PBAMO/GAP三嵌段共聚物的合成和表征

以GAP为起始剂,三氟化硼乙醚为引发剂,通过阳离子开环聚合反应合成出聚3-3-双叠氮甲基氧杂丁烷/叠氮缩水甘油醚(PBAMO/GAP)三嵌段共聚物。用IR、1 HNMR、GPC、DSC和TG方法对产物的结构和性能进行了表征。结果表明,PBAMO/GAP三嵌段共聚物的相对分子质量可控,官能度接近理论值,产物具有热塑性弹性体的性质。产物的分解温度为229℃,具有较好的热稳定性。     

A nonionic hydrogel from the telechelics by utilizing living polymerization of 2-oxazolines

N,N′-dimethyl-2,2′-tetramethylene-bis(2-oxazolinium) bis(methyl-p-toluene sulfonate) ( II ), a cationic polymerization initiator, was synthesized by the reaction of methyl p-toluene sulfonate with 2,2′-tetramethylene-bis-2-oxazoline ( I ) and a cationic ring-opening polymerization of 2-methyl-2-oxazoline [MeOZO] in the presence of ( II ) was carried out to produce poly(MeOZO) telechelics with various molecular weights. These telechelics were hydrolyzed with an aqueous solution of sodium carbonate to obtain hydroxy terminated telechelics of poly(MeOZO). A series of nonionic polyurethane hydrogels was prepared by the crosslinking reactions of the poly(MeOZO) glycol with pluriisocyanates in the presence of ferric acetylacetonate and DMF as the catalyst and reaction medium, respectively. The hydrogels showed good swelling degrees for water and hydrophilic solvents such as DMF, and bad swelling degree for a hydrophobic solvent such as toluene.     

端羟基聚环氧氯丙烷的合成与表征

以3–三氟氧硼–1–氯–2–丙氧基三苯基磷为引发剂,四氢呋喃为溶剂,三氟化硼为催化剂,进行环氧氯丙烷阳离子开环聚合,合成了黏均相对分子质量较高的端羟基聚环氧氯丙烷(PECH),探讨了起始剂和催化剂的比例、聚合反应温度和时间对产物的影响。结果表明,引发剂、催化剂与单体的摩尔比为1∶1∶200,在0℃下反应23 h,PECH收率大于90%。     

Enzymatic synthesis of polyphenols with longer conjugation lengths

Polyphenols containing Schiff base pendent groups, poly(4-[benzylidene-amino]-phenol) (PBP), and poly(4-[(anthracen-9-ylmethylene)-amino]-phenol) (PAP) have been synthesized through the combination of Schiff base reaction and enzymatic polymerization using horseradish peroxidase (HRP) as catalyst. The polymers were characterized by GPC, FTIR, ¹H NMR, and UV spectroscopy. It shows that PBP and PAP are composed of polyphenol main chains bearing Schiff base pendent side groups. The PBP exhibits better solubility than PAP in some common solvents. The PAP has a large red-shift of 86 nm compared with polyphenols, indicating the Schiff base pendent groups remarkably increase the conjugation lengths of polyphenols.     

乳酸/聚乙二醇嵌段共聚物的合成与表征

利用直接缩聚法制备了乳酸与聚乙二醇的嵌段共聚物(PLEG)。采用正交试验法考察了乳酸与聚乙二醇质量比、催化剂种类、催化剂含量、反应温度和反应时间对PLEG性能的影响。结果显示优化的反应条件:乳酸与聚乙二醇质量比为8.5∶1.5,采用自制的复合催化剂,催化剂质量分数0.6%,聚合温度160℃,聚合时间5h。另外还考察了扩链剂对PLEG性能的影响,结果表明扩链剂能够显著提高PLEG的相对分子质量。对合成的PLEG通过红外光谱、核磁共振、热分析进行了表征。     

HRP催化没食子酸与对羟基苯磺酸钠共聚物的制备及性能研究

没食子酸(GA)与对羟基苯磺酸钠(SHBS)在辣根过氧化物酶(HRP)/H2O2催化下以水为反应介质进行自由基共聚反应,制备了GA-SHBS共聚物。研究了共聚物制备过程中体系pH、HRP用量、反应时间、单体物质的量的比等因素对聚合反应的影响。得出最佳实验条件为:体系pH为7.5,过氧化酶用量为3 mg,n(GA)∶n(SHBS)为1∶1,反应4 h时得到的产物性能最佳。通过FTIR、NMR等对产物结构进行了表征,初步提出单体共聚反应机理及产物与皮纤维结合机理。将产品应用于皮革鞣制,结果表明其具有良好的溶解渗透性、鞣制性能和选择填充性。成革收缩温度可以达到75.6℃,革身柔软、均匀度好、粒面平细且无塑感。     

