TWI589585B - Xanthene-containing or thioxanthene-containing phosphinated compounds and preparation methods thereof - Google Patents
Xanthene-containing or thioxanthene-containing phosphinated compounds and preparation methods thereof Download PDFInfo
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本發明係揭露含有(1)氧雜蒽結構或(2)硫代氧雜蒽結構磷系化合物及其製造方法，該化合物可用以製備出高熱穩定性之磷系阻燃材。 The present invention discloses a phosphorus-based compound containing (1) xanthene structure or (2) thioxanthene structure and a process for producing the same, which can be used to prepare a phosphorus-based flame retardant material having high heat stability.
傳統防火材料大多為含鹵化合物所構成，雖具有抑燃效果，卻也同時產生具腐蝕性、毒性之化學物質，如戴奧辛(dioxin)，對人體、環境皆有極大的危害，因此對於鹵系化合物已漸列規範。 Most of the traditional fireproof materials are composed of halogen-containing compounds. Although they have a fire-retardant effect, they also produce corrosive and toxic chemical substances, such as dioxin, which are extremely harmful to the human body and the environment. Compounds have been progressively regulated.
近來，有機磷化合物於阻燃材料之應用已成為焦點，相較鹵系阻燃劑，磷系化合物燃燒不會產生有害物質，並具有加工性佳、添加量少、發煙量低等優勢。 Recently, the application of organophosphorus compounds in flame retardant materials has become a focus. Compared with halogen-based flame retardants, phosphorus compounds do not produce harmful substances, and have the advantages of good processability, low added amount, and low smoke generation.
於1991年，Smith,C.D.等人以磷系化合物9,10-二氫-9-氧雜-10-膦雜菲10-氧化物(DOPO)與苯醌反應，藉DOPO親核性，成功合成出10-(2',5'-雙(羥基)苯基)-9,10-二氫-9-氧雜-10-膦雜菲10-氧化物(DOPOBQ)，結構如下：
該單體為磷系雙酚化合物之先驅，但溶解度與反應性不佳，使其於工業應用受到限制。 This monomer is a precursor to phosphorus-based bisphenol compounds, but its solubility and reactivity are not good, which limits its industrial application.
於2010年(TW I449707)，本案發明人揭露一種磷系二酚之製造方法，獲得代表性二酚單體(DDP)，結構如下：
該單體合成簡易，並改善了反應性的問題，導入高分子中也確實賦予材料阻燃的效果，然而該結構之碳鏈架橋卻使其衍生材料之熱性質仍具有改善的空間。 The monomer is simple in synthesis and improves the problem of reactivity. The introduction into the polymer also imparts a flame retardant effect to the material. However, the carbon chain bridge of the structure still has an improved space for the thermal properties of the derivative material.
氧雜蒽(xanthene)為剛性環狀結構，近年，部分研究指出該結構將有助提升材料熱性質與機械特性。在1997年發表的文獻(Andrew J.Caruso et al.,J.Org.Chem.1997,62,1058-1063)中提及，以雙酚A(Bisphenol A,BPA)為原料，於酸性環境下與間甲基苯酚反應可得氧雜蒽環狀結構，該單體經酸化、酯化後可用以製備聚酯材料，且其Tg可達164℃，顯示此環狀結構導入高分子主鏈中將有助於提升材料熱性質，反應式如下：
於2010年之文章(YanFen Li et al.,Polym.Chem.,2010,1,485-493)中，Li等人發表以9-茀酮與間苯二酚為原料，合成主鏈具有環狀結構的含茀(fluorene)雙酚單體，並將其製備成二胺單體後與各式酸酐聚合為聚醚醯亞胺(PEI)材料，以3,3',4,4'-二苯酮四甲酸二酐(BTDA)系統之PEI為例，相較於1993年CHIN-PING YANG等人發表(CHIN-PING YANG et al.,J.Polym.Sci.,Part A：Polym.Chem.1993,31,2153)之主鏈不含環狀結構之含茀PEI，其Tg提升了約19℃，並表現出優異的有機可溶性，充分突顯出於主鏈導入環狀結構提升材料熱、機械特性之可行性，其結構式如下：
因此本發明旨為提供一系列含有氧雜蒽結構或硫代氧雜蒽結構的磷系化合物及其製造方法，用以擴大有機磷化合物的應用範圍。 Accordingly, the present invention is intended to provide a series of phosphorus-based compounds containing a xanthene structure or a thioxanthene structure and a process for producing the same, for expanding the range of application of the organophosphorus compound.
