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1.
A bio-based plasticizers, acetyl-oleate triethylene glycol (AOT), was successfully synthesized by using oleic acid as a raw material through esterification, epoxidation, and acetylation. Its structure was analyzed by Fourier transform infrared spectroscopy and 1H nuclear magnetic resonance. The plasticizing performances of this plasticizer was compared with those of two commercial ones: dioctyl terephthalate (DOTP) and dioctyl adipate (DOA). This was done by blending these plasticizers with PVC, respectively. Thermal gravimetric analysis results showed that the 5% weight loss temperature of PVC with AOT was 53°C higher than that of DOA and 36°C higher than that of DOTP. The tensile results showed that the AOT plasticized PVC had excellent stretchability: its elongation at break with 50 phr AOT reached 697.7%. Furthermore, its transmittance was as high as 90%, showing better compatibility of ATO with PVC.  相似文献   

2.
Two castor oil acid esters containing a ketal or ketone group (KCL or CL), as alternative plasticizers for poly(vinyl chloride) (PVC), were prepared. The structures were confirmed by 1H NMR and FTIR spectroscopies. The effects of the presence of a ketal or ketone group in these compounds on PVC plasticization were examined. The DMA and SEM results showed that both plasticizers were miscible with PVC and exhibited excellent plasticizing properties, compared to those of dioctyl phthalate (DOP). The PVC plasticized by KCL displayed a lower Tg value of 20.6 ° C, which was lower than that of PVC plasticized with DOP (22.3 ° C) and PVC plasticized with CL (40.5 ° C). Tensile tests indicated that PVC plasticized using KCL showed a 37% higher of elongation at break than PVC plasticized by CL and 30% higher than PVC plasticized by DOP. The plasticizing mechanism was also investigated. Moreover, exudation, volatility, and extraction tests, along with TGA indicated that the presence of ketal groups effectively improved the migration resistance of plasticizer and the thermal stability of PVC blends. Taken together, introducing ketal groups into plasticizer might be an effective strategy for improving its plasticizing efficiency.  相似文献   

3.
Two natural plasticizers derived from cardanol (CD), cardanol acetate (CA) and epoxidized cardanol acetate (ECA), were synthesized and characterized by 1H NMR and 13C NMR. The plasticizing effects of the obtained plasticizers on semi-rigid polyvinylchloride (PVC) formulations were also investigated. Two commercial phthalate ester plasticizers, dioctyl terephthalate (DOTP) and diisononyl phthalate (DINP), were used as controls. Mechanical and thermal properties, compatibility, thermal stability, microstructure, and workability were assessed by dynamic mechanical analysis (DMA), mechanical analysis, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and dynamic stability analysis, respectively. Results indicated that the natural plasticizer ECA had overallsuperior flexibility, compatibility, thermal stability, and workability comparable to both controls. The obtained CA and ECA have lower volatility resistance and similar extraction and exudation resistance than that of DOTP and DINP. The CA was further blended with DOTP in soft PVC films. Results of DMA, TGA and mechanicalanalysis indicated that CA can serve as a secondary plasticizer to improve the related properties of soft PVC formulations. These CD derived plasticizers show promise as an alternative to fully or partially replace petroleum-based plasticizers.  相似文献   

4.
We synthesized 2,5‐furandicarboxylate esters [i.e., dibutylfuran‐2,5‐dicarboxylate, diisoamylfuran‐2,5‐dicarboxylate, and di(2‐ethylhexyl)furan‐2,5‐dicarboxylate] and investigated their potential application as plasticizers of commercial poly(vinyl chloride) (PVC) products. Fourier transform infrared analysis, mechanical tests, scanning electron microscopy investigation, differential scanning calorimetry analysis, dynamic mechanical thermal analysis, thermogravimetric analysis (TGA), melt flow rate (MFR) measurement, and plasticizer migration measurements were used to the evaluate the comprehensive properties of the blended products. The results of the tensile tests demonstrate that the blends exhibited antiplasticization and flexible plastic characteristics at 10 and 50 phr in PVC, respectively. Moreover, flexural and impact test data indicate that the three types of blends exhibited a similar tendency: the hardness decreased continuously as the amount of plasticizer increased. Their morphology indicated that all of the plasticizers had good compatibility with PVC. The resulting glass‐transition temperature of the investigated plasticizers was lower than that of pure PVC, and reduction was largest for the plasticizer with the highest molecular weight. TGA revealed that the thermal degradation of blended polymers occurred in three stages and that all of the blends were stable up to 180°C. Finally, the MFRs of all of the specimens indicated that the addition of a higher concentration of lower molecular weight biobased esters resulted in improved fluidity, but these compounds migrated more easily from the blends. Hence, 2,5‐furandicarboxylic acid derived from biomass has potential as a plasticizer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40938.  相似文献   

