物理化学学报
物理化學學報
물이화학학보
ACTA PHYSICO-CHIMICA SINICA
2005年
8期
873-877
,共5页
彭静%朱轶才%翟茂林%乔金樑%魏根拴
彭靜%硃軼纔%翟茂林%喬金樑%魏根拴
팽정%주질재%적무림%교금량%위근전
OH自由基%聚二甲基硅氧烷(PDMS)乳液%辐射交联%辐射降解%交联剂
OH自由基%聚二甲基硅氧烷(PDMS)乳液%輻射交聯%輻射降解%交聯劑
OH자유기%취이갑기규양완(PDMS)유액%복사교련%복사강해%교련제
Hydroxyl radical%Polydimethylsiloxane latex%Radiation crosslinking%Radiation degradation%Crosslinking sensitizer
通过凝胶和溶胶分析与分子量测定的方法,研究了不同体系下,·OH对PDMS乳液γ辐射效应的影响.结果表明,·OH不仅可引发聚二甲基硅氧烷的分子间交联,也能促进其降解.对于纯PDMS乳液,在所研究的剂量范围内,·OH对其辐射交联行为影响较小.但若体系中加入H2O2、KIO4和N2O这些提高·OH生成产额的添加剂时,·OH对PDMS的促降解作用会随着吸收剂量增加而表现更明显,导致凝胶含量与纯乳液辐照情况相比下降较多.即使加入交联剂-三羟甲基丙烷三甲基丙烯酸酯(TMPTMA),在过量的·OH存在下,当吸收剂量大于40 kGy以上时,TMPTMA不仅没有提高交联度,反而会与·OH协同,使PDMS的凝胶含量下降更显著,同时产生更多的小分子聚合物,并使PDMS的平均分子量分布变窄.这可能是由于交联剂首先与·OH作用,形成的产物会加快PDMS的降解.
通過凝膠和溶膠分析與分子量測定的方法,研究瞭不同體繫下,·OH對PDMS乳液γ輻射效應的影響.結果錶明,·OH不僅可引髮聚二甲基硅氧烷的分子間交聯,也能促進其降解.對于純PDMS乳液,在所研究的劑量範圍內,·OH對其輻射交聯行為影響較小.但若體繫中加入H2O2、KIO4和N2O這些提高·OH生成產額的添加劑時,·OH對PDMS的促降解作用會隨著吸收劑量增加而錶現更明顯,導緻凝膠含量與純乳液輻照情況相比下降較多.即使加入交聯劑-三羥甲基丙烷三甲基丙烯痠酯(TMPTMA),在過量的·OH存在下,噹吸收劑量大于40 kGy以上時,TMPTMA不僅沒有提高交聯度,反而會與·OH協同,使PDMS的凝膠含量下降更顯著,同時產生更多的小分子聚閤物,併使PDMS的平均分子量分佈變窄.這可能是由于交聯劑首先與·OH作用,形成的產物會加快PDMS的降解.
통과응효화용효분석여분자량측정적방법,연구료불동체계하,·OH대PDMS유액γ복사효응적영향.결과표명,·OH불부가인발취이갑기규양완적분자간교련,야능촉진기강해.대우순PDMS유액,재소연구적제량범위내,·OH대기복사교련행위영향교소.단약체계중가입H2O2、KIO4화N2O저사제고·OH생성산액적첨가제시,·OH대PDMS적촉강해작용회수착흡수제량증가이표현경명현,도치응효함량여순유액복조정황상비하강교다.즉사가입교련제-삼간갑기병완삼갑기병희산지(TMPTMA),재과량적·OH존재하,당흡수제량대우40 kGy이상시,TMPTMA불부몰유제고교련도,반이회여·OH협동,사PDMS적응효함량하강경현저,동시산생경다적소분자취합물,병사PDMS적평균분자량분포변착.저가능시유우교련제수선여·OH작용,형성적산물회가쾌PDMS적강해.
By measuring the gel fraction and GPC spectra of irradiated polydimethylsiloxane (PDMS) samples, the radiation effect of PDMS in latex form was investigated. Results showed that the ·OH radical could not only initiate the radiation crosslinking of PDMS latex, but also accelerate the scission of PDMS molecular chain. For the PDMS latex without additives, the effect of ·OH on the crosslinking behavior is not obvious. However, the addition of H2O2 or KIO4 or N2O which could increase the concentration of ·OH would enhance the radiation degradation of PDMS.Moreover, with the increase of absorbed dose, the degradation is more predominant to lead to the drop of gel fraction.Particularly, in the presence of crosslinking sensitizer-trimethylol propane trimethacrylate (TMPTMA), when the dose was above 40 kGy, the excess ·OH radical accelerated remarkably the degradation of PDMS chain which resulted in the narrow polydispersity of molecular weight and increase in content of PDMS with low molecular weight, and decrease of gel fraction, comparing with those of irradiated PDMS latex without TMPTMA. This suggested that the synergetic interaction perhaps existed between TMPTMA and excess ·OH radical. This might be attributed to that the ·OH radicals react with TMPTMA firstly, the resulted product might accelerate the degradation of PDMS.