CN103408577B - Aminosilane compound and a preparation method based on aromatic diamine - Google Patents

Aminosilane compound and a preparation method based on aromatic diamine Download PDF

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CN103408577B
CN103408577B CN 201310350590 CN201310350590A CN103408577B CN 103408577 B CN103408577 B CN 103408577B CN 201310350590 CN201310350590 CN 201310350590 CN 201310350590 A CN201310350590 A CN 201310350590A CN 103408577 B CN103408577 B CN 103408577B
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徐彩虹
林先凯
罗永明
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中国科学院化学研究所
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Abstract

本发明公开了一种基于芳基二胺的胺基硅烷化合物及其制备方法。 The present invention discloses a method for its preparation aminosilane compound based on the aromatic diamine. 该胺基硅烷化合物如式I所示,式I中,苯环为邻位取代、间位取代或对位取代;R1选自O原子、–CH2–、–C(CH3)2–、–C(CF3)2–、–SO–、–SO2–或–O–Ph–SO2–Ph–O–;R2、R3和R4均选自H原子、C1–12烷基、C2–12链烯基、C6–12芳基或三氟丙基。 The aminosilane compound of formula I as shown in formula I, the benzene ring is substituted ortho, meta or para substitution substituent; Rl atoms selected from O, -CH2 -, - C (CH3) 2 -, - C (CF3) 2 -, - SO -, - SO2- or -O-Ph-SO2-Ph-O-; R2, R3 and R4 are selected from an H atom, a C1-12 alkyl group, an alkenyl group of C2-12, C6-12 aryl group or trifluoropropyl. 本发明提供了上述胺基硅烷化合物的制备方法,包括如下步骤:式II所示芳基二胺与式III所示三有机基氯硅烷进行胺解反应得到所述胺基硅烷化合物;式II中,R1选自O原子、–CH2–、–C(CH3)2–、–C(CF3)2–、–SO–、–SO2–或–O–Ph–SO2–Ph–O–;式III中,R2、R3和R4均选自H原子、C1–12烷基、C2–12链烯基、C6–12芳基或三氟丙基。 The present invention provides a method for preparing the above-described aminosilane compound, comprising the steps of: an aryl group of formula II with a diamine of formula III triorgano chlorosilane solution of the amine compound obtained by reacting the aminosilanes; formula II , R1 is selected from O atom, -CH2 -, - C (CH3) 2 -, - C (CF3) 2 -, - SO -, - SO2- or -O-Ph-SO2-Ph-O-; formula III , R2, R3 and R4 are selected from an H atom, C1-12 alkyl, C2-12 chain 6 alkenyl, C6-12 aryl group or trifluoropropyl. 式I? Formula I? 式II? Type II? ? ? ? ? ? ? ? ? ? ? ? 式III。 Type III.

Description

基于芳基二胺的胺基枯烧化合物及其制备方法 Cumyl compounds and methods of burning aromatic diamine-based amine

技术领域 FIELD

[0001] 本发明设及一种基于芳基二胺的胺基硅烷化合物及其制备方法。 [0001] The present invention is provided aminosilane compound and its preparation method based on aromatic diamine.

背景技术 Background technique

[0002] 随着科技的进步,对材料的性能提出了更高的要求。 [0002] As technology advances, the performance of the material put forward higher requirements. 有机无机杂化材料作为一种新型材料,不但具有机高分子的易加工成型、柔初性好、价格低廉等优点,而且兼具有无机材料的耐高溫、高强度、耐溶剂等优点,在宇航、国防、机械、环保和生物等领域展现出广阔的应用前景。 Organic-inorganic hybrid material as a new material not only having a high polymer easy processing, good early flexible, low cost, etc., and an inorganic material with high temperature and high strength, solvent resistance, etc., in aerospace, defense, machinery, environmental protection and biotechnology and other areas show a broad application prospects. 运其中,含娃有机无机杂化材料一直是人们研究的热点,在有机材料中引入娃,不但能增强或保持材料的耐热性能,而且可W使其具有的优良的界面性能和高溫陶瓷化性能等,在耐热材料、光学材料、涂层材料、电学材料和催化材料等方面都具有重大的研究和应用价值。 Wherein the transport, baby-containing organic-inorganic hybrid materials has been a hot research topic, baby in the organic material is introduced, not only can enhance or maintain the heat resistance material, and W it may have excellent interfacial properties and high temperature ceramic performance, in terms of heat-resistant materials, optical materials, coating materials, electrical materials, and catalytic materials are of great research and application.

[0003]目前对于含娃有机无机杂化材料的研究主要集中在含Si-0键的单体或聚合物, 对于含Si-N键的杂化材料的报道并不多。 [0003] For the current baby-containing organic-inorganic hybrid materials research focused on a monomer or polymer containing Si-0 bond, not much is reported for hybrid materials containing Si-N bond. Si-N键的键能比Si-0键高,聚娃氮烧普遍具有较高的热稳定性,因此含Si-N键的有机无机杂化材料是一种很有前途的耐高溫材料。 Si-N bond energy than Si-0 bond, the nitrogen burn baby polyethylene generally have high thermal stability, and therefore an organic-inorganic hybrid material containing Si-N bonds is a promising high-temperature materials. 芳胺与氯硅烷反应生成胺基硅烷小分子,其可作为制备含Si-N键有机无机杂化材料的单体化合物,然而一些基于芳基二胺的胺基硅烷化合物及其制备方法还鲜见报道。 Aromatic amine silane with aminosilane chlorine generating a small molecule, which may be prepared as a monomeric compound containing Si-N bonds of the organic-inorganic hybrid material, but some of the aminosilane compounds and aromatic diamine-based preparation is also fresh reported.

