甲基丙烯酸十二氟庚酯的合成研究

以浓硫酸为催化剂、环己烷为共沸剂,采用十二氟庚醇（DFH）与甲基丙烯酸（MA）直接酯化的方法制备甲基丙烯酸十二氟庚酯（DFHMA）。通过Minitab软件合理地设计实验,考察各因素对合成产率的影响,确定了最优反应条件：n（MA）：n（DFH）=2：1;m（硫酸）=0．2m（DFH）;m（环己烷）=0．5m（DFH）;反应时间7．6h。在此条件下,甲基丙烯酸十二氟庚酯收率可达87．97％。     

甲基丙烯酸聚乙二醇单酯的合成与表征

以聚乙二醇单甲醚-400与甲基丙烯酸直接酯化反应,以甲苯为带水剂、对甲苯磺酸为催化剂,合成甲丙烯酸聚乙二醇单酯。通过实验确定酯化反应的最佳条件：甲基丙烯酸与聚乙二醇单甲醚-400的摩尔比为2．5：1,反应温度115℃,阻聚剂对苯二酚为0．78％（以醇酸总质量计）,反应时间为9h,催化剂对甲苯磺酸为3％（以醇酸总质量计）,产率为87．5％。产品结构经IR和^1HNMR,^13CNM表征,证明为目标产物。     

甲基丙烯酸二元醇酯的合成及分析

以对甲苯磺酸为催化剂,对苯二酚为阻聚剂,采用酸醇直接酯化新方法合成了二（甲基丙烯酸）乙二醇酯,二（甲基丙烯酸）二甘醇酯,二（甲基丙烯酸）聚乙二醇－２００酯。所得产物颜色浅,纯度及收率高。并对产物进行了ＧＣ、ＩＲ、１ＨＮＭＲ、ＭＳ分析     

甲基丙烯酸环氧酯及其乳液的合成研究

采用乳液聚合方法,以甲基丙烯酸环氧酯(EM)和丙烯酸酯类单体为原料,制备丙烯酸改性的水性环氧乳液,其中EM是由环氧树脂和甲基丙烯酸发生开环酯化反应生成的含有双键的改性环氧树脂。实验研究了EM的合成工艺和乳液聚合中乳化剂的种类和用量、引发剂用量、丙烯酸单体与EM的用量等因素对乳液聚合的影响。实验结果表明:采用OP-10和十二烷基苯磺酸钠质量比为2∶1的复合乳化剂体系,其用量为8%,引发剂用量为0.7%,丙烯酸类单体和EM的质量比为1∶1时,得到的乳液性能优异。     

气相色谱法测定甲基丙烯酸十八酯

利用毛细管气相色谱法,以甲苯为溶剂,正十二酯为内标物质,对甲基丙烯酸十八酯进行定性和定量分析。     

磷钨酸催化合成没食子酸十二烷醇酯

以磷钨酸为催化剂,以1,4－二氧六环作溶剂,由没食子酸和十二烷醇合成没食子酸十二烷醇酯,研究了催化酯化合成各种影响因素,获得了适宜的反应条件。     

α-甲基丙烯酸十一烯酯的合成

以α-甲基丙烯酸和十一烯醇为原料,对甲苯磺酸催化下,n（α-甲基丙烯酸）/n（十一烯醇）=2.5,温度控制在110～l20℃加热回流,反应时间8 h,合成了α-甲基丙烯酸十一烯酯,其产率达到88.3%。酯化产物经红外光谱测定,证明所得产物为α-甲基丙烯酸十一烯酯。     

聚醚与甲基丙烯酸十二烷基酯共改性硅油的制备与表征

以氯铂酸为催化剂,烯丙醇聚氧乙烯聚氧丙烯醚(F-6)、甲基丙烯酸十二烷基酯(LMA)和含氢硅油(PHMS)为原料,通过硅氢加成制备了聚醚与甲基丙烯酸十二烷基酯共改性硅油(PMS),并用红外光谱和核磁共振氢谱对其结构进行了表征。考察了硅氢键与碳碳双键的量之比、反应温度、反应时间、催化剂用量对Si—H转化率的影响,确定了最佳工艺为:甲苯的质量分数30%～40%,Si—H与CC的量之比1.00∶1.20,催化剂用量为30×10-6,反应温度为90℃,反应时间为6 h,Si—H转化率达到92.35%。产物水溶液的临界胶束浓度为0.6 g/L,PMS的临界表面张力为22.236 mN/m,表现出低表面能的特点。     

