四臂星型聚合物P（tBMA-Br）4的ATRP合成与动力学研究

以二溴异丁酸季戊四醇四酯(PT-Br)为引发剂,N,N,N’,N″,N″-五甲基二亚乙基三胺(PMDETA)为配体,CuCl为催化剂,在DMF中使tBMA进行ATRP反应,得到了末端带有溴原子的星形聚合物P(tBMA-Br)4。在NaOH存在的条件下进行水解,水解后聚合物的分子量接近水解前的1/4,表明所合成的聚合物四臂长度基本相同,为聚甲基丙烯酸叔丁酯星形聚合物。     

ATRP法合成两亲性三嵌段共聚物

采用原子转移自由基活性聚合(ATRP)的方法,先以苯乙烯(St)为单体,α-溴代异丁酸乙酯(Ei B-Br)为小分子引发剂,Cu Br/PMDETA为催化体系,通过本体聚合制备出大分子引发剂聚苯乙烯(PS-Br)。再以PS-Br为引发剂引发第二单体甲基丙烯酸二甲氨基乙酯(DMAEMA)的本体聚合,得到PS-b-PDMAEMA-Br二嵌段共聚物,接着用PS-b-PDMAEMA-Br分别引发第三单体甲基丙烯酸甲酯(MMA)和甲基丙烯酸叔丁酯(t BMA)的本体聚合,得到三嵌段共聚物PS-b-PDMAEMA-b-Pt BMA,运用GPC、1H-NMR以及FTIR等对三嵌段共聚物进行表征;最后通过酸性水解得到PS-b-PDMAEMA-b-PMAA两亲性嵌段共聚物,并初步探究其表面活性。结果表明所得两亲性三嵌段共聚物具有一定的降低表面张力的能力,但弱于硬脂酸类小分子表面活性剂。     

含甲基丙烯酸叔丁酯单元聚合物的合成及其酸解性能研究

本研究合成了甲基丙烯酸叔丁酯(TBMA)单体及其均聚物,并与甲基丙烯酸(MAA)共聚合成了二元共聚物。同时以对甲苯磺酸作为酸源,比较系统地研究了聚合物中甲基丙烯酸叔丁酯单元的酸姐情况及其影响因素。研究表明,酸含量的增加和烤版温度的适当升高对甲基丙烯酸叔丁酯单元的酸解有利,烤版时间对甲基丙烯酸叔丁酯单元的酸解比例有一定影响。     

中国专利

原子转移自由基聚合制备聚甲基丙烯酸叔丁酯大分子单体,一种消除聚合物中残留单体N-乙烯基吡咯烷酮的方法，用于气相烯烃聚合的负载型催化剂，用于烯烃聚合的组分和催化剂,制备用于皮肤和头发组合物的乙烯基酰胺聚合物的方法[编者按]     

基于ATRP/CuAAC反应的降冰片烯类大分子单体的制备

利用原子转移自由基聚合合成了聚丙烯酸叔丁酯聚苯乙烯嵌段共聚物,通过取代反应在聚合物末端修饰叠氮基团,随后采用铜催化的叠氮-炔基环加成反应将含有炔基的顺-5-降冰片烯-外-2,3-二酸酐衍生物与嵌段共聚物偶联,得到大分子单体,最后通过大分子单体的开环易位聚合,制备了具有"Y"形的聚合物。通过核磁共振波谱仪、凝胶渗透色谱仪、原子力显微镜等研究了聚合物的结构与形貌。结果表明:通过活性可控聚合技术可以得到设计良好的具有复杂拓扑结构的聚合物。     

一步法合成甘氨酸叔丁酯及其盐酸盐

甘氨酸叔丁酯一般经由先合成氨基被保护的甘氨酸叔丁酯,再加氢脱去保护基而间接生成。采用溴乙酸叔丁酯与过量的液氨(1mol溴乙酸叔丁酯 600mL液氨)在-33～-35℃反应,成功地直接合成了甘氨酸叔丁酯。在甘氨酸叔丁酯的乙醚溶液中通入干燥的HCl气体,控制pH值大于6 5,且反复沉淀、过滤的操作方式,制得了甘氨酸叔丁酯盐酸盐。产物分子结构用元素分析、红外光谱及核磁共振谱(1HNMR)进行了鉴定。此法总得率86 3%,目标物的质量分数≥98%。     

