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1.
A crosslinking system consisting of 1,1‐di‐t‐butylperoxy‐3,3,5‐trimethyl cyclohexane peroxide and trimethylolpropane trimethacrylate (TMPTMA) has been used to introduce crosslinks into unplasticized poly(vinyl chloride) (PVC). The influence of the concentration of both reagents has been investigated, and crosslinking monitored by determination of the remaining sample weight after Soxhlet extraction with tetrahydrofuran. The system used (i.e., 0.5–2.0 phr peroxide with 5 to 15 phr TMPTMA) has been shown to be effective for crosslinking PVC. Gel contents of 30–40% have been obtained, premature crosslinking during processing is largely avoided, but thermal stability still needs to be improved. Considerable improvements in elevated temperature mechanical properties can be attained using an appropriate TMPTMA/peroxide concentration. The best tensile properties were obtained with 0.5 phr peroxide and 15 phr TMPTMA. Observed increases in Tg, also achievable with only 0.5 phr peroxide, but only slightly dependent on TMPTMA concentration, represent a useful increase in service temperature for the resulting compound. Lower peroxide levels may be adequate to achieve property improvements. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2657–2666, 2000 相似文献
2.
Omari E Ansong Susan Jansen Yen Wei Gregory Pomrink Shuxi Li Alpa Patel 《Polymer International》2008,57(6):863-871
BACKGROUND: This investigation evaluates the effectiveness of initiator adducts for living and controlled polymerization of methacrylates, crosslinking of dimethacrylates and thermal stabilities of the resulting polymers. Adducts of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy with benzoyl peroxide and with azobisisobutyronitrile were prepared and evaluated as stabilized unimolecular initiators for the free radical polymerization of methacrylate monomers using sulfuric acid as catalyst. The monomers used were methyl methacrylate, triethylene glycol dimethacrylate (TEGDMA) and ethoxylated bisphenol A dimethacrylate (EBPADMA). RESULTS: Successful polymerization was achieved at 70 and 130 °C with reaction times ranging from 45 min to 120 h. The dispersity (D) of poly(methyl methacrylate) (PMMA) was 1.09–1.28. The livingness and extent of control over polymerization were confirmed with plots of Mn evolution as a function of monomer conversion and of the first‐order kinetics. The glass transition temperature (Tg) for PMMA was 123–128 °C. The degradation temperature (Td) for PMMA was 350–410 °C. Td for poly(TEGMA) was 250–310 °C and for poly(EBPADMA) was 320–390 °C. CONCLUSION: The initiators are suitable for free radical living and controlled polymerization of methacrylates and dimethacrylates under mild thermal and acid‐catalyzed conditions, yielding medium to high molecular weight polymers with low dispersity, high crosslinking and good thermal stability. Copyright © 2008 Society of Chemical Industry 相似文献
3.
《国际聚合物材料杂志》2012,61(3-4):117-132
Abstract The dynamic mechanical properties of ethylene vinyl acetate (EVA) rubber filled with different loadings of carbon black and at different degrees of crosslinking were studied over a wide range of temperatures (-150° to +200°C). The loss tangent (tan δ) versus temperature plots indicated presence of different transitions. The α-transition (or the glass-rubber transition) corresponding to the maximum in tan δ value, occurred at ?17°C, which is the principal glass-transition temperature (abbreviated as T g) of EVA rubber. The γ-transition occurred in the temperature region of ?125° to ?135°C, while the β-transition appeared as a shoulder in the temperature region of ?65° to ?75°C. Besides, there was also a high tempeature transition around +62°C which is known as liquid to liquid transition (T 1.1). Incorporation of carbon black filler did not cause any shift of T g, while the tan δ peak values at T g decreased sequentially with increase in filler loading. The γ- and β-relaxations were found to be insensitive to filler loading. The T 1.1 transition, however, was found to be suppressed by incorporation of carbon black filler particularly at high loading. Extent of crosslinking did not influence the T g But, the T 1.1 transition, which was prominent with the lightly crosslinked system was found to be suppressed at high level of crosslinking. Strain dependent dynamic mechanical properties under isothermal conditions showed that the secondary structure breakdown of carbon black filler under the effect of strain amplitude is influenced by the degree of crosslinking of EVA rubber. 相似文献
4.