甲基丙烯酸十二氟庚酯改性水性聚氨酯

采用聚已二酸丁二醇酯(PBA)、异氟尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)、甲基丙烯酸十二氟庚酯(MBFA-12)等原料合成了含氟水性聚氨酯乳液(WPU-F),考察了MBFA-12的用量对WPU-F乳液的粒径与黏度,WPU-F胶膜的吸水率、接触角、附着力、硬度、拉伸强度、热力学性能等的影响.结果表明:用MBFA-12改性水性聚氨酯,在提高水性聚氨酯胶膜的拉伸强度、附着力、热力学性能的同时,由于侧链上密集的-CF3作用,接触角从70.7(°)增加到107.6(°),胶膜吸水率从61.3%降到15%以下,大大提高了聚氨酯的耐水性.     

月桂醇高选择性酯化合成单十二烷基磷酸酯

在月桂醇与高浓度磷酸酯化合成单十二烷基磷酸酯的反应中,考察了磷酰化剂的制备方法、磷酸质量分数、酸醇摩尔比、反应温度、反应时间等对单十二烷基磷酸酯的选择性及月桂醇转化率的影响。实验结果表明,在以85%磷酸与P2O5混合(摩尔比为3/7)作为磷酰化剂,磷酸含量为110%,酸醇摩尔比为2.1∶1,80℃反应8 h的条件下,单十二烷基磷酸酯的选择性为97%以上,月桂醇的转化率为96%以上。产物经水洗分离后,得到单十二烷基磷酸酯质量分数在95%以上,双十二烷基磷酸酯质量分数低于2.7%,磷酸质量分数低于1%的磷酸酯产品。     

Efficiency of ligands in atom transfer radical polymerization of lauryl methacrylate and block copolymerization with methyl methacrylate

Atom transfer radical polymerization of lauryl methacrylate (LMA) was carried out in the presence of various ligands using ethyl-2-bromoisobutyrate as initiator and CuBr as catalyst in toluene at 95 °C. The ligands used were 2,2′-bipyridyl,4,4′-dimethyl-2,2′-bipyridyl, N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA) and N-(n-propyl)-2-pyridylmethanimine (PPMI). Controlled polymerization was observed with PMDETA and PPMI ligands and poly(LMA)s with narrow molecular weight distribution (MWD) (M_w/M_n≤1.2) were obtained. The first-order time-conversion plot showed the presence of termination in the presence of PMDETA. A linear first-order time-conversion plot with a small induction period (∼10 min) was observed in the presence of PPMI ligand. Di-block copolymers of LMA and methylmethacrylate with controlled molecular weight and narrow MWDs were synthesized via sequential monomer addition.     

Research on butyl methacrylate–lauryl methacrylate copolymeric fibers for oil absorbency

By adding hydroethyl methacrylate as potential crosslinker, the butyl methacrylate‐lauryl methacrylate copolymeric (CPMA) fibers with oil‐absorptive function were prepared using heat crosslinking technology after spinning. The effect of monomer feed ratio showed that by controlling the monomer ratio, crosslinker concentration, and crosslinking conditions, the maximum absorbencies of prepared fibers to different oil were 8 g (kerosene)/g (fiber), 15 g (toluene)/g (fiber), and 34.75 g (chloroform)/g (fiber). The structures of fibers were characterized by FTIR, DSC, and SEM. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1248–1251, 2006     

Nonaqueous emulsion copolymerization of ethyl methacrylate/lauryl methacrylate in propylene glycol. I. Evaluation of stabilizing efficiency for PEO‐PS‐PEO triblock copolymers

Sixteen poly(ethylene oxide)–polystyrene–poly(ethylene oxide) (PEO‐PS‐PEO) triblock copolymers were synthesized by anionic polymerization. They were characterized by gel permeation chromatography and proton NMR. The molecular weight of these 16 PEO‐PS‐PEO triblock copolymers ranged from 5100 to 13,300. The polystyrene (PS) block length was between 13 and 41. The PEO block length was between 41 and 106. The polydispersity index for these PEO‐PS‐PEO triblock copolymers were 1.05 ± 0.02. When using these stabilizers in the emulsion copolymerization of ethyl methacrylate and lauryl methacylate in propylene glycol, only a narrow window of stability was observed. Stable latexes were formed only when the molecular weights of the PEO blocks were within the range of 5300–7700 and the molecular weights of the PS blocks were 2000–4000. The stabilizer ability for these triblock copolymers was correlated with their molecular weight and conformation in propylene glycol. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1951–1962, 2001     