本發明揭露一種含有(1)氧雜蒽結構或(2)硫代氧雜蒽結構之磷系化合物，導入高分子材料內除可提升材料阻燃性外，亦能提升材料熱性質。 The invention discloses a phosphorus-based compound containing (1) xanthene structure or (2) thioxanthene structure. In addition to improving the flame retardancy of the material, the introduction into the polymer material can also improve the thermal properties of the material.
根據本發明，提出一種磷系化合物，具有如式(I)所示之結構：
其中R1至R4可獨立地為氫、C1-C6烷基及C1-C6烷氧基；R5可為氫、C1-C6烷基、C1-C6烷氧基或苯基；B、D可分別選自由-OH、-SH、 C1-C6烷基及C1-C6烷氧基所組成之群組；X可為O及S；可為苯環、萘環或吡啶。 Wherein R 1 to R 4 may independently be hydrogen, C 1 -C 6 alkyl and C 1 -C 6 alkoxy; R 5 may be hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy Or a phenyl group; B, D may be selected from the group consisting of -OH, -SH, C 1 -C 6 alkyl and C 1 -C 6 alkoxy; X may be O and S; It may be a benzene ring, a naphthalene ring or a pyridine.
本發明所提供之磷系化合物之實例包括式(I-i)化合物，其中對應式(I)中R1至R4為氫，R5為甲基，X為O，B與D為相較於X位於間
位之-OH，為苯環：
本發明所提供之磷系化合物之實例亦包括式(I-ii)化合物，其中對應式(I)中R1至R4為氫，R5為氫，X為O，B與D為相較於X位於間
位之-OH，為苯環：
本發明所提供之磷系化合物之實例亦包括式(I-iii)化合物，其中對應式(I)中R1至R4為氫，R5為甲基，X為O，B與D為相較於X位於
間位之-OH，為萘環：
本發明所提供之磷系化合物之實例亦包括式(I-iv)化合物，其中對應式(I)中R1至R4為氫，R5為甲基，X為S，B為相較於X位於間位
之-OH，D為相較於X位於間位之-SH，為苯環：
本發明所提供之磷系化合物之實例亦包括式(I-v)化合物，其中對應式(I)中R1至R4為氫，R5為甲基，X為O，B為相較於X位於對位
之-OH，D為相較於X位於間位之-OH，為苯環：
本發明所提供之磷系化合物不意欲限制於僅包含上述化合物。 The phosphorus-based compound provided by the present invention is not intended to be limited to only the above compounds.
本發明亦提出一種合成含氧雜蒽結構或硫代氧雜蒽結構磷系化
合物之製造方法，包含利用如通式(i)所示之有機環狀磷化物、通式(ii)所示之酮或醛類化合物及通式(iii)所示之化合物，
合成具有如式(I)所示結構之磷系化合物，其中R1至R5、B及D之定義如前所述。其反應流程例示如下：
本發明上述方法亦可在酸觸媒存在下進行。 The above process of the present invention can also be carried out in the presence of an acid catalyst.
本發明上述方法中，在合成包含氧雜蒽結構(即X為O)之如式(I)所示結構之磷系化合物時，所使用之通式(ii)化合物之A與通式(iii)化合物之C皆為-OH；在合成包含硫代氧雜蒽結構(即X為S)之如式(I)所示結構之磷系化合物時，所使用之通式(ii)化合物之A與通式(iii)化合物之C中一者為-OH，另一者為-SH。 In the above method of the present invention, in the synthesis of a phosphorus-based compound having a structure of the oxonium structure (i.e., X is O) as shown in the formula (I), the compound of the formula (ii) used and the formula (iii) C of the compound is -OH; in the synthesis of a phosphorus-based compound having a structure of the formula (I) comprising a thioxanthene structure (i.e., X is S), the compound of the formula (ii) used One of C and the compound of the formula (iii) is -OH and the other is -SH.
