CN103965384A - Preparation method of polymethyl methacrylate - Google Patents
Preparation method of polymethyl methacrylate Download PDFInfo
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- CN103965384A CN103965384A CN201410208532.4A CN201410208532A CN103965384A CN 103965384 A CN103965384 A CN 103965384A CN 201410208532 A CN201410208532 A CN 201410208532A CN 103965384 A CN103965384 A CN 103965384A
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- polymethylmethacrylate
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 39
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 diphenylsulfoxide ionic compound Chemical class 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 67
- 238000003756 stirring Methods 0.000 claims description 34
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 8
- 239000004593 Epoxy Chemical class 0.000 claims description 7
- 229910015900 BF3 Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims 1
- ZNNSPZOSKINXHF-UHFFFAOYSA-N 5-sulfinylcyclohexa-1,3-diene Chemical class O=S=C1CC=CC=C1 ZNNSPZOSKINXHF-UHFFFAOYSA-N 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- UCAOGXRUJFKQAP-UHFFFAOYSA-N n,n-dimethyl-5-nitropyridin-2-amine Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=N1 UCAOGXRUJFKQAP-UHFFFAOYSA-N 0.000 claims 1
- 125000000466 oxiranyl group Chemical group 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 11
- 239000003999 initiator Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 238000005227 gel permeation chromatography Methods 0.000 description 18
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- ARQHHDLVPMYRHR-UHFFFAOYSA-N 1-ethenyl-2,4-dioxabicyclo[1.1.0]butane Chemical compound C=CC12OC1O2 ARQHHDLVPMYRHR-UHFFFAOYSA-N 0.000 description 1
- VDOKWPVSGXHSNP-UHFFFAOYSA-N 2-methylprop-1-en-1-one Chemical compound CC(C)=C=O VDOKWPVSGXHSNP-UHFFFAOYSA-N 0.000 description 1
- MHNVXQGFSXEDIT-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hept-1(6)-ene Chemical compound C1CCCC2=C1O2 MHNVXQGFSXEDIT-UHFFFAOYSA-N 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及一种聚甲基丙烯酸甲酯的制备方法。The invention relates to a preparation method of polymethyl methacrylate.
背景技术Background technique
聚甲基丙烯酸甲酯(PMMA)的密度低、机械强度较高、熔点较低、透光率较高等优异的性能，使它成为一种重要的聚合物。对其聚合方法的研究也比较多，除了传统的自由基聚合的方法生产的聚甲基丙烯酸甲酯外，活性高分子聚合方法‘基团转移聚合’能够合成出聚甲基丙烯酸甲酯聚合物。与传统的自由基聚合方法相比，这种聚合方法得到的聚合物分子量分布窄，分子量大小可控，分子结构可设计。这种聚合方法的特点是(1)聚合反应温度低。(2)催化剂用量少。(3)分子量大，分子量分布窄。(4)单体和引发剂的转化率较高。Polymethyl methacrylate (PMMA) has excellent properties such as low density, high mechanical strength, low melting point, and high light transmittance, making it an important polymer. There are also many studies on its polymerization method. In addition to the polymethyl methacrylate produced by the traditional free radical polymerization method, the living polymer polymerization method 'group transfer polymerization' can synthesize polymethyl methacrylate polymer. . Compared with the traditional free radical polymerization method, the molecular weight distribution of the polymer obtained by this polymerization method is narrow, the molecular weight size is controllable, and the molecular structure can be designed. This polymerization method is characterized by (1) low polymerization reaction temperature. (2) The amount of catalyst is less. (3) Large molecular weight and narrow molecular weight distribution. (4) The conversion rate of monomer and initiator is higher.
美国专利USP4417034提供了以二甲基乙烯酮甲基三甲基硅氧基缩醛为引发剂，以含F-，HF2 -，CN-等的化合物或适当的Lewis酸为催化剂，进行了甲基丙烯酸脂、丙烯酸脂的基团转移聚合方法。U.S. Patent USP4417034 provides using dimethyl ketene methyl trimethylsiloxy acetal as initiator, with F- , HF 2- , CN - compounds such as, or appropriate Lewis acid as catalyzer, carried out forma Acrylate, group transfer polymerization method of acrylate.