催化合成L-吡咯烷酮羧酸月桂酯

以L-吡咯烷酮羧酸和月桂醇为原料,固载催化剂A,通过酸醇酯化反应直接合成L-吡咯烷酮羧酸月桂酯。探讨催化剂种类、用量、物料比、反应时间和温度对酯化反应影响,确定适宜合成工艺条件:n(月桂醇)∶n(L-吡咯烷酮羧酸)=1.0∶1.3,环己烷为带水剂,每0.1 mol月桂醇加入催化剂A 3.5 g,170℃反应4 h,酯化率达98.6%。固载催化剂A具有较好的活性,重复使用9次时酯化率仍可达93.4%。     

十二烷基苄醇聚氧乙烯醚的合成及性能

以十二烷基苯为原料,经氯甲基化、水解及环氧乙基化等步骤得到平均乙氧基(EO)数为9.5的十二烷基苄醇聚氧乙烯醚(LBAEOn)。分别用FTIR和1HNMR表征了产物LBAEOn的结构特征,并用ESI-MS确定了LBAEOn中的EO分布。以表面张力法测得在25℃时LBAEOn的cmc和γcmc分别为1.83×10-6mol.L-1和39.0 mN.m-1;与脂肪醇聚氧乙烯醚(AEO9)和壬基酚聚氧乙烯醚(NPEO10)相比较,除钙皂分散性能大致相当以外,LBAEOn的表面活性较好、发泡力较低、对正辛醇的增溶能力较强和对帆布的润湿性能较差。     

磷钨酸/二氧化钛催化合成甲基丙烯酸丁酯的研究

采用浸渍法制备了磷钨酸／二氧化钛催化剂，用于催化合成甲基丙烯酸丁酯，其性能优于硫酸，在酸醇物质的量的比为1：1．15，催化剂用量为甲基丙烯酸质量的1．3％，酯化温度为120℃，反应时间75min的条件下，酯化率达91．7％，产品质量分数大于98％，并且催化剂可以使用多次。     

Kinetic study of emulsion copolymerization of ethyl methacrylate/lauryl methacrylate in propylene glycol,stabilized with poly(ethylene oxide)–block–polystyrene–block–poly(ethylene oxide) triblock copolymer

The kinetics of emulsion copolymerization of ethyl methacrylate (EMA)/lauryl methacrylate (LMA) in propylene glycol is very similar to the emulsion copolymerizations of water‐soluble monomers in water because of the high solubility of EMA/LMA in propylene glycol. The initial rate of polymerization depends only on initiator concentration and is not affected by either monomer concentration or stabilizer concentration. The overall rate of polymerization is only slightly dependent on monomer concentration and stabilizer concentration and is independent of initiator concentration. The final particle number density increases with increasing amount of stabilizer and decreases with increasing monomer concentration. The total surface area increases with stabilizer concentration and is not governed by either initiator concentration or monomer concentration. Homogeneous nucleation is the dominant mechanism of particle nucleation, as shown by the kinetic data on seeded polymerization and monomer partition behavior. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1691–1704, 2001     

聚乙二醇单甲醚甲基丙烯酸酯的合成工艺研究

以甲基丙烯酸（MAA）和聚乙二醇单甲醚（MPEG）为主要原料,通过酯化反应制备聚乙二醇单甲醚甲基丙烯酸酯（1330）。研究了催化剂及其用量,阻聚剂用量,n（MAA）：n（MPEG）,酯化反应时间和酯化温度对酯化反应的影响,得到了最佳酯化条件：n（MAA）：n（MPEG）=1.6：1,负载磺酸型催化剂用量2.5%,阻聚剂用量250×10~（-6）,酯化温度11 5～120℃,反应回流5.5h。结果表明,在该条件下合成的聚乙二醇单甲醚甲基丙烯酸酯酯化率较高,在97.5%以上。     

新型梳形聚羧酸系减水剂大分子的制备与性能研究

以甲基丙烯酸、丙烯酸和聚乙二醇为主要原料,以甲苯为带水剂,混酸为催化剂,对苯二酚为阻聚剂,通过酯化反应合成出甲基丙烯酸聚乙二醇单酯活性大单体,最佳反应条件为:原料醇酸物质的量比为1∶2,催化剂的用量为4%(以聚乙二醇的质量计),阻聚剂对苯二酚的用量为0.3%(以甲基丙烯酸的质量计),温度为95℃,反应时间为8 h,酯化率达86.4%。