基于纤维素-糠醛-油脂的热塑性材料的合成和性能表征

以乙基纤维素(EC)、甲基丙烯酸四氢糠基酯(THFMA)和甲基丙烯酸月桂酯(LMA)为原料,通过"从主链接枝"的原子转移自由基聚合(ATRP)法制备了基于纤维素-糠醛-油脂的全生物质基热塑性弹性体材料EC-g-P(LNA-co-THFMA),采用FT-IR、~1H NMR、GPC、DSC和应力-应变测试对制备的接枝共聚物进行结构表征和性能分析,并初步探讨了THFMA/LMA投料比对接枝共聚物性能的影响。DSC测试表明:当n(THFMA)∶n(LMA)为200∶100~400∶100时,乙基纤维素接枝共聚物的玻璃化转变温度(Tg)在13~27℃;机械性能研究发现,随着投料中THFMA比例的增加,拉伸强度由5.1 MPa逐渐增加到13.7 MPa;通过与具有相同THFMA/LMA组成的线性共聚物P(LMA-co-THFMA)相比,EC的引入使得拉伸强度提高了3.7倍;在制备的EC基接枝共聚物投料中EC质量分数为0.91%~1.42%,这表明少量EC的引入便可极大地改善接枝共聚物的机械性能。     

SI-ATRP法制备纳米纤维素增强热塑性弹性体及其性能研究

以脱脂棉为原料制备纳米纤维素(CNCs),并通过表面引发原子转移自由基聚合法(SI-ATRP),在牺牲引发剂2-溴代异丁酸乙酯(EBiBr)存在的条件下,将甲基丙烯酸月桂酯(LMA)和甲基丙烯酸四氢糠基酯(THFMA)接枝到CNCs的表面,制备了CNCs增强的复合热塑性弹性体材料(CTPEs),并通过FT-IR、1H NMR和GPC证明成功制备了CTPEs。采用DSC和拉伸试验机对CTPEs的热力学性能和机械性能进行分析,DSC测试表明:随着THFMA含量的增加,CTPEs的玻璃化温度(Tg)由-0.04℃逐渐增加到22.58℃,CTPEs的拉伸强度由0.14 MPa增加到6.17 MPa。此外,通过比较具有相同THFMA/LMA单体投料比的CTPE-3与线性共聚物P(LMA-coTHFMA)的机械性能发现:CTPEs的拉伸强度较P(LMA-co-THFMA)提高了3倍,表明接枝后的CNCs可以实现CTPEs力学性能的增强。     

蓖麻油基阻燃多元醇的合成及在聚氨酯泡沫中的应用

以蓖麻油为原料,经过甘油醇解反应、双氧水环氧化反应、磷酸二乙酯与环氧基团开环反应生成蓖麻油基阻燃多元醇,然后与多聚异氰酸酯(MDI)形成聚氨酯泡沫。蓖麻油基阻燃多元醇的结构采用FT-IR、1H NMR进行表征,聚氨酯泡沫的力学性能和阻燃性能采用万能试验机、极限氧指数仪和热重分析仪进行测量。结果表明:通过一系列的反应生成了蓖麻油基阻燃多元醇,在不采用任何阻燃剂的情况下,虽然蓖麻油基阻燃多元醇的P元素仅有1%,但是聚氨酯泡沫的氧指数与醇解蓖麻油制备的聚氨酯泡沫相比从20.1%提高到23.8%,说明蓖麻油基阻燃多元醇制备的聚氨酯泡沫具有很好的阻燃性能;制备的蓖麻油基阻燃多元醇的羟值与醇解蓖麻油相比,由408 mg/g提高到了420 mg/g;随着蓖麻油基阻燃多元醇含量的提高,聚氨酯泡沫的压缩强度从0.118提高到0.128 MPa,热稳定性也有所增强。     

月桂烯源乙烯基酯树脂单体的合成、表征及其紫外光固化物性能研究

以天然产物月桂烯(MY)为基体原料与马来酸酐、环氧氯丙烷和丙烯酸依次进行D-A加成、缩聚和环氧开环酯化反应制得一种新型月桂烯源乙烯基酯树脂单体(AE-MYM),并采用FT-IR、GPC对制得的产物结构进行了分析。研究表明目标产物已成功合成,相对分子质量485,且树脂单体在50 s内双键转化率可达到70%以上。动态热机械性能(DMA)分析表明制备树脂的紫外光固化产物的玻璃化转变温度达到65℃,储能模量达到4 400 MPa以上;拉伸性能测试结果表明制备的光固化产物的拉伸强度可达到50 MPa以上。以上结果分析表明制备的树脂单体固化产物是一种性能优异的刚性材料。     

