Curing reaction and mechanism of phenol-formaldehyde novolac resins for foundry

In this study on the curing dynamics of phenol-formaldehyde novolac resins(PFNR) and hexamethylene tetramine(HMTA), two typical commercial PFNR were selected as examples and the curing reactions of the resins with HMTA were studied by differential scanning calorimetry(DSC). Based on the data calculated by the Kissinger equation and the Crane equation, a thermocuring dynamic model was established, from which the process conditions, activation energy, reaction kinetics equation and a f irst-order reaction of the curing reactions were derived.

Study on binder system of CO_2-cured phenol-formaldehyde resin used in foundry

A new aqueous alkaline resol phenol-formaldehyde resin has been prepared from phenol and formaldehyde using NaOH as catalyst; the optimum synthetic process has been determined. With addition of some cross-linking agents, after passing carbon dioxide gas through the resin bonded sand, high as-gassed strength and 24 h strength are achieved. The bonding bridge of the resin bonded sand fracture has been analyzed by using SEM.

Reinforcement of Lignin-Based Phenol-Formaldehyde Adhesive with Nano-Crystalline Cellulose (NCC): Curing Behavior and Bonding Property of Plywood

The curing behavior of lignin-based phenol-formaldehyde (LPF) resin with different contents of nano-crystalline cellulose (NCC) was studied by differential scanning calorimetry (DSC) at different heating rates (5, 10 and 20&degC/min) and the bonding property was evaluated by the wet shear strength and wood failure of two-ply plywood panels after soaking in water (48 hours at room temperature and followed by 1-hour boiling). The test results indicated that the NCC content had little influence on the peak temperature, activation energy and the total heat of reaction of LPF resin at 5 and 10&degC/min. But at 20&degC/min, LPF0.00% (LPF resin without NCC) showed the highest total heat of reaction, while LPF0.25% (LPF resin containing 0.25% NCC content) and LPF0.50% (LPF resin containing 0.50% NCC content) gave the lowest value. The wet shear strength was affected by the NCC content to a certain extent. With regard to the results of one-way analysis of variance, the bonding quality could be improved by NCC and the optimum NCC content ranged from 0.25% to 0.50%. The wood failure was also affected by the NCC content, but the trend with respect to NCC content was not clear.

含磷POSS阻燃乙烯基酯树脂性能研究

将含磷POSS(DMPOSS)以5wt%、10wt%和15wt%的添加量添加到乙烯基酯树脂中,通过差示扫描量热仪(DSC)、热重分析(TG)、极限氧指数(LOI)、锥形量热仪和扫描电镜(SEM)测试研究了DMPOSS对乙烯基酯树脂玻璃化转变温度、热稳定性和燃烧性能的影响。DSC测试结果表明:DMPOSS的加入能够明显提升乙烯基酯树脂的玻璃化转变温度。LOI测试结果表明:添加DMPOSS改性的乙烯基酯树脂的氧指数随DMPOSS含量的增加而逐渐升高。当添加15wt%DMPOSS时,乙烯基酯树脂的氧指数达到23.8%。锥形量热仪测试结果表明:DMPOSS的加入能够有效降低乙烯基酯树脂的热释放。当添加15wt%DMPOSS时,乙烯基酯树脂的热释放速率峰值降低了44.9%,总的热释放降低了30.4%。

赛克季戊四醇混合改性树脂的制备及性能

以六羟甲基三聚氰胺(HMM)、赛克和季戊四醇(PER)为原料,磷酸为催化剂,通过干法醚化和缩聚合成了一种新型的赛克季戊四醇混合改性树脂成炭剂。结果表明:该混合改性树脂的热稳定性和对聚丙烯(PP)的阻燃性能介于PER改性树脂和赛克改性树脂之间,但混合改性明显改善了阻燃材料的颜色。赛克和PER的物质的量比对混合改性树脂的热稳定性、阻燃性能及阻燃材料的颜色有影响,赛克与PER最合适的物质的量比为1.3∶1.0。

