新型生物降解材料--含氢键聚乳酸的制备

采用熔融固相聚合制备了乳酸-氨基酸共聚物。结果表明：熔融聚合的最佳工艺条件为，催化剂是实验室制备，用量为0．5％～1％、聚合时间为10h、氨基酸含量为0．5％～1％；固相聚合的工艺条件为，聚合时间20h、催化剂为实验室制备。此工艺条件可制得相对分子质量大于50000的共聚物。     

新型生物降解材料——含氢键聚乳酸的制备

采用熔融固相聚合制备了乳酸-氨基酸共聚物，并用HNMR IR DSC GPC对共聚物进行了袁征。结果表明：熔融聚合的最佳工艺条件为，催化剂辛酸亚锡用量为0．5％-1％、聚合时间为10h、氨基酸含量为0．5％-1％；固相聚合的工艺条件为，聚合时间20h、催化剂为辛酸亚锡。此工艺条件可制得分子量大于50000的共聚物。     

高性能聚芳酯纤维的研制和表征

介绍了热致性液晶聚芳酯纤维的制备。选用双酚A、对苯二甲酸、间苯二甲酸为单体进行熔融聚合,制得具有不同相对分子质量的双酚A-对/间苯二甲酸共聚酯,探索了后续固相聚合工艺,研究了后续固相聚合对原熔融聚合物相对分子质量、热性能以及力学性能的影响。原聚合物再经固相聚合及不经固相聚合的两种聚芳酯在不同的纺丝和热处理工艺条件下,可以获得力学性能相近的聚芳酯纤维,为进一步研制热致液晶型聚芳酯纤维生产路线提供可靠的工艺数据。     

中国塑料专利

<正>专利名称:生产液晶聚酯的方法专利号:CN102898634公开日:2013.01.30本发明提供了生产液晶聚酯的方法,该方法包括:(1)使原料单体在熔融聚合容器中熔融聚合以得到聚合物熔体的步骤;(2)从该熔融聚合容器中排出该聚合物熔体,并粒化该聚合物熔体以得到颗粒的步骤;(3)使所述颗粒在固相聚合容器中进行固相聚合,以得到固相聚合物的步骤;以及(4)对包含该固相聚合物的所述固相聚合容器施加冲击,并从该固相聚合容器中取出该固相聚合物的步骤。     

固相聚合PET及饮料瓶的热性能研究

应用 DSC、 TGA和 TMA研究了固相聚合 PET树脂的双重熔融行为、热稳定性及瓶坯、包装瓶的结晶性能和膨胀性。结果表明 ,固相聚合 PET树脂在不同升温速度下的双重熔融行为反映出树脂结晶结构的完整性 ,可为确定固相聚合生产的工艺条件提供参考。对具有不同结晶性能和热稳定性的固相聚合 PET树脂 ,其制坯及吹瓶工艺条件应作必要调整。     

磷酸二氢钾盐对热致液晶聚合物的合成与性能影响研究

以对羟基苯甲酸、联苯二酚、对苯二甲酸、间苯二甲酸为单体,分别以醋酸酐和乙酸镁为酰化剂和催化剂,并在合成过程中添加0.000%～0.030%(基于单体总质量)磷酸二氢钾盐(KH2PO4),采用预聚合-固相聚合工艺制备热致液晶聚合物(TLCP)。研究了KH2PO4添加量对预聚合、固相聚合工艺以及所得树脂热性能、色泽和力学性能的影响。结果表明:磷酸二氢钾对预聚合与固相聚合有催化作用,TLCP树脂的熔融温度随磷酸二氢钾添加量的增加而提高,当添加0.025%的KH2PO4合成的树脂色泽以及力学综合性能最优。     

