Development of room-temperature curing aqueous emulsion-type acrylic adhesive I: effect of monomer composition on the initial adhesive strength

For the purpose of developing a new aqueous emulsion-type adhesive for wood or paper use that does not release formaldehyde or volatile organic solvents, a honeymoon-type acrylic adhesive was examined. An adhesive system consisting of acrylic monomers copolymerized with functional monomers and a cross-linking agent was selected for the purposes of increasing initial adhesive strength and ensuring room-temperature curing. The initial adhesive strength increased by the use of cross-linkers such as dihydrazides and also polymeric methylene diphenyl diisocyanate (pMDI). Thus an adhesive with reasonable to good initial adhesive strength and room-temperature curing was obtained. The effect of pMDI on the initial adhesive strength was not significant and decreased when the amount of acrylamide in a copolymer was high.     

单宁和纳米SiO2改性大豆基胶黏剂的制备及其性能

为制备无甲醛的环保型生物基木材胶黏剂,以单宁和纳米SiO₂改性脱脂豆粉制备大豆基胶黏剂（DSF）,并分析了改性大豆基胶黏剂的性能。研究结果显示：单宁和纳米SiO₂二元复合改性大豆基胶黏剂（DSF-T-SiO₂）在固化过程中能够形成稳定的交联结构;TG分析表明单宁和SiO₂改性显著提高了胶黏剂的热稳定性;单宁改性大豆基胶黏剂（DSF-T）可提高干态和湿态胶合性能,纳米SiO₂改性大豆基胶黏剂（DSF-SiO₂）的干态胶合性能略有提高,但湿态胶合性能无明显改善。经分析以25 g脱脂豆粉、 5 g单宁、 0.1 g纳米SiO₂和70 g去离子水混合均匀搅拌得到的改性胶黏剂DSF-T-SiO₂-2的起始黏度比未改性的DSF降低了79.58%;DSF-T-SiO₂-2的固化胶层水溶解率为（27.5±0.05）%,比对照组DSF下降了28.4个百分点。此外,DSF-T-SiO₂-2...     

Micromechanical properties of the interphase in pMDI and UF bond lines

Micromechanical properties of cured polymeric diphenylmethane diisocyanate (pMDI) and urea formaldehyde (UF) adhesive and wood cell walls (beech) in adhesive contact compared with cell walls without adhesive contact were measured in situ by means of nanoindentation. Using UV-microphotometry obtained absorbance spectra of micromechanical investigated cell wall regions gave a strong indicator for the presence of pMDI compounds in wood cell walls. Nanoindentation results reveal that both pure UF and UF-penetrated cell walls show a very brittle character. In contrast, pMDI adhesive is very tough and soft at the same time, and when diffused in cell walls, it does not mechanically embrittle the cell structure.     

水性异氰酸酯交联剂的应用研究

采用不同链长的聚醚多元醇与多亚甲基多苯基多异氰酸酯（PAPI）反应,制备了两种不同结构的水性异氰酸酯（P-C、P-D）,联剂分别加入到氧化玉米淀粉胶黏剂和脲醛树脂胶黏剂中,以改善胶黏剂的胶接性能。通过粘接强度测试研究不同结构、不同用量的水性异氰酸酯对改性胶黏剂的胶接强度和耐水性的影响。实验结果表明：氧化玉米淀粉和脲醛树脂中加入水性异氰酸酯交联剂制备胶合板,胶接强度及耐水性均有显著提高。氧化玉米淀粉胶黏剂中加入10%的水性异氰酸酯P-D后,所制备胶合板的干态剪切强度可达2.64MPa。脲醛树脂胶黏剂中加入7.5%的P-D后,干态、湿态剪切强度分别为1.24MPa和1.23MPa,甲醛释放量为0.31mg/L,达到E0级标准。     

Effect of the ethylene/vinyl acetate ratio of ethylene-vinyl acetate emulsion on the curing behavior of an emulsion polymer isocyanate adhesive for wood

