CN102936305A - Method for preparing branched polymer through suspension polymerization - Google Patents
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- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 16
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
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- 230000035484 reaction time Effects 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
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- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract description 30
- 238000009826 distribution Methods 0.000 abstract description 16
- 239000007864 aqueous solution Substances 0.000 abstract description 12
- 239000004005 microsphere Substances 0.000 abstract description 8
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 6
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000004793 Polystyrene Substances 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 12
- SOEPBBSDDDZIJZ-UHFFFAOYSA-N 3-sulfanylhexyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCCC(CCC)S SOEPBBSDDDZIJZ-UHFFFAOYSA-N 0.000 description 8
- 238000000149 argon plasma sintering Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 238000000569 multi-angle light scattering Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 229920002689 polyvinyl acetate Polymers 0.000 description 5
- 239000011118 polyvinyl acetate Substances 0.000 description 5
- LKFHAOJSRPBTLK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCCOC(CCS)=O LKFHAOJSRPBTLK-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
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- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
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- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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Abstract
本发明公开了悬浮聚合制备支化聚合物的方法，属于功能聚合物制备领域。以含有可聚合双键和链转移巯基的功能单体为支化单体，采用聚乙烯醇水溶液为分散剂，偶氮二异丁腈（AIBN）为引发剂，苯乙烯、（甲基）丙烯酸酯或醋酸乙烯酯等为单体，搅拌速度为300~500r/min，于65~90℃下进行聚合3-12小时，成功得到支化聚合物微球。本发明以含有可聚合双键和链转移巯基的功能单体为支化单体，用悬浮聚合合成了粒径均匀的透明支化聚合物微球，聚合体系稳定，操作简单，后处理方便。所得支化聚合物的分子量相对于溶液聚合高，分子量分布窄，且其支化程度、分子量以及分子量分布可控。
The invention discloses a method for preparing a branched polymer by suspension polymerization, and belongs to the field of functional polymer preparation. Use functional monomers containing polymerizable double bonds and chain transfer mercapto groups as branched monomers, use polyvinyl alcohol aqueous solution as a dispersant, azobisisobutyronitrile (AIBN) as an initiator, styrene, (meth)acrylic acid Ester or vinyl acetate is used as a monomer, the stirring speed is 300~500r/min, and the polymerization is carried out at 65~90°C for 3-12 hours to successfully obtain branched polymer microspheres. The invention uses functional monomers containing polymerizable double bonds and chain transfer mercapto groups as branched monomers to synthesize transparent branched polymer microspheres with uniform particle diameters by suspension polymerization. The polymerization system is stable, and the operation is simple and the aftertreatment is convenient. The molecular weight of the obtained branched polymer is higher than that of the solution polymerization, the molecular weight distribution is narrow, and the branching degree, molecular weight and molecular weight distribution are controllable.
Description
技术领域 technical field
本发明涉及一种制备支化聚合物的实施方法：悬浮聚合，其特征是所得支化聚合物为微球。属于高分子合成，功能聚合物制备领域。 The invention relates to a method for preparing branched polymers: suspension polymerization, which is characterized in that the obtained branched polymers are microspheres. It belongs to the field of polymer synthesis and functional polymer preparation.
背景技术 Background technique
支化聚合物由于其独特的三维球状结构，因此相比于线型聚合物而言，具有较低的熔融黏度和溶液黏度，可以用于制备无溶剂涂料和高固体含量聚合物溶液及改善高分子材料成型加工性能等。 Due to its unique three-dimensional spherical structure, branched polymers have lower melt viscosity and solution viscosity than linear polymers, and can be used to prepare solvent-free coatings and high solid content polymer solutions and improve high Molecular material molding and processing properties, etc.