木质素亲水改性研究

为提高木质素的功能性,利用2-溴代异丁酰溴改性木质素制备木质素基引发剂,然后采用原子转移自由基聚合(ATRP)法将亲水单体甲基丙烯酸羟乙酯(HEMA)、乙酸乙烯酯(VAC)和丙烯酸(AA)分别接枝到木质素上,合成亲水性木质素基接枝共聚物。对接枝聚合物进行接触角测试和红外光谱分析,结果表明:接枝单体甲基丙烯酸羟乙酯时,木质素接枝聚合物亲水效果最佳;木质素接枝前后接触角分别为45°、21.6°,接枝后木质素亲水性能提高。红外光谱分析显示,木质素接枝甲基丙烯酸羟乙酯(Lignin-g-PHEMA)共聚物中具有HEMA的特征峰,表明单体甲基丙烯酸羟乙酯成功接枝到木质素分子上。     

松香-油脂和糠醛-油脂基半互穿网络结构压敏胶的制备及性能研究

以松香基甲基丙烯酸缩水甘油酯(RGMA)和糠醛基单体甲基丙烯酸四氢糠基酯(THFMA)为硬单体，油脂基单体甲基丙烯酸月桂酯(LMA)为软单体，通过自由基聚合反应得到THFMA-10、THFMA-20和RGMA-20系列聚丙烯酸酯共聚物，并通过光固化反应制备半互穿交联网络光固化压敏胶。采用红外光谱(FT-IR)和凝胶渗透色谱(GPC)对光固化压敏胶进行结构表征，并对其热性能、紫外光吸收性能、力学性能和流变性能进行分析。研究结果表明：3种共聚物的数均相对分子质量(M_n)位于40 000～60 000之间，分散性指数(PDI)分布在2～3之间，M_n对压敏胶黏附性能的影响可忽略不计；FT-IR分析证明光固化压敏胶成功制备；DSC分析证明样品中半互穿网络结构与共聚物具有良好的相容性，以二缩三乙二醇二丙烯酸酯(TPGDA)作交联剂，用量5%时，丙烯酸酯共聚物经交联光固化后弹性和内聚性均显著提高，相比于THFMA,由RGMA单体制得的压敏胶分子链的刚性更高；TG分析表明光固化后压敏胶的热稳定性明显提升。以RGMA为硬单体所制备的压敏胶的紫外光吸收性能优于T...     

ATRP法制备纤维素-油脂-糠醛热塑性弹性体及性能表征

通过"从主链接枝"原子转移自由基聚合(ATRP)法,采用分步聚合策略,成功制备了一种乙基纤维素接枝嵌段共聚物乙基纤维素-g-甲基丙烯酸月桂酯-b-甲基丙烯酸四氢糠基酯(EC-g-P(LMA-b-THFMA))。对聚合物的热力学性能研究发现:共聚物中存在两个热转变,分别发生在-35℃和49～56℃时,表明该共聚物存在微相分离;机械性能分析表明该共聚物具有优异的热塑性弹性体行为,伸长率为89%～147%,拉伸强度为1.7～9.5 MPa。循环拉伸机械性能研究表明EC-g-P(LMA-b-THFMA200)的弹性恢复系数高达92%以上。乙基纤维素接枝共聚物的机械性能具有明显的增强作用,较线性聚合物P(LMA-b-THFMA)的机械强度提高了1.36倍。     

高抗冻性油墨用二聚酸基醇溶聚酰胺树脂的性能研究

通过熔融缩聚法用二聚酸和异弗尔酮二胺(IPDA)等单体合成了一系列油墨用聚酰胺树脂,力学性能测试和差示扫描量热法(DSC)显示,IPDA制备的聚酰胺具有较高的邵氏硬度和剪切强度,但熔点(Tm)和玻璃化转变温度(Tg)有不同程度的降低.随着共聚二元胺单体中IPDA-乙二胺(EDA)比例的升高,聚酰胺树脂醇溶液的冻点逐渐降低,而软化点则先降低后升高.IPDA和二聚酸制备的聚酰胺(1009I)的软化点为103℃,其加%固含量正丙醇溶液在25℃的黏度208 mPa·s,玻璃化转变温度为44.2℃,邵氏硬度79,拉伸剪切强度14.64 MPa,溶解度参数17.87×10-3(J·m-3)2/1,能够溶于正丙醇、四氢呋喃和乙酸正丁酯,但IPDA不能提高聚酰胺树脂在乙醇中的溶解性.其20%正丙醇溶液的冻点达到-35℃,具有良好的抗冻性.     