We investigated the curing behavior of an emulsion polymer isocyanate adhesive for wood with different ethylene-vinyl acetate (EVA) emulsions, because it was found that the ethylene/vinyl acetate weight composition (E/VA ratio) of EVA could control the volume of gas emitted from the adhesive. EVA with higher VA content reduced the volume of gas emitted at the initial stage, which was caused by the extent of the reaction between the NCO groups and water. The reaction scheme of NCO could not be determined because the broad infrared (IR) absorptions due to CaCO3 and water masked the information of the NCO products in IR spectra. Examination of the degree of swelling suggested that the adhesive films stored for 3 weeks had the same degree of cross-linking structure in spite of the variation of EVA. This result was supported by IR spectroscopy, which showed the same amounts of NCO remained in these films. All the adhesives prepared in this study had satisfactory bond performance. The findings indicate that the E/VA ratio affects the curing behavior of the adhesive in the initial curing stage, whereas the cross-linking structure and the bond performance were independent of the E/VA ratio after storage for 3 weeks. Part of this report was presented at Wood Adhesives 2005, November 2–4 2005, San Diego, CA, USA     

竹展平板拉伸剪切胶合性能

竹展平板是竹筒最大化利用的一种方式,以竹展平板为单元制备竹质人造板可减少胶黏剂使用量,还有利于加工,具有良好的应用前景.然而,竹材是一种天然梯度复合材料,纤维含量在竹壁径向呈现梯度变异,不同纤维含量的胶合面对竹展平板的胶合性能有重要影响.以无刻痕竹展平板为研究对象,参照拉伸剪切强度测试方法,探讨不同纤维含量的竹展平板胶...     

Influence of growth ring angle,adhesive system and viscosity on the shear strength of adhesive bonds

Abstract

To investigate the influence of growth ring angle, adhesive system and viscosity on the bonding properties of adhesive bonds, shear tension tests according to DIN EN 302-1 (2004) were conducted using one-component moisture-curing polyurethane, polyvinylacetate and urea-formaldehyde. Significant differences between the systems could be detected, which were reflected in the predominant failure behaviour for each system. Specimens showing wood failure were influenced mainly by the wood factors, whereas samples which had failed in the adhesive part of the bond differed only in the adhesive properties. The growth ring angle showed the same tendencies as it does in plain wood. Therefore, to gain more information on the adhesive performance in the bond, a loading along the LT plane seems more appropriate for beech wood used in DIN EN 302-1 (2004).     

秸秆板贴面用异氰酸酯胶的改性

通过对异氰酸酯(API)主剂进行改性,从而减少交联剂的用量,降低API胶黏剂的生产成本。将改性API胶黏剂用于秸秆板薄木贴面的试验表明,当主剂、交联剂、填料之比为100∶4∶30,热压温度为60~110℃时,秸秆板的贴面效果达到相关国标要求。     

Bondability of tropical fast-growing tree species III: curing behavior of resorcinol formaldehyde resin adhesive at room temperature and effects of extractives of <Emphasis Type="Italic">Acacia mangium</Emphasis> wood on bonding

The effects of curing time at room temperature and methanol extracts from Acacia mangium on the curing behavior of resorcinol formaldehyde (RF) adhesive were examined by using the thermomechanical analysis spring method. For a specimen that was cured for 3 months at room temperature, the relative elasticity (E _r) curve did not change to a hard glass state from room temperature to 200°C and the adhesive had cured completely. The initial temperature of the reactive zone for chemical and mechanical changes was 15° and 25°C higher than that for the control when 10 and 15 parts by weight methanol extract was added to the liquid adhesive, respectively. It appears that the extractives of A. mangium in RF adhesive interferes with the chemical cure of the adhesive. It is suggested that a combination of curing time and sweeping by methanol on the laminae surface can improve the bonding performance of A. mangium laminates bonded with RF at room temperature.     