目前支化聚合物的合成技术主要是活性/可控自由基溶液聚合以及在链转移功能单体存在下的常规自由基溶液聚合。这些聚合反应所得支化聚合物的分子量相对较低，分子量分布较宽。溶液聚合的后处理工序较为繁琐，要消耗大量溶剂和沉淀剂，得到的聚合物通常为粉料。支化聚合物用作改善高分子材料成型加工性能时，如果以粉料形式加入，则与基体材料（通常为粒料）混合不均匀，且在成型加工过程中不易塑化。这些问题一定程度上限制了支化聚合物规模化应用的发展。 The current synthesis techniques of branched polymers are mainly living/controlled free radical solution polymerization and conventional free radical solution polymerization in the presence of chain transfer functional monomers. These polymerizations result in branched polymers with relatively low molecular weights and broad molecular weight distributions. The post-treatment process of solution polymerization is cumbersome, and consumes a lot of solvent and precipitant, and the obtained polymer is usually powder. When branched polymers are used to improve the molding and processing performance of polymer materials, if they are added in the form of powder, they will not be mixed uniformly with the matrix material (usually pellets), and it is not easy to be plasticized during the molding process. These problems limit the development of large-scale application of branched polymers to some extent.
追求合成方法的简便化，廉价化是支化聚合物研究的一个重要方向。悬浮聚合具有反应体系粘度低，传热和温度容易控制；产品分子量及分子量分布比较稳定；后处理工序比乳液聚合和溶液聚合简单，生产成本低等优点。悬浮聚合所得聚合物为微球，与基体材料成型加工时，易混合，易塑化。 Pursuing the simplification and cheapness of the synthesis method is an important direction in the research of branched polymers. Suspension polymerization has the advantages of low viscosity of the reaction system, easy control of heat transfer and temperature; relatively stable product molecular weight and molecular weight distribution; post-treatment process is simpler than emulsion polymerization and solution polymerization, and the production cost is low. The polymer obtained by suspension polymerization is a microsphere, which is easy to mix and plasticize when forming and processing with the base material.
本发明采用实施条件简单、后处理方便的悬浮聚合合成支化聚合物，期望得到分子量相对高、分子量分布较窄，且具有高支化度的支化聚合物微球。该发明对支化聚合物规模化应用具有重要的意义。 The invention adopts suspension polymerization with simple implementation conditions and convenient post-treatment to synthesize branched polymers, and expects to obtain branched polymer microspheres with relatively high molecular weight, narrow molecular weight distribution and high degree of branching. The invention is of great significance to the large-scale application of branched polymers.
the
发明内容 Contents of the invention
本发明公开了一种悬浮聚合合成支化聚合物的方法，其特征是以含有可聚合双键和链转移巯基的功能单体为支化单体，聚合反应实施条件简单，后处理方便，所得支化聚合物为微球，而且聚合物分子量、分子量分布和支化程度可以控制。 The invention discloses a method for synthesizing a branched polymer by suspension polymerization, which is characterized in that a functional monomer containing a polymerizable double bond and a chain transfer mercapto group is used as a branched monomer. Branched polymers are microspheres, and the polymer molecular weight, molecular weight distribution and degree of branching can be controlled.
悬浮聚合制备支化聚合物的方法，其特征在于按照下述步骤进行：采用含有可聚合双键和链转移巯基的功能单体为支化单体，以聚乙烯醇水溶液为分散剂，偶氮二异丁腈（AIBN）为引发剂，在设定的搅拌速度和聚合温度下进行悬浮聚合得到粒径均匀的支化聚合物微球，搅拌速度为300~500r/min，聚合反应温度控制在65~90℃，聚合反应时间控制为3-12小时。 The method for preparing branched polymers by suspension polymerization is characterized in that it is carried out in accordance with the following steps: adopting functional monomers containing polymerizable double bonds and chain transfer mercapto groups as branched monomers, using polyvinyl alcohol aqueous solution as a dispersant, azo Diisobutyronitrile (AIBN) is used as the initiator, and suspension polymerization is carried out at the set stirring speed and polymerization temperature to obtain branched polymer microspheres with uniform particle size. The stirring speed is 300~500r/min, and the polymerization reaction temperature is controlled at 65~90℃, the polymerization reaction time is controlled at 3-12 hours.