A two-stage, multistep soapless emulsion polymerization was employed to prepare various sizes of reactive core–shell particles (CSPs) with butyl acrylate (BA) as the core and methyl methacrylate (MMA) copolymerizing with various concentrations of glycidyl methacrylate (GMA) as the shell. Ethylene glycol dimethacrylate (EGDMA) was used to crosslink either the core or shell. The number of epoxy groups in a particle of the prepared CSP measured by chemical titration was close to the calculated value based on the assumption that the added GMA participated in the entire polymerization unless it was higher than 29 mol %. Similar results were also found for their solid-state 13C-NMR spectroscopy. The MMA/GMA copolymerized and EGDMA-crosslinked shell of the CSP had a maximum glass transition temperature (Tg) of 140°C, which was decreased with the content of GMA at a rate of −1°C/mol %. However, the shell without crosslinking had a maximum Tg of 127°C, which decreased at a rate of −0.83°C/mol %. The Tg of the interphasial region between the core and shell was 65°C, which was invariant with the design variables. The Tg of the BA core was −43°C, but it could be increased to −35°C by crosslinking with EGDMA. The Tg values of the core and shell were also invariant with the size of the CSP. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2069–2078, 1998 相似文献
5.
Prativa Kar Sandip Maiti Nilesh K. Shrivastava Saptarshi Dhibar B.B. Khatua 《Polymer Composites》2012,33(11):1977-1986
Positive temperature coefficient to resistivity (PTCR) characteristics of polystyrene (PS)/Ni‐powder (40 wt%) composites in the presence of multiwall carbon nanotubes (MWCNTs) has been investigated with reference to PS/carbon black (CB) composites. The PS/CB (10 wt%) composites showed a sudden rise in resistivity (PTC trip) at ≈110°C, above the glass transition temperature (Tg) of PS (Tg ≈95°C). Interestingly, the PTC trip temperature of PS/Ni‐powder (40 wt%)/MWCNT (0.75 phr) composites appeared at ≈90°C (below Tg of PS), indicating better dimensional stability of the composites at PTC trip temperature. The PTC trip temperature of the composites below the Tg of matrix polymer (PS) has been explained in terms of higher coefficient of thermal expansion (CTE) value of PS than Ni that led to a disruption in continuous network structure of Ni even below the Tg of PS. The dielectric study of PS/Ni‐powder (40 wt%)/MWCNT (0.75 phr) composites indicated possible use of the PTC composites as dielectric material. Dynamic mechanical analysis (DMA) and thermogravimetric analysis studies revealed higher storage modulus and improved thermal stability of PS/Ni‐powder (40 wt%)/MWCNT (0.75 phr) composites than the PS/CB (10 wt%) composites. POLYM. COMPOS., 33:1977–1986, 2012. © 2012 Society of Plastics Engineers 相似文献
6.
Positive temperature coefficient of resistivity (PTCR) characteristics of poly(styrene‐co‐acrylonitrile) copolymer (SAN)/stainless steel (SS) powder (80 wt %) composites prepared by melt‐mixing method has been investigated with reference to SAN/carbon black (CB) composites. The SAN/CB (10 wt %) composites showed a sudden rise in resistivity (PTC trip) at 125°C, above the glass transition temperature (Tg) of SAN (Tg ≈ 107°C). However, the PTC trip temperature of SAN/SS (80 wt %) composites appeared at 94°C, well below the Tg of SAN. Addition of 1 phr of nanoclay increased the PTC trip temperature of SAN/CB (10 wt %) composites to 130°C, while SAN/SS (80 wt %)/clay (1 phr) nanocomposites showed the PTC trip at 101°C. We proposed that the mismatch in coefficient of thermal expansion (CTE) between SAN and SS played a key role that led to a disruption in continuous network structure of SS even at a temperature below the Tg of SAN. The dielectric properties study of SAN/SS (80 wt %) composites indicated possible use of the PTC composites as dielectric material. DMA results showed higher storage modulus of SAN/SS composites than the SAN/CB composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 相似文献
7.
