一代端羧基超支化聚合物的制备与表征

首先采用二乙醇胺(DEA)与丙烯酸甲酯(MA)反应得到AB2型单体N,N-二羟乙基-3-氨基丙酸甲酯;然后以三羟甲基丙烷为核,在对甲苯磺酸的催化下,与N,N-二羟乙基-3-氨基丙酸甲酯反应得到端羟基超支化聚合物(HPAE-OH);最后采用顺丁烯二酸酐对端羟基超支化聚合物进行端基改性,制得端羧基超支化聚合物(HPAE-C)。优化的一代端羧基超支化聚合物的合成条件为:催化剂质量分数0.7%(基于反应物料总质量),反应投料比n(OH)∶n(马来酸酐)=1∶1.1,反应时间4 h,反应温度80℃。采用IR、1HNMR和13CNMR对端羧基超支化聚合物的分子结构进行了表征,采用表面张力仪研究了聚合物的表面活性。     

超支化聚(酰胺-酯)的合成与改性

以邻苯二甲酸酐和二乙醇胺为原料,制得AB2型单体;加入三羟甲基丙烷为核,采用一步法合成了超支化聚(酰胺-酯),并用硬脂酸对所得聚合物进行封端改性.应用红外光谱对改性前后超支化聚合物进行了表征.结果表明,所合成的聚合物与理论结构相吻合,且硬脂酸与端羟基发生了酯化反应,成功地接到了聚合物上.     

端羟基超支化聚酰胺酯改性研究

以二乙醇胺(DEA)与丁二酸酐(SA)为初始原料,经酯化反应得到AB2型单体;然后在对甲苯磺酸的催化下,采用"准一步法"反应得到端羟基的超支化聚合物(HBPEA);最后采用2-溴异丁酰溴(BB)对端羟基超支化聚合物进行端基改性,制得端基带有碳溴键的超支化聚合物(HBPEA-Br)。并采用傅里叶红外光谱仪(FT-IR),核磁共振氢谱(1H-NMR)对产物结构进行表征。探讨了常温反应时间和滴加温度对接枝率的影响。改性后的产物支化度在0.4~0.5之间。     

一代端羧基超支化聚合物的制备与表征

首先采用二乙醇胺(DEA)与丙烯酸甲酯(MA)反应得到AB2型单体N,N-二羟乙基-3-胺基丙酸甲酯,然后以三羟甲基丙烷为核,在对甲苯磺酸的催化下,与N,N-二羟乙基-3-胺基丙酸甲酯反应得到端羟基超支化聚合物（HPAE-OH）,最后采用顺丁烯二酸酐对端羟基超支化聚合物进行端基改性,制得端羧基超支化聚合物（HPAE-C）。优化了一代端羧基超支化聚合物的合成条件：催化剂用量为0.7%,反应投料比n(OH) ∶n(马来酸酐)=1∶1.1,反应时间为4h,反应温度为80℃。采用 IR、1H-NMR和13C-NMR仪器分析法对端羧基超支化聚合物的分子结构进行了表征,采用表面张力仪研究了聚合物的表面活性。     

超支化 UV 自引发聚合物的合成及其涂膜性能

通过n(二乙醇胺):n(甲基丙烯酸甲酯)=1:1.05进行Michael加成反应,制得N,N'一二羟乙基-3-氨基甲基丙酸甲酯(MMB).以季戊四醇为核,MMB为支化单体,采用准一步法合成第2代端羟基的超支化聚合物(PM-2).通过甲苯-2,4一二异氰酸酯(TDI)分别与甲基丙烯酸-β-羟乙酯(HEMA)、2-羟基-2-甲基-1-苯基丙酮(HMPP)反应,制得含双键的功能单体TDI-HEMA和含光引发基团的功能单体TDI-HMPP,通过这两种单体对PM-2进行端基改性反应,得到超支化UV自引发聚合物(PM-UV).最后通过调节PM-UV中双键和光引发基团的物质的量之比制得各种PM-UV,并研究各种PM-UV的涂膜性能.结果表明改性单体物质的量之比不同的PM-UV均具有耐热性好、凝胶含量高、成膜硬度好、耐冲击性高等优点.     