环酰亚胺化三聚氰胺的制备及其阻燃环氧树脂应用

三聚氰胺(MEL)因其热稳定性高、耐水解、不易迁移、成炭高、价格低廉等优势,成为阻燃领域关注的热点。然而,六元氮杂环的共轭高化学稳定芳香结构导致其反应活性较低,难以修饰加工。为进一步拓展MEL体系的应用,以MEL、1,2-环己二甲酸酐(HHPA)为原料,制备环酰亚胺化MEL(RFR)并将其应用于环氧树脂(EP)阻燃。通过调控反应原料物质的量比、时间、溶剂、温度等优化RFR的制备工艺条件,采用傅里叶变换红外光谱(FTIR)、核磁共振和元素分析等表征RFR结构;将其加入至EP中,以4,4-二氨基二苯甲烷为固化剂,制得阻燃型EP。利用极限氧指数(LOI)、垂直燃烧测试、万能拉伸试验机、FTIR、热重分析、扫描电子显微镜等手段综合评估改性EP的结构、力学性能、残炭率及阻燃性能。结果表明,当RFR添加质量分数为7.5%时,成炭率相比于未改性EP提升了20.5%,阻燃EP的LOI值达到26.3%,阻燃等级达到UL94 V-1级。从阻燃机理分析,该阻燃剂通过三嗪骨架和环烷基侧基协同发挥了凝聚相和气相阻燃。

Impregnated Paper-Based Decorative Laminates Prepared from Lignin-Substituted Phenolic Resins

High Pressure Laminates(HPL)panels consist of stacks of self-gluing paper sheets soaked with phenol-formaldehyde(PF)resins.An important requirement for such PFs is that they must rapidly penetrate and saturate the paper pores.Partially substituting phenol with bio-based phenolic chemicals like lignin changes the physico-chemical properties of the resin and affects its ability to penetrate the paper.In this study,PF formulations containing different proportions of lignosulfonate and kraft lignin were used to prepare paper-based laminates.The penetration of a Kraft paper sheet was characterized by a recently introduced,new device measuring the conductivity between both sides of the paper sheet after a drop of resin was placed on the surface and allowed to penetrate the sheet.The main target value measured was the time required for a specific resin to completely penetrate the defined paper sample(“penetration time”).This penetration time generally depends on the molecular weight distribution,the flow behavior and the polarity of the resin which in turn are dependent on the manufacturing conditions of the resin.In the present study,the influences of the three process factors:(1)type of lignin material used for substitution,(2)lignin modification by phenolation and(3)degree of phenol substitution on the penetration times of various lignin-phenolic hybrid impregnation resins were studied using a complete twolevel three-factorial experimental design.Thin laminates made with the resins diluted in methanol were mechanically tested in terms of tensile and flexural strains,and their cross-sections were studied by light microscopy.

NaOH and Ba(OH)_2 Compound Catalyzed PhenolResorcinol-Formaldehyde Copolycondensation Resin Adhesive for Recombined Bamboo

In order to reduce the curing temperature, shorten the curing time of phenol-formaldehyde(PF) resin adhesive, and ensure the good water-solubility, NaOH and Ba(OH)_2 were used as compound catalysts. The influences of the adding time of Ba(OH)_2, the adding amount of NaOH, Ba(OH)_2 and resorcinol on the properties of adhesives were studied. The properties of NaOH catalyzed phenol-formaldehyde(PF) adhesive, NaOH and Ba(OH)_2 compound catalyzed PF adhesive, NaOH and Ba(OH)_2 compound catalyzed phenol-resorcinol-formaldehyde(PRF) adhesive, and the prepared recombinant bamboo with three kinds of adhesives were compared. The experimental results show that NaOH and Ba(OH)_2 compound catalyst not only shortens the curing time of PF adhesive, but also guarantees the suitable water solubility of adhesive. After copolycondensation with resorcinol, the curing time of adhesive is further shortened, the water solubility is improved obviously, and the highest bonding strength is obtained. Infrared spectrum analysis shows that the reaction activity point of NaOH and Ba(OH)_2 compound catalyzed PRF adhesive will increase, so that both the curing temperature and curing enthalpy decrease.

Thermal and Mechanical Properties of Epoxy Resin Modified with N-(4-hydroxyphenyl)terahydrophthalic Anhydrideimide

A novel epoxy-imide resin based on diglycidyl ether of bisphenol-A and N-（4-hydroxyphenyl）terahydrophthalic anhydrideimide（HTAM） was synthesized. The structural characterization of the epoxy-imide resin was conducted by FT-IR spectra. 4,4＇-diaminodiphneylmethane（DDM） was used as a curing agent for the epoxy-imide resin. The thermal properties of the cured resin were evaluated with dynamic mechanical analyses（DMA） and thermogravimetric analysis（TGA）. The results showed that the cured resin exhibited a high glass transition temperature（Tg） of 186 ℃ when the molar amount of HTAM was 0.04 mol in the resin. The yields of the cured resin at 800 ℃ raised from 16.45% to 19.41%. The flexural properties were also measured, the flexural strength raised from 79.4 to 95.7 MPa, and the flexural modulus exhibited from 2.6 to 3.0 GPa.