发明内容 SUMMARY

[0004] 本发明的目的是提供一种基于芳基二胺的胺基硅烷化合物及其制备方法。 [0004] The object of the present invention is to provide an aminosilane compound and a preparation method based on aromatic diamine.

[0005] 本发明提供的基于芳基二胺的胺基硅烷化合物,其结构通式如式I所示: [0005] The present invention provides amine-based aromatic diamine silane compound structural formula as shown in formula I:

[0006] [0006]

Figure CN103408577BD00041

[0007]式I [0007] Formula I

[0008] 所述式I中,苯环上的取代基为邻位取代、间位取代或对位取代; [0008] In the formula I, substituents on the phenyl ring ortho, meta or para substitution substituted;

[0009]r1 为0原子、-邸2-、-"邸3)2"、-C(CF3)2"、-SO-、-S〇2"或-o-化-S〇2-Ph-〇-; [0009] r1 is 0 atom, - Di 2 -, - "Di 3) 2", - C (CF3) 2 ", - SO -, - S〇2" or -o- of -S〇2-Ph- 〇-;

[0010]R2、R郝R4相同或不同,均选自Η原子、C1-C12的烷基、C2-C12的链締基、C6-C12 的芳基、含有取代基的C6-C12的芳基和Ξ氣丙基中的任意一种; [0010] R2, R R4 are the same or different Hao, are selected from Η atoms, C1-C12 alkyl, C2-C12 chain associative group, C6-C12 aryl group, C6-C12 aryl-containing substituent group and any of one Ξ gas propyl;

[0011] 所述含有取代基的Ce_i2芳基中,取代基选自Ci_e烷基中的任意一种。 [0011] Ce_i2 aryl group containing a substituent, the substituent is selected from any one Ci_e alkyl.

[0012] 具体的,所述式I中,R2、R呀PR4中至少一个取代基为C1-C12的链締基; [0012] Specifically, the Formula I, R2, R PR4 die at least one substituent is a C1-C12 chain associative group;

[001引所述R2、R呀PR4中,烷基的碳原子总数为1-6;所述烷基具体为甲基、乙基或己基; [001 the primer R2, R PR4 way, the total number of carbon atoms in the alkyl group is 1-6; and the alkyl group particularly methyl, ethyl or hexyl;

[0014] 链締基的碳原子总数为2-6;所述链締基具体为乙締基或締丙基; The total number of carbon atoms [0014] associative chain groups of 2 to 6; the chain B associative groups specifically associated propyl group or association;

[0015] 所述含有取代基的C6-C12的芳基中,取代基选自C1-C6的烷基中的任意一种; [0015] The substituent containing C6-C12 aryl group, any one substituent group selected from a C1-C6 alkyl;

[0016] 所述含有取代基的C6-C12的芳基具体为对甲基苯基或间甲基苯基。 [0016] containing C6-C12 aryl group substituted for the specific methylphenyl or meta-methylphenyl.

[0017] 更具体的,所述式I所示化合物为式IV-式VIII所示化合物中的任意一种: [0017] More specifically, as shown in FIG any one compound of formula IV- compound of formula VIII the Formula I:

[0018] [0018]

Figure CN103408577BD00051

[0027]式VIII [0027] Formula VIII

[002引所述R2、R呀PR4中至少一个取代基为C1-C12的链締基、Ri的定义与式I相同的式I化合物具体为式V、式VI或式VIII所示化合物。 The compounds of formula I [002 the primer R2, R PR4 die at least one substituent is a C1-C12 chain associative group is the same as the definition of formula I Ri is specifically of formula V, a compound of formula VI or formula VIII.

[0029] 本发明提供上述胺基硅烷化合物的制备方法,包括如下步骤:将式II所示芳基二胺与式III所示Ξ有机基氯硅烷于溶剂中进行胺解反应,得到所述式I所示化合物; [0029] The present invention provides a method for preparing the above-described aminosilane compound, comprising the steps of: an aryl group of formula II with a diamine of formula III in an organic chloride Ξ silane Amination in a solvent, to give the formula compound I shown;

Figure CN103408577BD00052

[0030] [0030]

[0031] [0031]

[0032] 所述式II中,苯环为邻位取代、间位取代或对位取代;Ri的定义与前述式I相同; [003引所述式III中,R2、r3和R4的定义与前述式I相同。 [0032] In the formula II, the benzene ring is substituted ortho, meta or para substituted substitution; the same definition as Ri in the above formula I; [003 incorporated in the formula III, R2, R3 and R4 are as defined with the same as formula I.

[0034] 上述制备方法中,所述式II所示芳基二胺与式III所示Ξ有机基氯硅烷的投料摩尔比为(1~20): (2~80),优选(1~13): (2~55),具体可为1:2、2:5、4:9、5:14、 7:22、9: :34、13:55、2-9:5-34、4-5:9-14 或2-7:5-22。 [0034] In the above production method, an organic group Ξ feeding the chlorosilane of formula II with an aromatic diamine of formula III in a molar ratio of (1 to 20): (2 ~ 80), preferably (1 to 13 ): (2 ~ 55), in particular may be 1: 2,2: 5,4: 9,5: 14, 7: 22,9:: 34,13: 55,2-9: 5-34,4- 5: 9-14 or 2-7: 5-22.

[0035]所述溶剂由组分a和组分b组成; [0035] The solvent component A and a component b of the composition;

[003引所述组分a为丙酬、四氨巧喃或乙腊; [003 primer component a propionyl paid, tetraamine acetate or wax clever furans;

[0037] 所述组分b为二异丙基乙基胺、化晚或Ξ乙胺。 [0037] The component b is diisopropyl ethyl amine, or Ξ LATE ethylamine.

