由对苯二甲酰胺二醇合成聚酯酰胺及其扩链反应的研究

以N,N′-二(2-羟乙基)对苯二甲酰胺与己二酸及丁二醇缩聚,合成了同时带有端羧基与端羟基的聚酯酰胺预聚体,研究了不同扩链剂的扩链反应,获得了特性黏度达1.05 dL/g的聚酯酰胺.对预聚体及扩链后聚合物进行了红外与核磁表征,研究了聚合物的结构,并对聚合物进行了DSC与TG分析.     

四羟乙基己二酰胺的合成及应用研究

羟乙基二酰胺是重要的化工产品 ,广泛用于日化、表面活性剂、涂料等领域[1] 。目前合成四羟乙基二酰胺类的方法主要有 :( 1 )二元酸与二乙醇胺直接反应 ,该法得到的是酰胺及酯的混合物。( 2 )采用二元酰胺与环氧乙烷或氯乙醇反应 ,可得到纯度较高的产品。但环氧乙烷沸点低 ,爆炸极限宽 ,操作不便且不安全。 ( 3 )采用二酸酯与二乙醇胺在碱催化下反应是国内外目前使用的主要方法。该法主要的问题是制得的产品纯度不高 ,有较多的三羟乙基及二羟乙基 ,甚至一羟乙基化合物及聚酯等。本文采用中性的锆酸酯为催化剂[2 ] ,将己二酸二酯与二乙醇胺进…     

基于己内酰胺和乙醇胺的聚酯酰胺合成及表征

以己内酰胺及乙醇胺进行开环聚合,合成了聚酰胺预聚物(PrePA),并采用N,N'-碳酰双己内酰胺(CBC)和1,4-双(2-噁唑啉)苯(PBOX)对其进行了扩链反应.进一步将PrePA与己二酸缩聚,制备了聚酯酰胺预聚体(PrePEA),以CBC和PBOX复合扩链剂扩链,获得了特性黏数达0.74 dL/g的聚酯酰胺.并采用红外、核磁及WAXS对聚合物的结构和晶型进行了表征,以DSC和TGA测定了聚合物的热性能,同时对聚合物的力学性能进行了测定.     

双噁唑啉对聚碳酸1,2-环己二酯的扩链研究

采用马来酸酐封端聚碳酸1,2-环己二酯(PCHC),使其末端羟基转变为端羧基(MA-PCHC),并以2,2'-双-(2-噁唑啉)(BOZ)为扩链剂进行扩链反应.研究发现,BOZ与MA-PCHC中的羧基等摩尔情况下,扩链效果最佳.扩链后的PCHC的数均分子量从扩链前的5.6×104增长到12.4×104.扩链后的PCHC...     

非异氰酸酯法合成脂肪族热塑性聚氨酯及其性能研究

利用二氨酯二醇氨酯交换的非异氰酸酯法合成高分子量的脂肪族热塑性聚氨酯.以己二氨酯二醇(BHCH)的自缩聚,合成了Mn为29200的聚己二氨酯(PBHCH),其熔点为154.31℃,拉伸强度为28.41MPa,断裂伸长率为3.91%;利用己内酰胺与乙醇胺的共聚合成了同时带有端氨基及端羟基的尼龙-6低聚物,并与己内酯反应转化为端羟基尼龙-6低聚体,经与BHCH在170℃常压反应4 h及180℃减压反应6.5 h,获得了数种带有短尼龙-6段的酰胺型聚氨酯(s-PAUs),红外、核磁、GPC、广角X-射线衍射、DSC、TGA和力学性能表征表明,此类s-PAUs的Mn在26000以上、熔点在123.85~170.89℃之间、拉伸强度达28.53 MPa、断裂伸长率达299.0%.     