然而，这种甲基丙烯酸脂的聚合方法的缺点是：聚合反应条件较苛刻，需在无水、无氧的条件下操作。引发剂制备较复杂。However, the disadvantage of this methacrylate polymerization method is that the polymerization reaction conditions are relatively harsh, and it needs to be operated under anhydrous and oxygen-free conditions. Initiator preparation is more complicated.
发明内容Contents of the invention
本发明的目的在于提出一种聚甲基丙烯酸甲酯的制备方法，其制备方法简单，原料易得，且反应条件温和。The object of the invention is to propose a kind of preparation method of polymethyl methacrylate, and its preparation method is simple, and raw material is easy to get, and reaction condition is gentle.
本发明解决上述技术问题所采用的技术方案是：聚甲基丙烯酸甲酯的制备方法，其特征在于向二苯亚砜离子化合物溶液中加入催化剂和精制的甲基丙烯酸甲酯，在无水有机溶剂存在下，控制温度为0℃～50℃，经过聚合、终止聚合反应，然后向溶液中加入沉淀剂分离出聚甲基丙烯酸甲酯。The technical scheme adopted by the present invention to solve the above-mentioned technical problems is: the preparation method of polymethyl methacrylate, it is characterized in that adding catalyst and refined methyl methacrylate to diphenyl sulfoxide ionic compound solution, in anhydrous organic In the presence of a solvent, the temperature is controlled at 0°C to 50°C, after polymerization, the polymerization reaction is terminated, and then a precipitating agent is added to the solution to separate polymethyl methacrylate.
按上述方案，所述的二苯亚砜离子化合物的制备方法，包括有以下步骤：向反应容器中依次加入四氢呋喃、二苯亚砜和三氟化硼和环氧化合物，常温下搅拌10～30分钟，得到二苯亚砜离子化合物溶液。According to the above scheme, the preparation method of the described diphenyl sulfoxide ionic compound includes the following steps: sequentially add tetrahydrofuran, diphenyl sulfoxide, boron trifluoride and epoxy compound into the reaction vessel, stir at room temperature for 10-30 Minutes to obtain a solution of diphenylsulfoxide ionic compound.
按上述方案，所述的环氧化合物为环氧乙烷、环氧丙烷、环氧丁烷、环氧氯丙烷、环氧苯乙烯、环氧异丁烯、环氧环己烯、单环氧丁烯和双环氧丁烯中的任意一种。According to the above scheme, the epoxy compound is ethylene oxide, propylene oxide, butylene oxide, epoxy chlorohydrin, styrene oxide, epoxy isobutylene, epoxy cyclohexene, monoepoxybutene and any one of diepoxybutene.
按上述方案，所述的聚甲基丙烯酸甲酯，具有通式Ⅰ表示的结构通式：According to the above scheme, the polymethyl methacrylate has a general structural formula represented by the general formula I:
其中，式中n为大于50的整数，R为氢、甲基、乙基、氯甲基、苯基或异丙基。Wherein, n in the formula is an integer greater than 50, and R is hydrogen, methyl, ethyl, chloromethyl, phenyl or isopropyl.
按上述方案，所述的催化剂为三氟化硼和三氯化铝的混合物。According to the above scheme, the catalyst is a mixture of boron trifluoride and aluminum trichloride.
按上述方案，所述的无水有机溶剂为经过精制四氢呋喃。According to the above scheme, the anhydrous organic solvent is refined tetrahydrofuran.
按上述方案，所述的聚合反应的温度优选为20℃～35℃。According to the above scheme, the temperature of the polymerization reaction is preferably 20°C to 35°C.
按上述方案，所述的聚合反应的时间为65～120小时。According to the above scheme, the time of the polymerization reaction is 65 to 120 hours.