其中所述的支化单体:引发剂:聚合单体的摩尔投料比为0.25~2:0.5~3:100，其中所述的聚乙烯醇水溶液的水:聚合单体的质量比（水油比）为5~10:1。 Wherein said branched monomer: initiator: the molar feed ratio of polymerized monomer is 0.25～2:0.5～3:100, wherein said water of polyvinyl alcohol aqueous solution: the mass ratio of polymerized monomer (water oil Ratio) is 5~10:1.
其中所述的分散剂聚乙烯醇水溶液中的聚乙烯醇的重量百分比为0.24%~0.35%。 Wherein the weight percent of the polyvinyl alcohol in the dispersant polyvinyl alcohol aqueous solution is 0.24%-0.35%.
其中所述的聚合方法为悬浮聚合，聚合机理为自由基聚合。 The polymerization method described therein is suspension polymerization, and the polymerization mechanism is free radical polymerization.
其中所述的支化单体是兼有可聚合双键和链转移巯基的功能单体，具体为甲基丙烯酸-3-巯基己酯或甲基丙烯酸巯基丙酰氧基乙酯，结构式如下： Wherein the branched monomer is a functional monomer having a polymerizable double bond and a chain transfer mercapto group, specifically 3-mercaptohexyl methacrylate or mercaptopropionyloxyethyl methacrylate, the structural formula is as follows:
（甲基丙烯酸巯基丙酰氧基乙酯）。 (Mercaptopropionyloxyethyl Methacrylate).
the
其中所述的聚合单体苯乙烯，（甲基）丙烯酸酯或醋酸乙烯酯等。 The polymerized monomers styrene, (meth)acrylate or vinyl acetate etc. are described therein.
其中所述的聚合体系为苯乙烯、（甲基）丙烯酸酯或醋酸乙烯酯等单体均聚或这些单体的共聚。 The polymerization system mentioned therein is the homopolymerization of monomers such as styrene, (meth)acrylate or vinyl acetate or the copolymerization of these monomers.
本发明优点：以含有可聚合双键和链转移巯基的功能单体为支化单体，用悬浮聚合合成了粒径均匀的透明支化聚合物微球，聚合体系稳定，操作简单，后处理方便。所得支化聚合物的分子量相对于溶液聚合高，分子量分布窄，且其支化程度、分子量以及分子量分布可控。 Advantages of the present invention: using functional monomers containing polymerizable double bonds and chain transfer mercapto groups as branched monomers, transparent branched polymer microspheres with uniform particle size are synthesized by suspension polymerization, the polymerization system is stable, the operation is simple, and post-treatment convenient. The molecular weight of the obtained branched polymer is higher than that of the solution polymerization, the molecular weight distribution is narrow, and the branching degree, molecular weight and molecular weight distribution are controllable.
the
附图说明 Description of drawings
图1为实施例1，2，4所得支化聚苯乙烯与线型聚苯乙烯物的特性粘度随分子量变化图。 Fig. 1 is embodiment 1,2,4 obtained branched polystyrene and the intrinsic viscosity of linear polystyrene thing change figure with molecular weight.
图2为实施例5所得支化聚甲基丙烯酸甲酯与线型聚甲基丙烯酸甲酯的特性粘度随分子量变化图。 Fig. 2 is the intrinsic viscosity of branched polymethyl methacrylate obtained in embodiment 5 and linear polymethyl methacrylate as a function of molecular weight.
图3为实施例7所得支化聚醋酸乙烯酯与线型聚醋酸乙烯酯的特性粘度随分子量变化图。 Fig. 3 is the intrinsic viscosity of branched polyvinyl acetate obtained in embodiment 7 and linear polyvinyl acetate as a function of molecular weight.