采用ATRP反应合成嵌段共聚物P(n-BMA-b-NIPAM)的研究

采用原子转移自由基聚合(ATRP)反应合成了甲基丙烯酸正丁酯/N-异丙基丙烯酰胺嵌段共聚物(P(n-BMAb-NIPAM))。考察了引发剂、催化剂、反应温度等对聚合反应结果的影响,最终确定较为合适的反应条件,制备出分子量确定、分子量分布较窄的大分子引发剂,并成功引发第二单体继续通过ATRP反应,获得P(nBMA-b-NIPAM)。研究结果表明:所确定的ATRP反应体系能实现n-BMA的可控聚合,获得末端带溴原子的聚甲基丙烯酸正丁酯(P(n-BMA-Br))作为大分子引发剂继续通过ATRP反应引发N-异丙基丙烯酰胺(NIPAM),最后获得分子量确定、分子量分布较窄的嵌段共聚物P(n-BMA-b-NIPAM)。实验证明,利用高价态铜络合体系可以实现单体的可控聚合,而且可以保持聚合物末端较高的卤官能度。     

ATRP合成线性苯乙烯-丙烯腈共聚物

以α-溴代异丁酸叔丁酯(t-BBiB)为引发剂,CuBr/2,2′-联二吡啶(Bpy)为催化体系,在70℃下经原子转移自由基聚合(ATRP)反应进行苯乙烯(St)和丙烯腈(AN)共聚合合成苯乙烯/丙烯腈共聚物。采用GC、~1H NMR和GPC对聚合反应过程和聚合产物进行了分析和表征。结果表明:单体浓度的半对数曲线与聚合时间呈线性关系,聚合物摩尔质量随单体转化率的上升而线性增加,而且摩尔质量分布在1.2～1.3之间,表现出活性聚合反应特征。随着聚合反应的进行,共聚物组成趋向于原始单体组成,大分子链存在梯度结构。     

PSt-b-PtBA嵌段共聚物的AGET-ATRP法合成

采用活性自由基聚合方法,第一步以苯乙烯为单体,引发剂为溴化苄(BzBr),氯化铁为催化剂,三苯基膦为配体,电子活化再生原子转移自由基聚(AGET-ATRP)法合成得到了聚苯乙烯(PSt-Cl)大分子引发剂;第二步用溴化亚铜(CuBr)为催化剂,联吡啶(bpy)作为配体,用原子转移自由基聚合(ATRP)法得到了嵌段共聚物聚苯乙烯-b-聚丙烯酸叔丁酯(PSt-b-PtBA)。产物的表征用凝胶渗透色谱(GPC)、红外、核磁;得到当温度为95℃时,n(tBA)/n(PSt-Cl)/n(CuBr)/n(bpy)=100∶1∶1∶2,反应时间为28h时,PSt-b-PtBA的分子量为11261,分子量分布(PDI)为1.43。     

超支化聚苯乙烯-线型聚四氢呋喃-超支化聚甲基丙烯酸(N,N.二甲胺基乙酯)三嵌段共聚物的制备与表征

合成了超支化聚苯乙烯-线型聚四氢呋喃-超支化聚(甲基丙烯酸N,N-二甲胺基乙酯)三嵌段共聚物(HPS-b-LPTHF-b-HPDMAEMA).首先分别以丙烧醇和2.溴乙醇引发四氢呋喃的阳离子开环聚合,然后得到的聚四氢呋喃(PTHF)末端的羟基用带有援基的三硫代碳酸酯酯化,得到大分子RAFT试剂,并把溴端基用叠氮基取代.接着在大分子RAFT试剂存在情况下,通过自缩合原子转移自由基共聚合分别制得端烧基HPS-b-LPTHF和端叠氮基HPDMAEMA-b-LPTHF两嵌段聚合物.最后将两种两嵌段聚合物通过点击反应偶联得到超支化-线型-超支化三嵌段共聚物HPS-b-LPTHF-b-HPDM AEMA.核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)结果表明:所得产物分子量可控,得到了预期结构的聚合物.     