按上述方案，所述的终止聚合反应的搅拌时间为20～50分钟，终止反应的温度在20℃～50℃下进行。According to the above scheme, the stirring time for terminating the polymerization reaction is 20-50 minutes, and the temperature for terminating the reaction is carried out at 20°C-50°C.
按上述方案，所述的终止聚合反应的终止剂为KOH，NaOH,Na2CO3或NaHCO3的水或醇溶液。According to the above scheme, the terminator for terminating the polymerization reaction is KOH, NaOH, Na 2 CO 3 or NaHCO 3 water or alcohol solution.
本发明所涉及反应方程式是:The reaction equation involved in the present invention is:
与已有技术相比较，本发明已达到的技术效果：通过本发明的方法制备的聚甲基丙烯酸甲酯为白色固体，有利于其后续产品的加工，所制备的聚甲基丙烯酸甲酯的数均分子量大于5000，分子量分散指数小于2.0，所使用的引发剂制备简单，聚合条件温和，聚合产物产率高。Compared with prior art, the technical effect that the present invention has reached: the polymethyl methacrylate prepared by the method of the present invention is white solid, helps the processing of its follow-up product, the polymethyl methacrylate prepared The number average molecular weight is greater than 5000, the molecular weight dispersion index is less than 2.0, the initiator used is easy to prepare, the polymerization conditions are mild, and the yield of polymerization products is high.
具体实施方式Detailed ways
为了更好的理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the following examples.
实施例1：Example 1:
在装有搅拌子的三口烧瓶中依次加入20ml精制过的四氢呋喃，0.1g二苯亚砜、0.1g环氧氯丙烷和0.5ml1M BF3溶液，常温下搅拌25分钟后，再加入0.5ml1M BF3溶液，将0.13gAlCl3溶于5.15g甲基丙烯酸甲酯的溶液加入到三口烧瓶中，保持系统温度30℃，反应72小时后，加入20ml丙酮，在搅拌下滴加2ml含有NaOH的质量分数为10％的水溶液，在20℃下搅拌50分钟后终止反应。在体系冷却到室温时，加入50ml甲醇沉淀聚合物。然后聚合物分离。在40℃下真空干燥。所得聚合物产率为93％，在以使用聚苯乙烯为标样，四氢呋喃(THF)为流动相的凝胶渗透色谱(GPC)测试中，得聚甲基丙烯酸甲酯，数均分子量为49415，分子量分散指数为1.56。Add 20ml of refined tetrahydrofuran, 0.1g of diphenyl sulfoxide, 0.1g of epichlorohydrin and 0.5ml of 1M BF 3 solution to a three-necked flask equipped with a stirring bar, and stir for 25 minutes at room temperature, then add 0.5ml of 1M BF 3 solution, 0.13g AlCl 3 dissolved in 5.15g methyl methacrylate solution was added to a three-necked flask, and the system temperature was kept at 30°C. After 72 hours of reaction, 20ml of acetone was added, and 2ml of NaOH was added dropwise under stirring. 10% aqueous solution, the reaction was terminated after stirring at 20°C for 50 minutes. When the system was cooled to room temperature, 50 ml of methanol was added to precipitate the polymer. The polymer is then isolated. Dry under vacuum at 40 °C. The resulting polymer yield was 93%. In the gel permeation chromatography (GPC) test using polystyrene as a standard sample and tetrahydrofuran (THF) as a mobile phase, polymethyl methacrylate was obtained with a number average molecular weight of 49415. The molecular weight dispersion index was 1.56.