The synthesis and the nonlinear optical (NLO) properties of crosslinkable copolymers based on a novel NLO azo‐dye chromophore bearing two functions: one used the free‐radical copolymerization, that is, the methacrylate group, and the other one used for the crosslinking process, that is, the carboxylic acid function, are described. Copolymerization of this new monomer with glycidyl methacrylate leads to novel soluble crosslinkable NLO copolymers bearing free epoxy and carboxylic groups. The poling process, before crosslinking, is achieved at a temperature (Tp) close to the glass transition temperature, Tg (<70°C), of the copolymers. At this temperature, no reaction takes place between epoxy and carboxylic acid functions. In fact, crosslinking begins to start at a higher temperature, Tc (Tc ≫ Tp ≈ Tg). After the optimization of the poling and crosslinking processes, the NLO crosslinked polymer with 30 mol % of the chromophore exhibits a Tg of 157°C and a high quadratic susceptibility (d33) of 30 pm/V at 1320 nm. This coefficient is stable at 85°C for several weeks. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 974–982, 1999 相似文献
8.
Anna Laskowska Anna Marzec Gisele Boiteux Marian Zaborski Olivier Gain Anatoli Serghei 《Polymer International》2013,62(11):1575-1582
We investigated the influence of hydrophilic and hydrophobic imidazolium ionic liquids on the curing kinetic, mechanical, morphological and ionic conductivity properties of nitrile rubber composites. Two room temperature ionic liquids with a common cation—1‐ethyl‐3‐methylimidazolium thiocyanate (EMIM SCN; hydrophilic) and 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM TFSI; hydrophobic)—were used. Magnesium–aluminium layered double hydroxide (MgAl‐LDH; also known as hydrotalcite) was added to carboxylated acrylonitrile–butadiene rubber (XNBR) whereas fumed silica Aerosil 380 was used in acrylonitrile–butadiene rubber (NBR) as reinforcing fillers. NBR compounds were vulcanized with a conventional sulfur‐based crosslinking system whereas XNBR compounds were cured with MgAl‐LDH. The optimum cure time reduction and tensile properties improvement were obtained when both ionic liquids were added at 5 parts per hundred rubber (phr). The results revealed that EMIM SCN and EMIM TFSI induced an increase in the AC conductivity of nitrile rubber composites from 10?10 to 10?8 and to 10?7 S cm?1, respectively (at 15 phr ionic liquid concentration). The presence of ionic liquids in NBR slightly affected the glass transition temperature (Tg) whereas the presence of EMIM TFSI in XNBR contributed to a shift in Tg towards lower temperatures from ?23 to ?31 °C, at 15 phr loading, which can be attributed to the plasticizing behaviour of EMIM TFSI in the XNBR/MgAl‐LDH system. Dynamic mechanical analysis was also carried out and the related parameters, such as the mechanical loss factor and storage modulus, were determined. © 2013 Society of Chemical Industry 相似文献
9.
Positive temperature coefficient of resistivity (PTCR) behavior of poly(methyl methacrylate) PMMA/silver (Ag)‐coated glass bead composites has been investigated with reference to the conventional PMMA/carbon black (CB) composites. The PMMA/CB composites showed a sudden rise in resistivity (PTC trip) at 115°C, close to the glass transition temperature (T g, 113°C) of the PMMA. However, the PTC trip temperature (92°C) of PMMA/Ag‐coated glass bead composites was appeared well below the T g of PMMA. The room temperature resistivity and PTC trip temperature of the composites were also very much stable upon thermal cycling. Addition of 1 phr of nanoclay increased the PTC trip temperature of PMMA/CB composites to 120°C, close to the T g (118°C) of PMMA/clay nanocomposites, while PMMA/clay/Ag‐coated glass bead nanocomposites showed the PTC trip at 98°C. We proposed that the mismatch in coefficient of thermal expansion (CTE) between PMMA and glass beads played a key role that led to a disruption in continuous network structure of Ag‐coated glass beads even at a temperature well below the T g of PMMA. The decrease in dielectric permittivity of PMMA/Ag‐coated glass bead composites on increasing frequency indicated possible use of the PTC composites as dielectric material. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers 相似文献
10.
