WO2011144015A1

WO2011144015A1 - Polymercapto compound and synthesis method thereof

Info

Publication number: WO2011144015A1
Application number: PCT/CN2011/074170
Authority: WO
Inventors: 王跃川; 胡张燕; 马金鑫
Original assignee: Wang Yuechuan; Hu Zhangyan; Ma Jinxin
Priority date: 2010-05-17
Filing date: 2011-05-17
Publication date: 2011-11-24
Also published as: CN101824149A; CN101824149B

Abstract

A polymercapto compound and synthesis method thereof are disclosed. The main chain of the polymercapto compound is linear or branched structure and comprises thioether bond. Each molecule at least comprises two mercapto groups; the mass content of sulfur element in the compound is 8%-25%; the content of mercapto groups is 0.1mmol/g-6mmol/g, and the weight-average molecular weight of the compound is 800g/mol-180,000g/mol. The starting materials include hydrogen sulfide gas, a compound containing at least two (meth)acrylate functional groups or a polyepoxy compound with at least two functionalities, catalyst and organic solvent containing nitrogen atom. The reaction steps are as follows: adding solid and liquid reactants into a reactor, introducing gas reactant to maintain the pressure of the system at 3000Pa-70,000Pa, and reacting for 0.5-8h at 0℃-90℃ under stirring.

Description

一种多 ^化合物及其合成方法技术领域本发明涉及一种含多巯基的化合物以及该多巯基化合物的合成方法，具体而言，本专利涉及一种通过硫化氢与含有至少两个（甲基）丙烯酸酯官能团的化合物、或者至少两官能度的多环氧化合物反应制备得到的多琉基化合物及其合成方法。背景技术琉基化合物具有很多优异的化学性能，如琉基-烯体系独特的自由基 -逐步加成反应具有反应速度快、抗氧阻聚、转化率高、产物均一性好等特点，含有琉基化合物的材料在透明性、机械性能、耐候性方面等具有特殊的性能，例如，可参见文献 Charles E. Hoyle, Thiol-Enes: Chemistry of the Past with Promise for the Future J. Polym. Sci. Part A: Polym. Chem.: Vol.42(2004)和 Christopher N. Bowman and Christopher J. Kloxin, Toward an Enhanced Understanding and Implementation of Photopolymerization Reactions, AIChE Journal Vol.54(2008)。然而，琉基化合物在工业生产及人们日常生活中并没有得到广泛应用，究其原因，一是琉基化合物具有严重令人不悦的恶臭味，二是琉基化合物的稳定性差、储存期短，从而使其广泛应用受到了限制。日本立邦公司（ Nippon Shokubai Co. ) 在 US Patent 5,821,382 中公开了一种由硫化氢气体、单官能丙烯酸（酯）合成单巯基化合物的方法，该方法所需原料廉价易得，工艺流程相对简单，产物的选择性及产率都较高，故工业上可操作性强。但是，该方法所得产物是只含有一个琉基官能团或一个硫醚键的小分子巯基化合物，其挥发性强，从而不可避免的具有强烈的恶臭味。 TECHNICAL FIELD The present invention relates to a compound containing a polyfluorenyl group and a method for synthesizing the polyfluorenyl compound. Specifically, the present patent relates to hydrogen sulfide and at least two (methyl) A polythiol compound prepared by reacting an acrylate functional compound or a polyfunctional epoxy compound having at least two functionalities and a method for synthesizing the same. BACKGROUND OF THE INVENTION Sulfhydryl compounds have many excellent chemical properties, such as a unique radical-step addition reaction of a mercapto-ene system, which has the characteristics of high reaction speed, anti-oxidation inhibition, high conversion rate, good product homogeneity, and the like. The material of the base compound has special properties in terms of transparency, mechanical properties, weather resistance, etc., for example, see Charles E. Hoyle, Thiol-Enes: Chemistry of the Past with Promise for the Future J. Polym. Sci. A: Polym. Chem.: Vol. 42 (2004) and Christopher N. Bowman and Christopher J. Kloxin, Toward an Enhanced Understanding and Implementation of Photopolymerization Reactions, AIChE Journal Vol. 54 (2008). However, sulfhydryl compounds have not been widely used in industrial production and people's daily life. The reasons are: thiol compounds have serious unpleasant malodors, and second, sulfhydryl compounds have poor stability and shelf life. Short, so its wide application is limited. Nippon Shokubai Co., in U.S. Patent No. 5,821,382, the disclosure of which is incorporated herein by reference to the entire entire entire entire entire entire entire entire entire entire entire disclosure The selectivity and yield of the product are high, so the industrial operability is strong. However, the product obtained by this method is a small molecule mercapto compound containing only one mercapto functional group or one thioether bond, which is highly volatile and inevitably has a strong malodor.

