E_1级胶合板用改性脲醛树脂胶粘剂的制备方法研究

选用弱酸-弱碱-弱酸-弱碱工艺制备脲醛树脂(UF)胶粘剂,研究了n[甲醛(F)]∶n[尿素(U)]、初始p H、反应温度和三聚氰胺(M)掺量对游离F含量和胶接强度的影响。研究结果表明:当n(F)∶n(U)=1.2∶1.0、起始p H为6.5、反应温度为85℃和w(M)=6%(相对于U总质量而言)时,UF胶粘剂的游离F含量(0.17%)符合国家标准要求(≤0.3%),胶合板的F释放量(1.17 mg/L)达到GB/T 9846.3—2004标准中E1级指标要求(≤1.5 mg/L),胶接强度(从0.46 MPa提高到0.97 MPa)达到了国家标准中II类胶合板的指标要求,耐水性也明显提高。     

DSC法研究乙二醛-尿素树脂的固化性能

为从源头上降低UF树脂及其胶合板材的甲醛释放对环境和人体健康所造成的危害,选用乙二醛(G)取代甲醛(F)与尿素(U)反应,制备乙二醛-尿素(GU)树脂。用差示扫描量热分析(DSC)方法研究了原料物质的量比、反应pH、反应时间、反应温度、pH调节剂对所合成GU树脂固化性能的影响规律;并用不同原料物质的量比的GU树脂制备刨花板并测定了其各项性能。结果表明,GU树脂的较优合成条件为:在弱酸性条件下,乙二醛与尿素物质的量比(G/U)=1.2∶0～1.4∶1.0,反应温度70～80℃,反应时间3h;此条件下合成的GU树脂胶合的刨花板内结合强度IB达到0.44MPa、弹性模量MOE达2298MPa、静曲强度MOR为10.5 MPa,且无甲醛释放。     

硫代硫酸钠/三聚氰胺改性脲醛树脂制备工艺研究

以硫代硫酸钠和M(三聚氰胺)作为复合改性剂,F(甲醛)和U(尿素)作为主要原料,采用弱酸-弱碱-弱酸-弱碱法合成了改性UF(脲醛树脂),并着重探讨了不同因素对UF中的游离F含量、胶合板的胶接强度及F释放量的影响。研究结果表明:合成改性UF的最佳工艺条件是反应温度为85℃,n(F)∶n(U)=1.10∶1,起始pH为5.0,M第2批加入,硫代硫酸钠第4批加入且加入量为U总质量的2%,U分批加入比例为55%、20%、15%和10%;此时UF中的游离F含量(降至0.11%)符合GB/T 14732—2006标准中的指标要求,胶合板的胶接强度(为1.05 MPa)满足国家标准中II类胶合板的指标要求、F释放量(为1.26 mg/L)达到普通胶合板通用技术条件中的E1级指标且耐水性也明显提高。     

低游离甲醛含量脲醛树脂胶粘剂的合成工艺研究

研究了在弱酸-弱碱-弱酸条件下,加入改性剂合成脲醛(UF)树脂胶的工艺过程。实验结果表明,甲醛与尿素的配比[即n(F)/n(U)比值]、体系pH值、尿素的加料方式和改性剂对UF树脂胶中游离甲醛的含量和胶合强度有很大的影响;当n(F)/n(U)=1.06、缩聚反应阶段体系的pH值为4.75～4.80、尿素分3批加入、反应温度为90℃、加入适量的聚乙烯醇(PVA)和三聚氰胺改性剂时,制得的UF树脂胶中游离甲醛的含量不大于0.10%(符合GB/T14 074.16-1993标准中的指标要求)、粘接强度为4.70 MPa且综合性能优良。     

低毒脲醛树脂胶的合成及胶液中游离甲醛的测定

探讨了改性剂对降低游离甲醛含量、改善胶粘剂性能的作用机理,研究了三聚氰胺、聚乙烯醇（PVA）改性脲醛树脂胶粘剂（UF胶）的制备工艺和配方,实验得出：采用弱碱-弱酸-弱碱的工艺,添加适量三聚氰胺和聚乙烯醇,反应最高温度控制在90℃,反应时间2~3 h,n（尿素）∶n（甲醛）=1∶1.4,尿素按7.0∶2.0∶1.0的质量比分3次投料,可制得低毒脲醛树脂胶粘剂。     

