相转移催化合成N,N-二乙基氨基乙基-4-甲基苄基醚

以二乙氨基乙醇和对甲基氯化苄为原料,以四丁基溴化铵为相转移催化剂,合成了N,N－二乙基氨基乙基－4－甲基苄基醚,产率最高可达87．78％。考察了催化剂、温度、反应时间以及氢氧化钠用量对反应的影响,确定了最佳反应条件。产物经过沸点、折光率、红外光谱、氢质子核磁共振谱认证。     

N,N-二乙基氨基乙基-4-甲基苄基醚及其类似物的合成

采用相转移催化的方法合成了5个N,N-二烷基氨基乙基-4-甲基苄基醚化合物,产率为73%~89%。适宜的反应条件是:以二烷基氨基乙醇、4-甲基氯化苄为原料,四丁基溴化铵为相转移催化剂(PTC),氢氧化钠为碱,甲苯为溶剂,摩尔比n(R1R2NCH2CH2OH)∶n(MeArCH2C1)∶n(NaOH)∶n(PTC)=1.1∶1∶2∶0.05,反应时间为2 h,温度为70℃。产物经过沸点、元素分析、红外光谱、氢质子核磁共振谱给予确证。     

N,N-二烷基氨基乙基-4-氯苄基醚的合成

采用相转移催化的方法合成了5个N,N-二烷基氨基乙基-4-氯苄基醚化合物,产率为67%～82%.适宜的反应条件是:以二烷基氨基乙醇、4-氯氯化苄为原料,四丁基溴化铵为相转移催化剂,氢氧化钠固体为碱,甲苯为溶剂,n(R1R2NCH2CH2OH):n(ClArCH2Cl):n(NaOH):n(PTC)=1:1:2:0.05,反应时间为2 h,温度为70℃.产物经过沸点、元素分析、红外光谱、氢质子核磁共振谱给予确证.     

相转移催化合成N,N-二乙基氨基乙基-3,4-二氯苄基醚

以二乙氨基乙醇、3,4 二氯氯化苄为原料 ,四丁基溴化铵为相转移催化剂 (PTC) ,氢氧化钠固体为碱 ,苯为溶剂 ,经Williamson醚化反应合成N ,N 二乙基氨基乙基 3,4 二氯苄基醚 ,产率最高可达 84 5 % ,质量分数为 98 7%。最佳合成条件 :n(Et2 NCH2 CH2 OH)∶n(Cl2 ArCH2 Cl)∶n(NaOH)∶n(PTC) =1 2∶1∶2∶0 0 5 ,反应时间为 2h ,反应温度为 6 0℃。产物经过沸点、折光率、红外光谱、氢质子核磁共振谱给予确认     

N-苯基硫代氨基甲酸酯类二硫醚的合成

用二醋酸碘苯氧化N-苯基硫代氨基甲酸酯,生成二硫醚化合物。该反应在室温下即可以进行,具有操作简便、反应速度快、产率高的特点。     

N,N-二乙基氨基乙基-3,4-二氯苄基醚及其类似物的合成

用相转移催化法合成了5个N,N-二乙基氨基乙基-3,4-二氯苄基醚及其类似物,产率为72%~86%。适宜的反应条件是:以二烷基氨基乙醇、3,4-二氯氯化苄为原料,在固体氢氧化钠作用下,四丁基溴化铵为相转移催化剂,甲苯为溶剂,n(R1R2NCH2CH2OH)∶n(C l2ArCH2C l)∶n(NaOH)∶n(PTC)=1.1∶1∶2∶0.05,反应时间2 h,温度70℃。产物经沸点、元素分析、红外光谱、核磁共振氢谱予以确证。     

4-(N-乙基,N-2-羟乙基)氨基苯甲醛的制备

以4－（N－乙基，N－2－羟乙基）氨基苯为起始原料经乙酸酐酯化，苯环对位甲酰化，再水解制得4－（N－乙基，N－2－羟乙基）氨基苯甲醛，每步反应平衡，并用TLC跟踪每一步反应进行的程度，总收率达60％。     

4-(N,N-二乙基胺基)苯乙酮的制备

介绍了一种制备4 (N,N 二乙基胺基)苯乙酮的方法,该方法以N,N 二乙基苯胺为原料经Vilsmeier反应制得4 (N,N 二乙基胺基)苯甲醛,再与盐酸羟胺成肟脱水得到4 (N,N 二乙基胺基)苯甲腈,最后与氯甲烷格氏试剂反应水解后而得。经过工艺改进,反应各步收率分别达到80%、90%、85%,合成总收率达到了60%。     