US Patent 4,092,293中公开了一种由^■化氢气体、多官能的婦丙基醚、苯或脂肪族溶剂及偶氮类催化剂组成的反应体系，通过自由基加成反应得到多巯基树脂，所得多琉基树脂，由于分子量较高，故气味小。但该方法合成条件比较苛刻，所需硫化氢气体的压强较高（压力要大于 5.6x l0⁵ Pa ) , 有一定的危险性。发明内容本发明旨在克月艮上述方法中的缺陷，提供一种分子中含有^■醚键，主链具有线性或支化结构，分子中至少含有两个琉基、不具有恶臭味的多琉基化合物；同时提供一种既能在实验室简易操作，又适合大规模工业化生产，并能保证产物中琉基含量可调、平均分子量可调、产率高且不具有恶臭味的多琉基化合物的合成方法。为此，在本发明的一个方面提供了一种多琉基化合物的合成方法，包括原料： A: 硫化氢气体， B: 选自含有至少两个（甲基）丙烯酸酯官能团的化合物、或者至少两官能度的多官能环氧化合物；且 A与 B中反应官能团的摩尔比大于 0.5; C: 用量为 B质量的 0% -6%, D:催化剂，为质子酸或者路易斯碱，用量为 B质量的 0.5%-5%, E:含氮原子的有机溶剂，用量为 B质量的 50% - 1000%, 反应步 4聚为：（ 1 ) 将反应物8、 C、 D和溶剂 E加入反应器，通入反应物 A使反应体系的压力保持在 3,000 Pa - 700,000 Pa, 在 0°C -90 °C挽拌下反应 0.5-8个小时；（ 2 ) 脱除溶剂得到多巯基化合物。进一步地，上述反应步骤（ 1 ) 中，反应体系中 A的压力保持在 6,000 PaUS Patent 4,092,293 discloses a reaction system consisting of hydrogen peroxide gas, polyfunctional propyl propyl ether, benzene or aliphatic solvent and azo catalyst, which is obtained by a free radical addition reaction to obtain a polyfluorene-based resin. Multi-mercapto resin, because of its high molecular weight, has a low odor. However, the synthesis conditions of the method are relatively harsh, and the pressure of the hydrogen sulfide gas required is relatively high (pressure is greater than 5.6×10 ⁵ Pa), which is dangerous. SUMMARY OF THE INVENTION The present invention is directed to the defects in the above method, and provides a molecule containing an ether bond, the main chain having a linear or branched structure, having at least two sulfhydryl groups in the molecule, and having no malodor. Multi-fluorenyl compound; at the same time, it provides a simple operation in the laboratory and is suitable for large-scale industrial production, and can ensure that the content of sulfhydryl in the product is adjustable, the average molecular weight is adjustable, the yield is high, and there is no foul smell. A method for synthesizing a polythiol compound. To this end, in one aspect of the invention, there is provided a process for the synthesis of a polyfluorenyl compound comprising a starting material: A: hydrogen sulfide gas, B: selected from compounds containing at least two (meth) acrylate functional groups, or at least a bifunctional polyfunctional epoxy compound; and a molar ratio of reactive functional groups in A to B is greater than 0.5; C: in an amount of 0% to 6% by mass of B, D: a catalyst, a protonic acid or a Lewis base, in an amount of B 0.5%-5% by mass, E: organic solvent containing nitrogen atom, the amount is 50% - 1000% of B mass, and the reaction step 4 is: (1) The reactants 8, C, D and solvent E are added to the reaction. Into the reactant A, the pressure of the reaction system was maintained at 3,000 Pa - 700,000 Pa, and the reaction was carried out at 0 ° C - 90 ° C for 0.5-8 hours; (2) The solvent was removed to obtain a polyfluorenyl compound. Further, in the above reaction step (1), the pressure of A in the reaction system is maintained at 6,000 Pa

-100,000 Pa , 在 5°C -25 °〇¾拌下反应 0.5-4个小时。进一步地，上述的反应物 A和 B的官能团的摩尔比为 0.8-10。进一步地，上述的含有至少两个（甲基）丙烯酸酯官能团的化合物选自含有二至六个（甲基）丙烯酸酯官能团的化合物中的一种或多种。进一步地，上述的环氧化合物为双酚 A型环氧 †脂、环烃型环氧 †脂、酚醛型环氧^"脂、环氧^ ^植物油、双缩水甘油醚、多缩水甘油醚中的一种或多种。进一步地，上述的质子酸为三氟醋酸、对甲苯磅酸、 4 酸、磷酸的一种或多种。进一步地，上述的路易斯碱为：有机胺及铵盐类、碱金属、碱土金属的氢氧^ ^物或氧 4 物中的一种或多种。进一步地，上述的有机溶剂 E, 既可以是含有氮原子的单一溶剂，也可以是一种或几种含有氮原子的溶剂与其他不含氮原子的溶剂组成的混合溶剂。进一步地，上述的含氮原子的有机溶剂为液体的酰胺、脲、吡咯烷酮中的一种。进一步地，上述的溶剂 E用量为反应物 B质量的 200%〜 800%。另一方面，本发明还提供了一种多琉基化合物，该多琉基化合物的分子主链为线性或支化结构且含有硫醚键，每个分子中至少含有两个琉基，化合物中石克元素的质量含量为 8% - 25%, 巟基含量为 0.1mmol/g - 6mmol/g, 合物的重均分子量 Mw为 800g/mol - 180,000g/mol„ 进一步地，上述多巯基化合物的重均分子量 Mw为 800g/mol - 20,000g/mol; 数均分子量 Mn为 400g/mol - 7,000g/mol。进一步地，上述多琉基化合物由上述的合成方法制备而成。本发明的有益效果：本发明所提供的多巯基化合物的合成方法，既能在实验室简易操作，又适合大规模工业化生产，并能保证产物中琉基含量可调、平均分子量可调、产率高。同时，由该多琉基化合物的合成方法所制备的多琉基化合物具有较高的分子量，故而无恶臭味。具体实施方式下列非限制性实施例用于说明本发明：有必要指出的是，以下的实施例只用于对本发明故进一步的说明，不能理解为对本发明保护范围的限制，所属领域技术熟悉人员才艮据上述发明内容，对本发明故出一些非本质的改进和调整，应仍属于本发明的保护范围。在含氮原子的有机溶剂中和碱或酸催化剂的作用下，硫化氢分子可与（甲基）丙烯酸酯中 c=c不饱和双键进行加成反应，疏化氢分子也可以和环氧化合物发生开环加成反应。申请人发现，如果用含有两个或两个以上（甲基）丙烯酸 (酯）官能团的化合物、或者多官能的环氧化合物为原料与化氢气体反应，在含氮有机溶剂中，并在酸或碱催化剂的作用下，即使硫化氢气体压强较低和反应时间较短，也能获得含有多巯基的化合物或树脂。与前述公开方法不同的是，一方面，我们使用含有两个或两个以上的可反应基团化合物为反应物，且-100,000 Pa, react at 0.5 ° C -25 ° 〇 3⁄4 for 0.5-4 hours. Further, the molar ratio of the functional groups of the above reactants A and B is from 0.8 to 10. Further, the above compound containing at least two (meth) acrylate functional groups is selected from one or more of compounds containing two to six (meth) acrylate functional groups. Further, the epoxy compound is a bisphenol A epoxy epoxide, a cyclic hydrocarbon epoxy resin, a phenolic epoxy resin, an epoxy resin, a diglycidyl ether, a polyglycidyl ether. Further, the above protonic acid is one or more of trifluoroacetic acid, p-toluic acid, tetraacid, and phosphoric acid. Further, the above Lewis base is: organic amine and ammonium salt Or one or more of an alkali metal, an alkaline earth metal hydroxide or an oxygen. Further, the above organic solvent E may be a single solvent containing a nitrogen atom, or may be one or several A mixed solvent of a solvent containing a nitrogen atom and another solvent containing no nitrogen atom. Further, the above-mentioned nitrogen atom-containing organic solvent is one of a liquid amide, urea, and pyrrolidone. Further, the solvent E is used in an amount of from 200% to 800% by mass of the reactant B. In another aspect, the present invention also provides a polyfluorenyl compound having a molecular main chain which is linear or branched and contains a thioether bond, and each molecule contains at least two fluorenyl groups. The mass content of the gram element is 8% - 25%, the sulfhydryl group content is 0.1 mmol / g - 6 mmol / g, and the weight average molecular weight Mw of the compound is 800 g / mol - 180,000 g / mol „ Further, the above polythiol compound The weight average molecular weight Mw is from 800 g/mol to 20,000 g/mol; and the number average molecular weight Mn is from 400 g/mol to 7,000 g/mol. Further, the above polythiol compound is prepared by the above synthesis method. The method for synthesizing the polyfluorenyl compound provided by the invention can be easily operated in the laboratory and is suitable for large-scale industrial production, and can ensure the sulfhydryl content in the product is adjustable, the average molecular weight is adjustable, and the yield is high. The polyfluorenyl compound prepared by the synthesis method of the polyfluorenyl compound has a relatively high molecular weight and thus has no malodor. DETAILED DESCRIPTION OF THE INVENTION The following non-limiting examples are illustrative of the invention: The following examples are only intended to further illustrate the present invention and are not to be construed as limiting the scope of the present invention. Those skilled in the art will be able to make some non-essential improvements and adjustments to the present invention. It should still fall within the scope of protection of the present invention. Under the action of a base or an acid catalyst in an organic solvent containing a nitrogen atom, the hydrogen sulfide molecule can undergo an addition reaction with a c=c unsaturated double bond in the (meth) acrylate. The hydrophobic hydrogen molecule can also undergo a ring-opening addition reaction with the epoxy compound. Applicants have found that if a compound containing two or more (meth)acrylic acid functional groups or a polyfunctional epoxy compound is used, The raw material reacts with the hydrogen-producing gas, and in the nitrogen-containing organic solvent, under the action of the acid or alkali catalyst, even if the hydrogen sulfide gas pressure is low and the reaction time is short, a compound or resin containing a polyfluorenyl group can be obtained. The disclosed method differs in that, on the one hand, we use a compound containing two or more reactive groups as a reactant, and