木塑复合材料阻燃改性中的主要影响因素

研究了木塑复合材料阻燃改性中的3个重要因素,即木塑比例、阻燃剂种类和阻燃剂的添加量对其性能的影响。结果表明:木塑比例对材料的综合性能影响最大,木粉与塑料的比例提高时,材料的耐水性能提高,而材料的阻燃性能降低,静曲强度降低;在不同种类的阻燃剂对材料的阻燃性能改性实验中,复合磷氮类阻燃剂效果最佳;阻燃剂的添加实验表明,随着阻燃剂添加的量增加,材料的阻燃性能提高,内结合强度加大,而耐水性能降低。     

磺化木质素基链转移剂的合成及其在水相RAFT聚合中的应用

以玉米秸秆木质素为原料，将木质素磺化改性，再利用二硫化碳、溴乙酸甲酯对磺化木质素(SL)进行黄原酸酯功能化改性，合成了磺化木质素基链转移剂(SL-CTA)，之后将其用于丙烯酰胺的水相RAFT聚合反应制备磺化木质素-丙烯酰胺共聚物(SL-g-PAM)，并采用多种方法对链转移剂及共聚物进行表征。研究结果表明：相比于磺甲基化改性，芳基磺化改性的效果更好，当1 g木质素与2 g氯磺酸在25℃下反应4 h时，改性效果最佳，此时磺化木质素含S量为1.83%,M_w/M_n为1.19，含总羟基量为4.86 mmol/g，且水溶性良好。FT-IR、¹³C NMR对磺化木质素基链转移剂的结构表征结果发现：红外谱图显示900 cm^-1处出现C—S伸缩振动吸收峰及1 738 cm^-1处出现C=O特征峰，¹³C NMR谱图中δ172处出现了C=S的碳原子峰，共同证明了SL-CTA的成功合成。探究丙烯酰胺的水相RAFT聚合体系中单体/链转移剂/引发剂比例、pH值及反应温度对单体转化率的...     

Lignosulfonate/APP IFR and its flame retardancy in lignosulfonate-based rigid polyurethane foams

Lignin containing substantial aromatic rings and high content of carbon has been employed as carbonizing agent to investigate the flame retardancy in the lignin/ammonium polyphosphate (APP) intumescent flame retardant (IFR) system. In addition, owing to the abundant phenolic and aliphatic hydroxyl groups, lignosulfonate, which is considered as a renewable aromatic macropolyols, substituted part of diethylene glycol (DEG) and copolymerized with isocyanate to produce lignosulfonate-based rigid polyurethane (LRPU) foams. Thermal stability was characterized by thermogravimetric analysis (TGA), and flame retardancy was investigated by limiting oxygen index (LOI) and cone calorimetry testing (CCT). Lignosulfonate increases thermal stability of LRPU foams and LRPU containing 15 wt% of lignosulfonate based on DEG (L₁₅RPU) give rise to the best thermal stability. When 15% of lignosulfonate incorporated in the LRPU, reduced the heat release rate (HRR) and total heat release (THR) value 21 kW/m² and 13 MJ/m², respectively, and postponed 96 s time-to-peak carbon monoxide production than that of pure DEG rigid polyurethane (RPU) foam, the LOI values increased progressively with lignosulfonate content increasing. These results showed that lignosulfonate polyol may substitute polyol to produce lignosulfonate-based RPU foam and the presence of lignosulfonate could improve the flame retardancy. The mass loss gradually decreases with increasing APP addition, and the highest char yield was obtained from LRPU5 foam which at the lignosulfonate-to-APP ratio is 1:5. At the lignosulfonate-to-APP ratio of 1:5, the LOI value increased over 30%, and the HRR value reduced and the time-to-peak HRR postponed significantly. In addition, LRPU5 foams give rise to the lowest effect heat combustion (EHC) value, less smoke, and carbon monoxide (CO) production. Lignosulfonate acts as carbonizing agent in the lignosulfonate/APP IFR system, and the best fire retardancy is obtained at 1:5 of lignosulfonate-to–APP ratio.     

发泡剂对膨胀型聚氨酯防火涂料阻燃性能的影响

本研究采用美国ATLAS公司制造的HRR3热释放率系统,按照美国航空标准(FAA)要求, 测定了加入尿素、双氰胺、尿素-双氰胺三种发泡剂的膨胀型聚氨酯防火涂料涂覆的胶合板试件的燃烧热释放率(HRR),并比较了其阻燃性能.结果表明,同时加入尿素和双氰胺的复合膨胀型聚氨酯防火涂料的阻燃效果最好.     

