聚碳酸亚酯多元醇在涂料中的应用

介绍了新型环保涂料中间体材料──聚碳酸亚酯多元醇的生产合成与应用,揭示了其在水性工业涂料中的功用。介绍了国内研发和生产该材料的企业或单位,对其未来市场需求作了重点说明和分析。     

Block copolymerization of carbon dioxide with cyclohexene oxide and 4-vinyl-1-cyclohexene-1,2-epoxide in based poly(propylene carbonate) by yttrium-metal coordination catalyst

The coordination system, Y(CF₃CO₂)₃ (I)-Zn(Et)₂ (II)-m-hydroxybenzoic acid (III), was found to be the most active catalyst to generate poly(propylene carbonate) (PPC) from carbon dioxide and propylene oxide (PO) in 1,3-dioxolane. A high yield and a high molecular weight could be obtained at the conditions of a II/I molar ratio of 20, a III/II molar ratio of 1.0, a temperature of 60 °C, and a pressure of 2.76 MPa. The carbonate content in the resultant PPC was found to be nearly 100%.The block copolymerization in the based PPC was carried out by in situ introducing an epoxide other than PO right after the copolymerization of carbon dioxide with PO using the same catalyst system. The IR and ¹H NMR spectra as well as the measured molecular weights verified the resulting copolymers were block copolymers. For the block copolymerization of CO₂ with cyclohexene oxide and CO₂ with 4-vinyl-1-cyclohexene-1,2-epoxide in the based PPC, the yield as well as the cyclohexene carbonate and the 4-vinyl-1-cyclohexene carbonate contents were found to increase with increasing temperature. The most appropriate temperature was around at 80 °C. The weight-average molecular weights of the block copolymers lay in a range from 2.44×10⁵ to 3.16×10⁵, the polydispersity in a range from 5.0 to 6.3, and the 10% weight loss temperature in a range from 226 to 253 °C. The thermal and mechanical properties of the resultant block copolymers lay between those of PPC, poly(cyclohexene carbonate), and poly(4-vinyl-1-cyclohexene carbonate), indicating the desired properties of a polymer can be achieved via block copolymerization.     

Effect of chemical structure on crystallization behavior of poly(phenylene alkylene dicarboxylate) (PPAD)

Various poly(p-phenylene alkylene dicarboxylates) (PPADs) were synthesized and their crystallization behavior was examined as functions of the length and the odd/even numbers of carbon atoms in the aliphatic component. PPADs with longer aliphatic units of even-numbered carbon atoms were found to crystallize faster than do those of other cases. The results are compared with the crystallization behavior of conventional poly(alkylene terephthalate)s (PATs), e.g., poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT), which have the same chemical composition as the corresponding PPAD but the reversed direction of the ester group. The effects of this structural difference on the melting temperature and the crystallization kinetics are also discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1575–1582, 1997     

Controllable preparation of poly(alkylene carbonate)s and observation on their structure-related odd-even effect

The primary aim of this paper is to explore the influence of the number of CH₂ groups per -(CH₂)_nOCOO- repeat unit (Num_c) on the properties of poly(alkylene carbonate)s. A series of poly(alkylene carbonate)s with different Num_c, including PTMC (Num_c = 3), PTeMC (Num_c = 4), PPMC (Num_c = 5), PHMC (Num_c = 6) and PDMC (Num_c = 10) were investigated for that purpose by DSC and XRD techniques. The method of Sn(Oct)₂-catalyzed ring-opening polymerization was developed to prepare poly(pentamethylene carbonate)s (PPMC), which presented a controllable feature. Regarding crystallization rate and Tm of poly(alkylene carbonate)s, an interesting odd-even effect was first reported related to the Num_c. The order of crystallizing ability of poly(alkylene carbonate) was: PTMC (Num_c = 3) < PPMC(Num_c = 5) < PTeMC (Num_c = 4) < PHMC (Num_c = 6) < PDMC (Num_c = 10). Poly(alkylene carbonate)s characterized with even Num_c appeared to readily crystallize relative to that with odd Num_c.     