"可反应基团 "不仅包括（甲基）丙烯酸酯的 C=C不饱和双键，还包括前述公开方法中未提及的环氧基团；另一方面，我们不是釆用前述公开方法中的自由基反应的方法，而是釆用特定催化剂催化的亲核或者亲电加成反应。在本发明的一种典型实施方式中，一种多琉基化合物的合成方法，使用的原料包括： A: 硫化氢气体， B: 选自含有至少两个（甲基）丙烯酸酯官能团的化合物、或者至少两官能度的多环氧化合物；这种至少两官能度的多环氧化合物为至少含有两个环氧基团的多官能环氧化合物。且 A与 B的官能团的摩尔比大于 0.5; C: 硫磺，用量为 B质量的 0% -6%, D:催化剂，为质子酸或者路易斯碱，用量为 B质量的 0.5%-5%, E:含氮原子的有机溶剂，用量为 B质量的 50% - 1000%, 反应步 4聚为：（ 1 ) 将反应物 B、 C、 D和溶剂 E加入反应器，通入反应物 A使反应体系的压力保持在 3,000Pa- 700,000 Pa,在 0°C -90°C¾拌下反应 0.5-8 个小时；（2 ) 脱除溶剂得到多巯基化合物。由于在本发明中所釆用的化氢和多官能可反应性化合物的化学反应中，The "reactive group" includes not only the C=C unsaturated double bond of the (meth) acrylate, but also the epoxy group not mentioned in the above disclosed method; on the other hand, we are not using the above disclosed method The method of free radical reaction is a nucleophilic or electrophilic addition reaction catalyzed by a specific catalyst. In an exemplary embodiment of the present invention, a method for synthesizing a polyfluorenyl compound, the raw materials used include: A: hydrogen sulfide gas, B: selected from compounds containing at least two (meth) acrylate functional groups, Or at least a bifunctional polyepoxide; such at least bifunctional polyepoxide is a polyfunctional epoxy compound containing at least two epoxy groups. And the molar ratio of the functional groups of A and B is more than 0.5; C: sulfur, the amount is 0% -6% of B mass, D: catalyst, protonic acid or Lewis base, the amount is 0.5%-5% of B mass, E : an organic solvent containing a nitrogen atom in an amount of 50% to 1000% by mass of B, and the reaction step 4 is: (1) the reactants B, C, D and solvent E are fed to the reactor, and the reactant A is introduced to cause a reaction. The pressure of the system is maintained at 3,000 Pa to 700,000 Pa, and the reaction is carried out at 0 ° C - 90 ° C 3⁄4 for 0.5-8 hours; (2) The solvent is removed to obtain a polyfluorenyl compound. Due to the chemical reaction between the hydrogen and the polyfunctionally reactive compound used in the present invention,