等离子体改性热塑性树脂薄膜制备环保胶合板试验

为获得无甲醛释放的环保胶合板,将热塑性树脂薄膜(低密度聚乙烯(LLDPE)、聚丙烯(PP)、聚氯乙烯(PVC))用作胶黏剂,并利用空气介质阻挡等离子体对热塑性树脂薄膜进行表面改性处理以提高薄膜与杨木单板的界面相容性,从而获得性能良好的环保胶合板。研究了等离子体处理对胶合板胶合性能的影响,并从等离子体处理对热塑性树脂薄膜表面化学组分及其对胶合板界面形貌的影响分析其胶合机理。结果表明:在等离子体处理功率为4.5 kW、处理时间为8 m/min的条件下处理热塑性树脂薄膜,胶合板的胶合强度得到显著提高,LLDPE/杨木胶合板的胶合强度从0.49 MPa增至0.81 MPa,PP/杨木胶合板的胶合强度从0.65 MPa提高到0.84 MPa,均达到Ⅱ类胶合板标准要求。其中用等离子体处理后PVC与杨木制备的胶合板能满足Ⅰ类胶合板的标准要求,胶合强度达到0.79 MPa。XPS分析表明,等离子体改性热塑性树脂薄膜的表面发生了氧化反应,引入了含氧官能团,提高了薄膜表面极性,有利于提高薄膜与杨木单板之间的相互作用,从而使得胶合板的界面胶合更为紧密,说明等离子体处理后树脂与杨木单板的相容性提高,树脂能在单板表面更好地附着。热塑性树脂薄膜与杨木单板制备的胶合板仅有极微量甲醛释放,其主要源于木材自身,远低于国家标准对人造板甲醛释放限量的要求。研究证明等离子体处理能明显改善热塑性树脂薄膜与杨木单板的界面相容性。     

Relationship between fracture toughness and acoustic emission during cleavage failure in adhesive joints

Summary Fracture toughness in mode I was determined for wood bonded with various adhesive systems. Tapered double-cantilever beam (TDCB) specimens were used, with attached transducer connected to instrumentation for monitoring acoustic emission. Adhesives used fro bonding the TDCB specimens included urea-formaldehyde resin, phenol-resorcinol resin, and emulsion polymer isocyanate, among others. Test parameters measured included critical load for cleavage fracture and number of events (stress waves) emitted, from which fracture toughness and cumulative count of acoustic emission were computed. It was found that there was a well defined, linear relation between fracture toughness and cumulative counts of acoustic emission per fracture area. The fracture toughness values of systems containing polyvinyl acetate and of epoxy resin were larger than those of thermosetting resins such as urea-or phenol formaldehyde. The high fracture toughness imparted by polyvinyl acetate was attributed to viscous movement of linear molecular chain segments, as compared with the more brittle behavior of the crosslinked molecular structure of such resins as ureaformaldehyde.     

Technologies of liquefaction of bamboo and preparation of adhesive

The technology of liquefying processed-waste bamboo with phenol is investigated by single factor trials and an orthogonal design. We studied the preparation technology and properties of adhesives from this phenol-liquefied bamboo with formaldehyde (BPF). The results show that temperature has a significant effect on liquefaction. The effect of the mass ratio of phenol to bamboo comes second and the catalyst dosage within the range of 2%–4% is the least effective. The optimum conditions of liquefaction are as follows: a mass ratio of phenol to bamboo 3.5, a catalyst dosage of 4%, liquefying temperature 145°C and liquefying time 60 min. The liquefaction rate of bamboo reached 99.1%. For the preparation of the adhesive, a mass ratio of liquefied bamboo products to formaldehyde (37%) is 100 to 164.8–199.5, while the ratio 100 to 108.2 is the best. This adhesive has a lower curing temperature than that of normal PF resin. At a hot-press temperature of 130 or 140°C, this new adhesive provides excellent bonding strength of plywood. The most favorable temperature for hot-pressing is 140°C. __________ Translated from Chemistry and Industry of Forest Products, 2007, 27(6): 65–70 [译自: 林产化学与工业]     

