TWI555781B - Liquid phosphorus stabilizer and its preparation method - Google Patents
Liquid phosphorus stabilizer and its preparation method Download PDFInfo
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本發明是有關於一種液態含磷穩定劑，特別是指一種在分子中具有三種不同結構的磷酸酯基團的液態含磷穩定劑及其製法。 The present invention relates to a liquid phosphorus-containing stabilizer, and more particularly to a liquid phosphorus-containing stabilizer having a phosphate group having three different structures in a molecule and a process for preparing the same.
一般有機聚合物材料(例如塑膠、樹酯、化妝品、色料、塗料、紡織品)容易受到光、熱、酸、鹼或氮氧化物所破壞，進而導致色變(黃變)或材料分解。若能在有機聚合物材料中添加適合的有機添加劑(例如抗氧化劑或光安定劑)，可保護該材料以降低損壞。例如，若添加具抗氧化能力或具紫外光吸收特性之化學物質，可以吸收或轉換紫外光的能量，進而維護材料的光澤與耐久性。 Generally, organic polymer materials (such as plastics, resins, cosmetics, colorants, coatings, textiles) are easily damaged by light, heat, acid, alkali or nitrogen oxides, which causes discoloration (yellowing) or decomposition of materials. If a suitable organic additive (such as an antioxidant or a light stabilizer) can be added to the organic polymeric material, the material can be protected to reduce damage. For example, if a chemical with anti-oxidation or ultraviolet absorption properties is added, the energy of the ultraviolet light can be absorbed or converted to maintain the gloss and durability of the material.
目前工業上普遍以上述添加添加劑的方式來提升有機聚合物材料的抗氧化特性，該添加劑大多屬於受阻酚型抗氧化劑或含磷有機抗氧化劑。然而含磷有機抗氧化劑雖能避免聚合物氧化黃變，但在室溫下多數為固體，且其對於高溫耐黃變性亦有不足。而現有液態磷系抗氧化劑如三(壬基酚)亞磷酸酯(TNPP，CAS No.26523-78-4)及聚(二丙二醇)苯基亞磷酸酯(CAS No.80584-86-7)並不耐高溫 ，易於高溫(>170℃)受熱分解而失去功能。 At present, it is common in the industry to increase the antioxidant properties of organic polymer materials by adding additives as described above. Most of the additives are hindered phenol type antioxidants or phosphorus-containing organic antioxidants. However, although the phosphorus-containing organic antioxidant can avoid yellowing of the polymer, it is mostly solid at room temperature, and it is also insufficient for high temperature yellowing resistance. Existing liquid phosphorus antioxidants such as tris(nonylphenol) phosphite (TNPP, CAS No. 26523-78-4) and poly(dipropylene glycol) phenyl phosphite (CAS No. 80584-86-7) Not resistant to high temperatures It is easy to be decomposed by heat at high temperature (>170 ° C) and loses its function.
因此，本發明之目的，即在提供一種液態含磷穩定劑，其在室溫下呈液態，且可提升有機聚合物在高溫環境下的耐黃變效果。 Accordingly, it is an object of the present invention to provide a liquid phosphorus-containing stabilizer which is liquid at room temperature and which enhances the yellowing resistance of the organic polymer in a high temperature environment.
於是本發明液態含磷穩定劑，包含如下式(Ⅳ)所示的第一亞磷酸酯化合物：
其中，R 1 表示C1至C18直鏈或支鏈烷基；R 2 表示，其中，R 21 表示氫或甲基，n表示2~10 ；及R 3 表示，其中，R 31 及R 32 是相同或不同 地表示氫或C1至C8直鏈或支鏈烷基。 Wherein R 1 represents a C 1 to C 18 straight or branched alkyl group; R 2 represents Wherein R 21 represents hydrogen or methyl, n represents 2 to 10; and R 3 represents Wherein R 31 and R 32 are the same or different represent hydrogen or a C 1 to C 8 straight or branched alkyl group.
