained polyarylene sulfide (III) was about the same as that described in Example 3 except that phosphorus pentoxide was not added. 5%, as shown in Table 2.
與比較例2相比,實施例3在將甲基苯基亞碸與化合物 (II)進行共聚合時,除了加入三氟甲基磺酸及二苯胺外,還進一步加入五氧化二磷。請參照表2,與比較例2相比,以實施例3所述方式製備聚芳硫醚(III),所得之轉換率明顯提高。 Compared with Comparative Example 2, Example 3 was in the case of methylphenyl fluorene and a compound. (II) When the copolymerization is carried out, in addition to the addition of trifluoromethanesulfonic acid and diphenylamine, phosphorus pentoxide is further added. Referring to Table 2, the polyarylene sulfide (III) was prepared in the manner described in Example 3 as compared with Comparative Example 2, and the conversion ratio obtained was remarkably improved.
雖然本揭露已以數個實施例揭露如上,然其並非用以限定本揭露,任何本技術領域中具有通常知識者,在不脫離本揭露之精神和範圍內,當可作任意之更動與潤飾,因此本揭露之保護範圍當視後附之申請專利範圍所界定者為準。 The present disclosure has been disclosed in the above several embodiments, but it is not intended to limit the disclosure, and any one skilled in the art can make any changes and refinements without departing from the spirit and scope of the disclosure. Therefore, the scope of protection of this disclosure is subject to the definition of the scope of the patent application.
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