H₂S无论与（甲基）丙烯酸酯中的 C=C不饱和双键、或者与环氧基团进行反应，第一步都将产生琉基，而生成的琉基与 c=c不饱和双键或者与环氧基团反应的活性不小于 H₂S的活性，如果 H₂S的投入量太少，第一步所生成的琉基将与可反应性官能团进一步反应，生成硫醚，使产物的分子量变大。如果 H₂S的投入量足够，巯基与可反应性官能团反应就可能被部分抑制，产物中的醚结构将很少， -SH基团得以保留，产物中琉基含量高。但如果 H₂S的投入量过大，硫醚结构可能少，产物的分子量不高，而且过量的 H₂S需要回收。控制硫化氢气体和多官能可反应性化合物的摩尔比可以调控硫醚结构和 -SH基团的含量，并调控产物的分子量。因此作为优选：硫化氢分子的摩尔数与多官能化合物的反应官能团的摩尔数的比值，简称为 A与 B的官能团的摩尔比，为 0.8-10。作为优选：上述的含有至少两个（甲基）丙烯酸酯的化合物选自二至六个 (甲基）丙烯酸酯官能团的化合物中的一种或多种，具体可为①二官能度的（甲基）丙烯酸酯类：例如， 1, 6-己二醇双（甲基）丙烯酸酯， 1, 4-丁二醇二丙烯酸酯，新戊二醇二丙烯酸酯，邻苯二甲酸乙二醇二丙烯酸酯，二缩丙二醇双丙婦酸酯，三缩丙二醇双丙烯酸酯，二缩乙二醇双（甲基）丙婦酸酯，三缩乙二醇双（甲基）丙婦酸酯，甘油双丙烯酸酯，二甘醇双丙烯酸酯，三甘醇双丙烯酸酯，四甘醇双丙婦酸酯，乙二醇双丙烯酸酯， 1,3-丙二醇双（甲基）丙烯酸酯，乙氧化双酚 A双（甲基）丙烯酸酯，聚乙二醇双（甲基）丙烯酸酯，新戊二醇二乙氧基双丙烯酸酯，新戊二醇二丙氧基双丙烯酸酯； ②三官能度的（甲基）丙烯酸酯类：三羟甲基丙烷三（甲基）丙烯酸酯，季戊四醇三丙烯酸酯，乙氧基化的三羟甲基丙烷三丙烯酸酯，乙氧基化的季戊四醇四丙烯酸酯，甘油三丙烯酸酯，丙氧基化的甘油三丙烯酸酯，三（2-羟乙基）异氰酸酯三丙烯酸酯，丙氧基化的三羟甲基丙烷三丙烯酸酯； ③四官能度以及更高官能度的（甲基）丙烯酸酯类：季戊四醇四丙烯酸酯，丙氧基化的季戊四醇四丙烯酸酯；二缩三羟甲基丙烷四丙烯酸酯，二季戊四醇五丙烯酸酯，二季戊四醇六丙烯酸酯； 4 二至四官能的环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂。作为优选：上述的环氧化合物为双酚 A型环氧树脂、环烃型环氧树脂、酚醛型环氧^"脂、环氧^ ^植物油、双缩水甘油醚、多缩水甘油醚中的一种或多种。作为优选：上述的质子酸为三氟醋酸、对甲苯磅酸、 4 酸、磷酸的一种或多种。作为优选：上述的路易斯碱为有机胺及铵盐类、碱金属、碱土金属的氢氧化物或氧化物中的一种或多种。质子酸或路易斯碱作为催化剂的原理是：它们引起 H-S键或不饱和官能团 (双键或环氧基 ) 的电荷分布不均匀，从而促进加成反应以亲核或者亲电加成的方式进行。作为优选：上述的有机溶剂 E, 既可以是含氮原子的单一溶剂，也可以是一种或几种含氮原子的溶剂与其他不含氮原子的溶剂组成的混合溶剂。作为优选：合成中所用的含氮原子的有机溶剂 E, 包括但不限于： 1 )酰胺类，如甲酰胺，乙酰胺， Ν,Ν-二甲基甲酰胺， Ν,Ν-二乙基甲酰胺， Ν,Ν-二甲基乙酰胺， Ν,Ν-二乙基乙酰胺等； 2 )脲类，如 Ν,Ν-二甲基五环脲，四甲基脲等。 3 ) 吡咯烷酮类，如 Ν-甲基 -2-吡咯烷酮， Ν-乙基吡咯烷酮等；作为优选：上述的溶剂 Ε用量为反应物 Β质量的 200%〜 800%。作为主要反应物之一的硫化氢气体 A , 既可以在实验室现场制备，经千燥后使用，也可以直接使用千燥的工业^■化氢气体；对前一种方法，可以通过控制石克化氢的发生量控制化氢的用量，对后一种方法，可以通过控制^■化氢的通入量控制^ ¾化氢的加入量，且反应体系中^ ¾化氢气体的压强为 3,000 Pa 〜 700,000 Pa。优选地，将疏化氢气体压力控制在 6,000 Pa -100,000 Pa, 利用上述催化剂、在 5 °C -25 °C温度下反应 0.5-4个小时完成反应，得到的多琉基化合物分子量分布相对集中，流动性好，琉基含量高，特别适合作为环氧树脂等的固化剂。合成反应中可以使用硫磺，但硫橫并不是该合成反应中的必需条件，其用量为含可反应基团化合物质量的 0%〜 6%。我们的研究表明，硫磺可与含氮溶剂形成倍增效应，从而使疏化氢与 C=C双键的加成反应速度加快，产物中的疏醚键减少。反应时，先将可反应基团的化合物 B、硫磺 C、催化剂 D和溶剂加到反应器中，然后通入硫化氢气体。如果需要仔细控制反应，也可以将 B以外的液体和固体原料先加入反应器，在通入硫化氢气体时逐步加入可反应基团化合物 B。在搅拌下反应 0.5〜8个小时，反应温度为 0°C 〜90°C。反应完成后，脱除溶剂得到透明的黏稠性产物即为多琉基化合物。反应所用反应器既可以是实验室用普通玻璃烧瓶，使用电磁搅拌，也可以是工业反应釜，体系的压力为 3,000 Pa〜 700,000 Pa, 使用机才成挽拌；反应温度为 0°C 〜90°C , 可通过冰水浴，水浴或加热浴来实现反应温度的控制。优选地，反应条件为，体系的压力 6,000Pa- 100,000Pa, 在 5 °C -25°C温度下反应 0.5-4 个小时。本发明提供的制备方法制备条件温和，既可以在实验室条件制备，又适合大规模工业化生产，琉基含量可调、平均分子量可调、产率高且没有特别恶臭味。在本发明的一种典型的实施方式中，还提供了一种多琉基化合物，该多巯基化合物由上述多琉基化合物的合成方法制备而成。该多琉基化合物，分子主链为线性或支化结构，且含有硫醚键，每个分子中至少含有两个巯基，化合物中石克元素的质量含量为 8% - 25%, 巟基含量为 0.1mmol/g - 6mmol/g, 4匕合物的重均分子量 M_w为 800g/mol - 180,000g/mol。对于大分子化合物或树脂而言，其分子大小不是单一的，而是由不同分子量的分子组成的混合物，分子量分布比较宽，通常重均分子量 M_w和数均分子量 ^^的比值，即分子量分布指数，可以达到 2 以上，本发明多琉基化合物的重均分子量 Mw为 800g/mol - 180,000g/mol。对于琉基混合物而言，化合物的气味和它的分子量大小有关，分子量大，挥发性就小，气味就小，反之，其分子量越小，琉基混合物的气味越大，特别是仅含几个碳原子的脂肪族硫醇，通常有强烈的恶臭。但是，也并非分子量越大越好，分子量过大，树脂的流动性就越小，不利于应用。考虑到应用需要，优选分子量范围： Mw为 800g/mol - 50,000g/mol, Mn 400g/mol - 7,000g/mol。以下将结合具体实施例 1-44进一步说明本发明的有益效果。合成的多巯基化合物其结构表征包括： H^NMR或化学滴定方法测定琉基含量；硫元素的质量含量釆用元素分析测定；数均分子量 M_n和重均分子量 ^^使用凝胶色谱分析（GPC ) 测定。代表实施例使用的原料及其简称如下： 1, 6-己二醇双丙烯酸酯（HDDA ) ；三缩丙二醇双丙烯酸酯（TPGDA ) ；二缩丙二醇双丙烯酸酯（DPGDA ) ；三羟甲基丙烷三丙烯酸酯（TMPTA ) ；季戊四醇四丙烯酸酯（PETTA ) ；二季戊四醇五丙烯酸酯（DPPA ) ；二季戊四醇六丙烯酸酯（DPHA ) ；臉醛型环氧于脂 F-44; 脂环型环氧 †脂（TDE-85 ) ；环氧脂 E-51 ; 乙二醇二缩水甘油醚；三乙胺（ Et₃N )；四丁基溴化胺；氢氧化钠（ NaOH )；盐酸（ HC1, 38wt% )；磷酸（ H₃PO₄, 85wt% )；三氟醋酸（ F₃CCOOH )；对羟基苯磺酸 ( HO-Ph-SO₃H )；阳离子交换树脂（001X7 ) ；阴离子交换树脂（201X4 ) ；四氢呋喃（THF ) ； Ν,Ν-二甲基甲酰胺 ( DMF ) ； Ν-甲基 -2-吡咯烷酮（ ΝΜΡ ) ； Ν,Ν-二甲基五环脲 ( DMEU ) ；疏磺（ S ) 。实施例 1——三官能丙烯酸酯与现场生成的 H₂S反应制备多巯基化合物在 500ml的三口烧瓶中，加入 DMF 120g, S 1.2g及 Et₃N 1.8g, 电磁挽拌形成暗红色溶液；将化学法生成的^ ^化氢气体从溶液底部通入到体系中；待体系中空气被排出后，保持体系具 1 X 10⁴ Pa 的恒压，使用定量泵緩慢加入 60g TMPTA。 TMPTA滴加完毕后，继续通入^ ¾化氢，在挽拌下维持反应 8小时，得深红色透明溶液。在 80 °C下减压蒸^ ¾脱出大部分溶剂，得无色无味透明略带粘稠产物。产物重均分子量 M_w为 3 X 10³ g/mol , 4元素含量为 18% , 巯基含量为 3.5mmol/g„ 实施^ ί列 2 ~ 实施^ ί列 16 操作方法与实施例 1相同，反应物的用量、反应条件及产物特征见表- 1。表 -1 Whether H ₂ S reacts with a C=C unsaturated double bond in a (meth) acrylate or with an epoxy group, the first step will produce a thiol group, and the resulting thiol group and c=c are unsaturated. a double bond or the active groups reactive with an epoxy group is not less than the activity of H ₂ S, if the input amount of H ₂ S is too small, the first step in the generated further reacted with the thiol reactive functional group may be, thioether, The molecular weight of the product is made larger. If the amount of H ₂ S is sufficient, the reaction of the thiol group with the reactive functional group may be partially inhibited, the ether structure in the product will be small, the -SH group will be retained, and the thiol content in the product will be high. However, if the input amount of H ₂ S is too large, the structure of the thioether may be small, the molecular weight of the product is not high, and excess H ₂ S needs to be recovered. Controlling the molar ratio of hydrogen sulfide gas to the polyfunctionally reactive compound can modulate the thioether structure and the -SH group content and modulate the molecular weight of the product. Therefore, it is preferable that the ratio of the number of moles of hydrogen sulfide molecules to the number of moles of reactive functional groups of the polyfunctional compound, abbreviated as a molar ratio of