Thermal analysis of FeCl3-doped poly(3-butylthiophene) and poly(3-dodecylthiophene)

Summary For neutral and FeCl₃-doped poly(3-butylthiophene) (P3BT) and poly(3-dodecylthiophene) (P3DDT), conductivity measurement and thermal analysis are performed. Before doping, the glass transition temperatures (T_g) of the P3BT and P3DDT are 75.4°C and 5.6°C respectively. No melting transition of an ordered phase for P3BT is observed. But for P3DDT, the melting temperatures of ordered side chains and main chains are 56.1°C and 116.3°C respectively. Upon doping, the T_g 's shift upward to 150.5°C and 51.2°C for P3BT and P3DDT respectively and the two melting peaks of the ordered phases of P3DDT disappear. The dopant anions decompose in the range of about 150 to 230°C. The conductivities increase with increasing temperature and reach maxima at 135°C and 28°C and drop sharply in the range of 160–200°C and 130–170°C for P3BT and P3DDT respectively. This indicates that the thermal motion of the main chains would lead to a drop of conductivity due to thermal undoping, while the dopant decomposition would lead to a rapid loss of conductivity and an occurrence of crosslinking reaction.     

Time resolved study of oriented crystallisation of poly(lactic acid) during rapid tensile deformation

Poly(l-lactic acid) with 4% d-lactic acid comonomer has been drawn in the amorphous state at 80, 90, 100, 110 and 120 °C at an extension rate of 4 s⁻¹ while simultaneously recording WAXS and SAXS patterns at intervals of 0.12 s. At 80, 90 and 100 °C, crystallisation is very rapid (1-4 s⁻¹) and follows a first order transformation process to give highly oriented crystals. SAXS patterns were barely detectable at these temperatures despite fractional crystallinity of ∼0.2. At 110 and 120 °C, crystallisation was very slow (∼0.01 s⁻¹) and gave rise to crystals with a lower degree of orientation. After eventual crystallisation at 120 °C, a two-point SAXS pattern develops with narrow lateral spread, suggesting ‘shish kebab’ morphology. When the 80 °C drawn sample was annealed at 120 °C, a strong four point SAXS pattern develops. The change in drawing and crystallisation behaviour at higher draw temperature is attributed to the onset of chain retraction relaxation processes. The WAXS fibre pattern after annealing shows sampling on intermediate layer lines that is consistent with the α crystal form with a 10₃ helix. However, prior to annealing, sampling indicates a different, less defined helical configuration.     

Segmented copolymers of uniform tetra-amide units and poly(phenylene oxide): 2. Crystallisation behaviour

The crystallisation behaviour of copolymers of telechelic poly(2,6-dimethyl-1,4-phenylene ether) segments with terephthalic methyl ester endgroups (PPE-2T), 13 wt% crystallisable tetra-amide segments of uniform length units (two-and-a-half repeating unit of nylon-6,T) and dodecanediol (C12) was studied. The crystallisation rate of the T6T6T units was found to be very high despite the high T_g/T_m ratio. The supercooling (T_m−T_c) as measured by DSC is 18 °C at a cooling rate of 20 °C/min. WAXD has elucidated that the tetra-amide units remain organised in the melt.     

Modification of poly(vinyl butyral) coatings using bis-silanes

A commercially available poly(vinyl butyral) (PVB) coating was modified using a combination of 1–10 wt.% bis(trimethoxysilylethyl)benzene and dibutyltin dilaurate as the hydrolysis catalyst. Results of attenuated total reflectance (ATR)–FTIR analysis indicated the modification resulted in a hybrid coating material containing silicate moieties covalently bonded to the PVB polymer chains. Gravimetric analysis indicted the bis-silane addition resulted in a reduction in the diffusion coefficient of the parent coating to 2-chloroethyl ethyl sulfide (2-CEES), dimethyl methylphosphonate (DMMP), diisopropyl methylphosphonate, and methyl salicylate; the most significant reduction was observed for 2-CEES and DMMP at temperatures ≥50 °C. Glass transition temperature, abrasion resistance, tensile strength, and coating hardness were increased upon incorporation of the bis-silane. Despite incorporation of an inorganic component, coating flexibility was retained at low temperature (−15 °C).     