Electron beam, thermal free radical, and cationic complexation mechanisms have been employed to investigate crosslinking in selected polyphosphazenes. In polyphosphazenes functionalized with o‐allylphenol to facilitate free radical crosslinking, maximum crosslink density was achieved after 10 min at 130°C utilizing benzoyl peroxide as an initiator. Electron beam radiation was found to give an increased crosslink density with increased dose. The dose–crosslink density relationship observed for a aryloxyphosphazene terpolymer PPXP also was seen in poly[bis(2,2′‐(methoxyethoxy)ethoxy)phosphazene] (MEEP). However, with two lots of a fluoroalkoxyphosphazene an initial crosslink density was achieved at a lower electron beam exposure with no additional crosslink density observed with increasing dose. These measurements are observations of net crosslinking, which is the result of crosslinking processes balanced by chain scission processes. DSC revealed that neither thermal‐ nor electron beam‐initiated crosslinking cause any significant change in the Tg of the polymer. Metal ion complexation with MEEP consistently gave Tg values that were higher than MEEP. The Tg values measured for both MEEP and the lithium‐complexed MEEP were unaffected by electron beam irradiation. These data suggest the location of lithium complexation may be at the nitrogen lone electron pair on the backbone, representing a new mechanism of lithium complexation in phosphazenes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 55–66, 2000 相似文献
11.
A copolymer series was synthesized for migration imaging applications from isobutyl methacrylate and isobutyl styrene such that each homopolymer and all copolymers had glass transition temperature (Tg) near 55°C. The Tg of poly (p-isobutylstyrene) was predicted from literature values of similar polymers to be near 55°C. Poly (p-isobutylstyrene) was synthesised by acetylation of isobutyl benzene, reduction of p-isobutylacetoph-enone to the carbinol, dehydration to p-isobutylstyrene and free radical polymerisation to the polymer. The Tg of the homopolymer was 55°C, in excellent agreement with the predicted value. Copolymers of isobutyl methacrylate and p-isobutyl styrene were synthesised and their Tg's measured across the series by DSC (57°C ± 5°C). refractive index temperature coefficient (42°C ± 5°C). The copolymer series was also characterised by melt viscosity measurements. 相似文献
12.
Taguchi method (orthogonal array, OA9) was used to design an epoxy insulator by evaluating its glass transition temperature (T g) for using in a double base (DB) propellant grain. In this design method, three epoxy resins based on diglycidylether bisphenol A (DGEBA), three polyamine curing agents and a DGEBA-based reactive diluent agent were used. The curing process of epoxy resins with polyamines was studied by Fourier transform infrared spectroscopy. The results showed that the curing process was completed at room temperature. The effects of four parameters including resin type, curing agent type, curing agent concentration and diluent quantity were investigated to design a resin formulation with a highest T g after curing. The obtained results were quantitatively evaluated by the analysis of variance (ANOVA). The results of ANOVA showed that the highest T g of 86.0 ± 9.0 °C was obtained for the optimum formulation of MANA POX-95 as epoxy resin, H-30 as curing agent and 52 phr H-30. The T g measured by the experiment was 78.0 ± 0.9 °C. In addition, the single lap shear strength (adhesion strength) of the optimized insulator was measured at 13.66 ± 1.02 MPa. Pull-off test performed on the surface of DB propellant resulted a 1.935 ± 0.003 MPa adhesion strength. 相似文献
13.
The technique of dynamic mechanical thermal analysis (DMTA), operated in the dual cantilever mode, was used to characterize the effects of frequency, crystallinity, molecular weight (MW) and the extent of thermal oxidation on the dynamic mechanical response of poly(ethylene oxide) (PEO). The glass transition temperature (Tg) of PEO (MW = 9 × 105 Dalton) was found to be ?44°C. For PEO (MW = 1 × 105 Dalton) the Tg is ?39°C and this value increases by 2–9°C for every decade increase in the measuring frequency. Two minor, second-order transitions of PEO are also discernible at ?33 and 32°C. An inverse dependence of Tg on molecular weight was found in the molecular weight range studied and this is contrary to the Fox-Flory theory. It was also found that a partially crystalline sample is obtained despite very rapid quenching of PEO from the melt into liquid nitrogen. Thermal oxidation of PEO before processing leads to an increase in the amplitude of the loss tangent peak. This reflects the effect of oxidation products in restricting polymer crystallization and the subsequent increase in the amorphous fraction of the polymer. The position of the Tg peak in PEO remains reasonably fixed with progressive ageing and this was attributed to crosslinking having occurred in addition to chain scission during thermal oxidation. 相似文献
14.