本發明上述方法中，通式(i)與通式(ii)化合物之莫耳數相等或接近，通式(i)與通式(iii)化合物莫耳比係約1：5至1：20，較佳為約1：5至1：10。 In the above method of the present invention, the molar number of the compound of the formula (i) and the formula (ii) is equal or close, and the molar ratio of the compound of the formula (i) to the formula (iii) is about 1:5 to 1:20. Preferably, it is from about 1:5 to 1:10.
本發明上述方法中，酸觸媒包含有機酸，如甲基磺酸(Methanesulfonic acid,MSA)、對甲苯磺酸(p-Toluenesulfonic acid,p-TSA)、草酸等；亦可為無機酸，如硫酸等；或路易士酸，如AlCl3、BF3、FeBr3、FeCl3等；亦可使用上述酸性觸媒之任何組合。酸觸媒用 量基於通式(i)化合物為0.1wt%~30wt%，較佳為1wt%~15wt%。 In the above method of the present invention, the acid catalyst comprises an organic acid such as Methanesulfonic acid (MSA), p-Toluenesulfonic acid (p-TSA), oxalic acid, etc., or a mineral acid such as Sulfuric acid or the like; or Lewis acid such as AlCl 3 , BF 3 , FeBr 3 , FeCl 3 or the like; any combination of the above acidic catalysts may also be used. The acid catalyst is used in an amount of from 0.1% by weight to 30% by weight, based on the compound of the formula (i), preferably from 1% by weight to 15% by weight.
本發明上述方法係加熱至約90℃至180℃，較佳約為100~140℃進行反應。 The above process of the present invention is carried out by heating to a temperature of from about 90 ° C to 180 ° C, preferably from about 100 to 140 ° C.
本發明上述方法中，反應時間係約6至48小時，較佳約為12至24小時。 In the above process of the present invention, the reaction time is about 6 to 48 hours, preferably about 12 to 24 hours.
圖1為化合物(I-i)之1H NMR光譜圖。 Figure 1 is a 1 H NMR spectrum of the compound (Ii).
圖2為化合物(I-i)之13C NMR光譜圖。 Figure 2 is a 13 C NMR spectrum of the compound (Ii).
圖3為化合物(I-i)、DOPOBQ以及DDP之熱重分析圖。 Figure 3 is a thermogravimetric analysis of compounds (I-i), DOPOBQ, and DDP.
以下實施例將對本發明作進一步之說明，唯非用以限制本發明之範圍，任何熟悉本發明技術領域者，在不違背本發明之精神下所得以達成之修飾及變化，均屬本發明之範圍。 The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention, and any modifications and variations which may be obtained without departing from the spirit of the invention are range.
以上之相關發明之實施將以下列之具體實施例說明。 The implementation of the above related inventions will be described in the following specific examples.
實施例1Example 1
化合物(I-i)之合成Synthesis of Compound (I-i)
化合物(I-i)係為通式(I)中R1至R4為氫；R5為甲基；B及D為間位-OH； 為苯環及X為O之化合物，其係以有機環狀磷化物DOPO、2',4'-二羥基苯乙酮與過量的間苯二酚於酸觸媒催化下反應而得，其合成步驟如下：在一250毫升三頸反應器中，加入10.00克(0.046mol)DOPO、7.04克(0.046mol)2',4'-二羥基苯乙酮、25.47克(0.046×5mol)間苯二酚以 及0.4克硫酸(4wt%，基於DOPO)，氮氣環境下加熱至120℃反應24小時。反應結束後倒入水中析出黏稠物，以丙酮清洗後抽氣過濾，濾餅以60℃真空乾燥，得淺黃色產物，產率約37%。 The compound (Ii) is wherein R 1 to R 4 in the formula (I) are hydrogen; R 5 is a methyl group; and B and D are a meta-OH; a compound which is a benzene ring and an X is O, which is obtained by reacting an organic cyclic phosphide DOPO, 2', 4'-dihydroxyacetophenone with an excess of resorcinol under acid catalyst catalysis. The procedure is as follows: In a 250 ml three-necked reactor, 10.00 g (0.046 mol) of DOPO, 7.04 g (0.046 mol) of 2',4'-dihydroxyacetophenone, 25.47 g (0.046 x 5 mol) of isophthalic acid are added. Phenol and 0.4 g of sulfuric acid (4 wt% based on DOPO) were heated to 120 ° C for 24 hours under nitrogen atmosphere. After the reaction was completed, the mixture was poured into water to precipitate a viscous material, which was washed with acetone and then suction filtered. The filter cake was dried under vacuum at 60 ° C to give a pale yellow product with a yield of about 37%.