多胺基聚合物改性室温固化型MUF树脂胶黏剂

为解决三聚氰胺-尿素-甲醛(MUF)树脂作为室外级结构集成材胶黏剂时存在的脆性大、易开裂的问题,得到韧性优秀且综合性能满足室外级结构集成材标准的室温固化型MUF树脂胶黏剂,本研究在MUF树脂合成中使用两种改性剂尿素-乙二胺(UE)、尿素-三(2-氨基乙基)胺(UD)分别替代部分三聚氰胺合成了MUF-UE、MUF-UD树脂胶黏剂。通过制备树脂拉伸试样以及胶合木考察改性后的MUF树脂的物理力学性能,借助DSC、DMA分析改性前后树脂的热性能,使用FT-IR、ESI-MS分析改性前后树脂的结构变化。试验结果表明:相较于未改性MUF树脂,MUF-UE树脂拉伸强度和断裂伸长率分别提高51.5%和30.8%,所制备胶合木剪切强度高达8.00 MPa,冷、沸水二次循环剥离率均为0%;MUF-UD树脂拉伸强度相比改性前会有所下降,但断裂伸长率以及胶合木剪切强度对比改性前有一定提高。结构分析表明,UE和UD能够参与MUF树脂合成反应并形成共缩聚产物,且不改变树脂体系中主要官能团结构。     

高支化聚脲对脲醛树脂胶黏剂耐水性能和甲醛释放量的影响

引入高分子量、高支化度以及端基为尿素的高支化聚脲(HBPU)用于低摩尔比脲醛树脂(UF)改性,利用HBPU与游离甲醛的反应以及与UF组分的共缩聚反应实现树脂耐水性能的提升和人造板甲醛释放量的降低,有效平衡胶合性能和甲醛释放量之间的矛盾。在无溶剂、无催化剂条件下,通过尿素(U)与三(2-氨基乙基)胺(TAEA)的脱氨缩合反应,一步合成了具有尿素端基的HBPU,并对HBPU的分子量分布和结构进行了表征。使用HBPU水溶液,采用UF合成反应后期加入和共混2种方法对UF进行改性,通过胶合板性能测试以及甲醛释放量测定,考察了HBPU添加量和添加方式的影响。凝胶渗透色谱和碳-13核磁共振分析表明,通过本研究的合成方法可以获得具有高分子量、高支化度、尿素为端基且水溶性良好的HBPU,并且随着U与TAEA摩尔比的提高,更多尿素封端产物形成。电喷雾电离质谱对改性树脂的分析结果表明,HBPU不仅与UF中的一部分游离甲醛发生羟甲基化反应,同时与UF组分反应生成了部分共缩聚产物。胶合板性能测试结果表明,共混以及反应后期加入HBPU两种方式得到的改性树脂耐水性能均显著提升。同时,使用添加5%HBPU改性树脂制备...     

Bond strength of end-grain joints and its dependence on surface roughness and adhesive spread

The effect of different machining processes on surface roughness and on adhesive tensile strength of end-grain-bonded spruce wood specimens was studied. Surfaces that had been cut with two different circular saws containing 48 and 96 teeth were compared with those that had been further processed by smoothing with a microtome, machine planing, or sanding. Two different adhesives and two different spreading quantities were used to join the test specimens by their end-grain surfaces. Increasing tensile strength of the bonded specimens was observed with increased surface roughness, which was ascribed to an enlarged bonding area in the case of circular-sawn samples with a rough surface. On the other hand, more pronounced starving of the bond line and thus decreased bond strength was observed in the more open cells of the smoothed end-grain surfaces. A positive effect regarding tensile strength was further observed with increased spreading quantity of the adhesives. Machining was found to particularly affect earlywood tracheids, whereas surface roughness of latewood tracheids was comparable for the differently treated end-grain surfaces     

Investigation of a new natural adhesive composed of citric acid and sucrose for particleboard

The development of a natural adhesive composed of materials derived from non-fossil resources is a very important issue. In this study, only citric acid and sucrose were used as adhesive materials for particleboard. A water solution in which citric acid and sucrose were dissolved was used as an adhesive, and the manufacture of particleboard with a target density of 0.8 g/cm³ was attempted under a press condition of 200 °C for 10 min. The optimum mixture ratio of citric acid and sucrose and the optimum resin content was 25–75 and 30 wt%, respectively. The modulus of rupture (MOR) and the modulus of elasticity in bending were 20.6 MPa and 4.6 GPa, respectively. The internal bond strength (IB) was 1.6 MPa, indicating that the adhesive had excellent bond strength. The thickness swelling (TS) after water immersion for 24 h at 20 °C was 11.9 %. The board did not decompose even under more severe accelerated treatments. This meant that the adhesion had good water resistance. The MOR, IB and TS of the board were comparable to or higher than the requirement of the 18 type of JIS A 5908 (2003). Consequently, there is a possibility that a mixture of citric acid and sucrose can be used as a natural adhesive for particleboard.     

