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991.
Tsuneyuki Sato Takashi Miyoshi Makiko Seno 《Journal of polymer science. Part A, Polymer chemistry》2000,38(3):509-515
Polymerization of 2‐methacryloyloxyethyl phosphorylcholine (MPC) was kinetically investigated in ethanol using dimethyl 2,2′‐azobisisobutyrate (MAIB) as initiator. The overall activation energy of the homogeneous polymerization was calculated to be 71 kJ/mol. The polymerization rate (Rp) was expressed by Rp = k[MAIB]0.54±0.05 [MPC]1.8±0.1. The higher dependence of Rp on the monomer concentration comes from acceleration of propagation due to monomer aggregation and also from retardation of termination due to viscosity effect of the MPC monomer. Rate constants of propagation (kp) and termination (kt) of MPC were estimated by means of ESR to be kp = 180 L/mol · s and kt = 2.8 × 104 L/mol · s at 60 °C, respectively. Because of much slower termination, Rp of MPC in ethanol was found at 60 °C to be 8 times that of methyl methacrylate (MMA) in benzene, though the different solvents were used for MPC and MMA. Polymerization of MPC with MAIB in ethanol was accelerated by the presence of water and retarded by the presence of benzene or acetonitrile. Poly(MPC) showed a peculiar solubility behavior; although poly(MPC) was highly soluble in ethanol and in water, it was insoluble in aqueous ethanol of water content of 7.4–39.8 vol %. The radical copolymerization of MPC (M1) and styrene (St) (M2) in ethanol at 50 °C gave the following copolymerization parameters similar to those of the copolymerization of MMA and St; r1 = 0.39, r2 = 0.46, Q1 = 0.76, and e1 = +0.51. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 509–515, 2000 相似文献
992.
Hajime Ohtani Aki Suzuki Shin Tsuge 《Journal of polymer science. Part A, Polymer chemistry》2000,38(10):1880-1888
The end groups of styrene–methyl methacrylate (St‐MMA) copolymers polymerized radically with 2,2′‐azobisisobutyronitrile (AIBN) as an initiator, which are difficult to characterize even by NMR, were investigated by pyrolysis–gas chromatography. On the resulting pyrograms, characteristic products that formed from the end‐group moiety due to AIBN, such as 2‐cyanopropane, 2‐cyanopropen, and various compounds consisting of an isobutyronitrile group and a monomer unit, were observed together with those from the main chain, such as St and MMA monomers and various dimeric and trimeric products. The relative abundance between the recombination and disproportionation termination reactions in the copolymerization process was estimated from the relative intensities between the characteristic peaks of the end group and those of the main chain. Thus, the estimated abundance for the termination reactions suggested that the polymerization process for this particular copolymer system terminated preferentially by recombination rather than by disproportionation. Furthermore, the relative abundance between the monomer units adjacent to the chain‐end AIBN residues was estimated on the basis of the peak intensities of the products consisting of an isobutyronitrile group and either monomer unit, which reflected the penultimate neighboring structure of the end group in the polymer chain. Thus, the observed results suggested that the isobutyronitrile radical formed by the dissociation of AIBN in the initiation reaction was predominantly adjoined by St monomer rather than by MMA monomer. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1880–1888, 2000 相似文献
993.
994.
p-(1-Methylcyclohexyloxy)styrene (PC6ST) was synthesized by acid catalyzed addition reaction of p-bromophenol with 1-methylcyclohexene, followed by Grignard coupling with vinyl bromide catalyzed by NiCl2(dppp). Radical polymerization of PC6ST in the presence or absence of TEMPO afforded poly(PC6ST) with narrow molecular weight distribution without the elimination of the protective group. The obtained poly(PC6ST) showed a higher deprotection ability in response to external stimulation such as an acid compared with poly(p-tert-butoxystyrene). 相似文献
995.