Multi-methacrylated star-shaped,photocurable poly(methyl methacrylate) macromonomers via quasiliving ATRP with suppressed curing shrinkage

Novel, star-shaped multifunctional poly(methyl methacrylate) (PMMA) macromonomers with well-defined average number of pendant methacrylate groups were synthesized by copolymerizing MMA with 2-hydroxyethyl methacrylate (HEMA) via quasiliving ATRP with a tetrafunctional initiator in methanol at 10 °C, followed by methacrylation of the hydroxyl groups of the HEMA units. The resulting tailor-made poly(methyl methacrylate-co-2-methacryloylethyl methacrylate), P(MMA-co-MEMA), multifunctional macromonomers were used as cross-linking agents in photocuring of MMA, a solvent for its own polymer, and thus chemically homogeneous PMMA networks were formed in which the tetrafunctional initiator moiety provides inherent, additional branching points in the resulting cross-linked materials. This approach, even in the presence of relatively low amounts of macromonomers of ∼35–45%, provides sol-free products and up to ∼40% less polymerization shrinkage than that by curing of MMA with a conventional low molecular weight bifunctional methacrylate. These new, unique star-shaped PMMA macromonomers are potential cross-linkers in a variety of solvent-free applications where low curing shrinkage and high conversions are critical requirements, such as in several engineering materials, coatings, dental fillings and restorations, bone cements etc.     

Synthesis of novel macromonomers with polyether possessing fluorine and their polymerization

Novel styrene-type and methacrylate (MA)-type macromonomers with polyether(poly(oxytetramethylene)) possessing a fluorobutyl terminal group were synthesized by the reaction between 4-aminostyrene or 2-hydroxyethyl methacrylate and polyether with a fluoroformyl group at one chain end (prepolymer), which was prepared by the ring-opening polymerization of THF with hexafluoropropylene oxide (HFPO) as an initiator. Macromonomers were easily prepared by mixing a solution containing the prepolymer with 4-aminostyrene or 2-hydroxyethyl methacrylate for several minutes at room temperature. The obtained macromonomers can polymerize with either radical or anionic initiator to afford polystyrene or poly(MA) with polyether grafted segment in each monomer unit.     

聚(N-乙烯基异丁酰胺)接枝聚苯乙烯微球的合成研究

合成了数均相对分子质量为 35 0 0和 6 30 0的两种聚 (N 乙烯基异丁酰胺 ) (PNVIBA)大分子单体 ,并以此大分子单体与苯乙烯 (St)在V(乙醇 )∶V(水 ) =7∶3的混合溶剂中进行自由基分散共聚 ,得到了稳定分散的PNVIBA接枝聚苯乙烯 (PSt)高分子微球。研究发现微粒的粒径随聚合体系中大分子单体相对分子质量和质量浓度的增加而减小 ,并发现当混合溶剂中水的体积分数增加到 ρ(水 ) =35 %时 ,微球的形态发生明显变化。     

UV固化生物基改性柔性环氧丙烯酸酯的合成及性能

以甲基丙烯酸羟乙酯、衣康酸为原料合成衣康酸甲基丙烯酸羟乙酯(HEMAIA),然后使之与环氧大豆油(ESO)进行开环反应,合成含有侧甲基和多个碳碳双键的ESO-HEMAIA。研究不同反应条件对ESO-HEMAIA合成的影响,采用红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)对所合成的产物进行表征分析,同时,对纯ESO-HEMAIA与环氧大豆油丙烯酸酯(AESO)的双键转化率及涂膜性能进行研究。结果表明,ESO-HEMAIA的官能度最高可达5. 2;虽然AESO的双键转化率高于ESO-HEMAIA,但纯ESO-HEMAIA比AESO涂膜有着更好的硬度、热稳定性,吸水率可降至1. 01%。     

线形和星形聚L-丙交酯大分子单体的合成

以辛酸亚锡为催化剂,分别以聚乙二醇、甲基丙烯酸羟乙酯、三羟甲基丙烷、季戊四醇、甘露醇和山梨醇等和L-丙交酯反应,得到末端为羟基的线形和星形聚L-丙交酯。通过和甲基丙烯酰氯反应,在上述线形和星形聚L-丙交酯成功引入双键,得到了相应的反应性大分子单体,其双键的存在经红外谱图和高锰酸钾试验得到证实。通过在过氧化二苯甲酰引发下的热交联,研究了上述大分子单体的反应性,发现端基数对交联产物的性质有一定影响。溶解试验、凝胶含量测定和热重分析表明,端基数目较多的大分子单体的交联产物有较高的凝胶含量,交联密度较大,热性能较好。     