梳型紫外光快速固化聚氨酯的制备及涂层性能

以1,3-丙二醇、甲基丙烯酸缩水甘油酯为主要原料,无水四氯化锡为催化剂,三氟乙酸为助催化剂,合成了一种具有光化学活性的聚醚(PGMA)。此聚醚以碳氧键为主链,以甲基丙烯酸酯基为梳型侧链,端基为羟基。将上述具有光化学活性的聚醚(PMGA)与异佛尔酮二异氰酸酯(IPDI)反应,制得具有光化学活性的聚氨酯[Poly(PGMA-IPDI)]。采用FTIR和~1HNMR对PGMA和Poly(PGMA-IPDI)进行表征。在上述聚氨酯中加入活性稀释剂和光引发剂,制备出一种能够快速光固化的树脂,固化时间可以达到1 s,柔韧性达到0.5 mm、附着力为最高级级,同时固化涂层在盐溶液、水溶液、碱溶液中浸泡无脱落,在酸性水溶液中脱落时间也达到36 h,涂层具有优异的性能。     

不同聚合方法合成聚1-丁烯热塑性弹性体的结构与性能

比较了分别通过溶液聚合和本体聚合所得聚1-丁烯热塑性弹性体的物理机械性能.结果表明,用溶液法制得的聚1-丁烯的物理机械性能要优于本体法,也更接近于热塑性弹性体.核磁共振和差示扫描量热分析表明,在相同的聚合条件下,用溶液法所得聚1-丁烯分子链的规整度要高于本体法聚合产物,其结晶程度也更高.     

Synthesis of end‐functionalized poly(N‐isopropyl acrylamide) with zinc porphyrin and its photocatalytic activity under visible light

A series of well‐defined linear poly(N‐isopropyl acrylamide) with an asymmetrical zinc(II) porphyrin (ZnPor–PAM) end group was synthesized by atom transfer radical polymerization, wherein 5,10,15,20‐tetra(p‐bromopropanoyloxyethylphenyl) zinc porphyrin tripropionate was used as the initiator and CuBr/tris(2‐dimeoethyl)amine was used as the catalyst system. The structure of the ZnPor–PAM was characterized by Fourier transform infrared spectroscopy and ¹H‐NMR. In addition, the polydispersity index (PDI) obtained by gel permeation chromatography indicated that the molecular weight distribution was narrow; thus, the polymerization was well controlled (1.05 < PDI < 1.21). Because of the incorporation of hydrophobic porphyrin, the lower critical solution temperature of ZnPor–PAM was lower than that of the N‐isopropyl acrylamide homopolymer. Most interestingly, the ZnPor–PAM possessed remarkable photocatalytic activity for the oxidative degradation of methylene blue in the presence of hydrogen peroxide under visible‐light radiation. Moreover, ZnPor–PAM could be reused through the uncomplicated procedure, which exploited the thermoresponsive properties of ZnPor–PAM without any significant loss in activity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40523.     

NMMO齐聚物的合成与表征

以1,4-丁二醇（BDO）为引发剂,三氟化硼·乙醚（BF3·OEt2）为催化剂,二氯甲烷（CH2CI2）为溶剂,3-硝酸酯甲基-3-甲基氧杂环丁烷（NMMO）经阳离子开环聚合得到端羟基聚3-硝酸酯甲基-3-甲基氧杂环丁烷（PNMMO）,然后将PNMMO的端羟基用硝酸／醋酐硝化后得到端硝酸酯基聚3硝酸酯甲基-3-甲基氧杂环丁烷（NTPNMMO）齐聚物增塑剂。通过IR、^13C-NMR、DSC对NTPNMMO的结构和性能进行了表征。结果表明NTPNMMO的玻璃化转变温度为-45．32℃,热分解峰温为213．47℃,作为含能增塑剂具有较好的应用前景。     

HRP催化下对羟基苯甲醛与对羟基苯磺酸钠共聚物的制备及性能研究

利用辣根过氧化物酶(HRP)/H2O2催化体系合成对羟基苯甲醛(PHB)和对羟基苯磺酸钠(PHS)的共聚物。首先,PHB和乙二醇反应生成对羟基苯甲醛乙二醇缩醛(PHBEA)以保护醛基,然后进行PHBEA和PHS酶催化聚合,最后在酸性条件下解除缩醛得到PHB-PHS共聚产物。研究了单体摩尔比、体系pH、反应温度、HRP用量和H2O2滴加时间对PHBEA和PHS共聚反应的影响。用FTIR、NMR、GPC表征了产物结构。应用结果表明,应用革收缩温度(Ts)从54℃(鞣制前)提高至74.5℃(鞣制后)。该产物具有助染、鞣制等性能。     