Investigation of a new natural particleboard adhesive composed of tannin and sucrose

In the face of dwindling fossil fuel resources and the environmental imperative to reduce emissions associated with petrochemistry, there is strong demand for a wood composite bonding procedure using natural alternatives. In this study, particleboards were manufactured with a new material adhesive composed of tannin and sucrose, and hot-pressed at 200 °C for 10 min, to a target density of 0.8 g/cm³. We found optimal values for the mat moisture content, the ratio of tannin to sucrose and the resin content of 3–6 wt%, 25/75 and 30–40 wt%, respectively. When the particleboards were manufactured under these optimum conditions, the modulus of rupture and the modulus of elasticity were in the range of 19.6–21.2 MPa and 4.6–5.0 GPa, respectively. The internal bond strength was in the range of 1.1–1.3 MPa. Based on these results, the mechanical properties of particleboard bonded with tannin and sucrose were higher than the requirements of the JIS A 5908 type 18 standard (2003). In the thickness swelling test (TS), the value was in the range of 20–23 %; as the ratio of sucrose and resin content increased, the TS value decreased. The reaction mechanism between tannin and sucrose was studied by fourier transform infrared spectroscopy, and the dimethylene ether bridges were observed. Consequently, it is possible that a tannin and sucrose mixture can be used as a natural adhesive for particleboard.     

高含水率单板胶接工艺的研究

研究了单组分湿固化异氰酸酯胶粘剂胶接高含水率单板的工艺条件,详细讨论了含水率、涂胶量、加压压力、加 压时间和养生时间对胶合性能的影响。结果表明:单板含水率、涂胶量是重要的影响因子,单组分湿固化异氰酸酯胶粘 剂可胶接含水率高达100％的单板,在保证胶接强度的前提下,涂胶量仅为传统胶粘剂的1／2-1／3。     

Combustion gas toxicity,hygroscopicity, and adhesive strength of plywood treated with flame retardants

Summary The results of tests of combustion toxicity, hygroscopicity, and adhesive strength for fire retardant-treated plywood are described. The plywood was prepared from veneers treated with diammonium phosphate and ammonium bromide, and from glue mixed with poly (ammonium phosphate). Furthermore, the plywood boards were coated with boric acid. High ammonium phosphate and low or 0 ammonium bromide contents with the boric acid-coatings gave the greatest improvement in the combustion toxicity. Influence of almost all the treatments on the hygroscopicity was not significant. In all treatments the dry adhesive strength and the cyclic boil adhesive strength were slightly and considerably reduced, respectively.     

新型酚醛树脂改性大豆蛋白基胶黏剂的研究

以脱脂大豆粉为原料制备大豆蛋白基胶黏剂(豆胶,S),以普通甲醛制备的酚醛树脂(PF_1)和高浓度甲醛制备的酚醛树脂(PF_2)为交联剂,使用前将两者直接混合得酚醛树脂改性豆胶(PF_1/S、PF_2/S)。利用差示扫描量热(DSC)、红外光谱(FT-IR)、动态热机械性能(DMA)和核磁共振碳谱(~(13) C NMR)分析对产品性能进行了测试与表征。结果表明:等物质的量之比条件下,高浓度甲醛较之普通甲醛制备的酚醛树脂改性豆胶胶合板干、湿剪切强度分别提高4.3%和11.6%,并且强度稳定性好;动态DSC分析表明,PF_2可以降低豆胶体系的固化温度和活化能,与豆胶的交联反应较容易;~(13) C NMR分析表明,PF_2体系羟甲基达88.73%,明显高于PF_1的80.91%;FT-IR分析证实酚醛树脂与豆胶中的氨基发生反应,并且PF_2反应效率更高;DMA分析表明,PF_2/S能够改善胶合产品的力学性能和热稳定性,降低豆胶的固化反应起始温度,提高固化反应速率。