本發明之另一目的，即在提供一種液態含磷穩定劑的製法，包含：一混合步驟、一第一反應步驟及一第二反應步驟。其中，該混合步驟是將R 1 OH與P(OR 3 ) 3 混合或將R 3 OH與P(OR 1 ) 3 混合，以得到一混合物；該第一反應步驟是將該混合物進行反應，以得到一中間產物；及該第二反應步驟是將該中間產物與HO-R 2 進行反應。 Another object of the present invention is to provide a liquid phosphorus-containing stabilizer comprising a mixing step, a first reaction step and a second reaction step. Wherein, the mixing step is to mix R 1 OH with P(OR 3 ) 3 or to mix R 3 OH with P(OR 1 ) 3 to obtain a mixture; the first reaction step is to react the mixture to An intermediate product is obtained; and the second reaction step is the reaction of the intermediate product with HO-R 2 .
本發明之功效在於：本發明液態含磷穩定劑中的第一亞磷酸酯化合物有助於提升有機聚合物在高溫環境 下的耐黃變效果，且能與其他添加劑併用。 The effect of the invention is that the first phosphite compound in the liquid phosphorus-containing stabilizer of the invention helps to raise the organic polymer in a high temperature environment It has a yellowing resistance and can be used in combination with other additives.
以下將就本發明內容進行詳細說明：
較佳地，本發明液態含磷穩定劑，還包含如下式(V)所示的第二亞磷酸酯化合物：
其中，R 1 、R 3 、R 21 及n的定義係如上所述。 Wherein, the definitions of R 1 , R 3 , R 21 and n are as described above.
較佳地，R 1 表示乙基、辛基或2-乙基己基。 Preferably, R 1 represents ethyl, octyl or 2-ethylhexyl.
較佳地，R 31 及R 32 是相同或不同地表示氫、第三丁基或辛基。 Preferably, R 31 and R 32 represent the same or different hydrogen, tert-butyl or octyl.
依據本發明液態含磷穩定劑的製法，較佳地，該混合物包括一無機鹼，以催化反應進行。 According to the process for preparing a liquid phosphorus-containing stabilizer according to the present invention, preferably, the mixture comprises an inorganic base to carry out the catalytic reaction.
較佳地，該第一反應步驟是在150~210℃下進行。更佳地，該第二反應步驟的反應溫度高於該第一反應步驟的反應溫度。 Preferably, the first reaction step is carried out at 150 to 210 °C. More preferably, the reaction temperature of the second reaction step is higher than the reaction temperature of the first reaction step.
較佳地，在該混合步驟後，還包含一分離步驟，是將反應產生的醇類或酚類副產物移除。更佳地，該分離步驟是以蒸餾法移除副產物。在本發明的具體實施例中，該醇類或酚類副產物是2,4-二-第三丁基苯酚(2,4-di-tert-butylphenol)、苯酚或乙醇。 Preferably, after the mixing step, a separation step is further included to remove the alcohol or phenolic by-product produced by the reaction. More preferably, the separation step removes by-products by distillation. In a particular embodiment of the invention, the alcohol or phenolic by-product is 2,4-di- tert- butylphenol, phenol or ethanol.
較佳地，R 1 OH與P(OR 3 ) 3 或R 3 OH與P(OR 1 ) 3 的莫耳比例範圍為0.9：1~1.1：1，其中，R 1 、R 2 及R 3 的定義係如上所述。 Preferably, the molar ratio of R 1 OH to P(OR 3 ) 3 or R 3 OH to P(OR 1 ) 3 ranges from 0.9:1 to 1.1:1, wherein R 1 , R 2 and R 3 The definition is as described above.
本發明將就以下實施例來作進一步說明，但應瞭解的是，該等實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。 The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.