The purpose of this study was to characterize the partial strain recovery of a thermoset shape‐memory polymer under a constraining stress. Three polymer networks were synthesized from tert‐butyl acrylate and poly(ethylene glycol) dimethacrylate (PEGDMA) solutions. The molecular weight and the weight fraction of the PEGDMA crosslinking monomer was altered systematically to maintain a constant glass transition temperature (Tg = 54°C) but tailorable rubbery moduli, which varied by almost an order of magnitude for the three polymer networks (E = 1.8–11.3°MPa). The shape‐recovery behavior of the polymers under a constraining stress was characterized for programming temperature below (20°C) and above (70°C) the Tg. The experiments revealed a peak in the recovered strain for samples programmed at 20°C. Recovered strain scaled linearly with the constraining stress by the rubbery modulus. The work performed by the shape‐memory polymer networks was observed to be primarily a function of constraining stress and crosslinking density, while programming temperature had a relatively mild influence; however, the efficiency of the shape‐memory effect was shown to be a function of constraining stress and programming temperature, but was independent of crosslinking density. Maximum work efficiencies (up to 45%) were observed for programming temperature of 70°C. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 相似文献
15.
Blends were prepared of poly(vinyl chloride) (PVC) with four different plasticizers; esters of aconitic, citric, and phthalic acids; and other ingredients used in commercial flexible PVC products. The thermal and mechanical properties of the fresh products and of the products after 6 months of aging were measured. Young's modulus of the PVC blends was reduced about 10‐fold by an increase in the plasticizer level from 15 to 30 phr from the semirigid to the flexible range according to the ASTM classification, but a 40‐phr level was required for PVC to retain its flexibility beyond 6 months. At the 40‐phr level, tributyl aconitate performed better than diisononyl phthalate (DINP) or tributyl citrate, in terms of lowering Young's modulus, both in the fresh materials and those aged for 6 months. The effects of the four plasticizers on the glass‐transition temperature (Tg) were similar, with Tg close to ambient temperature at the 30‐ and 40‐phr levels in freshly prepared samples and at 40–60°C in those aged for 6 months. The thermal stability of the PVC plasticized with DINP was superior among the group. Overall, tributyl aconitate appeared to be a good candidate for use in consumer products where the alleged toxicity of DINP may be an issue. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1366–1373, 2006 相似文献
16.
The physical and elastomeric properties of several DEXSIL 300 (10-SiB-3) samples were investigated. Modulus—temperature studies were used to determine the glass transition temperature Tg, the melting temperature Tm, and the oxidative crosslinking temperature Tox. Stress relaxation in air at elevated temperatures was used to compare the oxidative stability of the various formulations. It was found that the Tg of DEXSIL 300 is some 30°C lower than that of DEXSIL 200 (10-SiB-2) polymers, extending the elastomeric properties of DEXSIL 300 to lower temperatures. At high temperatures, both silica filler and ferric oxide are found to increase Tox to an ultimate value of 320°C. The effects of cure were also investigated, and γ-radiation-cured samples exhibit a slight degree of crystallinity with a melting temperature Tm = +40°C. No crystallinity was detected in similar peroxide-cured samples. Stress relaxation results are presented in support of the modulus—temperature studies. Formulations with a low Tox show oxidative effects earlier than those with a higher oxidation temperature. Silica-and ferric oxide-filled samples exhibit improved oxidative stability, as do samples filled with diphenylsilanediol. 相似文献
17.