以均苯四甲酰四二乙醇胺为核的水溶性超支化聚酰胺-酯的合成与表征

超支化聚酰胺-酯(HPAE)含有类似于球形状的分子结构和大量活性端基,因而在胶粘剂、涂料、流变改性剂及染料等领域中具有潜在的应用前景。以均苯四甲酸酐(PMDA)和二乙醇胺(DEA)为原料,合成出一种中心核(By);然后以2,2-二羟甲基丙酸(DMPA)为AB2单体,将其与By进行熔融缩聚反应,制成水溶性的HPAE。结果表明:By的数均相对分子质量(Mn)、重均相对分子质量(Mw)分别为1 697、1 889 g/mol,Mw/Mn=1.11,说明其相对分子质量分布较窄;HPAE分子骨架中含有强极性酰胺键、弱极性酯键和大量强极性羟基,易溶于水;水溶性HPAE的支化度为0.47,其Mn、Mw分别为2 195、3 676 g/mol,Mw/Mn=1.67。合成原料易得、工艺简单,适合大量制备超支化聚合物。     

二茂铁端基修饰的超支化聚（胺-酯）的合成与表征

首先以二乙醇胺和丙烯酸甲酯为原料,通过Michael加成反应制备A2B型前驱单体N,N-二羟乙基-3-氨基丙烯酸甲酯,然后以三羟甲基丙烷为反应中心核,采用有核准一步法合成羟端基超支化聚(胺-酯)(HPAE);最后利用二茂铁甲酸对HPAE进行端基改性,得到了二茂铁端基修饰的超支化聚(胺-酯)(HPAE-Fc)。HPAE-Fc的合成条件:w(催化剂)=2.5%(相对于反应物总质量),反应温度为140℃,反应物投料比n(OH)∶n(二茂铁甲酸)为1∶0.8,反应时间为4 h。采用FTIR、1HNMR、UV-vis、DSC和羟值等手段对HPAE-Fc的结构进行了表征,表明二茂铁基团成功地接枝到了HPAE分子表面,接枝率达70%。     

超支化聚氨酯钢结构防火涂料的研制

首先以二乙醇胺(DA)、甲基丙烯酸甲酯(MMA)和季戊四醇(PER)为原料合成端羟基超支化聚合物(PM-2),然后以四溴双酚A(TBA)与甲苯-2,4-二异氰酸酯(TDI)为原料合成异氰酸基封端的含溴单体(TBA-TDI)。最后用TBA-TDI上的异氰酸根与PM-2进行反应,得到含异氰酸根的阻燃型超支化聚合物(PM-TBA-TDI)。以PM-TBA-TDI、聚磷酸铵、三聚氰胺、季戊四醇、氯化石蜡、氢氧化铝、三氧化二锑、硅灰石复配得到超支化聚氨酯钢结构防火涂料A组分,以羟基丙烯酸树脂为B组分,制得超支化聚氨酯钢结构防火涂料。     

超支化聚合物的合成及光固化涂层性能

通过丙烯酸甲酯和乙二醇胺的Michael加成反应,制得了AB2型单体N,N’-二羟乙基-3-氨基丙烯酸甲酯,通过添加核单体和采用“准一步法”的合成途径,制备了端羟基超支化聚（酯-胺）。通过丙烯酸对该聚合物进行改性反应,得到了端丙烯酸酯基的超支化聚合物,研究了改性聚合物与丙烯酸异冰片酯的紫外光固化涂层性能。     

超支化聚(酰胺-酯)的合成及其光致变色性能研究

采用丁二酸酐、三羟甲基氨基甲烷为主要原料,在冰水浴条件下合成AB_3型单体,然后进行熔融缩聚制得超支化聚(酰胺-酯)(HBP);再将含羧基的螺吡喃光致变色基元通过反应活性基团羧基与AB_3超支化聚合物末端羟基的反应而引入到AB_3超支化聚合物末端上,得到具有光致变色性能的超支化聚合物(MHBP)。利用红外、核磁等对其结构进行了表征,利用紫外可见分光谱对超支化聚合物光致变色性进行了研究。结果表明:MHBP同时具有超支化聚合物的性能和光致变色性能。     