Study on the activity difference of macromonomers for preparing polycarboxylic superplasticizers

Polycarboxylic superplasticizers produced by polyether macromonomers have attracted widely attention recently. Polyether macromonomers can be divided into vinyl ether-based and vinyl alcohol-based macromonomers according to the starting agents (vinyl ether and vinyl alcohol, respectively). In this study, three vinyl ether-based macromonomers were synthesized to compare with vinyl alcohol-based macromonomers that commonly used at present. It was found that the three vinyl ether-based macromonomers all can be copolymerized at lower reaction temperature (5 °C) and shorter reaction time (30–45 min) when the same reaction conversion ratio was achieved. To better explain the high activity of vinyl ether-based macromonomers, the molecular structure of different polyether macromonomers was calculated. The results show that the electron cloud on the CC double bond of vinyl ether-based macromonomers exhibits more obvious deflection because of the direct connection with the oxygen atom, which makes it more easily to copolymerize with acrylic acid. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48844.     

Graft copolymers of poly(methyl methacrylate) backbone and poly(propylene oxide-b-ethylene oxide) branches

Summary Two mono-functional macromonomers of poly (propylene oxide-b-ethylene oxide) were synthesized by reaction with methacryloyl chloride. The macromonomers have the same molecular weight and ratio of ethylene oxide and propylene oxide sequences. The reactive methacrylate group can be linked to the ethylene oxide (BuPPOPEO) or to the propylene oxide (BuPEOPPO). These macromonomers showed self-gelling in one week even at low temperature and under a dry atmosphere. Graft copolymers were obtained by reaction of these macromonomers with methyl methacrylate upon free-radical initiation and they were characterized by GPC, VPO, IR and ¹H NMR spectra.     

Synthesis of hybrid free and nanoporous silica aerogel‐anchored polystyrene chains via in situ atom transfer radical polymerization

Polystyrene nanocomposite with mixed free and anchored chains was synthesized by atom transfer radical polymerization. Attachment of 3‐(trimethoxysilyl)propyl methacrylate with a double bond on the nanoporous silica aerogel surface results in a double bond grafted silica aerogel which could be incorporated into the polystyrene chains by a grafting‐through process. Conversion and molecular weight evaluation was carried out using gas chromatography and gel permeation chromatography, respectively. Double bond containing silica aerogel has an inconsiderable effect on conversion. There is no considerable discrepancy between the molecular weights of the free and anchored chains. Addition of silica aerogel with pendant CC bonds leads to increase of apparent rate constant of polymerization and also molecular weights. This is mainly because of initiator trapping in silica aerogel pores. Every percent of double bond containing silica aerogel with respect to styrene results in trapping of about 0.08 mol of ethyl alpha‐bromoisobutyrate among the silica pores. POLYM. COMPOS., 34:1648–1654, 2013. © 2013 Society of Plastics Engineers     

Drying and semidrying oil macromonomers. III. Styrenation of sunflower and linseed oils

Styrenation of drying and semidrying oils, namely sunflower and linseed oils, via the macromer technique was studied. For this purpose, the macromonomers of the oils were prepared by transesterification of methyl methacrylate (MMA) with the corresponding partial glycerides (PG). Subsequent styrenation was achieved by free radical copolymerization of the macromonomers with styrene using benzoyl peroxide as the initiator. The viscosity and the film properties of the products were studied and compared. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2373–2376, 2003     

聚羧酸系超塑化剂的合成及性能研究

以自制的大分子单体聚乙二醇(PEG,聚合度n=23,35,45)不饱和羧酸单酯(聚乙二醇顺丁烯二酸单酯和聚乙二醇丙烯酸单酯)及其它烯类单体为原料,过硫酸铵为引发剂,经共聚合反应得到了聚羧酸共聚物。研究了大分子单体种类和侧链长度对共聚物分散性、分散稳定性的影响。实验结果表明所合成的聚羧酸共聚物对水泥净浆具有优异的超分散性,在水灰比0.29及掺量0.3%时,水泥净浆流动度可达230 mm。