图4为实施例1，5，6，7，8所得支化聚合物的支化因子g′随分子量的变化图。（g′为相同分子量下支化聚合物与线型聚合物的特性粘度（Intrinsic Viscosity）比值g′=IV 支化 /IV 线型 ；g′越小，支化程度越高） Fig. 4 is the graph of the variation of the branching factor g ' of the branched polymer obtained in Examples 1, 5, 6, 7, and 8 with the molecular weight. ( g ' is the intrinsic viscosity (Intrinsic Viscosity) ratio of branched polymers and linear polymers at the same molecular weight g '=IV branched /IV linear ; the smaller g ', the higher the degree of branching)
具体实施方式 Detailed ways
实施例1 Example 1
将苯乙烯（10.4021g，0.1mol）、甲基丙烯酸-3-巯基己酯（0.0511g，0.25mmol）和偶氮二异丁腈（AIBN, 0.1104g，0.67mmol）溶解混合均匀后加入到重量百分浓度为0.24%的50g聚乙烯醇的水溶液中，氮气鼓泡排除氧气，在300 r/min的搅拌速度下，控制聚合反应温度为85℃，聚合反应5小时，聚合物收率为82％，得到直径为2mm左右的聚苯乙烯颗粒。采用三检测凝胶渗透色谱仪对聚合物进行分析，结果如下：光散射重均分子量M w.MALLS＝293300，分子量分布PDI＝6.30，Mark-Houwink指数α＝0.628，支化因子g′＝0.78，证实所得聚合物具有支化结构。图1为实施例1所得支化聚苯乙烯与线型聚苯乙烯物的特性粘度随分子量变化图。图4为实施例1所得支化聚合物的支化因子g′随分子量的变化图。（g′为相同分子量下支化聚合物与线型聚合物的特性粘度（Intrinsic Viscosity）比值g′=IV 支化 /IV 线型 ；g′越小，支化程度越高）。 Dissolve styrene (10.4021g, 0.1mol), 3-mercaptohexyl methacrylate (0.0511g, 0.25mmol) and azobisisobutyronitrile (AIBN, 0.1104g, 0.67mmol) and add to weight In an aqueous solution of 50 g of polyvinyl alcohol with a percentage concentration of 0.24%, nitrogen bubbles are used to remove oxygen, and at a stirring speed of 300 r/min, the polymerization reaction temperature is controlled to be 85°C, and the polymerization reaction is carried out for 5 hours, and the polymer yield is 82 %, to obtain polystyrene particles with a diameter of about 2mm. The polymer was analyzed by three-detection gel permeation chromatography, and the results were as follows: light scattering weight-average molecular weight Mw.MALLS = 293300, molecular weight distribution PDI=6.30, Mark-Houwink index α=0.628, branching factor g′=0.78 , confirming that the obtained polymer has a branched structure. Fig. 1 is the variation diagram of the intrinsic viscosity of branched polystyrene and linear polystyrene obtained in Example 1 as a function of molecular weight. Fig. 4 is the branching factor g ' of the branched polymer obtained in Example 1 as a function of molecular weight. ( g ' is the intrinsic viscosity (Intrinsic Viscosity) ratio of branched polymers and linear polymers at the same molecular weight g '=IV branched /IV linear ; the smaller g ' is, the higher the degree of branching).