实施例2：Example 2:
在装有搅拌子的三口烧瓶中依次加入15ml精制过的四氢呋喃，0.1g二苯亚砜、0.1g环氧丙烷和0.5ml1M BF3溶液，常温下搅拌25分钟后，再加入0.5ml1M BF3溶液，将0.11gAlCl3溶于5.06g甲基丙烯酸甲酯的溶液加入到三口烧瓶中，保持系统温度30℃，反应96小时后，加入20ml丙酮，在搅拌下滴加2ml含有NaHCO3的质量分数为10％的水溶液，在50℃下搅拌30分钟后终止反应。在体系冷却到室温时，加入50ml甲醇沉淀聚合物。然后聚合物分离。在40℃下真空干燥。所得聚合物产率为62.4％，在以使用聚苯乙烯为标样，四氢呋喃(THF)为流动相的凝胶渗透色谱(GPC)测试中，得聚甲基丙烯酸甲酯，数均分子量为67741，分子量分散指数为1.72。Add 15ml of refined tetrahydrofuran, 0.1g of diphenyl sulfoxide, 0.1g of propylene oxide and 0.5ml of 1M BF 3 solution to a three-necked flask equipped with a stirring bar, and stir for 25 minutes at room temperature, then add 0.5ml of 1M BF 3 solution , a solution of 0.11g AlCl 3 dissolved in 5.06g methyl methacrylate was added to a three-necked flask, and the system temperature was kept at 30°C. After reacting for 96 hours, 20ml of acetone was added, and 2ml of NaHCO 3 was added dropwise with mass fraction of A 10% aqueous solution was stirred at 50°C for 30 minutes to terminate the reaction. When the system was cooled to room temperature, 50 ml of methanol was added to precipitate the polymer. The polymer is then isolated. Dry under vacuum at 40 °C. The resulting polymer yield was 62.4%. In the gel permeation chromatography (GPC) test using polystyrene as a standard sample and tetrahydrofuran (THF) as a mobile phase, polymethyl methacrylate was obtained with a number average molecular weight of 67741. The molecular weight dispersion index was 1.72.
实施例3：Example 3:
在装有搅拌子的三口烧瓶中依次加入20ml精制过的四氢呋喃，0.1g二苯亚砜、0.15g环氧苯乙烯和0.5ml1M BF3溶液，常温下搅拌25分钟后，将0.26gAlCl3溶于5.16g甲基丙烯酸甲酯的溶液加入到三口烧瓶中。保持系统温度30℃，反应96小时后，加入20ml丙酮，在搅拌下滴加2ml含有KOH的质量分数为10％的水溶液，在20℃下搅拌60分钟后终止反应。在体系冷却到室温时，加入50ml甲醇沉淀聚合物。然后聚合物分离。在40℃下真空干燥。所得聚合物产率为37.1％，在以使用聚苯乙烯为标样，四氢呋喃(THF)为流动相的凝胶渗透色谱(GPC)测试中，得聚甲基丙烯酸甲酯，数均分子量为92935，分子量分散指数为1.45。Add 20ml of refined tetrahydrofuran, 0.1g of diphenyl sulfoxide, 0.15g of epoxy styrene and 0.5ml of 1M BF 3 solution to a three-necked flask equipped with a stirring bar, and stir for 25 minutes at room temperature, then dissolve 0.26g of AlCl 3 in A solution of 5.16 g of methyl methacrylate was added into a three-necked flask. Keep the system temperature at 30°C. After reacting for 96 hours, add 20ml of acetone, add 2ml of an aqueous solution containing KOH with a mass fraction of 10% dropwise under stirring, and stop the reaction after stirring at 20°C for 60 minutes. When the system was cooled to room temperature, 50 ml of methanol was added to precipitate the polymer. The polymer is then isolated. Dry under vacuum at 40 °C. The resulting polymer yield was 37.1%. In the gel permeation chromatography (GPC) test using polystyrene as a standard sample and tetrahydrofuran (THF) as a mobile phase, polymethyl methacrylate was obtained with a number average molecular weight of 92935. The molecular weight dispersion index was 1.45.