Analysis of the curing behavior of cyanate ester resin systems 总被引:1,自引:0,他引:1
The role of metal catalysts on the curing characteristics of bisphenol A-based cyanate ester resin systems was investigated using Fourier transform infrared spectroscopy, differential scanning calorimetry, and rheological measurements. Bisphenol A dicyanate was cured with the octoates and naphthenates of zinc and manganese and with cobalt acetylacetonate at concentrations ranging from 0 to 750 ppm metal. Nonylphenol at concentrations between 0 and 8 phr was used as the cocatalyst. The results show that at metal catalyst concentrations less than 100 ppm and nonylphenol concentrations less than 4 phr, a maximum glass transition temperature of 250 to 260°C is obtained, irrespective of the type of catalyst used. For samples cured without nonylphenol, the maximum Tg was 298 to 302°C. At high catalyst concentrations, the Tg decreases with increasing catalyst concentration for the zinc catalysts, whereas no concentration effect was observed for samples cured with either manganese or cobalt. Nonylphenol was effective as a cocatalyst in achieving high conversions; however, the Tg at full conversion was found to decrease with increasing nonylphenol levels. 相似文献
18.
It is demonstrated for the first time that an epoxy thermoset resin can be cured at temperatures well below its Tg∞. This study compared the use of a uniform variable frequency microwave (VFM) field to standard oven curing at temperatures above and below Tg∞. Using Tg, tan δ, modulus, and FTIR measurements, it is shown that the reaction of BFDGE with MDA to attain a product with Tg∞ of 133 °C is achieved by VFM at temperatures from 100 to 140 °C; in contrast, the thermal cure normally requires 170 °C to attain the same Tg∞ and the same extent of cure. By following the pregel cure reaction with 13C‐NMR spectroscopy, it was determined that the lower cure temperatures of VFM cure predominately lead to chain extension and smaller amounts of crosslinking compared to the thermal cure. To explain these results, it is suggested that, after gelation, with VFM cure there is higher mobility from dipole rotations that continues the cure to completion without vitrification. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44222. 相似文献
19.
Synergistic effect of SBS and trimethylopropane trimethacrylate (TMPTMA) on dynamically vulcanized SEBS/PP blends
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The SEBS/PP thermoplastic vulcanizates (TPVs) were prepared by melt blending. Di‐tert‐butyl peroxide (DTBP) was used as the curing agent in combination with trimethylopropane trimethacrylate (TMPTMA) and poly(styrene‐b‐butadiene‐bstyrene) (SBS) as the coagents for the curing process. The synergistic effect of TMPTMA and SBS on the structure and properties of TPVs was studied by means of FT‐IR, DSC, torque rheometer, and universal testing machine. Both SEBS and PP crosslinked and the network structure formed under the participation of TMPTMA and SBS. Compared with the sole addition of the coagent, simultaneous loading of both TMPTMA and SBS could provide the TPVs with better solvent‐resistance and excellent mechanical properties. The crosslinking mechanism of the TPVs was also proposed. The slight lower value of Tm for the TPVs indicated the improved miscibility between PP and SEBS due to the crosslinking reaction. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44392. 相似文献
20.
Crosslinking in AFR700B polyimide was studied using several techniques. Crosslinking could not be detected using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). Swelling in n-methyl pyrrolidone (NMP) showed network formation occurs at cure temperatures ≥325°C (617°F), but the reaction kinetics could not be determined from the data. Dynamic mechanical analysis (DMA) studies have shown that the storage modulus (G′) increased with increasing cure temperature up to 350°C (662°F), and was constant above 350°C (662°F), indicating that crosslinking via the reverse Diels-Alder reaction was occurring. A broad secondary transition was seen in the loss modulus (G″) curves, centered between 150 and 180°C (302 and 356°F). This secondary transition appeared at a cure temperature of 300°C (572°F) and became more dominant with increasing temperature and time. This secondary transition was not seen for cures <300°C (572°F) when the chains have not crosslinked. Therefore, this is likely due to a crosslink bond rather than one in the backbone. At 1 atm, crosslinking followed second-order kinetics based on the increase in glass transition temperature (Tg). The Arrhenius plot of the rate constant showed a break in the slope, possibly indicating a change in reaction mechanism. At 1.38 MPa (200 psi), the Tg data was too scattered to determine the kinetics. 相似文献