Impact of wetting and drying cycle treatment of intumescent coatings on the fire performance of thin painted red lauan (Parashorea sp.) plywood

Emulsion resins are widely used in wood-based materials for indoor furnishings. Previous studies have demonstrated that the ability of a material to retard flame arises from the interactions between four major components: i.e., binder resin (BR); carbonizing substrate (CS); foam-producing substance (FPS); and dehydrating agent (DA). Fire performance as influenced by wetting and drying cycle (WDC) treatment has not yet been reported. This study aimed to compare the fire performance of materials coated with EVAc (ethylene vinyl acetate copolymer) and PVAc (polyvinyl acetate copolymer) emulsion resins of differing BR/CS ratios, subjected to investigation by cone calorimeter. Intumescent formulation significantly enhanced the fire retardancy of painted plywood by exhibiting lower peak heat release rates (PHRR) and longer time to reach peak release rates. Additionally, lower BR content in the fire retardant systems further enhanced flame retardancy. The fire retardancy decreases with increasing the WDC treatment, caused by the weight loss of the coating materials. Infrared (FT-IR) analysis demonstrated that lower BR content extends the survival duration of the phosphorcarbonaceous structure of chars. The findings in this study enhance the state-of-the-art understanding of the effect of the intumescent.     

Study on Flame-retardation and Smoke-suppression Characteristics and Mechanism of NSCFR Flame Retardant or Wood

NSCFR flame retardant is one of key factors of non-smoke combustible wood-based materials.Thermal analysis,cone calorimetry,Py-GC/MS, scanning electron microscopy(SEM) were utilized to investigate the flame-retardation and smoke-suppression characteristics and mechanisms of NSCFR flame-retardant.The results show that NSCFR flame-retardant could significantly shorten the combustion duration of wood-based materials and completely eliminate the second peak of heat release rate curve,greatly reduce heat release rate, total smoke release,mass loss rate,specific extinction area,and carbon monoxide production and carbon dioxide production,obviously enhance the mass of combustion char residue,effectively retarding the combustion and inhibiting smoke release of the wood-based material;NSCFR flame-retardant exhibits the ability of flame retardancy on wood by the conjunct mechanism of capturing free radical, diluting combustible gas,and catalyzing charring; NSCFR flame-retardant displays smoke suppression effects on wood by absorption action of nano alveolate structure together with the active catalyzing action of ironic molybdate.     

含磷型聚合甘油脂肪酸酯阻燃增塑剂的制备与应用

为了提高油脂增塑剂的阻燃性,开发以生物柴油副产粗甘油为直接原料的高附加值产品,以粗甘油、油酸和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为主原料,经聚合、酯化、环氧化和开环反应,合成含磷型大分子阻燃增塑剂DOPO-环氧乙酰化聚合甘油脂肪酸酯(DOPO-EAPFAE),并通过红外谱图(FT-IR)和核磁共振(~1H NMR)确认了其结构。研究了DOPO-EAPFAE用量对聚氯乙烯(PVC)体系力学性能的影响;通过对PVC样条的热重分析(TG)、极限氧指数(LOI)测定和垂直燃烧测试等,分析了PVC制品的热稳定性和阻燃性能。结果表明:当DOPOEAPFAE代替邻苯二甲酸二辛酯(DOP)用量为60%时,PVC样条仍具有良好的力学性能;而LOI从21.3上升到了28.7,阻燃级别达到V0级;说明该阻燃增塑剂可有效地改善PVC增塑体系的阻燃性。与小分子阻燃剂磷酸三(2-氯丙基)酯(TCPP)相比,DOPO-EAPFAE阻燃性不仅优于TCPP,而且具有更好的热稳定性能。     

可膨胀石墨与聚磷酸铵对木粉/聚丙烯复合材料的协同阻燃作用(英文)

采用锥形量热仪(CONE)研究可膨胀石墨(EG)与聚磷酸铵(APP)对木粉/聚丙烯复合材料的协同阻燃作用。CONE测试结果表明:EG和APP均可降低木粉/聚丙烯复合体系的热释放速率(HRR)、总热释放(THR)和烟释放速率(RSR),提高成炭率;与APP相比,EG表现出更好的抑烟效果。当EG与APP的总添加量为15%、复配比例为2∶1时,能形成稳定致密的膨胀炭层,阻燃协同效应显著。力学性能测试结果表明:即使在马来酸酐接枝聚丙烯相容剂(MAPP)的存在下,EG和APP阻燃剂的添加对复合材料的冲击强度和弯曲强度仍有不利影响,但EG的添加可提高复合材料的弯曲模量。     