圖1與圖2分別為磷系化合物(I-i)之1H NMR圖譜與13C NMR圖譜。 Fig. 1 and Fig. 2 are 1 H NMR spectrum and 13 C NMR spectrum of the phosphorus compound (Ii), respectively.
實施例2Example 2
化合物(I-ii)之合成Synthesis of Compound (I-ii)
化合物(I-ii)為通式(I)中R1至R4為氫；R5為氫；B及D為間位-OH； 為苯環且X為O之化合物，其係以有機環狀磷化物DOPO、2',4'-二羥基苯乙酮與過量的間苯二酚於酸觸媒催化下反應而得，其合成步驟如下：在一250毫升三頸反應器中，加入10.00克(0.046mol)DOPO、6.39克(0.046mol)2',4'-二羥基苯乙酮、25.47克(0.046×5mol)間苯二酚以及0.4克硫酸(4wt%，基於DOPO)，氮氣環境下加熱至140℃反應24小時。反應結束後倒入水中析出黏稠物，以丙酮清洗後抽氣過濾，濾餅以60℃真空乾燥，得橘色產物，產率約28%。 The compound (I-ii) is that in the formula (I), R 1 to R 4 are hydrogen; R 5 is hydrogen; and B and D are meta-OH; a compound which is a benzene ring and X is O, which is obtained by reacting an organic cyclic phosphide DOPO, 2', 4'-dihydroxyacetophenone with an excess of resorcinol under acid catalyst catalysis. The procedure is as follows: In a 250 ml three-necked reactor, 10.00 g (0.046 mol) of DOPO, 6.39 g (0.046 mol) of 2',4'-dihydroxyacetophenone, and 25.47 g (0.046 x 5 mol) of isophthalic acid are added. Phenol and 0.4 g of sulfuric acid (4 wt% based on DOPO) were heated to 140 ° C for 24 hours under nitrogen atmosphere. After the reaction was completed, the mixture was poured into water to precipitate a thick substance, which was washed with acetone, and then suction-filtered. The filter cake was dried under vacuum at 60 ° C to give an orange product with a yield of about 28%.
實施例3Example 3
化合物(I-iii)之合成Synthesis of Compound (I-iii)
化合物(I-iii)係通式(I)中，R1至R4為氫；R5為甲基；B及D為間 位-OH；為萘環且X為O之化合物，其係以有機環狀磷化物DOPO、2',4'-二羥基苯乙酮與過量的1,3-二羥基萘於酸觸媒催化下反應而得，其合成步驟如下：在一250毫升三頸反應器中，加入10.00克(0.046mol)DOPO、6.39克(0.046mol)2',4'-二羥基苯乙酮、37.05克(0.046×5mol)1,3-二羥基萘以及0.4克硫酸(4wt%，基於DOPO)，氮氣環境下加熱至140℃反應24小時。反應結束後倒入水中析出粉體，以丙酮清洗後抽氣過濾，濾餅以60℃真空乾燥，得黃綠色產物，產率約35%。 The compound (I-iii) is in the formula (I), R 1 to R 4 are hydrogen; R 5 is a methyl group; and B and D are a meta-OH; a compound which is a naphthalene ring and X is O, which is obtained by reacting an organic cyclic phosphide DOPO, 2', 4'-dihydroxyacetophenone with an excess of 1,3-dihydroxynaphthalene under acid catalyst catalysis. The synthesis procedure is as follows: 10.00 g (0.046 mol) of DOPO, 6.39 g (0.046 mol) of 2',4'-dihydroxyacetophenone, and 37.05 g (0.046 x 5 mol) are added to a 250 ml three-necked reactor. 1,3-Dihydroxynaphthalene and 0.4 g of sulfuric acid (4 wt% based on DOPO) were heated to 140 ° C for 24 hours under a nitrogen atmosphere. After the reaction was completed, the powder was poured into water, and the mixture was washed with acetone, and then suction-filtered. The filter cake was dried under vacuum at 60 ° C to obtain a yellow-green product with a yield of about 35%.