Thermal analysis, X-ray and electron diffraction studies on crystalline phase transitions in solvent-treated poly(hexamethylene terephthalate)

The crystal polymorphism, transformation, and morphologies in chloroform solvent-cast poly(hexamethylene terephthalate) (PHT) were examined by using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and temperature in situ transmission electron microscopy (TEM). Solvent-induced crystallization of PHT at room temperature yielded an initial crystal of γ-form, as confirmed by WAXD. Upon DSC scanning, the original γ-form in PHT exhibited three endothermic peaks, whose origins and association were carefully analyzed. The first peak, much smaller than the other two, is in the temperature range of ca. 100-120 °C. It was found that the solvent-induced γ-form was transformed to β-form at 125 °C via a solid-to-solid transformation mechanism. In addition, WAXD showed that γ- and β-forms co-existed in the temperature range of 100-125 °C. These mixed crystal forms were further identified using TEM, and the selected-area electron diffraction (ED) patterns revealed that both γ- and β-form crystals co-existed and were packed within the same spherulite. Solid-solid transformation from the solvent-induced γ-form to β-form in PHT upon heat scanning was presented with evidence and discussed.     

Preparation of poly(acrylonitrile-butyl acrylate) gel electrolyte for lithium-ion batteries

Poly(acrylonitrile-butyl acrylate) gel polymer electrolyte was prepared for lithium ion batteries. The preparation started with synthesis of poly(acrylonitrile-butyl acrylate) by radical emulsion polymerization, followed by phase inversion to produce microporous membrane. Then, the microporous gel polymer electrolytes (MGPEs) was prepared with the microporous membrane and LiPF₆ in ethylene carbonate/diethyl carbonate. The dry microporous membrane showed a fracture strength as high as 18.98 MPa. As-prepared gel polymer electrolytes presented ionic conductivity in excess of 3.0 × 10⁻³ S cm⁻¹ at ambient temperature and a decomposition voltage over 6.6 V. The results showed that the as-prepared gel polymer electrolytes were promising materials for Li-ion batteries.     

Synthesis and properties of amphiphilic poly(ethylene oxide)-grafted cardo poly(aryl ether sulfone) copolymers

A series of comb-type amphiphilic copolymers (PES-g-PEO) with a stiff poly(aryl ether sulfone) backbone and flexible PEO side chains was synthesized via a “grafting onto” technique. By controlling the monomer feed ratios, high molecular weight copolymers with a range of PEO side chain content were prepared and used to form tough and flexible membranes. The PES-g-PEO membranes displayed high thermal stability (T_d > 230 °C) and good mechanical properties. The water contact angles of the PES-g-PEO membranes ranged from 60.5° to 66.7°, 20° lower than those of poly(aryl ether sulfone) membranes (82-86°), indicating that the PEO side chains improved the hydrophilicity of the membranes. Wide-angle X-ray diffraction results indicated that the PES-g-PEO membranes possessed an amorphous structure, that is, crystallization of the PEO side chains did not occur. The Li-ion conductivity reached 2.26 × 10⁻⁴ S/cm at room temperature, much higher than that of the pure PEO-based system (10⁻⁶ S/cm), due to the presence of the amorphous PEO side chains between the PES backbones, which provided an effective Li-ion transport pathway.     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.     

Polymorphism of syndiotactic poly(p-fluoro-styrene)

Syndiotactic poly(p-fluoro-styrene) (s-PPFS) has been prepared with a polymerization procedure which allows reaching high average molecular masses and satisfactory yields. The polymorphic behavior of the polymer has been mainly studied by X-ray diffraction, calorimetric and infrared analyses. The main crystalline phase of s-PPFS, obtained by melt processing or cold-crystallization, exhibits trans-planar chains, is orthorhombic (a = 9.5 Å, b = 28.7 Å, c = 5.1 Å) and melts at nearly 320 °C. The X-ray analysis shows a strict analogy of this orthorhombic phase with the β phase of s-PS, also as for the occurrence of two limit ordered (β″) and disordered (β′) modifications, which differ for the intensity of reflections characterized by h + k = 2n + 1. A metastable crystalline phase, also exhibiting trans-planar chains, has been observed for as-polymerized samples as well as for amorphous samples crystallized by sorption of toluene or 1,4-difluoro-benzene. Mainly on the basis of solvent sorption and desorption experiments, it is suggested that this metastable phase is a co-crystalline phase with the low-molecular-mass guest molecules.     