从N-乙基邻甲苯胺合成过渡液中分离N,N-二乙基邻甲苯胺

从Ｎ－二乙基邻甲苯胺合成过渡液（含Ｎ，Ｎ－二乙基邻甲苯胺１２％）中用苯磺酰氯分离出Ｎ，Ｎ－二乙基邻甲苯胺，其提出率为８１．６７％。由此破坏了剩余过渡液中的共沸组成，为过渡液中其他组分的回收利用创造了条件。     

相转移催化合成N,N-二烷基氨基乙基-4-乙氧基苄基醚

用相转移催化法合成了标题化合物,产率69%～82%。适宜的反应条件是:以4-乙氧基氯化苄、二烷基氨基乙醇为原料,在固体氢氧化钠作用下,四丁基溴化铵为相转移催化剂,甲苯为溶剂,物质的量比n(R1R2NCH2CH2OH):n(EtOArCH2Cl):n(NaOH):n(PTC)=1:1:2:0.05,反应时间2h,温度70℃。产物经过沸点、元素分析、红外光谱、氢质子核磁共振谱给予确证。     

Synthesis of functional polyisobutene I. Copolymerization of isobutene with 4-vinylbenzyl N,N-diethyldithiocarbamate

Summary A special monomer 4-vinylbenzyl N,N-diethyldithiocarbamate (VBDC) was synthesized firstly, and then the cationic copolymerization of VBDC with isobutene was investigated. The results of ¹H-NMR, EA and GPC (with UV detector) indicated that VBDC could copolymerize with isobutene and form the copolymer, and the units of VBDC incorporated into copolymer chains increased with the increasing of the feed ratio of VBDC. However, there has apparent discrepancy between the VBDC in the monomer feed and the VBDC incorporated into the copolymer chain, which is probably due to the relatively lower reactivity of VBDC. In the presence of VBDC, the MWD is narrower than that of in absence of VBDC under the similar experimental conditions. For cumyl methyl ether/TiCl₄ initiating system, the M_w/M_n could be slightly narrowed from 1.55 (no VBDC) to 1.33 (with VBDC) in the mixed solvents of n-hexane and CH₃Cl (15/10,V/V), while cumyl chloride /TiCl₄ initiating system, the M_w/M_n is narrowed from about 5.0 (no VBDC) to about 1.5 (with VBDC) with n-hexane and CH₂Cl₂ (10/10,V/V) as the mixed solvents. When benzyl N, N-diethyldithiocarbamate (BDC) was used as the model compounds instead of the VBDC, the similar results of M_w/M_n were obtained. These results demonstrated that the VBDC functions as the monomer electron donor (ED) in this polymerization system. Received: 23 August 2001/Revised version: 29 October 2001/ Accepted: 2 November 2001     

Cationic copolymerization of 1,3-pentadiene with endo-dicyclopentadiene

Copolymerizations of 1,3-pentadiene (PD) with endo-dicyclopentadiene (DCPD) initiated by aluminum trichloride were carried out in toluene. The addition of DCPD in the PD polymerization system does not affect the molecular weight but increases greatly the softening point of the polymer due to the introduction of cyclic structures. The Gardner color scale of the polymer is also raised by the introduction of unsaturated rings of DCPD. The copolymerization gives complete conversions but generates insoluble crosslinked gels at high DCPD contents due to a higher crosslinking reactivity of DCPD than PD. The low-conversion experiments were carried out with small amounts of DCPD in order to determine the reactivity ratio in this copolymerization system (M₁ = PD and M₂ = DCPD). The result of r₁ = k₁₁/k₁₂ = 4.5 demonstrates that DCPD has a lower reactivity than PD toward PD-growing carbocations, and hence, the copolymer shows a smaller DCPD proportion than the corresponding comonomer. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1719–1723, 1997     

Cationic copolymerization of 1 ,3-pentadiene-with isoprene

The cationic copolymerization of 1,3-pentadiene (PD) with isoprene (IP) initiated by AICl₃, was carried out in toluene. The microstructure of the copolymer chain was characterized by IR and ¹H NMR. IP is incorporated in the copolymer chain mainly in cyclic segments. The PD–IP copolymer has a much higher cyclic content than the PD homopolymer, which shows that the cyclization reaction during PD polymerization is enhanced by the addition of IP. In addition, the reactivity ratios for IP(M₁) and PD(M₂) determined by the Kelen–Tudos method from low-conversion data are r₁ = 1.22 and r₂ = 1.09.     