5-氟尿嘧啶-聚[N-(2-羟乙基)-L-谷酰胺]的合成及缓释性能研究

以聚谷氨酸苄酯为原料,用乙醇胺进行胺解得水溶性的可生物降解的聚[N-(2-羟乙基)-L-谷酰胺];用光气/甲苯液活化5-氟尿嘧啶,将其以共价键形式键合在高分子上,得5-氟尿嘧啶的高分子前药。用IR、UV、1HNMR及DSC对其结构进行表征,用紫外光谱测定其药物含量,载药高分子的接药率约为38.4%,高分子前药在pH=7.2的磷酸盐介质中42天内的药物累积释放量为57.53%。实验结果表明,5-氟尿嘧啶以共价键的形式键合在聚[N-(2-羟乙基)-L-谷酰胺]之上,在体外有明显的缓释效果。     

N,N′-二苯胺基己二酰胺β-晶型成核剂的热分解动力学分析

基于热重分析、微商热重分析及示差热分析研究了N,N′-二苯胺基己二酰胺β-晶型成核剂在空气气氛中的热分解动力学;通过利用Friedman方程和Flynn-Wall-Ozawa(FWO)方程对其热分解过程进行动力学分析求得了其热分解表观活化能;同时利用Achar-Brindly-Sharp方程和Coats-Redfern方程研究了其热分解机理,用等温热重分析法测得了失重10%时的寿命方程.结果表明,N,N′-二苯胺基己二酰胺β-晶型成核剂的表观活化能为138.66kJ.mol-1,其热分解反应的机理函数符合Mample法则,反应级数n=3/2,动力学方程为G(α)=α3/2,寿命方程为:lnτ=-51.877+2.922 2×104/T.     

(N,N′—二乙基)偶氮二异丁脒盐酸盐引发下的丙烯酰胺水溶液聚合

本文研究了(N,N′—二乙基)偶氮二异丁脒盐酸盐引发下丙烯酰胺水溶液聚合的反应动力学。得出了聚合速率方程式为RP=KP[EAIBA]05[AM]。测定了聚合表观活化能。并研究了聚合条件对产物分子量及其分布的影响。利用该引发—聚合体系,获得了相对分子量上千万超高分子量聚丙烯酰胺。     

聚(N,N′-二乙基丙烯酰胺)水凝胶的制备及其溶胀动力学

以N,N′-二乙基丙烯酰胺(DEA)为单体,偶氮二异丁腈(AIBN)为引发剂,分别采用疏水性的1,2-二乙烯苯(DVB)和水溶性的N,N′-亚甲基双丙烯酰胺(BIS)为交联剂制备了温度敏感水凝胶聚(N,N′-二乙基丙烯酰胺)(PDEA).制得的PDEA水凝胶的低临界溶解温度(LCST)在30 ℃附近,初步讨论了交联剂的用量和性质对水凝胶性能的影响.并对其在不同温度下达到溶胀平衡时的溶胀比,去溶胀动力学及干凝胶的再溶胀动力学过程进行了研究.     

乙酸稀土盐催化缩聚合成聚(对苯二甲酸乙二酯-co-己二酸乙二酯)

合成了一系列乙酸稀土盐(乙酸钇,乙酸镧,乙酸钕,乙酸镝),作为单组分催化剂,采用熔融缩聚法催化对苯二甲酸二甲酯、乙二醇和1,6-己二酸的共缩聚反应,制备了芳香族脂肪族共聚酯——聚(对苯二甲酸乙二酯-co-己二酸乙二酯)(PETA).通过1H-NMR,SEC,DSC及力学性能测试表征了聚合物的序列结构,分子量及分布,热性能及机械性能.结果表明,乙酸稀土盐单组分可催化共缩聚反应,效果优良,能够合成高分子量和较窄分子量分布的共聚酯,共聚酯具有较高的拉伸强度和断裂伸长率.     