Dual thermo- and pH-sensitive poly(N-isopropylacrylamide-co-acrylic acid) hydrogels with rapid response behaviors

Novel dual temperature- and pH-sensitive comb-type grafted poly(N-isopropylacrylamide-co-acrylic acid) (P(NIPAM-co-AAc)) hydrogels were successfully prepared by grafting PNIPAM chains with freely mobile ends onto the backbone of a cross-linked P(NIPAM-co-AAc) network. The prepared comb-type grafted P(NIPAM-co-AAc) hydrogels exhibited a more rapid deswelling rate than normal-type P(NIPAM-co-AAc) hydrogels in ultrapure water in response to abrupt changes from 25 °C to 60 °C. The same was true in buffer solution with a pH jump from 7.4 to 2.0 at 25 °C. Unexpectedly, the comb-type grafted P(NIPAM-co-AAc) hydrogels showed abnormal shrinkage behaviors in a buffer solution when the temperature increased from 25 °C to 60 °C with a pH value fixed at 7.4 or 2.0. In a buffer solution of pH 7.4, when the environmental temperature jumped from 25 °C to 60 °C, the grafted comb-type hydrogels shrank slower than the normal-type hydrogels, while at pH 2.0, the gels shrank faster than the normal-type gels in the beginning, which was followed by a slower shrinking. Interestingly, the much quicker shrinkage of the comb-type grafted P(NIPAM-co-AAc) hydrogels was observed because of the cooperative thermo-/pH-responses when the simultaneous temperature and pH stimuli met from pH 7.4/25 °C to pH 2.0/60 °C. The results of this study provide valuable information regarding the development of dual stimuli-sensitive hydrogels with fast responsiveness.     

Polyester-polyether block copolymers. I. Wide-angle X-ray diffraction studies of poly(hexamethylene terephthalate)/poly(oxytetramethylene) and related block polymers

The crystallisation and orientation of the individual structural components of poly(hexamethylene terephthalate)/poly(oxytetramethylene) block copolymers have been studied by wide-angle X-ray diffraction. The crystallisation behaviour in the unstretched state is determined by the proportions and molecular weights of the polyether blocks. For copolymers containing less than 60 wt% of polyether of m. w. ≯ 2000, only the polyester segments crystallise spontaneously, but with polyether m. w > 2000 two crystalline phases are formed. Similar behaviour was found in block polymers from other readily crystallising polyesters, but with non-crystallising polyesters the polyether segments crystallised spontaneously. Moderate tensile deformation of the block copolymers from polyether of m. w. 2000 leads to the stress-reversible highly oriented crystallisation of the polyether whilst the polyester remains undeformed. At higher extensions, irreversible orientation of the polyester segments occurs. The observations suggest that the polyester and polyether segments form discrete regions since otherwise homogeneous crystallisation should occur.     

Multiple melting behaviour of poly(ethylene terephthalate)

Differential scanning calorimetry (DSC) and temperature modulated DSC (MTDSC) have been used to investigate the melting behaviour of poly(ethylene terephthalate) (PET). Multiple melting endotherms were observed even at high heating rates, e.g. 160 K min⁻¹ and these have been attributed to the presence of two different distributions of lamella thickness and re-crystallisation (reorganisation) on heating. This has been confirmed by MTDSC—the presence of endotherms and an exotherm in the reversing component of the heat flow during heating. Examination of the endotherms of samples heating stepwise indicated that further crystallisation took place above the isothermal crystallisation temperature (T_c). Some part of this was associated with lamella thickening and crystal perfecting. The multiple melting endotherms observed are a consequence of the balance between the melting and re-crystallisation and the lamella thickness distribution existing within the sample, prior to heating. The triple melting endotherms observed are attributed to the melting of secondary and primary lamellae produced on crystallisation and to thickened lamellae produced during heating to the melting point.     