<實施例1>液態含磷穩定劑E1<Example 1> Liquid phosphorus-containing stabilizer E1
在1000毫升四頸反應瓶中加入323克亞磷酸三(2,4-二-第三丁基苯)酯[tris(2,4-di-tert-butylphenyl)phosphite]、65克正辛醇及15克氫氧化鈉混合得到一混合物，升溫至185℃至混合物呈熔融態後，攪拌反應2小時，再加入40.2克二異丙二醇(diisopropylene glycol)並升高溫度至200℃，反應5小時後降溫至130℃，以真空蒸出副產物2,4-二-第三丁基苯酚，以氮氣回壓破真空後降溫至60℃，過濾後得到的濾液即為實施例1的液態含磷穩定劑E1(熔點小於-10℃)。 In a 1000 ml four-necked reaction flask, 323 g of tris(2,4-di- tert- butylphenyl)phosphite, 65 g of n-octanol and 65 g of n-octanol and 15 g of sodium hydroxide was mixed to obtain a mixture. After heating to 185 ° C until the mixture was in a molten state, the reaction was stirred for 2 hours, and then 40.2 g of diisopropylene glycol was added and the temperature was raised to 200 ° C. After 5 hours of reaction, the temperature was lowered. To 130 ° C, the by-product 2,4-di-tert-butylphenol was distilled off under vacuum, and the vacuum was reduced by vacuum pressure to 60 ° C. The filtrate obtained after filtration was the liquid phosphorus-containing stabilizer of Example 1. E1 (melting point less than -10 ° C).
<實施例2>液態含磷穩定劑E2<Example 2> Liquid phosphorus-containing stabilizer E2
在1000毫升四頸反應瓶中加入155克亞磷酸三苯酯(triphenyl phosphite)、65克異辛醇及15克碳酸鈉混合得到一混合物，升溫至155℃至混合物呈熔融態後，攪拌反應2小時，再加入40.2克二異丙二醇並升高溫度至170℃，反應5小時後降溫至130℃，以真空蒸出副產物苯酚，以氮氣回壓破真空後降溫至60℃，過濾後得到的濾液即為實施例2的液態含磷穩定劑E2(熔點小於-10℃)。 In a 1000 ml four-necked reaction flask, 155 g of triphenyl phosphite, 65 g of isooctanol and 15 g of sodium carbonate were added to obtain a mixture, and the mixture was heated to 155 ° C until the mixture was in a molten state, and the reaction was stirred. In an hour, 40.2 g of diisopropyl diol was added and the temperature was raised to 170 ° C. After 5 hours of reaction, the temperature was lowered to 130 ° C, and the by-product phenol was distilled off under vacuum, and the pressure was reduced to 60 ° C by vacuuming with nitrogen, and the mixture was filtered. The filtrate was the liquid phosphorus-containing stabilizer E2 of Example 2 (melting point less than -10 ° C).
<實施例3>液態含磷穩定劑E3<Example 3> Liquid phosphorus-containing stabilizer E3
在1000毫升四頸反應瓶中加入166克亞磷酸三乙酯(triethyl phosphite)、210克4-辛基苯酚及35克碳酸鉀混合得到一混合物，升溫至155℃至混合物呈熔融態後，攪拌反應2小時，反應過程中會有副產物乙醇蒸出，當不再產生乙醇後，再加入175克二縮三乙二醇(triethylene glycol)並升高溫度至170℃，反應5小時後降溫至60℃，過濾後得到的濾液即為實施例3的液態含磷穩定劑E3(熔點小於-10℃)。 In a 1000 ml four-necked reaction flask, 166 g of triethyl phosphite, 210 g of 4-octylphenol and 35 g of potassium carbonate were added to obtain a mixture, and the mixture was heated to 155 ° C until the mixture was in a molten state, followed by stirring. After reacting for 2 hours, the by-product ethanol was distilled out during the reaction. When ethanol was no longer produced, 175 g of triethylene glycol was added and the temperature was raised to 170 ° C. After 5 hours, the temperature was lowered to The filtrate obtained after filtration at 60 ° C was the liquid phosphorus-containing stabilizer E3 of Example 3 (melting point less than -10 ° C).