functional groups of A and B, is from 0.8 to 10. Preferably, the above compound containing at least two (meth) acrylates is one or more selected from the group consisting of two to six (meth) acrylate functional compounds, specifically one difunctional (A) Acrylates: for example, 1,6-hexanediol bis(meth) acrylate, 1, 4-butanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol phthalate Acrylate, dipropylene glycol dipropionate, tripropylene glycol diacrylate, diethylene glycol bis(methyl) propionate, triethylene glycol bis(methyl) propionate, glycerin Diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol dipropionate, ethylene glycol diacrylate, 1,3-propanediol bis(meth) acrylate, ethoxylated double Phenol A bis(meth) acrylate, polyethylene glycol bis(meth) acrylate, neopentyl glycol diethoxy diacrylate, neopentyl glycol dipropoxy bisacrylate; 2 trifunctional (meth) acrylates: trimethylolpropane tris(methyl) propyl , Pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, glycerol Triacrylate, propoxylated triglyceride, tris(2-hydroxyethyl)isocyanate triacrylate, propoxylated trimethylolpropane triacrylate; 3 tetrafunctional and higher functionality (meth) acrylates: pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate; trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate; Tetrafunctional epoxy acrylic resin, urethane acrylic resin, polyester acrylic resin. Preferably, the epoxy compound is one of a bisphenol A epoxy resin, a cyclic hydrocarbon epoxy resin, a phenolic epoxy resin, an epoxy resin oil, a diglycidyl ether, and a polyglycidyl ether. Preferably, the protonic acid is one or more of trifluoroacetic acid, p-toluic acid, tetraacid, and phosphoric acid. Preferably, the Lewis base is an organic amine and an ammonium salt, and an alkali metal. One or more of hydroxides or oxides of alkaline earth metals. The principle of protonic acid or Lewis base as a catalyst is: they cause uneven charge distribution of HS bonds or unsaturated functional groups (double bonds or epoxy groups) Thereby, the addition reaction is promoted in a nucleophilic or electrophilic addition manner. Preferably, the above organic solvent E may be a single solvent containing a nitrogen atom or a solvent containing one or more nitrogen atoms. A mixed solvent with other solvents containing no nitrogen atom. Preferred: The organic solvent E containing a nitrogen atom used in the synthesis includes, but is not limited to: 1) amides such as formamide, acetamide, hydrazine, hydrazine-II A Carboxamide, hydrazine, hydrazine-diethylformamide, hydrazine, hydrazine-dimethylacetamide, hydrazine, hydrazine-diethylacetamide, etc.; 2) ureas such as hydrazine, hydrazine-dimethyl pentacycle Urea, tetramethylurea, etc. 3) Pyrrolidone, such as Ν-methyl-2-pyrrolidone, Ν-ethylpyrrolidone, etc.; preferably: The above solvent hydrazine is used in an amount of from 200% to 800% by mass of the reactant hydrazine. Hydrogen sulfide gas A, which is one of the main reactants, can be prepared on site in the laboratory. It can be used after drying, or it can directly use the dry industrial hydrogen gas. For the former method, it can be controlled by stone. The amount of hydrogen generated is used to control the amount of hydrogen. For the latter method, the amount of hydrogen added can be controlled by controlling the amount of hydrogen introduced, and the pressure of the hydrogen gas in the reaction system is 3,000 Pa to 700,000 Pa. Preferably, the pressure of the hydrogenated hydrogen gas is controlled to be 6,000 Pa - 100,000 Pa, and the reaction is carried out by using the above catalyst at a temperature of 5 ° C -25 ° C for 0.5-4 hours to obtain a polyhydrazine. The molecular weight distribution of the base compound is relatively concentrated, the fluidity is good, and the sulfhydryl content is high, especially Cooperation epoxy resin curing agent. Sulfur may be used in the synthesis reaction, but the sulfur cross-section is not an essential condition in the synthesis reaction, and is used in an amount of from 0% to 6% by mass of the reactive group-containing compound. Our research shows that sulfur can form a multiplying effect with a nitrogen-containing solvent, thereby increasing the rate of addition of hydrogenated hydrogen to the C=C double bond and reducing the ether linkage in the product. In the reaction, the reactive group-containing compound B, sulfur C, catalyst D and solvent are first introduced into the reactor, and then hydrogen sulfide gas is introduced. If it is necessary to carefully control the reaction, it is also possible to add the liquid and solid raw materials other than B to the reactor first, and gradually add the reactive group compound B when hydrogen sulfide gas is introduced. The reaction is carried out for 0.5 to 8 hours with stirring, and the reaction temperature is from 0 ° C to 90 ° C. After the reaction is completed, the solvent is removed to obtain a transparent viscous product which is a polythiol compound. The reactor used for the reaction can be a common glass flask for laboratory