the
实施例2 Example 2
将苯乙烯（10.4044g，0.1mol）、甲基丙烯酸-3-巯基己酯（0.1021g，0.5mmol）和偶氮二异丁腈（AIBN, 0.0821g，0.5mmol）溶解混合均匀后加入到重量百分浓度为0.3%的100g聚乙烯醇的水溶液中，氮气鼓泡排除氧气，在350 r/min的搅拌速度下，控制聚合反应温度为85℃，聚合反应4小时，再将聚合反应温度提高到90℃强化反应1小时，聚合物收率为89％，得到直径为0.5mm左右的聚苯乙烯颗粒。采用三检测凝胶渗透色谱仪对聚合物进行分析，结果如下：光散射重均分子量M w.MALLS＝805000，分子量分布PDI＝7.23，Mark-Houwink指数α＝0.677，支化因子g′＝0.53，证实所得聚合物具有支化结构。图1为实施例2所得支化聚苯乙烯与线型聚苯乙烯物的特性粘度随分子量变化图。 Dissolve styrene (10.4044g, 0.1mol), 3-mercaptohexyl methacrylate (0.1021g, 0.5mmol) and azobisisobutyronitrile (AIBN, 0.0821g, 0.5mmol) and add to the weight In an aqueous solution of 100g polyvinyl alcohol with a percentage concentration of 0.3%, nitrogen bubbles are used to remove oxygen, and at a stirring speed of 350 r/min, the polymerization reaction temperature is controlled at 85°C, and the polymerization reaction is carried out for 4 hours, and then the polymerization reaction temperature is increased. The reaction was strengthened at 90° C. for 1 hour, the polymer yield was 89%, and polystyrene particles with a diameter of about 0.5 mm were obtained. Polymer was analyzed by three-detection gel permeation chromatography, and the results were as follows: light scattering weight-average molecular weight Mw.MALLS =805000, molecular weight distribution PDI=7.23 , Mark-Houwink index α=0.677, branching factor g′=0.53 , confirming that the obtained polymer has a branched structure. Fig. 1 is the intrinsic viscosity of the obtained branched polystyrene and linear polystyrene in Example 2 as a function of molecular weight.
the
实施例3 Example 3
将苯乙烯（10.4037g，0.1mol）、甲基丙烯酸-3-巯基己酯（0.4083g，2mmol）和偶氮二异丁腈（AIBN, 0.4925g，3mmol）溶解混合均匀后加入到重量百分浓度为0.3%的50g聚乙烯醇的水溶液中，氮气鼓泡排除氧气，在500 r/min的搅拌速度下，控制聚合反应温度为85℃，聚合反应4小时，再将聚合反应温度提高到90℃强化反应1小时，聚合物收率为85％，得到直径为1mm左右的聚苯乙烯颗粒。采用三检测凝胶渗透色谱仪对聚合物进行分析，结果如下：光散射重均分子量M w.MALLS＝731900，分子量分布PDI＝7.87，Mark-Houwink指数α＝0.610，支化因子g′＝0.59，证实所得聚合物具有支化结构。 Styrene (10.4037g, 0.1mol), 3-mercaptohexyl methacrylate (0.4083g, 2mmol) and azobisisobutyronitrile (AIBN, 0.4925g, 3mmol) were dissolved and mixed uniformly and added to the weight percent In an aqueous solution of 50 g of polyvinyl alcohol with a concentration of 0.3%, nitrogen bubbles are used to remove oxygen, and at a stirring speed of 500 r/min, the polymerization reaction temperature is controlled at 85°C, and the polymerization reaction is carried out for 4 hours, and then the polymerization reaction temperature is increased to 90°C. The reaction was strengthened at ℃ for 1 hour, the polymer yield was 85%, and polystyrene particles with a diameter of about 1 mm were obtained. The polymer was analyzed by three-detection gel permeation chromatography, and the results were as follows: light scattering weight-average molecular weight Mw.MALLS =731900, molecular weight distribution PDI=7.87 , Mark-Houwink index α=0.610, branching factor g'=0.59 , confirming that the obtained polymer has a branched structure.