含马来酰亚胺结构的DOPO基反应型阻燃剂的合成及其对环氧树脂性能的影响

以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和N-对羧基苯基马来酰亚胺(pCPMI)为主要原料合成了一种新型的反应型阻燃剂DOPO-pCPMI,利用傅里叶变换红外光谱(FT-IR),核磁共振谱(1H-NMR、31P-NMR)对阻燃剂分子的结构及其组成进行了分析表征。随后将DOPO-pCPMI与环氧树脂预聚,再以4,4’-二氨基二苯基砜(DDS)为固化剂制备DOPO-pCPMI/EP复合材料。通过极限氧指数(LOI)、动态热机械分析(DTMA)、热失重分析研究了复合材料的阻燃性能和热性能。结果表明:当pCPMI的质量分数为6%时,DOPO-pCPMI/EP固化体系综合性能最佳,氧指数由24%提高至33.5%;玻璃化转变温度(Tg)为210℃;弯曲强度由90 MPa提升至127 MPa;在氮气气氛下不同组分树脂的浇铸体残炭率不断提高。对燃烧后炭层的红外分析和扫描电子显微镜(SEM)分析表明形成了含马来酰亚胺的刚性炭层,且炭层外部紧凑、完整,内部致密、多孔。

苯并噁嗪树脂烧蚀性能的初步研究

对苯并嗪树脂作为烧蚀树脂的应用进行了研究。采用TGA对四种中间体固化树脂的成碳率进行了测量 ,表明含有多个嗪环的PBOZ中间体和含有两嗪环的MDABOZ固化树脂和DRBOZ固化树脂成碳率较高 ,达到 60 %以上 ,而含有一个嗪环的SRBOZ固化树脂的成碳率相对较低。在以SRBOZ中间体为主体的树脂体系中引入MDABOZ中间体、DRBOZ中间体和APPFBOZ中间体后树脂体系的粘度较低而其固化产物的交联密度明显提高 ,成碳率达到 60 %以上。小发动机烧蚀试验表明PBOZ固化树脂的耐烧蚀性能较好 ,能够作为烧蚀树脂 ;

新型高残碳酚醛树脂的研究I.高残碳酚醛树脂的合成及其残碳率

合成了DA系列树脂改性剂和芳基改性酚醛树脂 ,并以DA改性剂改性芳基酚醛树脂。用热重、电子顺磁共振等方法研究了改性酚醛树脂的残碳率。研究表明 ,用DA改性剂来改性酚醛树脂是提高残碳率的有效方法 ,改性酚醛树脂的残碳率可达 6 9.87%。

高残炭率酚醛树脂的耐热性能研究

采用无水乙醇、水杨醛和水杨醛+Resorcinarenes杯芳烃分别对自制氨酚醛树脂进行改性处理,得到3种改性酚醛树脂A、B、C。通过傅立叶变换红外光谱、差示扫描量热法和热重法对3种改性酚醛树脂的分子结构、固化行为和耐热性能进行了对比分析,运用Ozawa等转化率法对改性酚醛树脂C进行了热降解动力学分析。结果表明,与改性酚醛树脂A、B相比,改性酚醛树脂C具有更好的热稳定性和更高的残炭率,它在700℃氮气气氛下的残炭率大于73%;水杨醛、Resorcinarenes杯芳烃与氨酚醛树脂相互作用,形成的芳环含量更高的共轭结构使改性酚醛树脂C的热解表观活化能大幅度提高,这是其具有优良耐热性能和高残炭率的主要原因。

石墨烯/酚醛树脂纳米复合材料的热解行为

将氧化石墨烯与自制酚醛树脂乳液（PF）共混，经水合肼还原和热固化制备石墨烯／酚醛树脂（GNS／PF）纳米复合材料。利用AFM、SEM、FTIR和TG—DTG技术考察石墨烯对GNS／PF复合材料的形貌、结构、热稳定性和残炭率的影响。结果表明，石墨烯片均匀分布在PF中，没有发生团聚，且石墨烯片与PF间具有良好的界面结合。石墨烯薄片对PF基体强烈的吸附作用增加了PF分子链的活性和有序性，显著提高了GNS／PF纳米复合材料内PF基体的固化交联密度．进而提高了PF基体的耐热性和高温残炭率。在300～450℃条件下，纯酚醛树脂的热分解峰值温度为382．7℃，添加质量分数0．65％的GNS后，热分解峰值温度提高到408℃。在隔绝空气下900℃热处理，纯酚醛树脂的残炭率为46．2％，添加0．65％氧化石墨烯后残炭率增至59．4％，提高了13．2％。