實施例4Example 4
化合物(I-iv)之合成Synthesis of compound (I-iv)
化合物(I-iv)係通式(I)中R1至R4為氫；R5為甲基；B為間位-OH； D為間位-SH；為苯環及X為S之化合物，其係以有機環狀磷化物DOPO、2',4'-二羥基苯乙酮與過量的1,3-苯二硫酚於酸觸媒催化下反應而得，其合成步驟如下：在一250毫升三頸反應器中，加入10.00克(0.046mol)DOPO、7.04克(0.046mol)2',4'-二羥基苯乙酮、32.92克(0.046×5mol)1,3-苯二硫酚以及0.4克硫酸(4wt%，基於DOPO)，氮氣環境下加熱至120℃反應24小時。反應結束後倒入水中析出黏稠物，以丙酮清洗後抽氣過濾，濾餅以60℃真空乾燥，得淺黃色產物，產率約45%。 The compound (I-iv) is a compound (I) wherein R 1 to R 4 are hydrogen; R 5 is a methyl group; B is a meta-OH; D is a meta-SH; a compound which is a benzene ring and X is S, which is reacted with an organic cyclic phosphide DOPO, 2', 4'-dihydroxyacetophenone and an excess of 1,3-benzenedithiol under acid catalyst catalysis. The synthesis procedure was as follows: 10.00 g (0.046 mol) of DOPO, 7.04 g (0.046 mol) of 2',4'-dihydroxyacetophenone, 32.92 g (0.046 x 5 mol) were added to a 250 ml three-necked reactor. 1,3-benzenedithiol and 0.4 g of sulfuric acid (4 wt% based on DOPO) were heated to 120 ° C for 24 hours under nitrogen atmosphere. After the reaction was completed, the mixture was poured into water to precipitate a thick substance, which was washed with acetone, and then suction-filtered. The filter cake was dried under vacuum at 60 ° C to obtain a pale yellow product. The yield was about 45%.
實施例5Example 5
化合物(I-v)之合成Synthesis of compound (I-v)
化合物(I-v)係通式(I)中R1至R4為氫；R5為甲基；B為對位-OH； D為間位OH；為苯環及X為O之化合物，其係以有機環狀磷化物DOPO、2',5'-二羥基苯乙酮與過量的間苯二酚於酸觸媒催化下反應而得，其合成步驟如下：在一250毫升三頸反應器中，加入10.00克(0.046mol)DOPO、7.04克(0.046mol)2',5'-二羥基苯乙酮、25.47克(0.046×5mol)間苯二酚以及0.4克硫酸(4wt%，基於DOPO)，氮氣環境下加熱至120℃反應24小時。反應結束後倒入水中析出黏稠物，以丙酮清洗後抽氣過濾，濾餅以60℃真空乾燥，得淺黃色產物，產率約30%。 The compound (Iv) is a compound (I) wherein R 1 to R 4 are hydrogen; R 5 is a methyl group; B is a para-OH; D is a meta-OH; a compound which is a benzene ring and an X is O, which is obtained by reacting an organic cyclic phosphide DOPO, 2', 5'-dihydroxyacetophenone with an excess of resorcinol under acid catalyst catalysis. The procedure is as follows: In a 250 ml three-necked reactor, 10.00 g (0.046 mol) of DOPO, 7.04 g (0.046 mol) of 2',5'-dihydroxyacetophenone, 25.47 g (0.046 x 5 mol) of isophthalic acid are added. Phenol and 0.4 g of sulfuric acid (4 wt% based on DOPO) were heated to 120 ° C for 24 hours under nitrogen atmosphere. After the reaction was completed, the mixture was poured into water to precipitate a viscous material, which was washed with acetone and then suction filtered, and the filter cake was dried under vacuum at 60 ° C to give a pale yellow product with a yield of about 30%.