Crystallization, spherulite growth, and structure of blends of crystalline and amorphous poly(lactide)s

The effects of incorporated amorphous poly(dl-lactide) (PDLLA) on the isothermal crystallization and spherulite growth of crystalline poly(l-lactide) (PLLA) and the structure of the PLLA/PDLLA blends were investigated in the crystallization temperature (T_c) range of 90-150 °C. The differential scanning calorimetry results indicated that PLLA and PDLLA were phase-separated during crystallization. The small-angle X-ray scattering results revealed that for T_c of 130 °C, the long period associated with the lamellae stacks and the mean lamellar thickness values of pure PLLA and PLLA/PDLLA blend films did not depend on the PDLLA content. This finding is indicative of the fact that the coexisting PDLLA should have been excluded from the PLLA lamellae and inter-lamella regions during crystallization. The decrease in the spherulite growth rate and the increase in the disorder of spherulite morphology with an increase in PDLLA content strongly suggest that the presence of a very small amount of PDLLA chains in PLLA-rich phase disturbed the diffusion of PLLA chains to the growth sites of crystallites and the lamella orientation. However, the wide-angle X-ray scattering analysis indicated that the crystalline form of PLLA remained unvaried in the presence of PDLLA.     

Dynamic interplay between phase separation and crystallization in a poly(?-caprolactone)/poly(ethylene glycol) oligomer blend

We have investigated the crystallization effect on the phase separation of a poly(?-caprolactone) and poly(ethylene glycol) oligomer (PCL/PEGo) blending system using simultaneous small-angle light scattering and differential scanning calorimetry (SALS/DSC) as well as simultaneous small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and DSC (SAXS/WAXS/DSC). When the PCL/PEGo system, of a weight ratio of 7/3, is quenched from a melt state (160 °C) to temperatures below the spinodal point and the melting temperature of PCL (63 °C), the structural evolution observed exhibits characteristics of (I) early stage of spinodal decomposition (SD), (II) transient pinning, (III) crystallization-induced depinning, and (IV) diffusion-limited crystallization. The time-dependent scattering data of SALS, SAXS and WAXS, covering a wide range of length scale, clearly show that the crystallization of PCL intervenes significantly in the ongoing viscoelastic phase separation of the system, only after the early stage of SD. The effect of preordering before crystallization revives the structural evolution pinned by the viscoelastic phase separation. The growth of SAXS intensity during the preordering period conforms to the Cahn-Hilliard theory. In the later stage of the phase separation, the PCL-rich matrix, of spherulite crystalline domains developed due to the faster crystallization kinetics, traps the isolated PEGo-rich domains of a slower viscoelastic separation.     

Synthesis and characterization of poly(ester amide)s containing crystallizable amide segments

High molecular weight segmented poly(ester amide)s were prepared by melt polycondensation of 1,4-butanediol, dimethyl adipate and a preformed bisamide-diol based on 1,4-diaminobutane and ε-caprolactone. By varying the ratio of the bisamide-diol and 1,4-butanediol, a series of polymers was obtained with a hard segment content between 10 and 85 mol%. FT-IR and WAXD analysis revealed that the poly(ester amide)s crystallize in an α-type phase similar to the α-phase of even-even nylons. These polymers all have a micro-phase separated structure with an amide-rich hard phase and an ester-rich flexible soft phase. The polymers have a low and a high melt transition, corresponding with the melting of crystals comprising single ester amide sequences and two or more ester amide sequences, respectively. The low melt transition is between 58 and 70 °C and is independent of polymer composition. By increasing the hard segment content from 10 to 85 mol% the high melt transition increased from 83 to 140 °C while the glass transition temperature increased from −45 to −5 °C. Likewise, the elastic modulus increased from 70 to 524 MPa, the stress at break increased from 8 to 28 MPa while the strain at break decreased from 820 to 370%. Thermal and mechanical properties can thus be tuned for specific applications by varying the hard segment content in these segmented polymers.     

The properties of poly(tetrafluoroethylene) (PTFE) in tension

Samples of DuPont 7A and 7C Teflon (PTFE, poly(tetrafluoroethylene)) were tested in tension at strain-rates between 2×10⁻⁴ and 0.1 s⁻¹ and temperatures between −50 and 150 °C. Additionally, using a Hopkinson bar, a temperature series was undertaken in tension between −50 and 23 °C at a strain rate of 800 s⁻¹. To investigate the small-strain response, strain gauges were used to measure axial and transverse strain allowing the Poisson ratio to be calculated. The effect of crystallinity was investigated using 7C material thermally processed to produce more amorphous material. As expected, the tensile mechanical properties of PTFE are significantly affected by strain-rate and temperature, but only to a limited extent by crystallinity. The Poisson ratio at small strains was found to differ in tension (≈0.36) and compression (≈0.46). Failure behavior and microstructure were correlated to temperature induced phase transitions.