Hiroyuki Nakamura Makiko Seno Tsuneyuki Sato 《Journal of polymer science. Part A, Polymer chemistry》1997,35(1):153-162
The effect of LiClO4 on the polymerization of di-2-[2-(2-methoxyethoxy)ethoxy]ethyl itaconate (DMEI) with dimethyl 2,2′-azobisisobutyrate (MAIB) was investigated in methyl ethyl ketone (MEK) kinetically and by ESR. The polymerization rate (Rp) at 50°C, where the concentrations of DMEI and MAIB were 1.00 and 5.00 × 10−2 mol/L, increased with increasing [LiClO4]. Marked acceleration was observed at higher [LiClO4]s than 1.0 mol/L. The molecular weight of resulting polymer (ca. 10,000) was relatively insensitive to [LiClO4], indicating occurrence of chain transfer. IR analysis of mixtures of LiClO4/DMEI and LiClO4/poly(DMEI) indicated complexation of LiClO4 with DMEI and its polymer. The rate constants of propagation (kp) and termination (kt) were determined by ESR. kp (1.7–10.5 L/mol s at 50°C) increased with [LiClO4]. kt (5.2–1.0 × 104 L/mol s at 50°C) showed remarkable decrease at higher [LiClO4]s than 1.0 mol/L. Rp of polymerization of equimolar complex of LiClO4/DMEI with MAIB at 50°C in MEK was expressed by Rp = k[MAIB]0.5[DMEI]2.4. kp increased and kt decreased with [DMEI]. The activation energies of overall polymerization, propagation and termination were estimated to be 34.5, 8.0, and 59.4 kJ/mol. Copolymerization of DMEI with styrene was also profoundly affected by the presence of LiClO4. Such large effects of LiClO4 on the homo- and copolymerization of DMEI are explicable in term of association of LiClO4-complexed DMEI monomers. © 1997 John Wiley & Sons, Inc. 相似文献
996.
Three styrene-type monomers having an oxadiazole group were prepared. The monomers were polymerized by a radical initiator into high molecular weight polymer. Polymers were soluble in many organic solvents such as chloroform, benzene and tetrahydrofuran. Polymer films were amorphous and transparent and showed no change after several months of preparation. The polymer had two reduction potentials around −2 V versus Ag/AgCl electrode. The polymer film dispersed with N,N,N′, N-tetraphenyldiaminobiphenyl (TPD) showed electroluminescence due to the exciplex with TPD. © 1997 John Wiley & Sons, Ltd. 相似文献
997.
998.
Tsuneyuki Sato Sumio Shimooka Makiko Seno 《Journal of polymer science. Part A, Polymer chemistry》1998,36(4):563-572
The polymerization of o-(1,3-dioxolan-2-yl)phenyl ethyl fumarate (DOPEF) initiated with dimethyl 2,2′-azobisiso-butyrate (MAIB) was studied kinetically in benzene. The polymerization rate (Rp) at 60°C was given by Rp = k [MAIB]0.76 [DOPEF]0.71. The overall activation energy of polymerization was calculated to be 98.3 kJ/mol. The number-average molecular weight of resulting poly(DOPEF) was in the range of 1000–3100. 1H- and 13C-NMR spectra of resulting polymers revealed that the radical polymerization of DOPEF proceeds in a complicated manner involving vinyl addition, intramolecular hydrogen abstraction, and further ring opening of the cyclic acetal at higher temperatures. From the copolymerization of DOPEF (M1) and styrene (St) (M2) at 60°C, the monomer reactivity ratios were obtained to be r1 = 0.02 and r2 = 0.20, the values of which are similar to those of the copolymerization of ethyl o-formylphenyl fumarate and St. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 563–572, 1998 相似文献
999.
Akihiro Suzuki Yoshinori Sato Toshio Kunugi 《Journal of Polymer Science.Polymer Physics》1998,36(3):473-481
A continuous zone-drawing/zone-annealing method was applied to poly(ethylene terephthalate) fibers in order to improve their mechanical properties. Apparatus used for this treatment was assembled in our laboratory. The continuous zone-drawing treatment was carried out at a drawing temperature of 103°C under an applied tension of 6.6 MPa to fully orient amorphous chains in the drawing direction without inducing thermal crystallization. The continuous zone-annealing treatment was carried out twice at an annealing temperature of 160°C under 102.2 MPa and at 183°C under 161.1 MPa to crystallize the highly oriented amorphous chains. The fiber was continuously drawn and annealed at a rate of 420 mm/min. The fiber obtained had a birefringence of 0.260, a degree of crystallinity of 55%, a tensile modulus of 18 GPa, and a storage modulus of 21 GPa at 25°C. Despite the large difference in the treating speed between the continuous zone-annealing and zone-annealing, their values are approximately equal to those of the zone-annealed PET fiber that was reported previously. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 473–481, 1998 相似文献
1000.
Itaru Sato Yohei Matsueda Kousuke Kadowaki Shigeru Yonekubo Takanori Shibata Kenso Soai 《Helvetica chimica acta》2002,85(10):3383-3387
1,3‐Disubstituted chiral allenes without any heteroatoms act as chiral initiators in the addition of (i‐Pr)2Zn to pyrimidine‐5‐carbaldehyde to afford, in combination with the subsequent asymmetric autocatalysis, chiral pyrimidin‐5‐yl alkanols with up to 98% ee. The absolute configuration of the pyrimidin‐5‐yl alkanol formed depend on that of the chiral allene. 相似文献