新型高残碳酚醛树脂的性能研究

采用热重和高效液相色谱法对高残碳酚醛树脂的性能进行分析。结果表明 ,与其它酚醛树脂相比 ,此树脂具有较高的热分解温度和表观活化能 ,70 0℃残碳率大于 75 % ,热性能和耐烧蚀性能优于传统烧蚀酚醛树脂 ,是良好的耐热、耐烧蚀基体材料 ;用高效液相色谱 (HPLC)初步探讨了树脂的反应机理 ,得出大分子量组成含量随聚合度变化 ,应作为树脂质量控制的指标之一。

RTM酚醛树脂研究进展

根据国内外酚醛树脂的研究现状 ,从树脂的合成、主要特征、工艺和性能等方面介绍了几种RTM酚醛树脂酚三嗪树脂、苯并嗪树脂、双马改性酚醛树脂和PAA树脂 ,同时指出了各种树脂的优缺点。

树脂热解炭制备碳化硅晶须

用自制的酚醛树脂热解炭作炭源，用ＳｉＯ２超细粉作硅源，根据碳热还原原理，利用常规加热和微波加热两种方式，分别制备了直径在纳米级的ＳｉＣ晶须。Ｘ射线衍射、透射电镜检测结果表明：制备工艺和条件对ＳｉＣ晶须的性质有较大的影响。

适用于RTM成型的新型耐烧蚀苯并噁嗪树脂的研究

在低黏度的双环苯并噁嗪中间体(B-BOZ)中加入一种新型的多官能基单环苯并噁嗪(AS-BOZ)或一种交联剂(TPA),复配制得了一种适用于RTM成型的新型耐烧蚀苯并噁嗪树脂,对树脂体系的黏度及固化物的热稳定性、力学性能、残碳率及碳的形貌进行了研究。结果表明,无论是AS-BOZ还是TPA的引入都使得双环苯并噁嗪体系黏度降低,同时提高体系的交联密度,使固化物的Tg和残碳率都大幅度提高。其中BA2-1固化物的Tg为250℃,800℃下氮气中残碳率为68%,质量烧蚀率为23.3 mg/s;BT2-1固化物的Tg为240℃,800℃下氮气中残碳率为70%,质量烧蚀率为20.1 mg/s,两体系高温下均能得到致密的碳层结构。

高残炭热固性酚醛树脂的合成及表征

以萘酚部分替代苯酚合成了高残炭热固性酚醛树脂。研究了萘酚用量、催化剂用量、反应温度和时间对残炭率的影响,确定了合成工艺条件。用IR和TGA对产品的化学结构与热性能进行了分析测定,结果表明,树脂分子链中不稳定的醚键含量低于普通酚醛树脂,产品的分解温度为460℃,残炭率可达61.3%,适用于碳/碳复合材料和耐烧蚀材料的树脂基体。

磷酸酯双三聚氰胺盐阻燃环氧树脂的燃烧性能和阻燃机理

以季戊四醇、三氯氧磷、三聚氰胺为原料合成了[1-氧-4-亚甲基-2,6,7-三氧-1-磷杂双环(2,2,2)辛烷]磷酸酯双三聚氰胺盐阻燃剂,将该阻燃剂加入到环氧树脂中制成阻燃环氧树脂。用TG、SEM、EDS和FT-IR进行表征,并采用极限氧指数法和垂直燃烧法测试材料的燃烧性能,结果表明,极限氧指数和垂直燃烧性能随阻燃剂含量的增加而提高,当阻燃剂含量达到30%时,氧指数达到36,垂直燃烧性能达到V-0级;阻燃剂对材料的成炭量影响不大,但改变了炭层的组成和物理性质,燃烧过程中形成的含有P、O、N的粘性高聚物将炭层连接在一起,起到了隔热、隔氧作用,发挥了凝聚相阻燃作用。此外,阻燃环氧树脂在燃烧过程中有NH3等不燃气体逸出,有效地稀释了气相中的氧气浓度,发挥了气相阻燃作用,对材料的阻燃有协同作用。