马来酸双酯聚合物的合成表征及其复鞣加脂作用研究

以十二醇马来酸单酯、十二醇正丁醇马来酸双酯为亲油单体、甲基丙烯酸为亲水单体,过硫酸铵为引发剂,采用活泼单体滴加的方式制备了马来酸双酯聚合物复鞣加脂剂。通过FTIR对聚合物的结构进行了表征。通过正交实验考察了单体摩尔比、引发剂用量等因素对产物性能的影响。结果表明,n(十二醇马来酸单酯)∶n(十二醇正丁醇马来酸双酯)=3∶2,n(亲水单体)∶n(亲油单体)=2.5∶1,过硫酸铵占单体总质量的7%,聚合温度80℃,甲基丙烯酸滴加时间1.5~2.0 h的条件下,所得产品具有较好的加脂性能和防水性能,产品质量分数为1%的水乳液在400 nm处,25℃乳液透光率为30.1%,处理的山羊兰湿革(削匀厚度0.5 mm)的动态透水次数为642。     

Azeotropy in terpolymerization of 2-pyrimidyl acrylamide with different alkyl acrylates and acrylonitrile

2-Pyrimidyl acrylamide monomer (2PA) has been prepared by the reaction of 2-amino pyrimidine with acrylolyl chloride in the presence of triethylamine as catalyst. Its structure was confirmed by IR and ¹H NMR spectroscopy. Ternary copolymerizations of 2-pyrimidyl acrylamide monomer (2PA) with methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (EA), butyl acrylate (BuA) and acrylonitrile (AN) were carried out in THF at 65°C in the presence of a free radical initiator. Experimental terpolymerization data agree well with calculations based on the Alfrey–Goldfinger equation. The determination of unitary, binary and ternary azeotropies of the various systems studied were easily handled by a computer. The ternary azeotropic compositions for 2PA–MA–AN and 2PA–MMA–AN were 32.20:17.5:50.30 and 13.54:52.64:33.82mol%, respectively. Pseudo-azeotropic regions were identified where the deviation between feed and polymer composition is very small.     

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。     

Production of leather‐like composites using chemically modified short leather fibers. I: Chemical modification by emulsion polymerization

In order to evaluate the possible use of short leather fibers to produce leather‐like composites, five kilograms of fibers (extracted from leather wastes) were modified by in situ emulsion polymerization of methyl methacrylate (MMA). This treatment was performed in order to increase the compatibility of leather fibers with several commodity polymers used in the shoe and furrier industries. The chemical modification was carried out by aqueous emulsion polymerization initiated by a redox system (potassium persulfate and sodium metabisulfite). The effects of the monomer and redox initiator content as well as the reaction temperature were evaluated. The modified short leather fibers were characterized by instrumental techniques such as Infrared Spectroscopy (IR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), X‐ray Diffraction and Scanning Electronic Microscopy (SEM). The results show that the polymer is formed on the exterior of fibers (deposited fraction) as well as in the interior (by grafting or forming interpenetrated networks). The treatment significantly improves the thermal stability of fibers. It also reduces their water adsorption capacity, as a coating of PMMA is produced over the leather surface, as microscopic analysis has revealed. The last characteristic could be an advantage in certain applications.     

Graft polymerization of methyl methacrylate onto short leather fibers

Summary In this work, the graft polymerization of methyl methacrylate (MMA) monomer onto short leather fibers (SLF) was investigated as a function of the monomer/leather fiber ratio. This chemical modification was made by aqueous emulsion polymerization initiated by a redox system. The effect of' the monomer concentration on the grafting parameters (deposited and grafted polymer, as well as grafting efficiency) were determined. Composites formulated with SLF without chemical modification have showed lower tensile and impact properties in comparison with composites formulated with treated fibers. However, the elongation at break values for both systems remained similar as the MMA content changed. The morphology of SLF grafted with MMA was examined by both optical light microscopy (OLM) and scanning electron microscopy (SEM). Micrographs have shown polymer deposition on individual fibers and bundles of SLF. They have also revealed that PMMA may interpenetrate the SLF network and be deposited in large and coarse aggregates around individual fibers, but without occupation of the free space in the fiber net. Received: 1 October 1998/Revised version: 25 January 1999/Accepted: 25 January 1999     

