WO2011144015A1 - 一种多巯基化合物及其合成方法 - Google Patents
一种多巯基化合物及其合成方法 Download PDFInfo
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- WO2011144015A1 WO2011144015A1 PCT/CN2011/074170 CN2011074170W WO2011144015A1 WO 2011144015 A1 WO2011144015 A1 WO 2011144015A1 CN 2011074170 W CN2011074170 W CN 2011074170W WO 2011144015 A1 WO2011144015 A1 WO 2011144015A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
- C08G59/1411—Polycondensates modified by chemical after-treatment with inorganic compounds containing sulfur
- C08G59/1416—Hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the present invention relates to a compound containing a polyfluorenyl group and a method for synthesizing the polyfluorenyl compound.
- 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.
- 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).
- 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.
- US 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.
- 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.
- 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 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.
- 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
- 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.
- 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.
- the above protonic acid is one or more of trifluoroacetic acid, p-toluic acid, tetraacid, and phosphoric acid.
- 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.
- 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.
- the above-mentioned nitrogen atom-containing organic solvent is one of a liquid amide, urea, and pyrrolidone.
- the solvent E is used in an amount of from 200% to 800% by mass of the reactant B.
- 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
- the weight average molecular weight Mw of the compound is 800 g / mol - 180,000 g / mol
- 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.
- 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.
- the hydrophobic hydrogen molecule can also undergo a ring-opening addition reaction with the epoxy compound.
- the method of free radical reaction is a nucleophilic or electrophilic addition reaction catalyzed by a specific catalyst.
- 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.
- 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,
- 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.
- 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.
- 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.
- the ratio of the number of moles of hydrogen sulfide molecules to the number of moles of reactive functional groups of the polyfunctional compound is from 0.8 to 10.
- 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, poly
- 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.
- the protonic acid is one or more of trifluoroacetic acid, p-toluic acid, tetraacid, and phosphoric acid.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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 (
- Example 1 - Trifunctional acrylate was reacted with H 2 S in situ to prepare a polyfluorenyl compound.
- 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.
- Example 17 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
- 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
- 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
- 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
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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。
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 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
"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,
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 Mw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 Mw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 Mn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 Mw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
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
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 Mw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
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
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
巯基树脂编号 外观 琉基含量 mmol/g 气味 ;疑胶时间 /min
1 粘稠, 可流动 3.5 2 20
16 粘性液体 2.1 4 7
39 粘性液体 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。
Claims
权 利 要 求 书
1. 多琉基化合物的合成方法, 其特征在于:
合成所述多巯基化合物用到的原料包括:
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;
且 A与 B中反应官能团的摩尔比大于 0.5;
C: ^^黄, 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%, 反应步骤为:
( 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 3,000 Pa - 700,000 Pa, 在 0°C -90°〇¾拌下反应 0.5-8个小时;
( 2 ) 脱除溶剂得到多琉基化合物。
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。
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。
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。
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。
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。
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。
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。
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%。
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„
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。
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。
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