use, electromagnetic stirring or industrial reactor. The pressure of the system is 3,000 Pa~ 700,000 Pa, and the machine is mixed; the reaction temperature is 0 ° C ~ 90 °C, the temperature of the reaction can be controlled by an ice water bath, a water bath or a heating bath. Preferably, the reaction conditions are such that the pressure of the system is from 6,000 Pa to 100,000 Pa, and the reaction is carried out at a temperature of from 5 ° C to 25 ° C for 0.5 to 4 hours. The preparation method provided by the invention has mild preparation conditions, can be prepared in laboratory conditions, and is suitable for large-scale industrial production, has adjustable sulfhydryl content, adjustable average molecular weight, high yield and no special malodor. In an exemplary embodiment of the present invention, there is further provided a polyfluorenyl compound prepared by the above synthesis method of a polyfluorenyl compound. The polyfluorenyl compound has a linear or branched structure and contains a thioether bond, and each molecule contains at least two fluorenyl groups. The mass of the gram element in the compound is 8% to 25%, and the thiol content is The weight average molecular weight M _w of 0.1 mmol/g - 6 mmol/g, 4 conjugate is from 800 g/mol to 180,000 g/mol. For macromolecular compounds or resins, the molecular size is not single, but a mixture of molecules of different molecular weights, the molecular weight distribution is relatively wide, usually the ratio of the weight average molecular weight M _w and the number average molecular weight ^ ^ , that is, the molecular weight distribution The index may be 2 or more, and the weight average molecular weight Mw of the polyfluorenyl compound of the invention is from 800 g/mol to 180,000 g/mol. For a thiol mixture, the odor of the compound is related to its molecular weight, the molecular weight is large, the volatility is small, and the odor is small. On the contrary, the smaller the molecular weight, the greater the odor of the thiol mixture, especially only a few A fatty thiol of a carbon atom usually has a strong malodor. However, the larger the molecular weight, the better, the molecular weight is too large, and the fluidity of the resin is smaller, which is disadvantageous for application. The molecular weight range is preferably selected in view of application requirements: Mw is from 800 g/mol to 50,000 g/mol, and Mn is from 400 g/mol to 7,000 g/mol. Advantageous effects of the present invention will be further described below in conjunction with Specific Embodiments 1-44. Multi-mercapto compound characterized by the structure comprising the synthesis: H ^ NMR or chemical titration method for measuring thiol content; mass preclude the use of elemental sulfur content determined by elemental analysis; number average molecular weight M _n and the weight average molecular weight ^^ gel chromatography using ( GPC) determination. The starting materials used in the examples and their abbreviations are as follows: 1, 6-hexanediol diacrylate (HDDA); tripropylene glycol diacrylate (TPGDA); dipropylene glycol diacrylate (DPGDA); trimethylolpropane Triacrylate (TMPTA); pentaerythritol tetraacrylate (PETTA); dipentaerythritol pentaacrylate (DPPA); dipentaerythritol hexaacrylate (DPHA); aldehyde-based epoxy ester F-44; alicyclic epoxy oxime lipid (TDE-85); aliphatic epoxy E-51; glycol diglycidyl ether; triethylamine (Et ₃ N); tetrabutylammonium bromide; sodium hydroxide (of NaOH); hydrochloric acid (HC1, 38wt Phosphoric acid (H ₃ PO ₄ , 85wt%); trifluoroacetic acid (F ₃ CCOOH ); p-hydroxybenzenesulfonic acid ( HO-Ph-SO ₃ H ); cation exchange resin (001X7); anion exchange resin (201X4) Tetrahydrofuran (THF); hydrazine, hydrazine-dimethylformamide (DMF); hydrazine-methyl-2-pyrrolidone (ΝΜΡ); hydrazine, hydrazine-dimethylpentacyclic urea (DMEU); ). Example 1 - Trifunctional acrylate was reacted with H ₂ S in situ to prepare a polyfluorenyl compound. In a 500 ml three-necked flask, DMF 120 g, S 1.2 g and Et ₃ N 1.8 g were added, and the mixture was electromagnetically mixed to form a dark red solution; The chemically generated hydrogen gas is introduced into the system from the bottom of the solution; after the air in the system is discharged, the system is maintained at a constant pressure of 1 X 10 ⁴ Pa, and 60 g of TMPTA is slowly added using a metering pump. After the completion of the TMPTA addition, the hydrogenation was continued, and the reaction was maintained for 8 hours while stirring to obtain a dark red transparent solution. The solvent was distilled off under reduced pressure at 80 ° C to remove most of the solvent to give a colorless, odorless, transparent, slightly viscous product. The weight average molecular weight M _w of the product is 3 X 10 ³ g/mol, the content of 4 elements is 18%, and the content of sulfhydryl group is 3.5 mmol/g. 实施列篇 2 实施实施 16 16 Operation method is the same as in Example 1, the reaction The amount of the materials, the reaction conditions and the characteristics of the products are shown in Table - 1. Table-1