比較例1Comparative example 1
參照Polymer,1999(40)p4387-4398揭示之製法，以DOPO與對苯醌反應，製得DOPOBQ，
步驟如下：在一250毫升三頸反應器中，加入10.00克(0.093mol)對苯醌、22.00克(0.093×1.1mol)DOPO以及100克2-乙氧基乙醇，氮氣環境下加熱至125℃反應4小時。反應結束後冷卻至室溫，以2-乙氧基乙醇與甲醇清洗，再以2-乙氧基乙醇再結晶，所得結晶以100℃真空乾燥，得白色晶體，產率約93%。 The procedure is as follows: 10.00 g (0.093 mol) of p-benzoquinone, 22.00 g (0.093 x 1.1 mol) of DOPO and 100 g of 2-ethoxyethanol are added to a 250 ml three-necked reactor, and heated to 125 ° C under a nitrogen atmosphere. Reaction for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, washed with 2-ethoxyethanol and methanol, and then recrystallized from 2-ethoxyethanol. The crystals obtained were dried in vacuo at 100 ° C to afford white crystals.
比較例2Comparative example 2
參照TW I449707揭示之製法，以DOPO、4'-羥基苯乙酮與過量苯酚於酸觸媒催化下反應，製得DDP，
步驟如下：加入10.81克(0.05mol)DOPO、6.81克(0.05mol)4'-羥基苯乙酮、23.28克(0.05×5mol)苯酚以及0.216克對-甲基苯磺酸(2wt%，基於DOPO)，氮氣環境下加熱至130℃反應24小時。反應結束後冷卻至室溫，以乙醇溶掉倒入熱水析出，抽氣過濾後濾餅以100℃真空乾燥，得白色產物，產率約85%。 The procedure was as follows: 10.81 g (0.05 mol) of DOPO, 6.81 g (0.05 mol) of 4'-hydroxyacetophenone, 23.28 g (0.05 x 5 mol) of phenol and 0.216 g of p-toluenesulfonic acid (2 wt%, based on DOPO) were added. The reaction was heated to 130 ° C for 24 hours under a nitrogen atmosphere. After the completion of the reaction, the mixture was cooled to room temperature, poured into ethanol and poured into hot water to precipitate. After suction filtration, the cake was vacuum dried at 100 ° C to obtain a white product. The yield was about 85%.
分析方法Analytical method
超導核磁共振光譜儀(600MHz Nuclear Magnetic Resonance，NMR)，型號：Varian Unity Inova-600，DMSO-d6化學位移為δ=2.49ppm。 Superconducting nuclear magnetic resonance spectrometer (600 MHz Nuclear Magnetic Resonance, NMR), model: Varian Unity Inova-600, DMSO-d 6 chemical shift was δ = 2.49 ppm.
熱重損失分析儀(Thermogravimetric Analysis，TGA)，型號：Thermo Cahn VersaTherm，氮氣流速為20mL/min，升溫速率為20℃/min。 Thermogravimetric Analysis (TGA), model: Thermo Cahn Versa Therm, nitrogen flow rate of 20 mL/min, heating rate of 20 ° C / min.
化合物熱穩定性測試Compound thermal stability test
以實施例1所得磷系二酚單體(I-i)與結構相似的比較實例1之DOPOBQ及比較實例2之DDP進行熱穩定性分析。圖3為三者熱重分析(TGA)結果，圖中可明顯看出本案帶有氧雜蒽結構的化合物(I-i)具有較佳的熱穩定性，500℃下本案之式(I-i)化合物之約80%，遠高於DOPOBQ或DDP焦炭殘餘率(低於10%)；而800℃下式(I-i)化合 物仍存有約46%的焦炭殘餘率，亦遠高於結構相似的DOPOBQ或DDP，顯示藉由導入(硫代)氧雜蒽結構限制苯環的轉動，可大幅提高其熱穩定性質。 The phosphorus-based diphenol monomer (I-i) obtained in Example 1 was subjected to thermal stability analysis with DOPOBQ of Comparative Example 1 and DDP of Comparative Example 2 having similar structures. Figure 3 shows the results of three thermogravimetric analysis (TGA). It can be clearly seen that the compound (Ii) with oxaxan structure in this case has better thermal stability, and the compound of formula (Ii) in this case at 500 °C About 80%, much higher than DOPOBQ or DDP coke residual rate (less than 10%); and 800°C formula (Ii) The material still has a coke residual ratio of about 46%, which is much higher than the structurally similar DOPOBQ or DDP. It shows that the thermal stability of the benzene ring can be greatly improved by introducing the (thio) oxonium structure to limit the rotation of the benzene ring.
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