实施例4：Example 4:
在装有搅拌子的三口烧瓶中依次加入20ml精制过的四氢呋喃，0.1g二苯亚砜、0.13g环氧丁烷和0.5ml1M BF3溶液，常温下搅拌25分钟后，再加入0.5ml1M BF3溶液，将0.13gAlCl3溶于5.16g甲基丙烯酸甲酯的溶液加入到三口烧瓶中，保持系统温度50℃，反应72小时后，加入20ml丙酮，在搅拌下滴加2ml含有NaOH的质量分数为10％的水溶液，在30℃下搅拌40分钟后终止反应。在体系冷却到室温时，加入50ml甲醇沉淀聚合物。然后聚合物分离。在40℃下真空干燥。所得聚合物产率为43.3％，在以使用聚苯乙烯为标样，四氢呋喃(THF)为流动相的凝胶渗透色谱(GPC)测试中，得聚甲基丙烯酸甲酯，数均分子量为103368，分子量分散指数为1.34。Add 20ml of refined tetrahydrofuran, 0.1g of diphenyl sulfoxide, 0.13g of butylene oxide and 0.5ml of 1M BF 3 solution to a three-necked flask equipped with a stirring bar, and stir for 25 minutes at room temperature, then add 0.5ml of 1M BF 3 solution, 0.13g AlCl 3 dissolved in 5.16g methyl methacrylate solution was added to a three-necked flask, and the system temperature was kept at 50°C. After 72 hours of reaction, 20ml of acetone was added, and 2ml of NaOH was added dropwise under stirring. A 10% aqueous solution was stirred at 30°C for 40 minutes to terminate the reaction. When the system was cooled to room temperature, 50 ml of methanol was added to precipitate the polymer. The polymer is then isolated. Dry under vacuum at 40 °C. The resulting polymer yield was 43.3%. In the gel permeation chromatography (GPC) test using polystyrene as a standard sample and tetrahydrofuran (THF) as a mobile phase, polymethyl methacrylate was obtained with a number average molecular weight of 103368. The molecular weight dispersion index was 1.34.
实施例5：Example 5:
在装有搅拌子的三口烧瓶中依次加入20ml精制过的四氢呋喃，0.1g二苯亚砜、0.12g环氧氯丙烷和0.5ml1M BF3溶液，常温下搅拌25分钟后，再加入0.5ml1M BF3溶液，将0.13gAlCl3溶于10.0g甲基丙烯酸甲酯的溶液加入到三口烧瓶中，保持系统温度30℃，反应72小时后，加入30ml丙酮，在搅拌下滴加2ml含有Na2CO3的质量分数为10％的水溶液，在50℃下搅拌50分钟后终止反应。在体系冷却到室温时，加入100ml甲醇沉淀聚合物。然后聚合物分离。在40℃下真空干燥。所得聚合物产率为52.5％，在以使用聚苯乙烯为标样，四氢呋喃(THF)为流动相的凝胶渗透色谱(GPC)测试中，得聚甲基丙烯酸甲酯，数均分子量为3244，分子量分散指数为1.53。Add 20ml of refined tetrahydrofuran, 0.1g of diphenyl sulfoxide, 0.12g of epichlorohydrin and 0.5ml of 1M BF 3 solution to a three-necked flask equipped with a stirring bar, and stir for 25 minutes at room temperature, then add 0.5ml of 1M BF 3 solution, 0.13g AlCl 3 dissolved in 10.0g methyl methacrylate was added to a three-necked flask, and the system temperature was kept at 30°C. After 72 hours of reaction, 30ml of acetone was added, and 2ml of Na 2 CO 3 was added dropwise under stirring. 10% aqueous solution was stirred at 50° C. for 50 minutes to terminate the reaction. When the system was cooled to room temperature, 100 ml of methanol was added to precipitate the polymer. The polymer is then isolated. Dry under vacuum at 40 °C. The resulting polymer yield was 52.5%. In the gel permeation chromatography (GPC) test using polystyrene as a standard sample and tetrahydrofuran (THF) as a mobile phase, polymethyl methacrylate was obtained with a number average molecular weight of 3244. The molecular weight dispersion index was 1.53.