[0038] 所述组分a与组分b的体积比为(1~60): (1~40),优选(1~40): (1~25), 具体可为20:20、30:20、30:22、30:14或40:15。 [0038] The volume of component b to component a ratio of (1 to 60): (1 to 40), preferably (1 to 40): (1 to 25), may be specifically 20: 20 and 30: 20,30: 22,30: 14 or 40:15.

[0039] 所述胺解反应步骤中,溫度为0°C~100°C,优选20°C~90°C,具体可为20°C、 40。 [0039] The amination reaction step, the temperature is 0 ° C ~ 100 ° C, preferably 20 ° C ~ 90 ° C, particularly may be 20 ° C, 40. (:、50。(:或70。(:。 (: 50 (: or 70. (:.

[0040] 所述胺解反应步骤中,时间为0. 5小时~72小时,优选0. 5小时~48小时,具体可为0. 5小时、2小时、6小时、18小时、24小时或48小时。 [0040] The amination reaction step, the time is 0.5 hours to 72 hours, preferably 0.5 hours to 48 hours, particularly may be 0.5 hours, 2 hours, 6 hours, 18 hours, 24 hours or 48 hours.

[0041] 上述制备方法中,所述反应在惰性气氛下进行,如氣气或氮气。 [0041] The above preparation method, the reaction is carried out under an inert atmosphere, such as air or nitrogen gas.

[0042] 另外,上述本发明提供的式I所示化合物在制备有机无机热固性树脂中的应用, 也属于本发明的保护范围。 [0042] Further, the present invention provides the use of a compound of formula I in the preparation of organic-inorganic thermosetting resin, also belong to the scope of the present invention.

[0043] 本发明提供的制备有机无机热固性树脂的方法,包括如下步骤:将前述本发明提供的R2、R呀PR4中至少一个取代基为C2_i2链締基的式I所示化合物、式IX所示硅烷化合物和卡斯泰德催化剂(也即Karste化催化剂)混匀进行娃氨加成反应,反应完毕得到所述有机无机热固性树脂; [0043] The method of preparing organic-inorganic present invention provides a thermosetting resin, comprising the steps of: the present invention provides the aforementioned R2, R PR4 die at least one substituent is a compound of formula IX as shown C2_i2 chain associative group of formula I Cass shown silane compound and Ted catalyst (i.e., catalyst Karste) for baby ammonia mixed addition reaction, the reaction was completed to obtain an organic-inorganic thermosetting resin;

[0044] [0044]

Figure CN103408577BD00061

[0045]式IX [0045] Formula IX

[0046] 所述式IX中,Rs选自Η原子、C1-C12的烷基、C2-C12的链締基、C6-C12的芳基、 含有取代基的C6-C12的芳基和Ξ氣丙基中的任意一种; [0046] In the formula IX, Rs is selected from Η atoms, C1-C12 alkyl, C2-C12 chain associative group, C6-C12 aryl group, C6-C12 aryl group-containing substituent group, and gas Ξ any one of a propyl group;

[0047] 所述含有取代基的C6-C12芳基中,取代基选自C1-C6烷基中的任意一种; C6-C12 aryl group [0047] containing substituents, substituents are selected from any one of C1-C6 alkyl group;

[004引X为0原子、-ΝΗ-、-邸2-或单键; [004 cited atom X is 0, -ΝΗ -, - Di 2- or a single bond;

[0049]η为3 - 1000 的整数。 [0049] η 3 - Integer 1000.

[0050] 上述方法所述式IX中,Rs选自Η原子、C1-C6烷基、C2-C6链締基、苯基和C1-C3烧基取代的苯基中的任意一种; [0050] The method of the above-described formula IX, Rs is selected from Η atoms, C1-C6 alkyl, C2-C6-chain associative group, a phenyl group, and substituted C1-C3 burn any one phenyl group;

[0051] 其中,所述C1-C6烷基具体为甲基、乙基或己基; [0051] wherein said C1-C6 alkyl in particular methyl, ethyl or hexyl;

[0052] 所述C2-C6链締基具体为乙締基或締丙基; [0052] The C2-C6 chain associative groups specifically associated propyl ethyl group or association;

[0053] 所述C1-C3烷基取代的苯基具体为对甲基苯基或间甲基苯基; [0053] The C1-C3 alkyl substituted by phenyl or methylphenyl specific for the m-methylphenyl;

[0054]η为3-100的整数,具体为3-50的整数,更具体为3-10的整数,最具体为4; [0054] η is an integer of from 3 to 100, particularly an integer of 3 to 50, and more specifically an integer of 3-10, and most specifically 4;

[00巧]式I所示化合物、式IX所示硅烷化合物和Karste化催化剂的投料摩尔用量比为α~2oo):α~loo):αxlo6~5oooxlo6),具体为2:l:(4oxlo6); [Qiao 00] the compound of Formula I, and a silane compound feed Karste catalyst of Formula IX with a molar ratio of α ~ 2oo): α ~ loo): αxlo6 ~ 5oooxlo6), in particular 2: l: (4oxlo6) ;

[0056] 所述娃氨加成反应步骤中,溫度为0°C~200°C,具体为50°C; [0056] The baby ammonia addition reaction step, the temperature is 0 ° C ~ 200 ° C, particularly of 50 ° C;

[0057] 时间为1小时~72小时,具体为12小时。 [0057] time of 1 hour to 72 hours, particularly 12 hours.