5.
In this work, poly(ε-caprolactone) (PCL) and liquid plasticizer were combined used to plasticize poly(vinyl chloride) (PVC), and the possibility of using PVC/PCL/plasticizer blends to fabricate soft PVC with enhanced migration resistance was investigated. Through partial replacement of liquid plasticizers in soft PVC by equal quantity of PCL, flexibility was maintained while extraction loss of plasticizer by organic solvent was reduced significantly. Furthermore, crystallization of PCL in PVC/PCL/plasticizer blends with low PCL content was observed, and crystallization rate of PCL was found to be influenced by plasticizer contents and structures. For instance, crystallization rate of PCL in PVC/PCL/diisononyl phthalate (DINP) (100/40/100) was 3.7 times faster than in PVC/PCL/DINP (100/40/80), while crystallization rate of PCL in PVC/PCL/dioctyl adipate(DOA)(100/40/100) was 8.3 times faster than in PVC/PCL/diisononyl cyclohexane-1,2-dicarboxylate (DINCH) (100/40/100). Low-field 1H NMR test manifested that different crystallization rate of PCL in PVC/PCL/plasticizer blends with different plasticizer structures was triggered by difference in plasticizers' compatibility with PVC, that is, the number of interaction point between PVC and plasticizers. It is concluded that PCL crystallization favored by liquid plasticizers in PVC/PCL/plasticizer blends was induced by interaction competition between PVC/plasticizer and PVC/PCL. As plasticizer content increases or its compatibility with PVC decreases, interaction competition becomes more intense and consequently faster crystallization of PCL occurs. Thus, to obtain soft PVC products with improve migration resistance while avoiding PCL crystallization, the total content of plasticizer (including both liquid plasticizer and PCL) should be lower than 66 phr (40 wt %). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48803.  相似文献   

6.
The poly(vinyl chloride) (PVC) industry plays an important role in today's total plastics industry. The major volume of PVC is used as soft and plasticized PVC. PVC applications consume approximately 80% of the total production of plasticizers. Most of the common plasticizers are aromatic esters of phthalic acid. In the majority of countries, phthalate plasticizers are banned due to their carcinogenic properties. The concern raised about toxicity led to a large demand for bio‐based non‐toxic plasticizers. Hence, there is an increasing interest in replacing the phthalate plasticizers with those produced from simple bio‐based materials. Dehydrated castor oil fatty acid (DCOFA) is a renewable resource which can be esterified and used as an environment friendly plasticizer for PVC. Benzyl ester (BE) was prepared by reacting DCOFA with benzyl alcohol in the presence of catalyst at 170–180 °C. Esterification was further confirmed by acid value, hydroxyl number, 1H NMR and Fourier transform IR spectroscopy. The modified plasticizer was used in various proportions as a co‐plasticizer in PVC for partial replacement of dioctyl phthalate (DOP). With an increase in the proportion of BE in PVC samples, a good plasticizing performance was observed. The incorporation of BE also resulted in a reduction in viscosity and viscosity pick‐up and improved mechanical, exudation, thermal degradation and chemical resistance properties. The presence of BE showed a reduction in the whiteness index due to presence of conjugated double bonds in the structure. The results of DSC, XRD and Shore hardness studies showed no significant variation in properties compared with those of DOP‐plasticized sheets and thus we can conclude that BE can be used as a co‐plasticizer in PVC. © 2013 Society of Chemical Industry  相似文献   