实施例6：Embodiment 6:
在装有搅拌子的三口烧瓶中依次加入20ml精制过的四氢呋喃，0.1g二苯亚砜、0.1g环氧氯丙烷和0.5ml1M BF3溶液，常温下搅拌25分钟后，再加入0.5ml1M BF3溶液，将0.13gAlCl3溶于5.10g甲基丙烯酸甲酯的溶液加入到三口烧瓶中，保持系统温度20℃，反应72小时后，加入20ml丙酮，在搅拌下滴加2ml含有Na2CO3的质量分数为10％的水溶液，在50℃下搅拌50分钟后终止反应。在体系冷却到室温时，加入50ml甲醇沉淀聚合物。然后聚合物分离。在40℃下真空干燥。所得聚合物产率为93％，在以使用聚苯乙烯为标样，四氢呋喃(THF)为流动相的凝胶渗透色谱(GPC)测试中，得聚甲基丙烯酸甲酯，数均分子量为108041，分子量分散指数为1.54。Add 20ml of refined tetrahydrofuran, 0.1g of diphenyl sulfoxide, 0.1g of epichlorohydrin and 0.5ml of 1M BF 3 solution to a three-necked flask equipped with a stirring bar, and stir for 25 minutes at room temperature, then add 0.5ml of 1M BF 3 solution, 0.13g AlCl 3 dissolved in 5.10g methyl methacrylate was added to a three-necked flask, and the temperature of the system was kept at 20°C. After 72 hours of reaction, 20ml of acetone was added, and 2ml of Na 2 CO 3 was added dropwise under stirring. 10% aqueous solution was stirred at 50° C. for 50 minutes to terminate the reaction. When the system was cooled to room temperature, 50 ml of methanol was added to precipitate the polymer. The polymer is then isolated. Dry under vacuum at 40 °C. The resulting polymer yield is 93%. In the gel permeation chromatography (GPC) test using polystyrene as a standard sample and tetrahydrofuran (THF) as a mobile phase, polymethyl methacrylate is obtained with a number average molecular weight of 108041. The molecular weight dispersion index was 1.54.
实施例7：Embodiment 7:
在装有搅拌子的三口烧瓶中依次加入20ml精制过的四氢呋喃，0.1g二苯基亚砜、0.1g环氧氯丙烷和0.5ml1MBF3溶液，常温下搅拌25分钟后，将0.13gAlCl3溶于5.15g甲基丙烯酸甲酯的溶液加入到三口烧瓶中。保持系统温度30℃。反应65小时后，加入20ml丙酮，在搅拌下滴加2ml含有Na2CO3的质量分数为10％的水溶液，在50℃下搅拌50分钟后终止反应。在体系冷却到室温时，加入50ml甲醇沉淀聚合物。然后聚合物分离。在40℃下真空干燥。所得聚合物产率为33％，在以使用聚苯乙烯为标样，四氢呋喃(THF)为流动相的凝胶渗透色谱(GPC)测试中，得聚甲基丙烯酸甲酯，数均分子量为185045，分子量分散指数为1.77。Add 20ml of refined tetrahydrofuran, 0.1g of diphenyl sulfoxide, 0.1g of epichlorohydrin and 0.5ml of 1MBF 3 solution to a three-necked flask equipped with a stirring bar, and stir for 25 minutes at room temperature, then dissolve 0.13g of AlCl 3 in A solution of 5.15 g of methyl methacrylate was added into a three-necked flask. The system temperature was maintained at 30 °C. After 65 hours of reaction, 20ml of acetone was added, and 2ml of an aqueous solution containing Na 2 CO 3 with a mass fraction of 10% was added dropwise with stirring, and the reaction was terminated after stirring at 50°C for 50 minutes. When the system was cooled to room temperature, 50 ml of methanol was added to precipitate the polymer. The polymer is then isolated. Dry under vacuum at 40 °C. The resulting polymer yield is 33%. In the gel permeation chromatography (GPC) test using polystyrene as a standard sample and tetrahydrofuran (THF) as a mobile phase, polymethyl methacrylate is obtained, and the number average molecular weight is 185045. The molecular weight dispersion index was 1.77.