<應用例1>熱塑性聚氨酯複合物A1<Application Example 1> Thermoplastic polyurethane composite A1
將熱可塑性聚氨酯(TPU，購自於台灣崑仲公司，型號為KOSLEN S-195AL)(定為100重量份)與0.013重量份實施例1的液態含磷穩定劑E1混合，並加入以下添加劑：0.025重量份Winox 1135(CAS No.125643-61-0，抗氧化劑，奕益實業提供)、0.055重量份硫系抗氧化劑硫代二丙酸二月桂酯(DLTDP)、0.018重量份Winox 1500[雙(N,N-二甲基肼碳醯-4-胺基苯基)甲烷，CAS No.85095-61-0，光穩定劑]、0.019重量份Wisorb 292(CAS No.41556-26-7，光穩定劑，奕益實業提供)，均勻混合後得到含有液態含磷穩定劑E1的TPU組成物。 A thermoplastic polyurethane (TPU, available from Kunzhong, Taiwan, model KOSLEN S-195AL) (defined as 100 parts by weight) was mixed with 0.013 parts by weight of the liquid phosphorus-containing stabilizer E1 of Example 1, and the following additives were added: 0.025 Weight parts of Winox 1135 (CAS No. 125643-61-0, antioxidant, supplied by Yiyi Industrial), 0.055 parts by weight of sulfur-based antioxidant dilauryl thiodipropionate (DLTDP), 0.018 parts by weight of Winox 1500 [double ( N , N -dimethylindolecarbon-4-ylaminophenyl)methane, CAS No. 85095-61-0, light stabilizer], 0.019 parts by weight Wisorb 292 (CAS No. 41556-26-7, light Stabilizer, supplied by Yuyi Industrial Co., Ltd.), uniformly mixed to obtain a TPU composition containing a liquid phosphorus-containing stabilizer E1.
接著，以雙螺桿押出機(台灣弘煜機械公司試驗機PSM20A)混合押出(溫度設定為13段：195℃、200℃、205℃、205℃、215℃、215℃、215℃、215℃、215℃、215℃、210℃、205℃、195℃，主螺桿轉速為200轉/分鐘，滯 留時間為30秒)上述TPU組成物，最後經過冷卻、風乾、切粒、乾燥以製備出具有複合式添加劑之熱塑性聚氨酯複合物A1。 Then, the twin-screw extruder (Taiwan Hongsheng Machinery Co., Ltd. test machine PSM20A) was mixed and extruded (the temperature was set to 13 segments: 195 ° C, 200 ° C, 205 ° C, 205 ° C, 215 ° C, 215 ° C, 215 ° C, 215 ° C, 215 ° C, 215 ° C, 210 ° C, 205 ° C, 195 ° C, the main screw speed is 200 rev / min, lag The TPU composition was left for 30 seconds. Finally, it was cooled, air-dried, pelletized, and dried to prepare a thermoplastic polyurethane composite A1 having a composite additive.
<應用例2>熱塑性聚氨酯複合物A2<Application Example 2> Thermoplastic polyurethane composite A2
應用例2之熱塑性聚氨酯複合物A2的製法與應用例1相同，差異之處在於：將TPU(定為100重量份)與0.13重量份實施例1的液態含磷穩定劑E1混合，並加入以下添加劑：0.04重量份Winox 1135、0.03重量份Wisorb 292，均勻混合後得到含有液態含磷穩定劑E1的TPU組成物。 The thermoplastic polyurethane composite A2 of Application Example 2 was produced in the same manner as in Application Example 1, except that TPU (100 parts by weight) was mixed with 0.13 parts by weight of the liquid phosphorus-containing stabilizer E1 of Example 1, and the following was added. Additive: 0.04 parts by weight of Winox 1135, 0.03 parts by weight of Wisorb 292, uniformly mixed to obtain a TPU composition containing a liquid phosphorus-containing stabilizer E1.