连续式固相增黏PET切片生产工艺优化

介绍了连续式固相聚合(SSP)的生产工艺流程,采用特性黏数([η])0.67 d L/g的聚对苯二甲酸乙二醇酯(PET)为原料,经SSP反应生产高黏度产品(PET_(SSP)),通过分析SSP反应的影响因素,提出了生产PET_(SSP)切片的工艺控制方法。结果表明:产品PET_(SSP)的质量主要受原料PET切片品质、预结晶工艺、SSP工艺、氮气(N_2)纯度等条件的影响;选择相对分子质量分布窄、端羧基含量低、杂质含量少的原料PET切片,控制预结晶器热空气温度165℃,预加热器中N_2温度205℃,SSP塔中冷N_2流量650 Nm~3/h,N_2中乙二醇含量低于30μg/g,生产的PET_(SSP)的[η]达1.22 d L/g,且可纺性良好,生产的涤纶工业丝断裂强度大于8.21 cN/dtex。     

四种乳酸聚合方法的比较

以乳酸为原料,辛酸亚锡为催化剂,采用乳酸直接聚合(一步法)、丙交酯开环聚合(两步法)、熔融-固相聚合、溶剂回流脱水等不同的实验方法分别合成出了不同相对分子质量的聚乳酸。实验结果表明:实验方法不同,所得聚合物的相对分子质量不同,其中丙交酯开环聚合(两步法)所得聚合物的相对分子质量最大,可达80万左右,溶剂回流脱水法的可达24000左右,熔融-固相聚合的为10800,乳酸的直接聚合(一步法)的只有5000。     

一种新型高强度大伸长涤纶工业丝的制备

以普通聚酯切片为原料,利用固相聚合装置对其干燥增黏,制得低含水率、高黏度聚酯切片,再经熔融纺丝制备出一种新型高强度、大伸长涤纶工业丝。采用X射线衍射仪、差示扫描量热仪对其进行了表征,并利用纤维强伸仪测试了纤维的力学性能。结果表明:固相聚合后的切片结晶度高达60%以上,含水率可达0.000 5%以下,特性黏度为1.105 d L/g。以此增黏切片为原料,可生产出纤度为472 dtex,断裂强度≥7.15 c N/dtex,断裂伸长率为23.7%的纤维。由于该产品具有强度高、伸长率大和毛丝数量少的特点,已在水处理的超滤膜支撑材料领域得到了应用。     

熔融聚合法直接合成生物降解材料PGLA50/50

以等摩尔乙醇酸、L-乳酸为原料 ,通过熔融聚合法直接合成生物降解材料聚乙醇酸 -乳酸 (PGLA50 / 50 )。当在 1 65℃、70Pa下熔融聚合 1 0h ,以质量分数为 0 .5 %的氯化亚锡为催化剂时 ,产物特性黏数最高可达 0 .1 993dL/g。     

Morphological consequences of interchange reactions during solid state copolymerization in poly(ethylene terephthalate) and polycarbonate oligomers

Poly(ethylene terephthalate) (PET) (IV:0.15 dL/g) oligomer was obtained by depolymerisation of high molecular weight PET. Polycarbonate (PC) oligomer (IV: 0.15 dL/g) was synthesized by standard melt polymerization procedure using bisphenol A and diphenyl carbonate in the presence of a basic catalyst. Blends of varying compositions were prepared by melt blending the chemically distinct PET and PC oligomers. The copolymer, poly(ethylene terephthalate-co-bisphenol A carbonate) was synthesized by simultaneous solid state polymerization and ester-carbonate interchange reaction between the oligomers of PET and PC. The reaction was carried out under reduced pressure at temperatures below the melting temperature of the blend samples. DSC and WAXS techniques characterized the structure and morphology of the blends, while ¹NMR spectroscopy was used to monitor the progress of interchange reactions between the oligomers. The studies have indicated the amorphisation of the PET and PC crystalline phases in solid state with the progress of solid-state polymerization and interchange reaction.     

Solid‐state polymerization of poly(ethylene 2,6‐naphthalate)