[0058] 本发明通过式II所示芳基二胺与式III所示Ξ有机基氯硅烷于溶剂中进行胺解反应,合成了式I所示胺基硅烷化合物。 [0058] The present invention is illustrated by an aryl group of formula II with a diamine of formula III Ξ organo chlorosilanes the amine in a solvent the reaction solution, the synthesized compound of Formula I as aminosilane. 该合成方法简便易行,条件溫和,所合成的胺基娃烧化合物具有优良的溶解性能,可作为合成含Si-N键有机无机杂化材料的单体化合物, 用于制备耐高溫热固性树脂,陶瓷前驱体等。 The synthesis method is simple, mild conditions, the synthesis of amine compounds having baby burn good dissolution properties, can be synthesized as a Si-N bond-containing organic-inorganic hybrid material monomer compounds for the preparation of high-temperature thermosetting resin, ceramic precursors and so on.

具体实施方式 detailed description

[0059] 下面结合具体实施例对本发明作进一步阐述,但本发明并不限于W下实施例。 [0059] The following embodiments in conjunction with specific embodiments of the present invention is further illustrated, but the present invention is not limited to the embodiments W. 所述方法如无特别说明均为常规方法。 The method according to a conventional method are not particularly described. 所述原材料如无特别说明均能从公开商业途径而得。 As the starting material can no special instructions obtained from commercial sources disclosed. 下述实施例中所用Karste化催化剂的CAS号为68478-92-2,中文名称为销(0)-1,3-二乙締-1,1,3, 3-四甲基二硅氧烷。 Used in the following examples Karste CAS Number 68478-92-2 as catalyst, the Chinese name pin (0) -1,3-diethyl associative-1,1,3,3-tetramethyldisiloxane .

[0060] 本发明下述实施例中所做的热失重(TGA)测试的热失重分析仪型号为:SII6300。 [0060] The following embodiments do embodiment TGA (TGA) testing of the present invention is thermogravimetric analyzer model: SII6300.

[0061] 实施例1、4,4'-双(N,N' -Ξ甲基娃基)胺基二苯讽设日式IV所示)的合成 Synthesis [0061] Example 1,4,4'- bis (N, N '-Ξ Wa-yl methyl) amino diphenyl provided Bitterness Japanese Formula IV) is

[006引氮气氛下,向100血二口瓶中依次加入4, 4'-二胺基二苯讽(1. 24g,5mmol)、丙酬(20血)和化晚(20血),揽拌溶解,升溫至40°C,将Ξ甲基氯硅烷(1. 09g,lOmmol)逐滴加入到上述溶液中,滴加完毕后进行胺解反应0. 5小时,冷却到室溫,过滤,减压除去溶剂后50°C真空干燥,得到淡黄色固体,产率91%,烙点168 - 170°C。 [006 cited under a nitrogen atmosphere, were added to 100 blood two bottles 4, 4'-diamino diphenyl Bitterness (1. 24g, 5mmol), propan-pay (blood 20) and of late (20 blood), football mix to dissolve, warmed to 40 ° C, the Ξ chlorotrimethylsilane (1. 09g, lOmmol) was added dropwise to the above solution, the amine solution addition was complete the reaction after 0.5 hours, cooled to room temperature, filtered, dried under reduced pressure 50 ° C the solvent was removed in vacuo to give a pale yellow solid, 91% yield, branded point 168 - 170 ° C.

[0063] 该产物的核磁、元素分析和高分辨质谱表征结果如下: [0063] NMR of the product, elemental analysis and high resolution mass spectrum as follows:

[0064]古-醒R(400MHz, CDC!3) :δ=7. 65(d, 4H), 6. 62(d, 4H), 3. 81(S,2H), 0. 27(s, 1 8H)."C - Mffi(400MHz,acetone-d6):5=153.62,131.71,129.65,116.58,- 0.20.29si-NMR(300MHz, acetone-dg) : δ =2. 80. Anal. Calcd. for CisHzsNzOzSSiz:。55. 05;H, 7. 20;N, 7. 1 4〇/〇.化und: C, 54. 75; H, 6. 86; N, 7. 08〇/〇. HRMS巧I) : Calcd. : 392. 1410;化und: 392. 1414. [0064] Old - wake R (400MHz, CDC 3!):. Δ = 7 65 (d, 4H), 6. 62 (d, 4H), 3. 81 (S, 2H), 0. 27 (s, 1 8H) "C - Mffi (400MHz, acetone-d6):. 5 = 153.62,131.71,129.65,116.58, - 0.20.29si-NMR (300MHz, acetone-dg): δ = 2 80. Anal Calcd... for CisHzsNzOzSSiz: .55 05; H, 7. 20; N, 7. 1 4〇 / square of und:.. C, 54. 75; H, 6. 86; N, 7. 08〇 / square HRMS clever. I): Calcd:. 392. 1410; oriented und: 392. 1414.

[0065] 由上述表征数据可知,该产物的结构式如式IV所示: [0065] From the above characterization data, as shown in the structural formula of the product of formula IV:

[0066] [0066]

[0067]式IV [0067] Formula IV

Figure CN103408577BD00071

[006引实施例2、4,4'-双(N,N'-二甲基乙締基娃基)胺基二苯讽巧日式V所示)及有机无机热固性树脂的合成 Synthesis Example 2,4,4-bis (N, N'- dimethylacetamide associative group Wa-yl) amine of formula V diphenyl Bitterness Japanese Qiao shown) inorganic and organic thermosetting resin [006 cited embodiment

[0069] 氮气氛下,向100血二口瓶中依次加入4,4'-二胺基二苯讽(1.74g,7mmol)、 四氨巧喃(30血)和二异丙基乙基胺(20血),揽拌溶解,20°C下,将二甲基乙締基氯硅烷(2. 1Ig,17. 5mmol)逐滴加入到上述溶液中,滴加完毕后胺解反应2小时,过滤,减压除去溶剂后50°C真空干燥,得到淡黄色固体,产率92%,烙点127 - 128°C。 Under [0069] nitrogen atmosphere, were successively added 4,4-diamino diphenyl irony (1.74g, 7mmol) to two blood bottle 100, tetraammine Qiao thiopyran (30 blood) and diisopropylethyl amine (blood 20), mixed with dissolved embrace, at 20 ° C, the associative dimethylacetamide chlorosilane (2. 1Ig, 17. 5mmol) was added dropwise to the above solution, the reaction solution after the amine addition was complete 2 hours. filtered, and dried under reduced pressure 50 ° C after the solvent was removed in vacuo to give a pale yellow solid, 92% yield, branded point 127 - 128 ° C.