三聚氰胺改性脲醛树脂工艺条件对体系游离甲醛含量的影响研究

本文采用"弱碱-弱酸-弱碱"工艺,以三聚氰胺为改性剂,制备了脲醛树脂胶粘剂,考察了甲醛与尿素摩尔比、出料p H值、三聚氰胺用量、尿素投料次数对UF树脂胶粘剂中游离甲醛含量的影响。结果表明,当U/F摩尔比为1.2、三聚氰胺改性剂用量2.5%、尿素分3批次投料时,合成的UF稳定性最好,UF中游离甲醛的含量为0.14%。     

三聚氰胺改性脲醛树脂胶黏剂的合成

介绍了在温度和pH值等条件不变的情况下,不同的甲醛(F)和尿素(U)配比对合成的脲醛树脂(UF)胶黏剂性能的影响,以及通过用不同质量分数的三聚氰胺(M)对脲醛树脂进行改性以达到合成低游离甲醛胶黏剂的目的.结果表明:F与U物质的量比升高,甲醛含量明显提高;随着F与U物质的量比以及三聚氰胺质量分数的增加,甲醛释放量明显降低.当n(F)∶n(U)=1.5,三聚氰胺的加入质量分数为5％时,甲醛含量最低.     

三聚氰胺改性脲醛树脂胶黏剂的合成工艺研究

介绍了在温度和pH值等条件不变的情况下,不同的甲醛(F)和尿素(U)配比对合成的脲醛树脂(UF)胶黏剂性能的影响,以及通过用不同质量分数的三聚氰胺(M)对脲醛树脂进行改性以达到合成低游离甲醛胶黏剂的目的。结果表明:随着F与U物质的量比增加,甲醛含量明显提高;随着F与U物质的量比以及三聚氰胺质量分数的增加,甲醛释放量明显降低。当n(F)∶n(U)=1.5、三聚氰胺的加入量为5%时,甲醛含量最低。     

三聚氰胺/纳米TiO_2联合改性脲醛树脂胶粘剂研究

以甲醛、尿素为原料,纳米TiO_2和三聚氰胺为改性剂,采用"碱-酸-碱"的合成工艺合成脲醛树脂,并对三聚氰胺/纳米TiO_2联合改性脲醛树脂工艺进行优化。研究结果表明:当纳米TiO_2用量不变,脲醛树脂的黏度、固含量、胶合强度随三聚氰胺加入量增加而增大,而固化时间和游离甲醛含量则呈现出相反的变化趋势;添加w(三聚氰胺)=1.5%(相对于尿素添加质量而言)改性后的脲醛树脂游离甲醛含量为0.41%,耐水胶合强度为1.25 MPa,对不同配比的甲醛/尿素(F/U)脲醛树脂,三聚氰胺/纳米TiO_2联合改性性能相似;改性后的脲醛树脂及纳米TiO_2能够均匀分布于木材表面,以保证较好的胶合强度和联合改性效果。     

花生壳苯酚液化产物-尿素-甲醛树脂胶黏剂的研究

以花生壳苯酚液化产物为原料,制备花生壳苯酚液化产物-尿素-甲醛（PLPUF）树脂胶黏剂。采用正交试验探讨了制备PLPUF树脂胶黏剂的最优配比,以提高其综合性能,结果表明：第一批尿素（U₁）/第二批尿素（U₂）物质的量比、液化产物（PL）/尿素（U_总）物质的量比以及液化产物和尿素总用量（PL+U_总）与甲醛（F）物质的量比为3：1、1：1.5和1：1是PLPUF树脂胶黏剂制备的最佳配比;此配比下胶合强度达到了0.83 MPa,含固体量为47.11%,游离甲醛的量为0.05%,以酚醛树脂胶黏剂为标准,PLPUF树脂胶黏剂能满足木材工业树脂的使用要求。PLPUF树脂在贮存过程中黏度逐渐上升,贮存5~15 d胶合强度为0.87~1.15 MPa,22 d后胶合强度降低至0.74 MPa,仍可满足使用条件。PLPUF树脂的FT-IR图中出现酰胺C=O和C—N等伸缩振动峰,表明尿素参与反应、改性树脂,而加入固化剂前后树脂的FT-IR吸收峰相同,结合DSC曲线表明固化剂的加入不改变树脂结构,但可以改善PLPUF树脂的固化过程,降低固化温度和固化反应热。     