7.
The aim of the present work is to provide information about the migration of phthalate and non‐phthalate plasticizers generally used in flexible polyvinyl chloride (PVC) applications. Plastisols (pastes) were prepared by mixing PVC, plasticizer, and thermal stabilizer. The plasticized PVC (p‐PVC) films are obtained by gelation at 160°C for 15 min. The p‐PVC films were heat treated at 50, 85, 100, 130, and 160°C up to 420 min to follow the mass loss to find out diffusivity of plasticizer out of films into air and to determine related activation energies. The films having di‐octyl terephthalate (DOTP) and di‐isononyl 1,2‐cyclohexanedicarboxylic acid (DINCH) exhibited the lowest mass loss in general, among the phthalate and non‐phthalate plasticizer having p‐PVC films, respectively, as confirmed by FTIR investigation. The same tendency was observed for diffusion coefficients and for the activation energies of migration. The diffusion coefficients were found to be around 3.5 × 10?18–2.1 × 10?17 m2/sec for the studied plasticizers in PVC at 50°C and around 4.0 × 10?15–9.9 × 10?14 m2/sec at 160°C. The activation energies for 85–160°C interval were determined to be between 70 and 153 kJ/mol (0.72–1.58 eV) for the plasticizers used herein those could be treated as a homologous series as deduced from the related compensation factors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

8.
In this study, bio‐based hyperbranched ester was synthesized from castor oil. The chemical structure of the bio‐based hyperbranched ester obtained was characterized with Fourier transform infrared and 1H NMR spectra. Soft polyvinyl chloride (PVC) materials were prepared via thermoplastic blending at 160 °C using bio‐based hyperbranched ester as plasticizer. The performances including the thermal stability, glass transition temperature (Tg), crystallinity, tensile properties, solvent extraction resistance and volatility resistance of soft PVC materials incorporating bio‐based hyperbranched ester were investigated and compared with the traditional plasticizer dioctyl phthalate (DOP). The results showed that bio‐based hyperbranched ester enhanced the thermal stability of the PVC materials. The Tg of PVC incorporating bio‐based hyperbranched ester was 23 °C, lower than that of PVC/DOP materials at 28 °C. Bio‐based hyperbranched ester showed a better plasticizing effect, solvent extraction resistance and volatility resistance than DOP. The plasticizing mechanism is also discussed. © 2018 Society of Chemical Industry  相似文献   

9.
The use of bio‐based polymeric plasticizers could expand the application range of plasticized poly(vinyl chloride) (PVC) materials. In this study, a novel bio‐based polyester plasticizer, poly(glutaric acid‐glyceryl monooleate) (PGAGMO), was synthesized from glutaric acid and glyceryl monooleate via a direct esterification and polycondensation route. The polyester plasticizer was characterized by gel permeation chromatography, 1H‐nuclear magnetic resonance, and Fourier‐transform infrared spectroscopy. The plasticizing effect of PGAGMO on PVC was investigated. The melting behavior, thermal properties, and mechanical properties of PVC blends were studied. The results showed that the PGAGMO could improve the thermal stability and reduce the glass transition temperature of PVC blends; when phthalates were substituted by PGAGMO in PVC blends, the thermal degradation temperature of PVC blends increased from 251.1°C to 262.7°C, the glass transaction temperature decreased from 49.1°C to 40.2°C, the plasticized PVC blends demonstrated good compatibility, and the decrement of the torque and the melt viscosity of PVC blends were conducive to processing. All results demonstrated that the PGAGMO could partially substitute for phthalates as a potential plasticizer of PVC. J. VINYL ADDIT. TECHNOL., 22:514–519, 2016. © 2015 Society of Plastics Engineers  相似文献   

10.
以2,5呋喃二甲酸为基体分别与反式2己烯醇、正己醇反应,制备出不同分子结构的生物基增塑剂。通过冲击、拉伸测试并结合动态力学分析考察增塑剂分子结构及添加量对聚氯乙烯(PVC)力学性能的影响;采用毛细管流变仪考察增塑剂分子结构及添加量对PVC熔体流动性的影响。结果表明,2种新型生物基增塑剂均能提高PVC材料的冲击强度,且2,5呋喃二甲酸二正己酯(DNHFDC)增塑效果优于2,5呋喃二甲酸二(反式2己烯)酯(DT2HFDC);当添加量为10份(质量份,下同)时,以DNHFDC为增塑剂的PVC材料比添加等量DOP时的冲击强度提高了0.28 kJ/m2,拉伸强度降低了4.2 MPa。  相似文献   