[0070] 该产物的核磁、元素分析和高分辨质谱表征结果如下: [0070] NMR of the product, elemental analysis and high resolution mass spectrum as follows:

[0071]iH-NMR(400MHz,CDC!3) :δ=7. 63(d, 4H),6. 65 (d, 4H),6. 18 (dd, 2H),6. 0 8(dd, 2H), 5.86(dd, 2H), 3. 83(s, 2H), 0. 32(s, 12H). 1化-應R(400MHz,acetone-ds) :δ =153. 36, 138. 09, 134. 28, 131. 92, 129. 52, 116. 82,- 1. 96 . 29si -應R(300MHz, a cetone-dg) : δ = - 7. 68. Anal. Calcd. for CzoHzsNzOzSSiz: C, 57. 65 ; H, 6. 79 ; N, 6. 72〇/〇. 化und:C,57. 43;H,6. 89;N,6. 40〇/〇. HRMS巧I) :Calcd. :416. 1410;化und:416. 1415. [0071] iH-NMR (400MHz, CDC 3!):.. Δ = 7 63 (d, 4H), 6 65 (d, 4H), 6 18 (dd, 2H), 6 0 8 (dd,.. . 2H), 5.86 (dd, 2H), 3. 83 (s, 2H), 0. 32 (s, 12H) 1 Adaptation - R (400MHz, acetone-ds): δ = 153 36, 138. 09. , 134. 28, 131. 92, 129. 52, 116. 82, - 1. 96 29si - shall R (300MHz, a cetone-dg):. δ = - 7. 68. Anal Calcd for CzoHzsNzOzSSiz: C.. , 57. 65; H, 6. 79; N, 6. 72〇 / square of und:.. C, 57 43; H, 6 89; N, 6 40〇 / square HRMS Qiao I):... Calcd .: 4,161,410; technology und: 416 1415..

[0072] 由上述表征数据可知,该产物的结构式如式V所示: [0072] From the above characterization data, the formula of the product shown in formula V:

[0073] [0073]

Figure CN103408577BD00081

[0074]式V [0074] Formula V

[00巧]将式V所示的胺基硅烷化合物(2.08g,5mmol)与归属式IX的1,3,5,7-四甲基环四硅氧烷(〇4扎0. 6〇g,2.Smmol,n=4)混合均匀,加入Karste化催化剂(100X 10 6mmol), 50°C进行娃氨加成反应12h,可得到有机无机杂化热固性树脂。 Amino silane compound represented by [Qiao 00] of formula V (2.08g, 5mmol) of formula IX with a home-tetramethyl-1,3,5,7-cyclotetrasiloxane (0.5 bar 〇4 6〇g , 2.Smmol, n = 4) uniformly mixed, added Karste catalyst (100X 10 6mmol), 50 ° C for 12h baby ammonia addition reaction, to obtain an organic-inorganic hybrid thermosetting resin.

[0076] 对树脂进行TGA测试。 [0076] TGA measurements of the resin. 测试条件如下:高纯氮气或空气氛,升溫速率为10°C/min。 Test conditions were as follows: high purity nitrogen or air atmosphere, heating rate of 10 ° C / min.

[0077] 测试结果为:氮气下热失重10%的溫度为428°C,800°C下残重为62. 1%;空气下热失重10%的溫度为404°C,800°C下残重为54. 5%。 [0077] Test results: 10% weight loss under nitrogen heat temperature of 428 ° C, the residual weight at 800 ° C was 62.1%; 10% weight loss hot air at a temperature of 404 ° C, 800 ° C at residues 54.5% weight.

[0078] 可见,所得有机无机杂化热固性树脂具有较高的热分解溫度和高溫残重,展现出优良的热稳定性和热氧化稳定性。 [0078] visible, the resulting organic-inorganic hybrid thermosetting resin having a higher thermal decomposition temperature and high residual heavy, exhibit excellent thermal stability and thermal oxidative stability.

[0079] 实施例3、4,4'-双(N,N'-二甲基乙締基娃基)胺基二苯酸巧日式VI所示)及有机无机热固性树脂的合成 Synthesis [0079] Example 3,4,4-bis (N, N'- dimethylacetamide Wa associative yl) amino acid diphenyl Qiao Japanese formula VI shown) inorganic and organic thermosetting resin

[0080] 氮气氛下,向250血二口瓶中依次加入4, 4'-二胺基二苯酸(2.OOg,lOmmol)、 乙腊(30血)和Ξ乙胺(22血),揽拌溶解,升溫至50°C,将二甲基乙締基氯硅烷(2. 71g, 22. 5mmol)逐滴加入到上述溶液中,滴加完毕后胺解反应18小时,过滤,减压除去溶剂后50°C真空干燥,得到黄褐色液体,产率96%。 [0080] Under a nitrogen atmosphere, were added to 250 blood two bottles 4, 4'-diamino diphenyl acid (2.OOg, lOmmol), wax B (30 blood) and Ξ ethylamine (22 blood), embrace stirred to dissolve, warmed to 50 ° C, the associative dimethylacetamide chlorosilane (2. 71g, 22. 5mmol) was added dropwise to the above solution, the reaction solution after the amine addition was complete 18 hours, filtered under reduced pressure removal of the solvent and dried in vacuo 50 ° C, to give a tan liquid, 96% yield.