以单体酸为原料制备生物柴油

研究了以单体酸为原料制备生物柴油的方法,反应以对甲苯磺酸为催化剂,单体酸与甲醇进行酯化反应获得脂肪酸甲酯。分别考察了酯化反应条件如甲醇与脂肪酸的摩尔比、反应时间、催化剂浓度以及反应温度对酯化率的影响。通过正交实验得到最佳酯化反应参数：醇酸摩尔比3∶1,反应时间3 h,对甲苯磺酸用量6%,反应温度60 ℃,该条件下单体酸酯化率达98.25%。实验制得的单体酸甲酯生物柴油的主要性能指标符合ASTM质量标准,并与0^#柴油性质接近。     

Influence of reaction between second monomer and vinyl group of seed polysiloxane on seeded emulsion polymerization

Seeded emulsion polymerization of methyl methacrylate (MMA) or styrene (ST) was carried in the presence of different vinyl‐containing polysiloxane latices (SV‐*) and the core‐shell particles with poly(methyl methacrylate) (PMMA) or polystyrene (PST), as the shells were obtained under different polymerization conditions. Besides the compatibility of the vinyl monomer and its polymer with polysiloxane and the reaction between vinyl monomer with vinyl group of polysiloxane, the content of vinyl group of seed polysiloxane has influence on the morphology and component of the resulted composite particles. The mechanism for the formation of core‐shell structure is discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2752–2758, 2001     

无皂微乳液聚合制备加脂型复鞣剂

采用甲基丙烯酸甲酯、丙烯酸丁酯、二乙烯基苯、丙烯酸、反应型乳化剂马来酸酐十二醇单酯钾盐和助乳化剂正戊醇制备得到无皂微乳液。通过正交实验优化出了反应型乳化剂的最佳合成条件:n(马来酸酐):n(十二醇)=1.15:1,反应温度80℃,反应时间3 h,制备出反应型乳化剂———马来酸酐十二醇单酯钾盐,代替外乳化剂十二烷基硫酸钠,进行无皂微乳液聚合制备具有增强作用的加脂型复鞣剂。将制得的加脂型复鞣剂用于猪二层革的复鞣实验,结果表明,反应型乳化剂与混合单体(丙烯酸丁酯、甲基丙烯酸甲酯和二乙烯基苯)的质量分别为120 g和180 g,活性单体丙烯酸质量为10 g时对皮革的复鞣效果最好。成革的物理机械性能得到了提高,其横向撕裂强度提高58.8%,纵向撕裂强度提高37.4%,崩破强度提高54.1%。     

Facile catalytic ring opening polymerization of lactic acid: Comparing the performance of Fe and Zn metal species

As a bio‐compatible/degradable polymer, poly(lactic acid) (PLA) has been widely noticed in tissue engineering and medical applications. Proper catalytic ring‐opening polymerization of lactic acid is pertinent to development of active metal species capable of producing high‐molecular‐weight polymers. In this work, ligand catalyst (2,4‐di‐tertio‐butyl‐6‐{[(2‐di‐methyl‐amino ethyl) methyl amino] methyl} phenol) was synthesized and then attached to Fe‐based and Zn‐based metal substitutes, and performance of metal species toward ring opening polymerization of lactic acid has been investigated. Regulation of reaction condition at 180°C for 36 h with Zn‐based catalyst allowed for late‐stage production of a high‐molecular‐weight PLA, while Fe‐based facilitated polymerization at early stages leading to PLAs with comparatively twofold higher molecular weight at lower time, monomer‐to‐initiator ratio, and temperature (at 170°C). A ratio of monomer to initiator of 5000 with Fe catalyst resulted in the highest molecular weight. Thus, polymerization has been facilitated by the use of Fe‐based catalyst. For this class of catalyst with Fe substitute, the product was characterized by means of ¹H‐NMR, Fourier transform infrared spectroscopy, and differential scanning calorimetry analyses. J. VINYL ADDIT. TECHNOL., 25:215–224, 2019. © 2018 Society of Plastics Engineers