11.
A new family of succinate-based plasticizers, consisting of molecules with a linear alkyl chain capped with n-alkyl succinates on both ends, was evaluated as potential bio-based plasticizers for stiff polymers. The influence of the central and side alkyl chain lengths on the mechanical and thermal properties as well as the migration behavior of poly(vinyl chloride) (PVC)/plasticizer blends was evaluated. The central chain length had the greatest influence on plasticizer performance, with shorter chains leading to blends with higher stress at break and surface hardness, whereas long chains produced softer blends. An optimum chain central length of five carbon atoms was observed, with longer chains leading to reduced compatibility and exudation of the plasticizer at higher plasticizer concentrations. The entire family of plasticizers performed comparably or better than the commercial plasticizer di(2-ethylhexyl) phthalate (DEHP) when incorporated into the blend at concentrations of 20–60 parts per hundred resin (phr). Overall, the succinate-based plasticizers/PVC blends all exhibited equal or improved tensile properties (by up to 77%), surface hardness (reduced by up to 43%), glass transition temperature (reduced by up to 11°C), and migration into organic media (reduced by up to 38%) when compared with blends with DEHP at 40 phr.  相似文献   

12.
Epoxidized rubber seed oil (4.5% oxirane content, ERSO) was prepared by treating the oil with peracetic acid generated in situ by reacting glacial acetic acid with hydrogen peroxide. The thermal behavior of the ERSO was determined by differential scanning calorimetry. The effect of the epoxidized oil on the thermal stability of poly (vinyl chloride) (PVC) plastigels, formulated to contain dioctyl phthalate (DOP) plasticizer and various amounts of the epoxidized oil, was evaluated by using discoloration indices of the polymer samples degraded at 160°C for 30 min and thermogravimetry at a constant heating rate of 10°C/min up to 600°C. The thermal behavior of the ERSO was characterized by endothermic peaks at about 150°C, which were attributed to the formation of network structures via epoxide groups, and at temperatures above 300°C, which were due to the decomposition of the material. Up to 50% of the DOP plasticizer in the PVC plastisol formulation could be substituted by ERSO without a marked deleterious effect on the consistency of the plastigel formed. In the presence of the epoxidized oil, PVC plastigel samples showed a marked reduction in discoloration and the number of conjugated double bonds, as well as high temperatures for the attainment of specific extents of degradation. These results showed that the ERSO retarded/inhibited thermal dehydrochlorination and the formation of long (n > 6) polyene sequences in PVC plastigels. The plasticizer efficiency/permanence of ERSO in PVC/DOP plastigels was evaluated from mechanical properties' measurements, leaching/migration tests, and water vapor permeability studies. The results showed that a large proportion of DOP could be substituted by ERSO in a PVC plastisol formulation without deleterious effects on the properties of the plastigels. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers.  相似文献   

13.
Dialkyl furan‐2,5‐dicarboxylates and epoxidized fatty acid esters (EFAE) of varying molecular weights and volatilities, as well as their mixtures, were investigated as alternative plasticizers for poly(vinylchloride) (PVC). The EFAE utilized were epoxidized soybean oil (ESO) and epoxidized fatty acid methyl ester (e‐FAME). All plasticizers were compatible with PVC, with plasticization efficiencies usually increasing with decreasing molecular weights of the plasticizers (except in the case of ESO, which was remarkably effective at plasticizing PVC, in spite of its relatively high molecular weight). In comparison with phthalate and trimellitate plasticizers, the alternatives generally yielded improved balance of flexibility and retention of mechanical properties after heat aging, with particularly outstanding results obtained using 30?50 wt % e‐FAME in mixtures with diisotridecyl 2,5‐furandicarboxylate. Although heat aging characteristics of the plasticized polymer were often related to plasticizer volatilities, e‐FAME performed better than bis(2‐ethylhexyl) 2,5‐furandicarboxylate, and bis(2‐ethylhexyl) phthalate of comparatively higher molecular weights. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42382.  相似文献   