马来海松基环氧纳米复合材料的制备及性能研究

以松香为原料,通过Diels-Alder加成制备了马来海松酸酐(MPA),再经过酯化、闭环反应得到了马来海松基环氧树脂(MPA-ER),并用FT-IR和1 H NMR对MPA和MPA-ER的结构进行了表征。进一步将多壁碳纳米管(MWCNTs)与MPA-ER共混制备了一系列的MPA-ER/MWCNTs复合材料,对其力学性能和热性能进行了表征,并探究了不同MWCNTs添加量对马来海松基环氧纳米复合材料力学性能和热性能的影响。研究结果表明:FT-IR和1 H NMR证实成功制备了MPA和MPA-ER。MWCNTs在MPA-ER中分散均匀,断面具有河流状纹路,MWCNTs的添加使得MPA-ER/MWCNTs的力学性能显著提高,当MWCNTs的添加量为1.2%(以MPA-ER质量计,下同)时,复合材料MPA-ER/MWCNTs(1.2)的力学性能达到最优,冲击韧性、拉伸强度、弯曲强度和断裂伸长率分别为15.11 kJ/m^2、40.42 MPa、105.45 MPa和14.80%,与MPA-ER相比分别增加了159%、160%、102%和135%。同时,锥形量热测试中MPA-ER/MWCNTs(1.2)复合材料的峰值热释放速率和残炭率分别为324 kW/m 2和9.18%,与MPA-ER相比,峰值热释放速率下降了14%,残炭率增加了68%,表明MWCNTs的添加使得MPA-ER/MWCNTs的热稳定性和阻燃性有所提高,MPA-ER/MWCNTs(1.2)复合材料阻燃性能的提高主要归因于添加MWCNTs有效地增加了环氧树脂的交联密度,使其在内部形成比较致密的炭层,进而通过部分隔绝外部热量和空气来达到阻燃的效果。     

FLAME RETARDANT OF GUANIDINE CONDENSED PHOSPHATE (GCP) FOR WOOD

Fireplaysanimportantroleinmakingmancivilization,butfirealsobringaboutdisastertoman.Somedevelopedcountriesdatashowedthatl%ofthegrossnationalproductisdevotedbyconflagrationseveryyear.Inrecentyears,firesoccurredabout3-4hundredtimeseveryyearinChina,di-recteconomiclosswas2Oo-3OOmillionChineseyuanL13,andmostfireswerecausedbywoodburning.Therefore,flameretardanttreatmentforwoodtodiminishorpreventfiredisasterisamosteffectivemeasureofstrategy.Forthisreason,thisresearchfieldhasbeenreceivingagreatat-tC…     

木质废料/无机胶黏剂刨花板的制备及其阻燃性能研究

以废旧建筑模板和家具为原料,使用环保型无机胶黏剂制备刨花板。利用扫描电子显微镜(SEM)观察刨花板的微观形貌,同时利用量热仪、氧指数测定仪、同步热分析仪等评价板材的阻燃性及热稳定性。结果表明:当板材密度为0.95g/cm^3时,除24h吸水厚度膨胀率外,其余物理力学性能均符合国标中的P3型刨花板要求;SEM观察到无机胶黏剂包覆刨花,填充板材孔隙,使板材物理力学强度大幅提高;选择氯化镁为固化剂,当表层/芯层刨花的固化剂用量为4.5%/5.0%时,压制的密度为0.95g/cm^3的刨花板,其氧指数为31%,具有较好阻燃性能。     

Effect of nanofillers on flame retardancy, chemical resistance, antibacterial properties and biodegradation of wood/styrene acrylonitrile co-polymer composites

Wood polymer nanocomposites (WPNCs) based on simul wood (Bombex ceiba, L.) were prepared by impregnation of styrene acrylonitrile copolymer, γ-methacryloyloxy trimethyl silane-modified TiO₂, SiO₂ nanoparticles and nanoclay intercalating mixture through vacuum impregnation. The impact of nanofillers on the physical properties, flame retardancy, water resistance, anti-swelling efficiency and biodegradability of the resultant WPNCs was investigated. Remarkable enhancement in wood properties such as flame retardancy, water resistance and anti-swelling efficiency was achieved with the treatment. The results showed that all the properties were maximum for wood samples treated with SAN/TiO₂ (0.5 %)/SiO₂ (0.5 %)/nanoclay (0.5 %). The presence of TiO₂ nanoparticles in WPNC exhibited antibacterial activity. The resistance to biodegradation was observed by incorporation of nanofillers into wood.