<應用例3>熱塑性聚氨酯複合物A3<Application Example 3> Thermoplastic polyurethane composite A3
應用例3之熱塑性聚氨酯複合物A3的製法與應用例1相同，差異之處在於：將TPU(定為100重量份)與0.13重量份實施例2的液態含磷穩定劑E2混合，並加入以下添加劑：0.04重量份Winox 1135、0.03重量份Wisorb 292，均勻混合後得到含有液態含磷穩定劑E2的TPU組成物。 The thermoplastic polyurethane composite A3 of Application Example 3 was produced in the same manner as in Application Example 1, except that TPU (100 parts by weight) was mixed with 0.13 parts by weight of the liquid phosphorus-containing stabilizer E2 of Example 2, and the following was added. Additive: 0.04 parts by weight of Winox 1135, 0.03 parts by weight of Wisorb 292, uniformly mixed to obtain a TPU composition containing a liquid phosphorus-containing stabilizer E2.
<應用例4>熱塑性聚氨酯複合物A4<Application Example 4> Thermoplastic polyurethane composite A4
應用例3之熱塑性聚氨酯複合物A3的製法與應用例1相同，差異之處在於：將TPU(定為100重量份)與0.13重量份實施例3的液態含磷穩定劑E3混合，並加入以下添加劑：0.04重量份Winox 1135、0.03重量份Wisorb 292，均勻混合後得到含有液態含磷穩定劑E3的TPU組成物。 The thermoplastic polyurethane composite A3 of Application Example 3 was produced in the same manner as in Application Example 1, except that TPU (100 parts by weight) was mixed with 0.13 parts by weight of the liquid phosphorus-containing stabilizer E3 of Example 3, and the following was added. Additive: 0.04 parts by weight of Winox 1135, 0.03 parts by weight of Wisorb 292, uniformly mixed to obtain a TPU composition containing a liquid phosphorus-containing stabilizer E3.
<比較應用例1>聚氨酯複合物B1<Comparative Application Example 1> Polyurethane Composite B1
比較應用例1之聚氨酯複合物B1的製法與應用例1相同，差異之處在於：將TPU(定為100重量份)加入以下添加劑：0.1重量份Winox 1010(CAS No.6683-19-8，抗氧化劑，奕益實業提供)、0.1重量份Winox 626(CAS No.26741-53-7，固態磷系抗氧化劑，熔點約為160~180℃，奕益實業提供)，均勻混合後得到含有固態磷系抗氧化劑的TPU組成物。 The polyurethane composite B1 of Comparative Example 1 was prepared in the same manner as in Application Example 1, except that TPU (100 parts by weight) was added to the following additives: 0.1 parts by weight of Winox 1010 (CAS No. 6683-19-8, Antioxidant, provided by Yiyi Industrial Co., Ltd., 0.1 parts by weight of Winox 626 (CAS No. 26741-53-7, solid phosphorus antioxidant, melting point of about 160-180 ° C, supplied by Yiyi Industrial), uniformly mixed to obtain solid state A TPU composition of a phosphorus-based antioxidant.
<比較應用例2>聚氨酯複合物B2<Comparative Application Example 2> Polyurethane Composite B2
比較應用例2之聚氨酯複合物B2的製法與應用例1相同，差異之處在於：將TPU(定為100重量份)加入以下添加劑：0.1重量份Winox 1010、0.1重量份Winox 168(CAS No.31570-04-4，固態磷系抗氧化劑，熔點約為184~187℃，奕益實業提供)，均勻混合後得到含有固態磷系抗氧化劑的TPU組成物。 The polyurethane composite B2 of Comparative Application Example 2 was prepared in the same manner as in Application Example 1, except that TPU (100 parts by weight) was added to the following additives: 0.1 parts by weight of Winox 1010, 0.1 parts by weight of Winox 168 (CAS No.). 31570-04-4, solid phosphorus antioxidant, melting point of about 184 ~ 187 ° C, provided by Yu Yi Industrial), evenly mixed to obtain a TPU composition containing solid phosphorus antioxidant.