耐水级MUF的固化特性对胶合板胶接性能的影响

采用一步法制备耐水级的三聚氰胺/脲醛树脂(MUF),并对缩聚阶段的n(F)∶n(U1)比例、固化剂的种类等对固化物的热性能和力学性能的影响进行了探讨。结果表明:固化物的力学性能随着固化体系的不同而异;对A固化体系(氯化铵、甲酸)而言,其峰值温度最低,固化速率最快,固化比较完全,胶接强度最高;而对潜伏性的C固化体系(氯化铵、甲酸、对苯磺酸)而言,其甲醛释放量最高,固化速率最慢。随着缩聚阶段n(F)∶n(U1)比例的增加,固化物的胶接强度增加、甲醛释放量降低。当n(F)∶n(U)=1.3∶1、n(F)∶n(U1)=1.9∶1和V(A固化剂)∶m(胶液)=6 mL∶100 g时,胶合板的综合性能最好;此时,胶合板的胶接强度为0.80 MPa,甲醛释放量(为0.35 mg/L)达到了E0级的国家标准。     

Effects of diatomite inorganic fillers on the properties of a melamine–urea–formaldehyde resin

In this study, a low‐cost diatomite was used to partly substitute wheat flour as one type of melamine–urea–formaldehyde (MUF) resin filler. Five‐ply plywood was fabricated, and its performance was measured. The crystallinity, fracture surface, and functional groups were tested to determine the effects of diatomite on the performance of the MUF resin. The results show that diatomite was well distributed in the MUF resin system and formed an embedding structure; this improved the wet shear strength of the resulting plywood by 33% to 1.36 MPa. Diatomite captured the free formaldehyde in the resin and the microporous structure formed in the resin accelerate formaldehyde release of the plywood. Consequently, the formaldehyde emission of the plywood was reduced. The diatomite partly replaced wheat flour as an MUF resin filler and could be applied in the plywood industry. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44095.     

低醛三聚氰胺树脂的制备与工艺研究

以三聚氰胺(M)、甲醛(F)和乙二醇(EG)为主要原料,三乙醇胺为催化剂,己内酰胺、H2O2为甲醛吸收剂,采用低n(F)∶n(M)比例、乙二醇醚化MF(三聚氰胺-甲醛)树脂、三聚氰胺分次加料和添加甲醛吸收剂等手段,制备MF树脂。研究结果表明:当n(F)∶n(M)=2.5∶1、n(EG)∶n(M)=2.0∶1、pH值为8～9、反应温度为80℃、三聚氰胺分次加料量为50∶40∶10(质量比)和n(己内酰胺)∶n(H2O2)∶n(甲醛)=10∶5∶100时,制成的MF树脂具有相对较低的游离甲醛含量(0.13%)和相对较长的储存稳定期(>120 d)。     

MUF MF共缩合改性树脂胶黏剂的研究

同时采用共聚和共混的方法,合成了一种脲醛-三聚氰胺甲醛复合树脂胶黏剂。研究了合成工艺、三聚氰胺用量、MF与MUF共混比例对胶黏剂性能的影响。结果表明,反应后期加入5%三聚氰胺改性MUF树脂,MUF和MF树脂按M/U为40%共混时,共混树脂游离甲醛含量较低,耐水性能优良,综合性能较好。     

Determination of formaldehyde and TVOC emission behavior from interior use plywood using various post heat treatment processes