the
实施例4 Example 4
将苯乙烯（10.4111g，0.1mol）、甲基丙烯酸巯基丙酰氧基乙酯（0.1093g，0.5mmol）和偶氮二异丁腈（AIBN, 0.0825g，0.5mmol）溶解混合均匀后加入到重量百分浓度为0.3%的100g聚乙烯醇的水溶液中，氮气鼓泡排除氧气，在350 r/min的搅拌速度下，控制聚合反应温度为85℃，聚合反应4小时，再将聚合反应温度提高到90℃强化反应1小时，聚合物收率为86％，得到直径为0.5mm左右的聚甲基丙烯酸甲酯颗粒。采用三检测凝胶渗透色谱仪对聚合物进行分析，结果如下：光散射重均分子量M w.MALLS＝795600，分子量分布PDI＝6.96，Mark-Houwink指数α＝0.667，支化因子g′＝0.68，证实所得聚合物具有支化结构。图1为实施例4所得支化聚苯乙烯与线型聚苯乙烯物的特性粘度随分子量变化图。 Styrene (10.4111g, 0.1mol), mercaptopropionyloxyethyl methacrylate (0.1093g, 0.5mmol) and azobisisobutyronitrile (AIBN, 0.0825g, 0.5mmol) were dissolved and mixed evenly and added to In an aqueous solution of 100g polyvinyl alcohol with a concentration of 0.3% by weight, nitrogen bubbles are used to remove oxygen, and at a stirring speed of 350 r/min, the polymerization reaction temperature is controlled to be 85°C, and the polymerization reaction is carried out for 4 hours. Increase the temperature to 90° C. to intensify the reaction for 1 hour, the polymer yield is 86%, and polymethyl methacrylate particles with a diameter of about 0.5 mm are obtained. The polymer was analyzed by three-detection gel permeation chromatography, and the results were as follows: light scattering weight-average molecular weight Mw.MALLS = 795600, molecular weight distribution PDI=6.96, Mark-Houwink index α=0.667, branching factor g'=0.68 , confirming that the obtained polymer has a branched structure. Fig. 1 is the variation diagram of the intrinsic viscosity of branched polystyrene and linear polystyrene obtained in Example 4 as a function of molecular weight.
the
实施例5 Example 5
将甲基丙烯酸甲酯（10.0211g，0.1mol）、甲基丙烯酸-3-巯基己酯（0.1020g，0.5mmol）和偶氮二异丁腈（AIBN, 0.0823g，0.5mmol）溶解混合均匀后加入到重量百分浓度为0.3%的100g聚乙烯醇的水溶液中，氮气鼓泡排除氧气，在350 r/min的搅拌速度下，控制聚合反应温度为75℃，聚合反应2小时，再将聚合反应温度提高到80℃强化反应0.5小时，聚合物收率为80％，得到直径为0.5mm左右的聚甲基丙烯酸甲酯颗粒。采用三检测凝胶渗透色谱仪对聚合物进行分析，结果如下：光散射重均分子量M w.MALLS＝1061000，分子量分布PDI＝6.65，Mark-Houwink指数α＝0.646，支化因子g′＝0.40，证实所得聚合物具有支化结构。图2为实施例5所得支化聚甲基丙烯酸甲酯与线型聚甲基丙烯酸甲酯的特性粘度随分子量变化图。图4为实施例5所得支化聚合物的支化因子g′随分子量的变化图。 Dissolve methyl methacrylate (10.0211g, 0.1mol), 3-mercaptohexyl methacrylate (0.1020g, 0.5mmol) and azobisisobutyronitrile (AIBN, 0.0823g, 0.5mmol) and mix well Add it to the aqueous solution of 100g polyvinyl alcohol with a concentration of 0.3% by weight, bubble nitrogen to remove oxygen, and control the polymerization reaction temperature to 75°C at a stirring speed of 350 r/min. The reaction temperature was increased to 80° C. to intensify the reaction for 0.5 hours, the polymer yield was 80%, and polymethyl methacrylate particles with a diameter of about 0.5 mm were obtained. Polymer is analyzed by three-detection gel permeation chromatography, the results are as follows: light scattering weight average molecular weight Mw.MALLS =1061000, molecular weight distribution PDI=6.65 , Mark-Houwink index α=0.646, branching factor g′=0.40 , confirming that the obtained polymer has a branched structure. Fig. 2 is the intrinsic viscosity of branched polymethyl methacrylate obtained in embodiment 5 and linear polymethyl methacrylate as a function of molecular weight. Fig. 4 is the branching factor g ' of the branched polymer obtained in Example 5 as a function of molecular weight.