Fully degradable antibacterial poly(ester‐phosphoester)s by ring‐opening polymerization, “click” chemistry,and quaternization

Fully degradable cationic poly(ester‐phosphoester)s with antibacterial properties were prepared by a combination of ring‐opening polymerization (ROP) and “click” reaction. First, poly(ester‐phosphoester)s‐bearing alkynyl groups were synthesized by the ring‐opening copolymerization of 2‐(2‐propynyloxy)?2‐oxo‐1,3,2‐dioxaphospholane (propynyl ethylene phosphate, PEP) and ε‐caprolactone (CL) using lanthanum tris(2,6‐di‐tert‐butyl‐4‐methylphenolate)s (La(DBMP)₃) as the catalyst. 2‐Azido‐N,N‐dimethylethanamine (DMEAN₃) was then attached to the copolymers by “click” reaction, resulting in poly(ester‐phosphoester)s with pendant tertiary amines. After the quaternization reactions between the copolymer and various alkyl bromides, cationic poly(ester‐phosphoester)s containing ammonium groups were obtained. Optical density (OD) measurement shows that the cationic copolymers have excellent antibacterial activity, which makes them potential candidates as biomaterials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42647.     

Core–shell latex particles consisting of polysiloxane–poly(styrene-methyl methacrylate-acrylic acid): Preparation and pore generation

Latexes with a poly(dimethyl siloxane) core and a poly(styrene-methyl methacrylate-acrylic acid) [poly(St-MMA-AA)] shell have been prepared in two steps in order to generate particles that have a core with a very low glass transition temperature. In the first step, poly(dimethyl siloxane) particles were obtained via the ring-opening emulsion polymerization of octamethyl tetracyclosiloxane (D₄). The polymerization was carried out using either an anionic or a cationic catalyst. In the first case, sodium hydroxide was used as catalyst and sodium dodecylbenzene sulfonate as surfactant, while in the second, the alkylbenzene sulfonic acid (ABSA) was used both as catalyst and surfactant. Using a PD₄ latex as seed, a seeded emulsion polymerization of St-MMA-AA was conducted to obtain PD₄–P(St-MMA-AA) core–shell particles. Numerous recipes were attempted and the most successful were those in which the seed was prepared with a cationic catalyst (ABSA) at a relatively low temperature (75°C). The core–shell structure of the particles was identified by transmission electron microscopy, but also via wetting angle, water absorption, and T_g measurements. Finally, pores were generated in the core–shell particles via an alkali–acid treatment. Because PD₄ has a very low glass transition temperature, it cannot be easily handled. However, protected by a shell, it could be used as a constituent of composite materials with enhanced impact strength, even at very low temperatures. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2235–2245, 1999     

Biomimetic Synthesis of a Water‐Soluble Conducting Polymer of 3,4‐Ethylene‐dioxythiophene

A novel biomimetic route for the synthesis of a water‐soluble poly(3,4‐ethylenedioxithiophene) (PEDT) in the presence of poly(styrene sulfonate) (PSS) and using iron(III)‐tetra(p‐sulfonatophenyl)porphyrin (Fe^IIITSPP), cobalt(III)‐tetra(p‐sulfonatophenyl)porphyrin (Co^IIITSPP), manganese(III)‐tetra(p‐sulfonatophenyl)porphyrin (Mn^IIITSPP), and copper(II)‐tetra(p‐sulfonatophenyl)porphyrin (Cu^IITSPP) as effective catalysts is presented. The reactions were performed with different monomer, catalyst, template, and initiator concentrations. The absorbance of the polaron bands at various pH values indicated pH 2 as the best condition for polymerization. Precipitation or salting out was highly dependent on the mentioned factors. The formation of PEDT was confirmed by UV‐Vis and FT‐IR spectroscopy. Cyclic voltammetry proved the convenient electroactivity of the synthesized polymer. The presence of PSS that serves as a charge‐compensating dopant provides processability and water solubility and, in addition, a distinct advantage over similar reactions employing native enzymes due to higher stability and lower cost of the catalysts.     