mmo g Mmo g

实施例 17 ~ 实施例 28 多官能丙蟑酸酯以及环氧化合物与 H₂S反应制备多 u基化合物操作方法与实施例 1相同，反应物的名称、用量、反应条件及产物的表征见表 -2。表 -2 Example 17 - Example 28 Polyfunctional propionate and epoxy compound were reacted with H ₂ S to prepare a poly-u-based compound. The operation method was the same as in Example 1. The name, amount, reaction conditions and product characterization of the reactants are shown in the table. -2. Table 2

实施例 29 工业 H₂S气体和压力釜制备多巯基化合物 450g NMP, 300g THF, 300g TMPTA, 9.0g Et₃N及 6.0g石克磺依次力口入到体积为 10L的反应釜中，搅拌均匀后，调节进气阀压强至 l.OxlO⁵ Pa, 通入千燥的^■化氢气体到溶液中，室温（25 V ) 反应 4 小时，得深红色透明溶液。夺深红色透明溶液抽滤一次，在 80 °C下减压蒸^ ¾ 5小时，得无色无味透明略带粘稠产物。经测定，产物数重均分子量 M_w为 1.3xl0⁵ g/mol, 疏元素含量为 14%, 巟基含量为 1.0mmol/g。实施列 30 ~ 实施列 36 操作方法与实施例 29相同，反应物的名称、用量、反应条件及产物的特征见表 -3。表 -3 Example 29 Industrial H ₂ S gas and autoclave preparation of polyfluorenyl compound 450 g NMP, 300 g THF, 300 g TMPTA, 9.0 g Et ₃ N and 6.0 g of stone sulfonate were sequentially introduced into a reactor having a volume of 10 L, and stirred uniformly. After that, adjust the pressure of the intake valve to l.OxlO ⁵ Pa, pass the dry hydrogen gas into the solution, and react at room temperature (25 V) for 4 hours to obtain a deep red transparent solution. The dark red transparent solution was suction filtered once, and steamed under reduced pressure at 80 ° C for 3⁄4 5 hours to obtain a colorless, odorless, transparent, slightly viscous product. The product had a weight average molecular weight M _w of 1.3 x ^{10 5} g/mol, an elemental content of 14%, and a mercapto group content of 1.0 mmol/g. The operation method of the column 30 to the embodiment 36 is the same as that of the embodiment 29, and the names, amounts, reaction conditions and characteristics of the products are shown in Table-3. table 3

mmo g Mmo g

实施例 37〜 44 操作方法与实施例 29相同，反应物的名称、用量、反应条件及产物的特征见表 -4。表 -4 Examples 37 to 44 The operation method was the same as in Example 29, and the names, amounts, reaction conditions and characteristics of the reactants are shown in Table -4. Table 4

表 -4中实施例 37〜 44的数据表明，在优选的反应条件下，反应可控性好，制备的多巯基化合物巯基含量高。多琉基化合物的特性从实施例 1-44中制备的多琉基化合物中选择 4个不同琉基含量的液态树脂作了特性评价试验。表 5列出了这 4个多琉基化合物的特性。表 5中琉基树脂编号是树脂制备实施例的编号；气味是以十二烷基硫醇的刺激性气味标度为 10 为基准，若样品的气味相当于将十二烷基硫醇稀释到 1/5 , 则气味为 2级，若相当于稀释到 2/5 , 则气味为 4级，以 jt匕类 4舞；化学活性是指固化环氧树脂的凝胶时间，进行环氧树脂固化试验的条件是： E51/多琉基树脂（环氧基团 /巯基， mol 比） = 1/0.8、催化剂 1,8-二氮杂环 [5,4,0]-十一烯（DBU ) , 0.3 Wt%, 试验温度 5 °C。琉基树脂作为固化剂，需要每个分子含有两个以上的巯基才能是环氧树脂固化。环氧树脂凝胶试验也检验巯基树脂固化剂是否含有两个以上的巯基。表 5. 多琉基化合物的特性

The data of Examples 37 to 44 in Table-4 show that under the preferred reaction conditions, the reaction is controllable and the prepared polythiol compound has a high thiol content. Characteristics of Polythiol Compounds Four different sulfhydryl content liquid resins were selected from the polyfluorenyl compounds prepared in Examples 1-44 for the property evaluation test. Table 5 lists the characteristics of these four polythiol compounds. The sulfhydryl resin number in Table 5 is the number of the resin preparation example; the odor is based on the stimulating odor scale of dodecyl mercaptan of 10, if the odor of the sample is equivalent to diluting the dodecyl mercaptan to 1/5, the scent is level 2, if it is equivalent to dilute to 2/5, the scent is level 4, and the dance is performed by jt ; class 4; chemical activity refers to the gel time of curing epoxy resin, curing epoxy resin The conditions tested were: E51/polynonyl resin (epoxy group/mercapto group, mol ratio) = 1/0.8, catalyst 1,8-diazacyclo[5,4,0]-undecene (DBU) , 0.3 Wt%, test temperature 5 °C. As a curing agent, a ruthenium-based resin requires two or more mercapto groups per molecule to cure the epoxy resin. The epoxy resin gel test also examined whether the ruthenium-based resin curing agent contained two or more sulfhydryl groups. Table 5. Characteristics of polythiol compounds

巯基树脂编号外观琉基含量 mmol/g 气味；疑胶时间 /min 巯Base resin number Appearance 琉 base content mmol/g odor; suspected glue time /min

1 粘稠，可流动 3.5 2 201 viscous, flowable 3.5 2 20

16 粘性液体 2.1 4 716 viscous liquid 2.1 4 7

39 粘性液体 3 4 539 viscous liquid 3 4 5

42 粘性液体 6.5 3 3 由表 5中数据表明，本发明方法合成的树脂气味小，含有两个以上的巯基, 化学活性高。 42 Viscous liquid 6.5 3 3 The data in Table 5 shows that the resin synthesized by the method of the present invention has a small odor and contains two or more sulfhydryl groups, and has high chemical activity.