[0081] 该产物的核磁和高分辨质谱表征结果如下: [0081] High resolution mass spectrum and NMR results of this product are as follows:

[008引iH-匪R(400MHz,CDC!3) :δ=6. 77 (d, 4H),6. 60 (d, 4H),6. 22 (dd, 2H),6. 06(dd, 2H), 5.86(dd, 2H), 3. 33(s, 2H), 0. 31 (s, 12H)."C-NMR(400MHz,DMSO-de) :δ=148. 85, 143. 18, 138. 55, 132. 93, 118. 91, 116. 63, - 1.86."®Si-NMR(300MHz,acetone-de) :δ= - 7. 58.HRMS巧I) :Calcd.for020&8成0812:368. 1740;Found:368. 1747. [008 cited iH- bandit R (400MHz, CDC 3!):.. Δ = 6 77 (d, 4H), 6 60 (d, 4H), 6 22 (dd, 2H), 6 06 (dd,.. 2H), 5.86 (dd, 2H), 3. 33 (s, 2H), 0. 31 (s, 12H) "C-NMR (400MHz, DMSO-de):. δ = 148 85, 143. 18,. 138. 55, 132. 93, 118. 91, 116. 63, - 1.86 "®Si-NMR (300MHz, acetone-de):. δ = - 7. 58.HRMS Qiao I): Calcd.for020 & 8 to 0812: 368. 1740; Found:. 368 1747.

[0083] 由上述表征数据可知,该产物的结构式如式VI所示: [0083] From the above characterization data, the formula of the product shown in formula VI:

[0084] [0084]

Figure CN103408577BD00082

[0085]式VI [0085] Formula VI

[0086] 将式VI所示的胺基硅烷化合物(1. 84g,5mmol)与归属式IX的1,3, 5, 7-四甲基环四硅氧烷(〇4扎0. 6〇g,2.Smmol,n=4)混合均匀,加入Karste化催化剂(100X 10 6mmol), 50°C进行娃氨加成反应12h,得到有机无机杂化热固性树脂。 [0086] The aminosilane compound of formula VI, (1. 84g, 5mmol) of formula IX with the home 3, 5, 7-tetramethyl-cyclotetrasiloxane (0.5 bar 〇4 6〇g , 2.Smmol, n = 4) uniformly mixed, added Karste catalyst (100X 10 6mmol), 50 ° C for an addition reaction of ammonia baby 12h, to give a thermosetting organic-inorganic hybrid resin.

[0087] 对树脂进行TGA测试。 [0087] TGA measurements of the resin. 测试条件如下:高纯氮气或空气氛,升溫速率为10°C/min。 Test conditions were as follows: high purity nitrogen or air atmosphere, heating rate of 10 ° C / min. [008引测试结果为:氮气下热失重10%的溫度为563。800°C下残重为80. 3%;空气下热失重10%的溫度为528 °C,800 °C下残重为60.1%。 [008 cited test results: 10% weight loss under nitrogen heat temperature of the residual weight of 80.3% at 563.800 ° C; thermal weight loss of 10% air at a temperature of 528 ° C, 800 ° C under a weight of residues 60.1%.

[0089] 可见,所得有机无机杂化热固性树脂具有很高的热分解溫度和较高的高溫残重, 展现出优良的热稳定性和热氧化稳定性。 [0089] visible, the resulting organic-inorganic hybrid thermosetting resin having a high thermal decomposition temperature and a high residual heavy high temperature, exhibits excellent thermal stability and thermal oxidative stability.

[0090]实施例4、4, 4'-双(N,Ν'-二甲基娃基)胺基二苯酸咖式VII所示)的合成[00川氮气氛下,向100血二口瓶中依次加入4, 4'-二胺基二苯酸(0. 90g,4. 5mmol)、 四氨巧喃(30血)和Ξ乙胺(14mL),揽拌溶解,20°C下,将二甲基氯硅烷(1.61g,17mmol)逐滴加入到上述溶液中,滴加完毕后胺解反应48小时,过滤,减压除去溶剂后50°C真空干燥, 得到淡黄色液体,产率95%。 [0090] Example 4,4, the 4'-bis (N, Ν'- dimethyl Wa-yl) amino acid diphenyl coffee formula VII shown) in [00 Sichuan nitrogen atmosphere, two blood 100 flask were added 4, 4'-diamino diphenyl acid (0. 90g, 4. 5mmol), tetraammine Qiao thiopyran (30 blood) and Ξ ethylamine (14mL), stirred embrace dissolved, at 20 ° C, dimethyl chlorosilane (1.61g, 17mmol) was added dropwise to the above solution, the reaction solution after the amine addition was complete 48 hours, filtered, and dried under reduced pressure 50 ° C the solvent was removed in vacuo to give a pale yellow liquid, yield 95%.

[0092] 该产物的核磁和高分辨质谱表征结果如下: [0092] High resolution mass spectrum and NMR results of this product are as follows:

[0093]iH-NMR(400MHz,CDCl3):5=6.81(d,4H),6.62(d,4H),4.75-4. 70 (m, 2H),3. 30 (S, 2H),0. 30 (d, 12H)."C-NMR(400MHz,acetone-dg) :δ=150. 54, 143. 83, 119. 97, 117. 17,- 2. 08."®Si-NMR(300MHz,acetone-dg) :δ= - 14. 14.HRMS巧I) :Calcd.for〇16&4成0812:316. 1427;Found:316. 1432. [0093] iH-NMR (400MHz, CDCl3): 5 = 6.81 (d, 4H), 6.62 (d, 4H), 4.75-4 70 (m, 2H), 3 30 (S, 2H), 0... . 30 (d, 12H) "C-NMR (400MHz, acetone-dg): δ = 150 54, 143. 83, 119. 97, 117. 17, - 2. 08.." ®Si-NMR (300MHz, acetone-dg): δ = - 14. 14.HRMS Qiao I): & Calcd.for〇16 4 to 0812: 316 1427; Found: 316 1432...