the
实施例6 Example 6
将丙烯酸甲酯（8.6112g，0.1mol）、甲基丙烯酸巯基丙酰氧基乙酯（0.1089g，0.5mmol）和偶氮二异丁腈（AIBN, 0.0820g，0.5mmol）溶解混合均匀后加入到重量百分浓度为0.35%的86g聚乙烯醇的水溶液中，氮气鼓泡排除氧气，在350 r/min的搅拌速度下，控制聚合反应温度为70℃，聚合反应2小时，再将聚合反应温度提高到80℃强化反应0.5小时，聚合物收率为82％，得到直径为0.5mm左右的聚丙烯酸甲酯颗粒。采用三检测凝胶渗透色谱仪对聚合物进行分析，结果如下：光散射重均分子量M w.MALLS＝422100，分子量分布PDI＝6.64，Mark-Houwink指数α＝0.610，支化因子g′＝0.53，证实所得聚合物具有支化结构。图4为实施例6所得支化聚合物的支化因子g′随分子量的变化图。 Dissolve methyl acrylate (8.6112g, 0.1mol), mercaptopropionyloxyethyl methacrylate (0.1089g, 0.5mmol) and azobisisobutyronitrile (AIBN, 0.0820g, 0.5mmol) and add In an aqueous solution of 86 g polyvinyl alcohol with a concentration of 0.35% by weight, nitrogen bubbles are used to remove oxygen, and at a stirring speed of 350 r/min, the polymerization reaction temperature is controlled to be 70 ° C, and the polymerization reaction is carried out for 2 hours, and then the polymerization reaction The temperature was increased to 80° C. to intensify the reaction for 0.5 hours, the polymer yield was 82%, and polymethyl acrylate particles with a diameter of about 0.5 mm were obtained. Polymer is analyzed by three-detection gel permeation chromatography, and the results are as follows: light scattering weight-average molecular weight Mw.MALLS = 422100, molecular weight distribution PDI=6.64, Mark-Houwink index α=0.610, branching factor g′=0.53 , confirming that the obtained polymer has a branched structure. Fig. 4 is the branching factor g ' of the branched polymer obtained in Example 6 as a function of molecular weight.
the
实施例7 Example 7
将醋酸乙烯酯（8.6091g，0.1mol）、甲基丙烯酸-3-巯基己酯（0.1023g，0.5mmol）和偶氮二异丁腈（AIBN, 0.0821g，0.5mmol）溶解混合均匀后加入到重量百分浓度为0.35%的86g聚乙烯醇的水溶液中，氮气鼓泡排除氧气，在350 r/min的搅拌速度下，控制聚合反应温度为65℃，聚合反应2小时，再将聚合反应温度提高到75℃强化反应1小时，聚合物收率为70％，得到直径为0.5mm左右的聚醋酸乙烯酯颗粒。采用三检测凝胶渗透色谱仪对聚合物进行分析，结果如下：光散射重均分子量M w.MALLS＝551500，分子量分布PDI＝6.79，Mark-Houwink指数α＝0.562，支化因子g′＝0.66，证实所得聚合物具有支化结构。图3为实施例7所得支化聚醋酸乙烯酯与线型聚醋酸乙烯酯的特性粘度随分子量变化图。图4为实施例7所得支化聚合物的支化因子g′随分子量的变化图。 Vinyl acetate (8.6091g, 0.1mol), 3-mercaptohexyl methacrylate (0.1023g, 0.5mmol) and azobisisobutyronitrile (AIBN, 0.0821g, 0.5mmol) were dissolved and mixed evenly and added to In an aqueous solution of 86 g polyvinyl alcohol with a concentration of 0.35% by weight, nitrogen bubbles are used to remove oxygen, and at a stirring speed of 350 r/min, the polymerization reaction temperature is controlled to be 65°C, and the polymerization reaction is carried out for 2 hours, and then the polymerization reaction temperature Increase the temperature to 75° C. to intensify the reaction for 1 hour, the polymer yield is 70%, and polyvinyl acetate particles with a diameter of about 0.5 mm are obtained. Polymer is analyzed by three-detection gel permeation chromatography, the results are as follows: light scattering weight average molecular weight Mw.MALLS = 551500, molecular weight distribution PDI=6.79, Mark-Houwink index α=0.562, branching factor g'=0.66 , confirming that the obtained polymer has a branched structure. Fig. 3 is the intrinsic viscosity of branched polyvinyl acetate obtained in embodiment 7 and linear polyvinyl acetate as a function of molecular weight. Fig. 4 is the branching factor g ' of the branched polymer obtained in Example 7 as a function of molecular weight.