Cationic copolymerization of 1,3-pentadiene with 1,3-cyclopentadiene

Copolymerizations of 1,3-pentadiene (PD) with 1,3-cyclopentadiene (CPD) initiated by aluminium trichloride were carried out in toluene. The addition of CPD in the PD polymerization system does not affect the molecular weight but greatly increases the softening point of the polymer due to the introduction of cyclic structures. The Gardner color scale of the polymer is also raised by introduction of unsaturated rings of CPD. The copolymerization gives a complete conversion but generates insoluble crosslinked gels at high CPD content due to the high crosslinking reactivity of CPD. The integral intensities of unsaturated protons from PD and CPD segments of the copolymer chain on the ¹H-NMR spectrum give a perfect correlation with the copolymer compositions. The low-conversion experiments were carried out with small amounts of CPD in order to determine the reactivity ratio in this copolymerization system (M₁ = PD and M₂ = CPD). The result of r₁ = k₁₁/k₁₂ = 0.46 demonstrates that CPD has a higher reactivity than PD toward PD growing carbocations, and hence the copolymer shows a higher CPD proportion than the corresponding comonomer. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1883–1887, 1997     

苯乙烯/N-丁基马来酰亚胺共聚合研究

以偶氮二异丁腈为引发剂,采用溶液聚合法合成了苯乙烯/N-丁基马来酰亚胺共聚物.详细研究了聚合温度、引发剂用量、单体配比对共聚合动力学的影响,并对共聚机理进行了初步探讨.     

Cationic graft copolymerization of tetrahydrofuran onto bromodeoxycellulose

Cationic graft copolymerization of tetrahydrofuran onto halodeoxycelluloses, which were prepared under homogeneous conditions, was studied with silver tetrafluoroborate as an initiator. 6-Bromo-6-deoxycelluloses gave graft copolymers, insoluble but swollen in tetrahydrofuran, whereas chlorodeoxycelluloses gave no graft copolymer. The graft copolymers were hydrolyzed in 2N HCl to give hydrolyzate solutions and insoluble solids. The hydrolyzate was found to be composed of 6-O-(4-hydroxybutyl) glucose and 6-O-(9-hydroxy-5-oxanonyl) glucose as well as oligomers of tetrahydrofuran by gas chromatography and gas chromatography–mass spectrometry after trifluoroacetylation. The insoluble solid was cross-linked polyoxytetramethylene, which could be hydrolyzed only very slowly in 2N HCl to yield oligomers of tetrahydrofuran. Thermal behavior of the graft copolymer was compared with that of cellulose and of homopolymer of tetrahydrofuran. © 1994 John Wiley & Sons, Inc.     

Photografting of PVC containing N,N‐diethyldithiocarbamate groups with vinyl monomers

Poly(vinyl chloride) (PVC) with pendent N,N‐diethyldithiocarbamate groups (PVC–SR) was prepared through the reaction of PVC with sodium N,N‐diethyldithiocarbamate (NaSR) in butanone and used as a photoinitiator for the grafting polymerization of three vinyl monomers [styrene (St), methyl methacrylate (MMA), and acrylamide (Am)]. The effects of ultraviolet (UV) irradiation time, PVC–SR amount, and the monomer amount on grafting and grafting efficiency were investigated. The results showed that PVC–SR could initiate the polymerization of three vinyl monomers effectively and obtained crosslinked copolymers. The grafting and grafting efficiency of styrene and methyl methacrylate were higher than those of acrylamide. The polymerization activity of three monomers was acrylamide > methyl methacrylate > styrene. By analyzing the UV spectrum of PVC–SR with a different irradiation time, it was confirmed that PVC–SR was dissociated mainly into macromolecular the sulfur radical PVC–S · and the small molecular carbon radical · C(S)N(C₂H₅)₂; the grafting polymerization mechanism was discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2569–2574, 2000     

Preparation of a new polyamide macromer having a vinylbenzyl group from bicyclic oxalactam and its radical copolymerization with styrene

Summary A new polyamide macromer having a vinylbenzyl end group (1), of which molecular weight was 3700–3800, was prepared by the anionic polymerization of bicyclic oxalactam (2) followed by the reaction with p-vinylbenzylamine. Its radical copolymerization with styrene was conducted to obtain a novel graft copolymer consisting of a polystyrene stock-chain and hydrophilic polyamide branches.