The solid‐state polymerization (SSP) of poly (ethylene 2,6‐naphthalate) (PEN) was studied and compared with that of poly(ethylene terephthalate) (PET). The SSP of PEN, like that of PET, could be satisfactorily described with a modified second‐order kinetic model, which was based on the assumptions that part of the end groups were inactive during SSP and that the overall SSP followed second‐order kinetics with respect to the active end‐group concentration. The proposed rate equation fit the data of the SSP of PEN quite well under various conditions. PEN prepolymers in pellet and cube forms with intrinsic viscosities (IVs) ranging from 0.375 to 0.515 dL/g, various particle sizes, and various carboxyl concentrations were solid‐state polymerized at temperatures ranging from 240 to 260°C to study the effects of various factors. The SSP data obtained in this study could be readily applied to the design of commercial PEN SSP processes. Because PEN and PET share the same SSP mechanism, in general, the SSP behaviors of PEN are similar to those of PET. Thus, the SSP rate of PEN increased with increasing temperature, increasing prepolymer IV, and decreasing prepolymer particle size. However, because of the much higher barrier properties of PEN, the prepolymer particle size and carboxyl concentration had much greater effects on the SSP of PEN than on the SSP of PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1075–1084, 2007     

Solid-state polymerization of poly(ethylene terephthalate)

Solid -state polymerization of poly(ethylene terephthalate) (PET) is carried out by heating the low molecular weight prepolymer at temperatures below its melting point but above its glass transition temperature. Postcondensation occurs and the condensation byproducts can be removed by applying vacuum or inert gas. Polymers obtained usually have high molecular weight, low carboxyl and acetaldehyde content, and can be used for beverage bottle or industrial yarns. Polyesters for textile purposes are manufactured by a melt process. Chemical reactions involved in the solid state polymerization are transesterification, esterification, as well as the diffusion of byproducts. Overall reaction rate was governed by the molecular weight, carboxyl content of prepolymer, crystallinity, particle size, reaction temperature, and time. Prepolymer for solid state polymerization should have intrinsic viscosity 0.4 dL/g or more, density 1.38 g/mL, and minimum dimension 3 mm or less. The reaction temperature could be 200–250°C. When textile grade PET is used as prepolymer, crystallization at 180–190°C for 1–2 h increases the density to 1.38 g/mL. Polymerization at 240–245°C for 3–5 h can raise the intrinsic viscosity to 0.72 dL/g and carboxyl content less than 20 meq/kg. Appropriate reaction conditions are subject to the properties of prepolymers and the design of reactors. Reactor used for solid state polymerization could be vacuum dryer type or stationary bed. The former is suitable for a small capacity and is run batchwise. The latter is a continuous process and is economically feasible for large -scale production.     

Solvent assisted post-polymerization of PET

We have examined the influence of the solvent mixture diphenyl ether-biphenyl (DPE-BP) on the post-polymerization of poly(ethylene terephthalate) (PET) of intrinsic viscosity (IV=0.42 dL/g) in the swollen state and in solution, by following the IV increase and the end-group depletion. During the swollen state polymerization (SwSP) of thin disks (180 μm) at 195 °C, the initially rapid step growth polymerization slows dramatically beyond IV=1.2 dL/g in 5 h, and is unable to proceed beyond 1.4 dL/g. This appears to be related to the temporarily restricted mobility of the end groups due to the observed solvent induced crystallization, because sufficient reactive end groups can be directly detected, and further post-polymerization in melt state is possible. When limitations due to crystallization are eliminated by carrying out post-polymerization in solution at 250 °C, it proceeds to IV=1.8 dL/g in a single step. Since solution polymerization eliminates the requirement of handling fine PET particles, it offers an attractive route to high molecular weight PET, particularly when the solution can be directly used for further processing, e.g. into fibers.     

熔融挤出-固相增黏循环处理对PET性能的影响

将特性黏数为0.679 dL/g的纤维级聚对苯二甲酸乙二酯(PET)切片进行5次熔融挤出-固相增黏循环处理,对固相增黏后的PET切片进行纺丝,分析了处理后的PET切片的热性能,测试了PET纤维的断裂强度及色值。结果表明:随着PET熔融挤出-固相增黏循环处理次数的增加,固相增黏后PET切片的特性黏数下降,熔点降低,纤维断裂强度和断裂伸长率下降,色值b值增加,L值减小;5次固相增黏后PET切片的特性黏数均大于0.75 dL/g,但其可纺性变差,纤维力学性能下降。     

Solid‐state polymerization of melt‐spun poly(ethylene terephthalate) fibers and their tensile properties