14.
A novel plasticizer epoxidized dimeric acid methyl ester (EDAMe) based on rubber seed oil was synthesized. Chemical structure of EDAMe was characterized by Fourier transform infrared (FTIR) and gel permeation chromatography (GPC). Effects of EDAMe as secondary plasticizer and its substitution of commercial plasticizer dioctyl terephthalate (DOTP) in soft poly(vinyl chloride) (PVC) films were studied. The thermal properties, mechanical properties and migration stabilities of PVC films were explored with DMA, TG, TG–FTIR, dynamic thermal stability analysis, tensile and migration tests. The results indicated that the epoxidized rubber seed oil based ester has significantly higher thermal stability than DOTP. When DOTP was substituted with 20% (m/m) EDAMe, the results of initial decomposition temperature (Ti), 10% and 50% mass loss temperatures (T10 and T50), and the first maximum weight‐loss temperature rate (TP1) reached 267.2 °C, 263.5 °C, 307.3 °C and 298.9 °C, respectively. Furthermore, flexibility of the obtained PVC films enhanced significantly with the adding of EDAMe. The migration stabilities of EDAMe was also investigated and showed good migration resistance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43668.  相似文献   

15.
Organic solvents cyclohexane, dichloromethane, hexane, and tetrahydrofuran were tested to separate the dioctylphthalate (DOP) as plasticizer from the poly(vinyl chloride) (PVC)‐based materials. It was found that the efficiency of ultrasound‐enhanced hexane extraction of the DOP from PVC is 70% and the efficiency of the separation of the DOP and other compounds from the PVC by dissolution in THF followed by subsequent precipitation was 98–99%. Differential scanning calorimetry (DSC) and thermogravimetry (TG) were used to characterize the thermal behavior of PVC materials before and after extraction of plasticizers. It was found that during heating in the range 20–800°C the total mass loss measured for the nontreated, extracted, and precipitated PVC samples was 71.6, 66.6, and 97%, respectively. In the temperature range 200–340°C, the release of DOP, HCl, and CO2 was observed by simultaneous thermogravimetry (TG)/FTIR. The effect of plasticizers on thermal behavior of PVC‐based insulation material was characterized by DSC in the range ?40–140°C. It was found that, concerning the PVC cable insulation material before treatment, the value of the glass transition temperature (Tg) was 1.4°C, whereas for the PVC sample extracted by hexane, the value of Tg was 39.5°C and for the PVC dissolved in THF and subsequently precipitated, the value of Tg was 80.4°C. Moreover, the PVC samples after extraction of plasticizers, fillers, and other agents were tested to characterize their thermal degradation. The TG and FTIR results of chemically nontreated, extracted, and precipitated samples were compared. The release of DOP, HCl, CO2, and benzene was studied during thermal degradation of the samples by FTIR. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 788–795, 2006  相似文献   

16.
A new bio-based plasticizer, VA8-8, was prepared derived from vanillic acid, and its structure was verified by nuclear magnetic resonance. It was incorporated into poly(vinyl chloride) (PVC) to replace dioctyl phthalate (DOP), and its plasticizing performance was evaluated. The results indicated that VA8-8 shows good compatible with PVC resin, and has a excellent plasticizing effect for PVC. When DOP was partially or completely substituted with VA8-8, the Tg value PVC blends dropped from 34.6 to 24.3°C and the elongation at break increased from 196.4% to 301.9%, suggesting the enhanced plasticizing efficiency of plasticizer. The plasticizing mechanism was also simulated, and the interactions between VA8-8 and PVC molecules were discussed. The thermogravimetric analysis showed VA8-8 can more effectively improve the thermal stability of PVC than DOP. In addition, the migration resistance of VA8-8 was generally superior to that of DOP. Therefore, VA8-8 is a comparable to or better plasticizer than DOP, and it is a promising alternative plasticizer for PVC.  相似文献   