实施例8：Embodiment 8:
在装有搅拌子的三口烧瓶中依次加入20ml精制过的四氢呋喃，0.1g二苯基亚砜、0.1g环氧氯丙烷和0.75ml1MBF3溶液，常温下搅拌25分钟后，将0.21gAlCl3溶于5.15g甲基丙烯酸甲酯的溶液加入到三口烧瓶中。保持系统温度30℃。反应72小时后，加入20ml丙酮，在搅拌下滴加2ml含有Na2CO3的质量分数为10％的水溶液，在50℃下搅拌50分钟后终止反应。在体系冷却到室温时，加入50ml甲醇沉淀聚合物。然后聚合物分离。在40℃下真空干燥。所得聚合物产率为24％，在以使用聚苯乙烯为标样，四氢呋喃(THF)为流动相的凝胶渗透色谱(GPC)测试中，得聚甲基丙烯酸甲酯，数均分子量为135089，分子量分散指数为1.65。Add 20ml of refined tetrahydrofuran, 0.1g of diphenyl sulfoxide, 0.1g of epichlorohydrin and 0.75ml of 1MBF 3 solution to a three-necked flask equipped with a stirring bar, and stir for 25 minutes at room temperature, then dissolve 0.21g of AlCl 3 in A solution of 5.15 g of methyl methacrylate was added into a three-necked flask. The system temperature was maintained at 30 °C. After 72 hours of reaction, 20ml of acetone was added, and 2ml of an aqueous solution containing Na 2 CO 3 with a mass fraction of 10% was added dropwise with stirring, and the reaction was terminated after stirring at 50°C for 50 minutes. When the system was cooled to room temperature, 50 ml of methanol was added to precipitate the polymer. The polymer is then isolated. Dry under vacuum at 40 °C. The resulting polymer yield is 24%. In the gel permeation chromatography (GPC) test using polystyrene as a standard sample and tetrahydrofuran (THF) as a mobile phase, polymethyl methacrylate is obtained, and the number average molecular weight is 135089. The molecular weight dispersion index was 1.65.
实施例9：Embodiment 9:
在装有搅拌子的三口烧瓶中依次加入20ml精制过的四氢呋喃，0.1g二苯基亚砜、0.1g环氧氯丙烷和0.75ml1MBF3溶液，常温下搅拌25分钟后，将0.13gAlCl3溶于5.15g甲基丙烯酸甲酯的溶液加入到三口烧瓶中。保持系统温度30℃。反应72小时后，加入20ml丙酮，在搅拌下滴加2ml含有NaHCO3的质量分数为10％的水溶液，在50℃下搅拌50分钟后终止反应。在体系冷却到室温时，加入50ml甲醇沉淀聚合物。然后聚合物分离。在40℃下真空干燥。所得聚合物产率为17.2％，在以使用聚苯乙烯为标样，四氢呋喃(THF)为流动相的凝胶渗透色谱(GPC)测试中，得聚甲基丙烯酸甲酯，数均分子量为132056，分子量分散指数为1.57。Add 20ml of refined tetrahydrofuran, 0.1g of diphenyl sulfoxide, 0.1g of epichlorohydrin and 0.75ml of 1MBF 3 solution to a three-necked flask equipped with a stirring bar, and stir for 25 minutes at room temperature, then dissolve 0.13g of AlCl 3 in A solution of 5.15 g of methyl methacrylate was added into a three-necked flask. The system temperature was maintained at 30 °C. After 72 hours of reaction, 20ml of acetone was added, and 2ml of an aqueous solution containing NaHCO 3 with a mass fraction of 10% was added dropwise with stirring, and the reaction was terminated after stirring at 50°C for 50 minutes. When the system was cooled to room temperature, 50 ml of methanol was added to precipitate the polymer. The polymer is then isolated. Dry under vacuum at 40 °C. The resulting polymer yield was 17.2%. In the gel permeation chromatography (GPC) test using polystyrene as a standard sample and tetrahydrofuran (THF) as a mobile phase, polymethyl methacrylate was obtained with a number average molecular weight of 132056. The molecular weight dispersion index was 1.57.
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| CN105541889A (en) * | 2016-01-23 | 2016-05-04 | 武汉工程大学 | Preparation method for boron difluoride diphenyl sulphur tetrafluoroborate compound |
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