The production of high modulus and high strength poly(ethylene terephthalate) fibers was examined by using commercially available melt‐spun fibers with normal molecular weight (intrinsic viscosity = 0.6 dL/g). First, molecular weight of as‐spun fibers was increased up to 2.20 dL/g by a solid‐state polymerization, keeping the original shape of as‐spun fibers. Second, the polymerized as‐spun fibers were drawn by a conventional tensile drawing. The achieved tensile modulus and strength of as‐drawn fibers (without heat setting) were 20.0 and 1.1 GPa, respectively. A heat setting was carried out for the as‐drawn fibers. Tensile properties of the treated fibers were greatly affected by the condition of the heat setting. This was related to the increase of sample crystallinity and molecular degradation during the treatments. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1791–1797, 2007     

熔体直纺260 dtex/144 f CDP-POY的开发

利用连续聚合装置合成阳离子可染共聚酯(CDP)熔体,经熔体输送管道直接纺丝生产CDP预取向丝(POY)。分析了CDP熔体的热性能;探讨了熔体直纺CDP-POY的生产工艺。结果表明:连续法合成的CDP熔体质量优良,熔体过滤器使用周期大于10d;通过增设熔体增压泵、熔体管道冷却器,选择熔体输送温度280℃,纺丝箱体温度293～295℃,无油丝的特性粘数降控制在0.014dL/g以内;采用外环吹和短程纺设备,控制纺丝速度2900～3000m/min,生产出的260dtex/144f CDP-POY质量优良。     

聚乳酸-己内酯直接熔融聚合工艺的研究

应用正交实验及SPSS统计软件研究聚乳酸-己内酯直接熔融聚合工艺。结果表明,质量分数 0．5％氯化亚锡为催化剂,乳酸与己内酯摩尔比为3/7,外消旋乳酸和左消旋乳酸与己内酯在180℃、70 Pa下分别直接熔融共聚12 h和16 h,可获得特性粘数分别为0．473 3 dL/g和0．412 1 dL/g的聚乳酸-己内酯。     

Relationships Between the Crystal Structures and the Multiple Melting Behaviors of Poly(ethylene 2,6‐naphthalate)

Summary: Poly(ethylene 2,6‐naphthalate) (PEN) can crystallize either from the glassy state or from the melt state. When crystallized from the glassy state, the sample was quenched from the melt in liquid nitrogen and then annealed at certain crystallization temperatures. When crystallized from the melt state, the sample was cooled to a preset temperature from the melt and then annealed for a certain time. The crystal modifications, morphologies and melting behaviors of PEN were investigated by means of wide‐angle X‐ray diffraction (WAXD), polarized optical microscopy (POM), small‐angle light scattering (SALS) and differential scanning calorimetry (DSC). The results show that an α crystal modification of PEN was obtained when PEN crystallized from the glassy state, whilst a β crystal modification was obtained when PEN crystallized from the melt state at a higher temperature. An hedritic morphology of PEN crystal was obtained with only one melting peak observed in DSC curves when PEN was crystallized at a higher temperature from either the glassy state or the melt state. The α crystal modification could also be obtained when PEN was crystallized at a lower temperature from the melt. Spherulitic or banded spherulitic morphologies of PEN crystals, exhibiting multiple melting peaks in DSC curves, were observed when PEN was crystallized at a lower temperature. The multiple melting behaviors of PEN crystals may be associated with spherulitic structures composed of lamellae of varying thickness.

WAXD patterns of PEN isothermally crystallized from different states.     

熔融/固相缩聚法制备聚乙醇酸甲酯的工艺条件优化

以乙醇酸甲酯为原料,先通过熔融缩聚法得到低聚物,然后进行固相缩聚法制备出高分子量的聚乙醇酸甲酯（PMG）。考察了工艺过程中催化剂的种类和用量、反应温度以及反应时间对PMG分子量的影响。并通过正交试验得到较优的合成条件为：催化剂二水合氯化亚锡的质量分数为0.5%,压力70 Pa,反应温度180 ℃,反应时间100 h,合成的PMG的特性黏度可达0.802 dL/g。采用傅里叶红外光谱（FT-IR）表征了PMG基团的特征吸收峰,差示扫描量热仪（DSC）表征了PMG的玻璃化温度、结晶温度和熔点。