17.
In this study, chemical recycling products of waste poly(ethylene terephthalate) with oligoesters were used as new plasticizers for poly(vinyl chloride) (PVC). The preparation conditions of the dry blend mixtures of the suspension PVC containing synthesised plasticizers were similar to the conditions of the preparing mixtures with commercial plasticizers. The plasticization efficiency of PVC plasticizers was then examined by analysis of the mechanical, physical and chemical properties, as well as the thermal resistance and migration of plasticizer molecules from polymer matrix. Test results proved that compositions with synthesised oligomeric plasticizers possessed similar or better properties than those containing commercial oligomeric plasticizers and much better properties than those having monomeric plasticizers. Thermal stabilities of the proposed plasticizers were higher than those of the commercial plasticizers either monomeric (bis(2-ethylhexyl)phthalate) or oligomeric, despite the fact that the synthesised oligoesters did not contain any antioxidant. The best properties, especially low volatility, very good mechanical properties, low migration were resulted of the transesterification of the waste PET with oligoesters based on adipic acid, triethylene glycol and 2-ethylhexanol which were selected as plasticizers synthesised on the technical scale. The tested plasticized PVC compositions possessed very good tear resistance, tensile strength, decrease of weight loss after 168 h at 80 °C and low migration. Processing properties of PVC compositions containing these synthesised plasticizers confirmed their effectiveness in these compositions for extrusion process.  相似文献   

18.
The effect of combinations of zinc borate with ammonium octamolybdate or zinc stannate on smoke suppression upon combustion of flexible PVC was studied. Effects on Oxygen Index and on residual char after ten minutes at 560°C were also evaluated. These studies were done using both a conventional dioctyl phthalate (DOP) plasticizer and a mixed plasticizer consisting of a 1:1 combination of DOP and an alkyl aryl phosphate ester. For both plsticizer systems, results showed that combinations of the zinc borate with either ammonium octamolybdate or zinc stannate gave an improved effect with respect to smoke reduction upon combustion. Thermogravimetric analysis (TGA) of PVC containing these additives showed no indication of interactions to explain this effect. TGA analyses indicated that PVC samples made with the mixed plasticizer had final decompositon temperatures which were slightly higher than those made with DOP as the plasticizer.  相似文献   

19.
Blends of poly(vinyl chloride) (PVC) with different copolymers have been studied to obtain a plasticized PVC with improved properties and the absence of plasticizer migration. The copolymers used as plasticizers in the blends were acrylonitrile butadiene rubber, ethylene vinyl acetate (EVA), and ethylene-acrylic copolymer (E-Acry). Blends were studied with regard to their processing, miscibility, and mechanical properties, as a function of blend and copolymer composition. The results obtained were compared with those of equivalent compositions in the PVC/dioctyl phthalate (DOP) system. Better results than PVC/DOP were obtained for PVC/acrylonitrile butadiene rubber blends. The plasticizing effect on PVC of EVA and E-Acry copolymers was similar to that of DOP. It is shown that crosslinking PVC/E-Acry blends or increasing the vinyl acetate content in PVC/EVA blends, are alternatives that can increase the compatibility and mechanical properties of these blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1303–1312, 2000  相似文献   

20.
The aim of this paper is the determination of the specific migration of epoxidized sunflower oil (ESO) from rigid and plasticized poly(vinyl chloride) (PVC) into food simulants. ESO was obtained by epoxidation of commercial sunflower oil and used as a thermal organic co-stabilizer for PVC. For that purpose, rigid and plasticized (0, 15, 30, and 45 wt% of dioctyl phthalate or DOP) PVC films stabilized with ESO in the presence of Zn and Ca stearates were used to perform migration testing in olive oil. The test conditions were 12 d at 20 and 40°C and 2 h at 70°C with and without agitation.

The determination of ESO migration was carried out by gas chromatography-mass spectrometry (GC-MS). ESO was quantified by an external standard addition method, using linoleic acid (C18:2) as the external standard. The influence of various parameters, such as the agitation and time of contact, the temperature, the presence or the absence of the plasticizer, and the plasticizer concentration, was considered.  相似文献   

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