[0094] 由上述表征数据可知,该产物的结构式如式VII所示: [0094] From the above characterization data, the formula of the product shown in formula VII:

[0095] [0095]

Figure CN103408577BD00091

[0096]式VII [0096] Formula VII

[0097] 实施例5、4,4'-双巧-(N-二甲基乙締基娃基)胺基苯氧基]二苯讽巧日式VIII所示)及有机无机热固性树脂的合成 Synthesis of (N- dimethylacetamide Wa associative yl) amino phenoxy] diphenyl Bitterness Qiao Japanese Formula VIII below) and the organic-inorganic thermosetting resin - [0097] Example 5,4,4'- bis Qiao

[0098] 氮气氛下,向250血二口瓶中依次加入4,4'-双(3-胺基苯氧基)二苯讽(5. 62g,13mmol)、乙腊(40血)和化晚(15血),揽拌溶解,升溫至70°C,将二甲基乙締基氯娃烧(6. 64g,55mmol)逐滴加入到上述溶液中,滴加完毕后胺解反应24小时,过滤,减压除去溶剂后50°C真空干燥,得到黄色固体,产率93%,烙点44 - 47°C。 [0098] Under a nitrogen atmosphere, were successively added 4,4-bis (3-aminophenoxy) diphenyl Bitterness (5. 62g, 13mmol) to two blood bottle 250, December acetate (40 blood) and of Night (15 blood), dissolved embrace mixed, warmed to 70 ° C, the associative dimethylacetamide baby burn chloride (6. 64g, 55mmol) was added dropwise to the above solution, the reaction solution after the amine addition was complete 24 hours , filtered, and the solvent was removed under reduced pressure and dried 50 ° C in vacuo to give a yellow solid, 93% yield, branded point 44 - 47 ° C.

[0099] 该产物的核磁和高分辨质谱表征结果如下: [0099] High resolution mass spectrum and NMR results of this product are as follows:

[0100]古-NMR(400MHz,CDC!3) :δ7. 85 化4田,7. 10 (t, 2H),7. 02 (d, 4田,6. 50 (d, 2H),6 .36 (d, 2H),6. 32 (s, 2H),6. 17 (dd, 2H),6. 03 (dd, 2H), 5. 81 (dd, 2H), 3. 56 (s, 2H), 0. 29 (s, 1 2H). 口C-NMR(400MHz,acetone-ds) :δ=162.66, 156. 81,150. 83, 138. 61,136. 64, 133. 85, 131. 13, 130. 47, 118.66, 113. 76, 109. 27, 108. 54, - 1. 86.29si-NMR(300MHz,acetone-ds) :δ= - 7. 64.HRMS巧I) :Calcd.for〇32&6成〇45812:600. 1934;Found:600. 1941. [0100] Old -NMR (400MHz, CDC 3!):. Δ7 85 fields of 4, 7 10 (t, 2H), 7 02 (d, 4 field, 6 50 (d, 2H), 6.... 36 (d, 2H), 6. 32 (s, 2H), 6. 17 (dd, 2H), 6. 03 (dd, 2H), 5. 81 (dd, 2H), 3. 56 (s, 2H ), 0. 29 (s, 1 2H) port C-NMR (400MHz, acetone-ds):. δ = 162.66, 156. 81,150 83, 138. 61,136 64, 133. 85, 131... 13, 130. 47, 118.66, 113. 76, 109. 27, 108. 54, - 1. 86.29si-NMR (300MHz, acetone-ds): δ = - 7. 64.HRMS Qiao I): Calcd.for . & 〇32 6 to 〇45812: 600 1934; Found:. 600 1941.

[0101] 由上述表征数据可知,该产物的结构式如式VIII所示: [0101] From the above characterization data, the formula of the product shown in formula VIII:

[0102] [0102]

Figure CN103408577BD00092

[0103]式VIII [0103] Formula VIII

[0104] 将式VIII所示的胺基硅烷化合物(3.OOg,5mmol)与归属式IX的1,3, 5, 7-四甲基环四硅氧烷(〇4扎0. 60g,2. 5mmol,n=4)混合均匀,Karste化催化剂(100X106mmol),50°C 进行娃氨加成反应12h,得到有机无机杂化热固性树脂。 [0104] The aminosilane compound represented by the formula VIII (3.OOg, 5mmol) and 1, 3, 5, 7-tetramethyl-home cyclotetrasiloxane of formula IX (〇4 tie 0. 60g, 2 . 5mmol, n = 4) mixed, Karste catalyst (100X106mmol), 50 ° C for an addition reaction of ammonia baby 12h, to give a thermosetting organic-inorganic hybrid resin.

[0105] 对树脂进行TGA测试。 [0105] TGA measurements of the resin. 测试条件如下:高纯氮气或空气氛,升溫速率为10°C/min。 Test conditions were as follows: high purity nitrogen or air atmosphere, heating rate of 10 ° C / min.

[0106] 测试结果为:氮气下热失重10%的溫度为474°C,800°C下残重为58.6%;空气下热失重10%的溫度为464°C,800°C下残重为50. 1〇/〇。 [0106] Test results: nitrogen heat 10% weight loss temperature of 474 ° C, the residual weight at 800 ° C was 58.6%; air heat 10% weight loss temperature of 464 ° C, at 800 ° C residue weight 50. 1〇 / square.