<熱烘耐黃變測試><Hot bake and yellowing resistance test>
將上述應用例1~4及比較應用例1~2的熱塑性聚氨酯複合物A1~A4及B1~B2分別放入150℃恆溫烘箱中5天及170℃恆溫烘箱中24小時，並量測其顏色變化[利用HunterLab公司的色差儀(型號為ColorQuest XE)測量YI值，並計算YI值上升量(△YI值)]，結果分別如下表1及表2所示。 The thermoplastic polyurethane composites A1 to A4 and B1 to B2 of the above Application Examples 1 to 4 and Comparative Application Examples 1 and 2 were respectively placed in a constant temperature oven at 150 ° C for 5 days and in a constant temperature oven at 170 ° C for 24 hours, and the color thereof was measured. Change [Using HunterLab's colorimeter (model ColorQuest XE) to measure the YI value and calculate the YI value rise amount (ΔYI value)], the results are shown in Table 1 and Table 2, respectively.
由於ΔYI值越小，表示其耐黃變效果越高，因此由表1及表2可以得知，在150℃中1至5天後及170℃中4至24小時後，經添加本發明液態含磷穩定劑E1~E4的TPU複合物A1~A4相對於經添加固態磷系抗氧化劑Winox 626及Winox 168的TPU複合物B1~B2，皆呈現出更佳的耐黃變效果(ΔYI值皆較小)，反映出本發明的液態含磷穩定劑可有效提升有機聚合物在150℃及170℃下的耐黃變效果。 Since the smaller the ΔYI value is, the higher the yellowing resistance is, the table 1 and Table 2 show that the liquid of the present invention is added after 1 to 5 days at 150 ° C and 4 to 24 hours at 170 ° C. The TPU composites A1~A4 containing phosphorus stabilizers E1~E4 exhibited better yellowing resistance than the TPU composites B1~B2 with the addition of solid phosphorus antioxidants Winox 626 and Winox 168 (ΔYI values are all Smaller, reflecting that the liquid phosphorus-containing stabilizer of the present invention can effectively enhance the yellowing resistance of the organic polymer at 150 ° C and 170 ° C.
綜上所述，本發明的液態含磷穩定劑在室溫下 呈液態，因此便於添加至各種聚合物材料中；且由於其中第一亞磷酸酯化合物在分子中具有三種不同結構的磷酸酯基團，因此可顯著提升有機聚合物在高溫環境下的耐黃變效果，且其合成方法簡便，並能與其他添加劑併用，故確實能達成本發明之目的。 In summary, the liquid phosphorus-containing stabilizer of the present invention is at room temperature It is liquid, so it is easy to add to various polymer materials; and because the first phosphite compound has three different structural phosphate groups in the molecule, it can significantly improve the yellowing resistance of organic polymers in high temperature environments. The effect is simple, and the synthesis method is simple and can be used together with other additives, so that the object of the present invention can be achieved.
惟以上所述者，僅為本發明之實施例而已，當不能以此限定本發明實施之範圍，凡是依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。 However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the equivalent equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still The scope of the invention is covered.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1699386A (en) * | 2004-05-19 | 2005-11-23 | 奕益实业有限公司 | Phosphinates compounds and their preparation process and use as stabilizer |
| US20080132712A1 (en) * | 2006-12-05 | 2008-06-05 | Denoux Michael G | Peroxide reduction in functionalized vegetable oils |
| CN102985474A (en) * | 2010-02-19 | 2013-03-20 | 多弗化学公司 | Alkylphenol free - liquid polymeric phosphite polymer stabilizers |
| CN103601916A (en) * | 2013-07-30 | 2014-02-26 | 双键化工（上海）有限公司 | stabilizer and composition comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1699386A (en) * | 2004-05-19 | 2005-11-23 | 奕益实业有限公司 | Phosphinates compounds and their preparation process and use as stabilizer |
| US20080132712A1 (en) * | 2006-12-05 | 2008-06-05 | Denoux Michael G | Peroxide reduction in functionalized vegetable oils |
| CN102985474A (en) * | 2010-02-19 | 2013-03-20 | 多弗化学公司 | Alkylphenol free - liquid polymeric phosphite polymer stabilizers |
| CN103601916A (en) * | 2013-07-30 | 2014-02-26 | 双键化工（上海）有限公司 | stabilizer and composition comprising the same |
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