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1、第44卷,第3期工程塑料應(yīng)用Vol.44,No.3122016年3月ENGINEERINGPLASTICSAPPLICATIONMar.2016doi:10.3969/j.issn.1001-3539.2016.03.003側(cè)鏈含酯基的聚對(duì)苯撐的合成及其水解性研究毛丹波,王躍川(四川大學(xué)高分子科學(xué)與工程學(xué)院,高分子材料工程國(guó)家重點(diǎn)實(shí)驗(yàn)室,成都610065)摘要:以自制的2,5-二氯苯甲酸甲酯和2,5-二氯苯甲酸異辛酯為單體,采用Ni/Zn催化體系,合成了側(cè)基分別為甲酯基、異辛酯基的聚對(duì)苯撐及其共聚物,利用凝膠滲透色譜法和差示掃描量熱法測(cè)試了3種聚合物的分子量及玻璃化轉(zhuǎn)變溫度(Tg),
2、并測(cè)試了它們?cè)谟袡C(jī)溶劑中的溶解性。結(jié)果表明,利用該催化體系能得到一定分子量的聚對(duì)苯撐均聚物和共聚物,兩種單體按投料比進(jìn)行了共聚;通過調(diào)整單體投料比,可以調(diào)控共聚物的Tg在–7.7~130℃之間變化,當(dāng)單體投料比為1∶1(物質(zhì)的量之比)時(shí),共聚物的Tg為87.7℃;當(dāng)引入大支鏈側(cè)基異辛酯基時(shí),聚對(duì)苯撐在有機(jī)溶劑中的溶解性大大提高。由于側(cè)基酯基水解的難易程度不同,通過一定的水解條件考察均聚物和共聚物的水解特性,發(fā)現(xiàn)在一定堿性條件下,含甲酯基的均聚物30min內(nèi)已全部水解,而含異辛酯基的均聚物在該時(shí)間內(nèi)幾乎不水解,水解完全需要12h。對(duì)單體投料比為1∶1的共聚物進(jìn)行水解,發(fā)現(xiàn)相同條件下完全
3、水解只需75min。水解后側(cè)基羧基的存在可為后續(xù)的改性比如交聯(lián)提供反應(yīng)活性點(diǎn)。關(guān)鍵詞:聚對(duì)苯撐;共聚;側(cè)鏈酯基;水解中圖分類號(hào):O632.7文獻(xiàn)標(biāo)識(shí)碼:A文章編號(hào):1001-3539(2016)03-0012-06SynthesisandHydrolysisofPoly(p-phenylene)swithEsterPendantGroupsMaoDanbo,WangYuechuan(CollegeofPolymerScience&Engineering,StateKeyLaboratoryofPolymerMaterialsEngineering,SichuanUniversity,
4、Chengdu610065,China)Abstract:Takingtwoestersubstituted2,5-dichlorobenzoates(substituent:methyl,iso-octyl)madebyselfasmonomers,thepoly(p-phenylene)swithmethylesteroriso-octylesterpendantgroupandtheircopolymerweresynthesizedwithNi-catalyzed/Zn-mediatedsystem.Themolecularweightandglasstransitionte
5、mperature(Tg)ofthethreekindsofpolymerswerecharacterizedbyGPCandDSC,theirsolubilityinorganicsolventswerealsotested.Theresultsshowthatpoly(p-phenylene)homopolymersandcopolymerwithacertainmolecularweightwereobtainedthroughNi-catalyzed/Zn-mediatedsystem,andalsothetwomonomersarecopolymerizedonthebas
6、isofchargeratio.Byadjustingdifferentmonomerchargeratios,Tgofthecopolymercanbetunedfrom–7.7℃to130℃,whenthechargeratiois1∶1(moleratio),Tgofthecopolymeris87.7℃.Thesolubilityinorganicsolventsaregreatlyenhancedbyintroducingbulkyiso-octylesterpendantgroupintopoly(p-phenylene).Moreover,thehydrolysisch
7、aracteristicsofesterpendantgroupsaredifferentbecauseofsterichindrance,andthehydrolysesofthehomopolymerswereinvestigatedinacer-tainalkalinecondition.Thehomopolymerwithmethylesterpendantgroupisabsolutelyhydrolyzedin30minwhilethehomo