Multiarm star with poly(ethyleneimine) core and poly(ε-caprolactone) arms as modifiers of diglycidylether of bisphenol A thermosets cured by 1-methylimidazole

Well-defined multiarm star copolymers, with hyperbranched poly(ethyleneimine) (PEI) as the core and poly(ε-caprolactone) (PCL) arms with different degree of polymerization were synthesized by cationic ring-opening polymerization of ε-caprolactone from a hyperbranched poly(ethyleneimine) core and used to modify diglycidylether of bisphenol A formulations cured with 1-methylimidazole as anionic initiator. The curing process was studied by dynamic scanning calorimetry (DSC) and FTIR. By rheometry the complex viscosity of the multiarm stars synthesized and the influence of their addition to the reactive mixture was analyzed in detail. The resulting materials were characterized by thermal and mechanical tests. The addition of the multiarm star to the formulation led to homogeneous materials with a slightly toughened fracture in comparison to neat DGEBA thermosets without compromising thermal characteristics.     

Photoinduced living cationic polymerization of tetrahydrofuran. I. Living nature of the system and its application to the diblock copolymer synthesis

The living nature of cationic polytetrahydrofuran (THF), photoinduced in the presence of diphenyliodonium hexafluorophosphate (initiator), was investigated. In the bulk polymerization of THF, the linear relationship between percent conversion and the number-average molecular weight of the resulting polymer strongly suggests the living nature of this polymer and this was confirmed by the monomer addition technique, that is, cationic poly(THF) is capable of initiating a newly added monomer. The loss of the living nature of the cationic poly(THF) in a polar solvent, dichloromethane, is explained in terms of the stabilization of the five-membered cyclic oxonium ion, a propagating species of cationic polymerization of THF, by ion-pair formation with a less nucleophilic counterion, hexafluorophosphate. Based on the living nature of cationic poly(THF), a diblock copolymer, composed of THF and N-2-(hydroxyethyl)ethyleneÍimine (HEEI) was synthesized by subsequent monomer addition method; however, it was found that the HEEI block of the compolymer has a nonlinear structure. The factors affecting the structure of the HEEI block are also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 611–618, 1998     

丙烯改性合成C_5石油树脂

以C_5馏分和少量丙烯为原料,采用正离子聚合反应,合成出了更易于乳化制成施胶剂的改性石油树脂.结果表明其最佳合成工艺条件为:热聚温度130℃、热聚压力0.70 MPa、反应温度40℃、反应时间3 h、催化剂质量分数1.8%、溶剂体积分数40%,在该工艺条件下产品色相达到8(Gardnar级),收率大于52%,软化点小于80℃,熔融黏度250 mPa·s左右.     

Synthesis of syndiotactic poly(methacrylic acid) by free‐radical polymerization of the pseudo‐divinyl monomer formed with methacrylic acid and catechol

Syndiotactic poly(methacrylic acid) (Syn‐PMAA, r diad = 91 mol %) was synthesized by free radical polymerization of methacrylic acid (MAA) with catechol. The pseudo‐divinyl monomer was formed with one catechol and two MAA molecules by the hydrogen bonding between OH groups of catechol and COOH group of MAA. When the free radical polymerization of the pseudo‐divinyl monomer was carried out, intra‐ and intermolecular addition proceeded with racemic addition. The hydrogen bonding was the driving force to control tacticity. We discussed the effects of solvent, temperature, and the concentrations of MAA and catechol on the pseudo‐divinyl monomer formation. The highly syndiotactic PMAA was successfully obtained. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

生物可降解聚乳酸的制备及其性能研究

以L-乳酸(LLA)为原料合成L-丙交酯,通过L丙交酯开环聚合制备高分子量的聚乳酸(PLA)。考察反应温度、反应时间以及催化剂用量对PLA的影响,获得优化的聚合工艺条件。GPC测得PLA的重均分子量可达21.9×104g/mol。FTIR和旋光度测试表明产物为聚L-乳酸(PLLA)。DSC和XRD测试证明:PLLA为结晶性材料,熔点为170℃,属于α'-和α-相共存的混合晶型。拉伸测试表明:高分子量的PLLA具有良好的力学性能。     

ATRP法合成两亲性聚乙二醇-聚丙烯酸叔丁酯嵌段共聚物

以mPEG-Br为大分子引发剂,CuBr/PMDETA为催化体系,采用原子转移自由基聚合法(ATRP)合成了两亲性嵌段共聚物聚乙二醇-聚丙烯酸叔丁酯(mPEG-b-PtBA),并采用FT-IR,1H-NMR和GPC等表征了聚合物的结构.考察了单体与引发剂的配比、反应时间、反应温度及催化剂与配体的比例等因素对产物的分子量...