Claims

权利要求书 Claims

1. 多琉基化合物的合成方法，其特征在于： A method for synthesizing a polythiol compound, which is characterized by:

合成所述多巯基化合物用到的原料包括： The raw materials used in the synthesis of the polyfluorenyl compound include:

A: 硫化氢气体， A: hydrogen sulfide gas,

B: 选自含有至少两个（甲基）丙烯酸酯官能团的化合物、或者至少两官能度的多环氧化合物； B: selected from a compound containing at least two (meth) acrylate functional groups, or a polyfunctional epoxy compound having at least two functionalities;

且 A与 B中反应官能团的摩尔比大于 0.5; And the molar ratio of reactive functional groups in A and B is greater than 0.5;

C: ^^黄，用量为 B质量的 0% -6%, C: ^^Yellow, the dosage is 0% -6% of B mass,

D:催化剂，为质子酸或者路易斯碱，用量为 B质量的 0.5%-5%, E:含氮原子的有机溶剂，用量为 B质量的 50% - 1000%, 反应步骤为： D: a catalyst, which is a protonic acid or a Lewis base, in an amount of 0.5% to 5% by mass of B, and an organic solvent containing a nitrogen atom in an amount of 50% to 1000% by mass of B. The reaction steps are:

( 1 )将反应物 B、 C、 D和溶剂 E加入反应器，通入反应物 A使反应体系的压力保持在 3,000 Pa - 700,000 Pa, 在 0°C -90°〇¾拌下反应 0.5-8个小时； (1) The reactants B, C, D and solvent E are fed to the reactor, and the reactant A is introduced to maintain the pressure of the reaction system at 3,000 Pa - 700,000 Pa, and the reaction is stirred at 0 ° C - 90 ° 〇 3⁄4. 8 hours;

( 2 ) 脱除溶剂得到多琉基化合物。 (2) The solvent is removed to obtain a polyfluorenyl compound.

2. 根据权利要求 1所述的多琉基化合物的合成方法，其特征在于：所述反应步骤（ 1 )中，反应体系中 A的压力在 6,000 Pa -100,000 Pa, 在 5 °C-25 °C搅拌下反应 0.5-4个小时。 The method for synthesizing a polyfluorenyl compound according to claim 1, wherein in the reaction step (1), the pressure of A in the reaction system is 6,000 Pa - 100,000 Pa at 5 ° C - 25 ° C is stirred for 0.5-4 hours.

3. 根据权利要求 1所述的多巯基化合物的合成方法，其特征在于：所述的反应物 A和 B的官能团的摩尔比为 0.8-10。 The method for synthesizing a polyfluorenyl compound according to claim 1, wherein the molar ratio of the functional groups of the reactants A and B is from 0.8 to 10.

4. 根据权利要求 1所述的多琉基化合物的合成方法，其特征在于：所述的含有至少两个（甲基）丙烯酸酯官能团的化合物选自含有二至六个（甲基）丙烯酸酯官能团的化合物中的一种或多种。根据权利要求 1所述的多琉基化合物的合成方法，其特征在于：所述的环氧化合物为双酚 A型环氧脂、环烃型环氧脂、酚醛型环氧于脂、环氧^ ^植物油、双缩水甘油醚、多缩水甘油醚中的一种或多种。 The method for synthesizing a polyfluorenyl compound according to claim 1, wherein the compound containing at least two (meth) acrylate functional groups is selected from the group consisting of two to six (meth) acrylates. One or more of the functional group compounds. The method for synthesizing a polyfluorenyl compound according to claim 1, wherein the epoxy compound is bisphenol A epoxy resin, cyclic hydrocarbon epoxy resin, phenolic epoxy resin, epoxy resin. ^ ^ One or more of vegetable oil, diglycidyl ether, polyglycidyl ether.

6. 根据权利要求 1所述的多琉基化合物的合成方法，其特征在于：所述的质子酸为三氟醋酸、对甲苯磅酸、酸、磷酸中的一种或多种。 The method for synthesizing a polyfluorenyl compound according to claim 1, wherein the protic acid is one or more of trifluoroacetic acid, p-toluic acid, acid, and phosphoric acid.

7. 根据权利要求 1所述的多琉基化合物的合成方法，其特征在于：所述的路易斯碱为：有机胺及铵盐类、碱金属、碱土金属的氢氧化物或氧化物中的一种或多种。 The method for synthesizing a polyfluorenyl compound according to claim 1, wherein the Lewis base is: one of an organic amine and an ammonium salt, an alkali metal, an alkaline earth metal hydroxide or an oxide. Kind or more.

8. 根据权利要求 1所述的多琉基化合物的合成方法，其特征在于：所述的有机溶剂 E, 是含有氮原子的单一溶剂，或者是一种或几种含有氮原子的溶剂与其他不含氮原子的溶剂组成的混合溶剂。 The method for synthesizing a polyfluorenyl compound according to claim 1, wherein the organic solvent E is a single solvent containing a nitrogen atom, or one or more solvents containing a nitrogen atom and the like. A mixed solvent composed of a solvent containing no nitrogen atom.

9. 根据权利要求 8所述的多琉基化合物的合成方法，其特征在于：所述的含氮原子的有机溶剂为液体的酰胺、脲、吡咯烷酮中的一种。 The method for synthesizing a polyfluorenyl compound according to claim 8, wherein the nitrogen atom-containing organic solvent is one of a liquid amide, urea, and pyrrolidone.

10. 根据权利要求 9所述的多巯基化合物的合成方法，其特征在于：所述的溶剂 E用量为反应物 B质量的 200%〜 800%。 The method for synthesizing a polyfluorenyl compound according to claim 9, wherein the solvent E is used in an amount of from 200% to 800% by mass of the reactant B.

11. 多琉基化合物，其特征在于：该多琉基化合物的分子主链为线性或支化结构且含有醚键，每个分子中至少含有两个巯基，化合物中^■元素的质量含量为 8% - 25%, 巟基含量为 0.1mmol/g - 6mmol/g, 合物的重均分子量 Mw为 800g/mol - 180,000g/mol„ 11. A polyfluorenyl compound, characterized in that: the molecular chain of the polyfluorenyl compound is linear or branched and contains an ether bond, and each molecule contains at least two sulfhydryl groups, and the mass of the compound in the compound is 8% - 25%, thiol content of 0.1mmol / g - 6mmol / g, the weight average molecular weight Mw of the compound is 800g / mol - 180,000g / mol „

12. 才艮据权利要求 11所述的多巯基化合物，其特征在于：所述多巯基化合物的重均分子量 Mw为 800g/mol - 20,000g/mol;数均分子量 Mn为 400g/mol — 7,000g/mol。 12. The polyfluorenyl compound according to claim 11, wherein the polyfluorenyl compound has a weight average molecular weight Mw of from 800 g/mol to 20,000 g/mol; and the number average molecular weight Mn is from 400 g/mol to 7,000 g. /mol.

13. 根据权利要求 11或 12所述的多巯基化合物，其特征在于：由权利要求 1-10中任一项所述的合成方法制备而成。 The polyfluorenyl compound according to claim 11 or 12, which is produced by the synthesis method according to any one of claims 1 to 10.