To reduce the formaldehyde/TVOC emissions from plywood with melamine–urea–formaldehyde (MUF) resin, four heat treatment procedures were designed and applied. Five‐ply plywood was fabricated, and its formaldehyde/TVOC emissions and wet shear strength were tested. Results showed that a simple low/no pressure post heat treatment procedure was effective and practical to decrease the formaldehyde/TVOC emissions from plywood. This was attributed to completely cured of MUF resin, the breakage of unstable chemical bonds, the acceleration of free formaldehyde releasing, and the exposed surface of the plywood. Meanwhile, this process also balanced the interior force of the resultant plywood and improved its wet shear strength. Under a 12 h oven heat treatment procedure after hot press, the formaldehyde and TVOC emissions from plywood decreased to 0.020 and 0.036 ppm, respectively, while the surface and core layer wet shear strength of plywood was improved to 1.24 and 1.08 MPa. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44909.     

Chemical composition of melamine-urea-formaldehyde (MUF) resins assessed by near-infrared (NIR) spectroscopy

Melamine-urea-formaldehyde (MUF) resins are commonly used in the production of wood-based panels. The composition of the resin influences many properties of the final product. In industrial production, some properties, such as viscosity, pH, solid content, or molar ratio, are assessed after resin production in order to evaluate if they are within the desired parameters. These properties are useful for quality control of amino resins. However, almost no information is obtained if a certain type of reagent or filler is wrongly added to the formulation, even though the resin's final adhesive performance will be affected. Evaluation of the molar ratio of the reagents might be the only of the few industrially used tests capable of making this assessment. Near-infrared spectroscopy (NIR) is a fast and reliable technique for quality control of amino resins and can give a wide range of information regarding chemical composition of these products. This work intends to test the capability of NIR to assess several properties related to MUF resins’ chemical composition. The approach considered two types of problems: 1) whether there was a flaw on resin manufacture process and 2) which raw-material (amount or kind) was incorrectly added to the reactor. Using NIR spectra of a wide range of MUF resins, several models were established to predict the molar ratio of formaldehyde and urea (F/U), molar ratio of formaldehyde and melamine (F/M), molar ratio of formaldehyde and amino groups (F/(NH₂)₂), total urea (% U) and total melamine (% M). These models were constructed using the multivariate technique of Partial Least Squares (PLS) and could successfully determine the properties of a set of industrial resins. The coefficients of variation (CV) obtained were equal or lower than 5%, except for the property of F/M, which was 17%. A more thorough analysis of the established models reveals that spectral components of melamine are harder to extract by PLS than components of formaldehyde or urea.     

改性三聚氰胺-尿素-甲醛共缩聚树脂胶粘剂的合成

通过三聚氰胺-尿素-甲醛(MUF)共缩聚树脂胶粘剂的合成,探讨了三聚氰胺的用量对该MUF树脂耐水性能的影响及其规律。实验结果表明,当w(三聚氰胺)=43%～65%时,该MUF树脂的湿强度从0.93 MPa增加到2.74 MPa,耐沸水性明显提高;但是,当w(三聚氰胺)>65%时,该MUF树脂的湿强度增长极其缓慢,其耐沸水性提高并不明显;通过引入复合改性剂和适量的水,可使该MUF树脂的游离甲醛含量降低50%、成本降低10%～15%、固含量基本不变、胶合强度和耐沸水性均有所提高且适用期良好。     

酸-碱-酸-碱工艺合成脲醛树脂

以酸-碱-酸-碱工艺合成一种聚乙烯醇(PVA)、三聚氰胺改性脲醛树脂,研究了原料配比、pH值、反应时间等对产品性能的影响。结果发现,当n甲醛:n尿素=1.6:1,聚乙烯醇加入量为甲醛和尿素总质量的1%,三聚氰胺加入量为甲醛和尿素总质量的3%,酸性条件下pH=5.5,碱性条件pH=8.5～9.0,反应温度为80℃左右时,合成的脲醛树脂的机械强度较好,游离甲醛的含量较低。