Synthesis and Characterization of Biodegradable Alternating Polyesteramides from Mixed Diamidediols and Sebacic Acid

A series of polyesteramide prepolymers[PrePEA（0/4,8）s] having mixed alternating bisesterdiamide units was synthesized via melt polycondensation from N,N＇-bis（2-hydroxyethyl）oxamide（0） and N,N＇-bis（2-hydroxyethyl）-adipamide（4） with sebacic acid（8） at different molar ratios.Chain extension of them was conducted with 2,2＇-（1,4-phenylene）-bis（2-oxazoline） and adipoyl biscaprolactamate as combined chain extenders.The chain extended polyesteramides[ExtPEA（0/4,8）s] were characterized by proton nuclear magnetic resonance（1H NMR）,gel permeation chromatography（GPC）,differential scanning calorimetry（DSC）,thermogravimetry analysis（TGA）,wide angle X-ray scattering,tensile test and enzymatic degradation.The results show that ExtPEA（0/4,8）s were crystalline polyesteramides.They had Tm up to 136.5 ℃ and initial decomposition temperature above 297.5 ℃.They crystallized in similar crystallites into Nylon-66 and degraded under the catalysis of protease or lipase.They are thermoplastic materials with tensile strength up to 21.5 MPa and elongation at break above 64.0％.     

SYNTHESIS AND CHARACTERIZATION OF A NEW POLYSILOXANE CONTAINING N,N’-BIS(DIPHENYLSILYL)TETRAPHENYLCYCLODISILAZANE

A new kind of polysiloxane containing N,N'-bis(diphenylsilyl)tetraphenylcyclodisilazane was prepared by anionicnon-equilibrium polymerization with a "seed solution" as initiator. The monomer, N,N'-bis(hydroxydiphenylsilyl)-tetraphenyl-cyclodisilazane (BHPTPC), was synthesized via the hydrolysis of N,N'-bis(chlorodiphenylsilyl)tetraphenyl-cyclodisilazane (BCPTPC). A new method for the preparation of BCPTPC is also reported here with high yield and simplermanipulation. The synthesized polysiloxane containing N,N'-bis(diphenylsilyl)tetraphenylcyclodisilazane was characterized by ~1H-NMR, ~(29)Si-NMR, gel permeation chromatography (GPC) and intrinsic viscosity.     

Synthesis and characterization of poly(butylene terephthalates) modified by hydroquinone bis(2-hydroxyethyl)ether

A series of thermoplastic poly(butylene-co-hydroquinone bis(2-hydroxyethyl)ether terephthalates) (PBHT), with different molar ratios of hydroquinone bis(2-hydroxyethyl)ether (HQEE)/1,4-butanediol 9/91, 18/82 and 27/73, were synthesized via melt polycondensation. The compositions, thermodynamics and crystallization properties of the obtained copolyesters were characterized in detail by ¹H NMR, differential scanning calorimeters (DSC), thermogravimetric analysis (TGA) and X-ray diffraction (XRD). These results showed that the PBHTs were successfully synthesized, and the incorporation of the HQEE group significantly improved thermal properties of the polymers. However, HQEE did not change the crystal structure of PBT. The T_m values of the copolymers decreased (from 208?°C to 174?°C) with increasing content of HQEE segments, on the contrary, T_g values increased (from 37?°C to 43?°C). The temperatures for 5% weight loss did not decrease and appeared at a range of 373–377?°C.     

SYNTHESIS OF NOVEL SOLUBLE AROMATIC POLYPYROMELLITIMIDE CONTAINING ORDERED 1,2,4-TRIAZINE IN THE MAIN CHAIN

A new heat-resistant, soluble polymer, poly(phenyl-1,2,4-triazine imide), has been prepared via a two-step methodof polycondensation of N,N'-bis(4-benzil)pyromellitimide and terephthalamidrazone in cresol, followed by curing at highertemperature. The rigid 1,2,4-triazine group increases the solubility of the polyimide so that the polymer is soluble in cresol,N-methyl-2-pyrrolidone (NMP), trifluoroacetic acid and concentrated sulfuric acid, etc. Thermogravimetric analysis (TGA)indicates that this novel polyimide has good thermal stability with a high decomposition temperature of 447℃ in air and of423℃ in N_2. It has a tensile strength of 107.4 MPa with an elongation at break of around 7.6%.     