the
实施例8 Example 8
将苯乙烯（5.2011g，0.05mol）、甲基丙烯酸甲酯（5.0091g，0.05mol）、甲基丙烯酸-3-巯基己酯（0.0511g，0.25mmol）和偶氮二异丁腈（AIBN, 0.0823g，0.5mmol）溶解混合均匀后加入到重量百分浓度为0.3%的100g聚乙烯醇的水溶液中，氮气鼓泡排除氧气，在350 r/min的搅拌速度下，控制聚合反应温度为75℃，聚合反应10小时，再将聚合反应温度提高到85℃强化反应2小时，聚合物收率为80％，得到直径为0.5mm左右的聚苯乙烯和甲基丙烯酸甲酯共聚物颗粒。采用三检测凝胶渗透色谱仪对聚合物进行分析，结果如下：光散射重均分子量M w.MALLS＝522900，分子量分布PDI＝5.35，Mark-Houwink指数α＝0.702，支化因子g′＝0.69，证实所得聚合物具有支化结构。图4为实施例8所得支化聚合物的支化因子g′随分子量的变化图。 Styrene (5.2011 g, 0.05 mol), methyl methacrylate (5.0091 g, 0.05 mol), 3-mercaptohexyl methacrylate (0.0511 g, 0.25 mmol) and azobisisobutyronitrile (AIBN, 0.0823g, 0.5mmol) was dissolved and mixed evenly, and then added to the aqueous solution of 100g polyvinyl alcohol with a concentration of 0.3% by weight, nitrogen was bubbled to remove oxygen, and at a stirring speed of 350 r/min, the polymerization reaction temperature was controlled to be 75 ℃, polymerization reaction for 10 hours, and then increase the polymerization reaction temperature to 85 ℃ to intensify the reaction for 2 hours, the polymer yield is 80%, and obtain polystyrene and methyl methacrylate copolymer particles with a diameter of about 0.5mm. The polymer was analyzed by three-detection gel permeation chromatography, and the results were as follows: light scattering weight-average molecular weight Mw.MALLS = 522900, molecular weight distribution PDI=5.35, Mark-Houwink index α=0.702, branching factor g'=0.69 , confirming that the obtained polymer has a branched structure. Fig. 4 is the branching factor g ' of the branched polymer obtained in Example 8 as a function of molecular weight.
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| CN104313796A (en) * | 2014-09-09 | 2015-01-28 | 天津工业大学 | Manufacturing method for fibrous membrane for oil-water separation |
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| CN102108108A (en) * | 2011-01-05 | 2011-06-29 | 常州大学 | Method for synthesizing branched polymer by using vinyl benzyl sulfydryl propionate as a functional monomer |
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| CN104313796A (en) * | 2014-09-09 | 2015-01-28 | 天津工业大学 | Manufacturing method for fibrous membrane for oil-water separation |
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