[0107] 可见,所得有机无机杂化热固性树脂具有很高的热分解溫度和较高的高溫残重, 展现出优良的热稳定性和热氧化稳定性。 [0107] visible, the resulting organic-inorganic hybrid thermosetting resin having a high thermal decomposition temperature and a high residual heavy high temperature, exhibits excellent thermal stability and thermal oxidative stability.

Claims (6)

  1. 1. 一种制备有机无机热固性树脂的方法,包括如下步骤:将R2、R3和R 4中至少一个取代基为C2 - C12链烯基的式I所示化合物、1,3, 5, 7-四甲基环四硅氧烷和卡斯泰德催化剂混匀进行硅氢加成反应,反应完毕得到所述有机无机热固性树脂; 1. A method of preparing an organic-inorganic thermosetting resin, comprising the steps of: R2, R3 and R 4 at least one substituent of C2 - C12 alkenyl compound represented by Formula I, 1,3, 5, 7- tetramethyl cyclotetrasiloxane and Ted Cass catalyst for hydrosilylation reaction mix, the reaction was completed to obtain an organic-inorganic thermosetting resin;
    Figure CN103408577BC00021
    所述式I中,苯环上的取代基为邻位取代、间位取代或对位取代; R1 为〇原子、-CH2-、-C(CH3)2-、-C(CF3) 2-、- SO-、-SO2- gSc -O-Ph-SO2-Ph-O -; 妒、1?3和1?4相同或不同,均选自! Of formula I, the substituents on the phenyl ring is substituted ortho, meta or para substitution substituted; Rl is square atom, -CH2 -, - C (CH3) 2 -, - C (CF3) 2-, - SO -, - SO2- gSc -O-Ph-SO2-Ph-O -; jealous, 13 and 14 are the same or different, are selected from??! 1原子、(:1-(:12的烷基、02-(:12的链烯基、06-(:12的芳基、三氟丙基和含有取代基的C6-C12的芳基中的任意一种; 所述含有取代基的C6 - C12的芳基中,取代基选自Cl - C6的烷基中的任意一种。 1 atom, (: l - (: alkyl of 12, 02 - (: 12 alkenyl group, 06 - (: 12 aryl group, trifluoropropyl group, and a C6-C12 aryl-containing substituents of any one of; a substituent of the C6 - C12 aryl group, the substituents are selected from Cl - C6 alkyl group in any one of.
  2. 2. 根据权利要求1所述的方法,其特征在于:所述式I中,C1-C12的烷基的碳原子总数为1-6 ; C2-C12的链烯基的碳原子总数为2-6。 2. The method according to claim 1, wherein: said formula I, the total number of carbon atoms of the C1-C12 alkyl group is 1-6; the total number of carbon atoms, C2-C12 alkenyl group is 2 6.
  3. 3. 根据权利要求2所述的方法,其特征在于:所述式I中,C1-C6的烷基为甲基、乙基或己基; 所述C2-C12的链烯基为乙烯基或烯丙基; 所述含有取代基的C6-C12的芳基为对甲基苯基或间甲基苯基。 3. The method according to claim 2, wherein: in the formula I, C1-C6 alkyl groups are methyl, ethyl or hexyl group; a C2-C12 alkenyl group is vinyl or alkenyl propyl; containing substituted C6-C12 aryl group is p-methylphenyl or m-methylphenyl.
  4. 4. 根据权利要求1所述的方法,其特征在于:所述式I所示化合物为式V、式VI和式VIII所示化合物中的任意一种: 4. The method according to claim 1, characterized in that: in any one of the compound of formula I is a compound of Formula V, Formula VI and Formula VIII below:
    Figure CN103408577BC00022
  5. 5. 根据权利要求1-4中任一所述的方法,其特征在于:所述式I所示化合物、1, 3,5,7_四甲基环四硅氧烷和卡斯泰德催化剂的投料摩尔用量比为(1~200): (1~ 100) : (1X 10 6~5000X 10 6); 所述娃氢加成反应步骤中,温度为〇°C~200°C ; 时间为1小时~72小时。 5. The method according to any one of claims 1-4, wherein: the compound 1, 3,5,7_ tetramethyl cyclotetrasiloxane and Kas I Ted catalyst shown in the formula the molar use ratio of (1 ~ 200): (1 ~ 100): (1X 10 6 ~ 5000X 10 6); the baby hydrogen addition reaction step, the temperature is square ° C ~ 200 ° C; time 1 hour to 72 hours.
  6. 6.根据权利要求5所述的方法,其特征在于:所述式I所示化合物、1,3, 5, 7-四甲基环四硅氧烷和卡斯泰德催化剂的投料摩尔用量比为2 :1 : (40X 10 6); 所述硅氢加成反应步骤中,温度为50°C ; 时间为12小时。 6. The method according to claim 5, wherein: the compound, 1, 3, 5, 7-tetramethyl cyclotetrasiloxane and Ted Cass catalyst feed shown by the molar ratio of Formula I is 2: 1: (40X 10 6); said hydrosilylation reaction step, the temperature is 50 ° C; for 12 hours.
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US4393180A (en) * 1981-06-30 1983-07-12 Ciba-Geigy Corporation Curing agents for epoxide resins and compositions containing them
US5889128A (en) * 1997-04-11 1999-03-30 Massachusetts Institute Of Technology Living olefin polymerization processes

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US4393180A (en) * 1981-06-30 1983-07-12 Ciba-Geigy Corporation Curing agents for epoxide resins and compositions containing them
US5889128A (en) * 1997-04-11 1999-03-30 Massachusetts Institute Of Technology Living olefin polymerization processes

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