用ATRP法构筑核壳型梯度极性的多羟基多臂星状超支化聚合物及聚合物刷——双层聚合物刷的合成与表征

设计并通过原子转移自由基聚合方法 (ATRP)合成了核壳型多羟基多臂星状超支化聚合物刷 .以 2 溴异丁基酰溴封端的超支化聚 (3 乙基 3 羟甲基氧杂环丁烷 ) (HP Br)作为大分子引发剂 ,采用Cu(I)Br和N ,N ,N′ ,N′ ,N″ 五甲基二乙基三胺 (PMDETA)催化体系 ,在丁酮与丙醇的混和溶液中 ,通过甲基丙烯酸羟乙酯(HEMA)的ATRP溶液聚合 ,得到了一系列含有大量羟基的多臂星状超支化聚合物刷 (HP g PHEMA) ,并考察了其羟基的活性 ,发现羟基还可以与苯甲酰氯发生反应 .产物的结构和热性能用1 H NMR、FTIR、GPC、TGA、DSC等进行了表征和测试 .     

Thermal Functional Polymeric “Iniferters” Based on Phosphorus-Containing Poly(Thiuram Disulfides); Synthesis and Characterization

Secondary amine end-terminated oligomeric poly(phosphonamides) and poly(phosphorylamides) were synthesized by the condensation reaction of phenylphosphonic dichloride, ethyl dichlorophosphate, 2,2,2-tribromoethyl dichlorophosphate, and 2,2,2-trichloroethyl dichlorophosphate with an excess of piperazine or N,N′-dimethyl-1,6-hexanediamine. The macrodiamines were chain extended by reaction with CS₂ to the macrobis(dithiocarbamates) followed by oxidative coupling to the corresponding poly(thiuram disulfides) bearing the phosphorus functions. The diamine precursors and their polythiuram disuffides were characterized by elemental analysis, spectral analysis, thermal analysis, and viscosity measurements. The thermal stabilities of the prepolymers were correlated with their structures. The composition of the thiuram disulfide functions could be determined by TGA, whereas the kinetics of their thermal decomposition in the solid state was studied by DSC analysis. The activation energy varied with the chemical structure of the backbone but was quite independent of the chain length. Alternatively, oligomeric polythiuram disulfides containing phenyl phosphonate groups were synthesized by the condensation reaction of phenylphosphonic dichloride with N,N′-diethyl-N,N′-bis(2-hydroxyethyl)thiuram disulfide.     

Synthesis and characterization of yellow water-borne polyurethane using a diol colorant as extender

<正>A novel and facile method toward a series of yellow water-borne polyurethane was developed by using an intrinsically colored diol in this paper.The yellow aqueous dispersion PCLD-HENA-PU was synthesized based on isophorone diisocyanate(IPDI), polycaprolactonediol(PCLD) and 2,2-dimethylol propionic acid(DMPA) using a yellow diol N,N-bis(2-hydroxyethyl)-4-nitroaniline (HENA) as a chain extender.Due to the complete reaction of OH group in colorant HENA with NCO group in diisocyanate,a series of stable yellow polyurethanes could be obtained conveniently and easily.The structure of PCLD-HENA-PUs was confirmed by means of Fourier transform infrared spectroscopy.The UV-visible absorption analysis showed a blue shift effect of about 7 nm when HENA was blocked into polyurethane chain.The absorption intensity of PCLD-HENA-PUs increased with increasing HENA content.It was found that the tensile strength enhanced from 8.6 to 19.6 MPa with HENA content increased from 0 to 18.0%,while the extensibility decreased from 449 to 300%.The thermal gravimetric analysis presented that the initial decompose temperature began from about 250℃,and had a little increase with increasing the HENA content.