CN101323772A - Ultra-thin stone and aluminum honeycomb composite modified epoxy adhesive and preparation thereof - Google Patents

Ultra-thin stone and aluminum honeycomb composite modified epoxy adhesive and preparation thereof Download PDF

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CN101323772A
CN101323772A CN 200810031999 CN200810031999A CN101323772A CN 101323772 A CN101323772 A CN 101323772A CN 200810031999 CN200810031999 CN 200810031999 CN 200810031999 A CN200810031999 A CN 200810031999A CN 101323772 A CN101323772 A CN 101323772A
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component
powder
weight
epoxy adhesive
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CN 200810031999
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CN101323772B (en )
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辉 刘
李冬月
王理尧
袁素珍
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湖南神力实业有限公司
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The invention relates to a modified epoxy adhesive, in particular to a modified epoxy adhesive used in composite preparation of ornamental stone materials by ultra-thin stone materials and aluminum honeycombs. A component A of the adhesive is made from 20 percent to 40 percent of epoxy resin, 5 percent to 15 percent of reactive diluent, 1 percent to 5 percent of nanometer powder material, 10 percent to 30 percent of polyurethane prepolymer and 40 percent to 60 percent of inorganic powdery filler, while a component B is made from 20 percent to 30 percent of modified amine curing agent, 1 percent to 5 percent of accelerant, 1 percent to 5 percent of organic silicon coupling agent, 5 percent to 10 percent of glass flake and 40 percent to 60 percent of inorganic powdery filler; the proportion by weight between the component A and the component B is 2.5 to 3.5: 1. The modified epoxy adhesive is applied to composition of the ultra-thin stone materials and aluminum honeycombs, the key technical indexes of which meet the national building material industry standards of ultra-thin natural stone composite boards.

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一种超薄型石材与铝蜂窝复合的改性环氧胶粘剂及其制备方法技术领域:本发明涉及一种薄型石材复合用的胶粘剂,尤其涉及一种超薄型石材与铝蜂窝复合的改性环氧胶粘剂。 An ultra-thin type of aluminum honeycomb composite stone and epoxy adhesive and a modified TECHNICAL FIELD: The present invention relates to an adhesive with a thin stone composite, particularly to an ultra-thin aluminum honeycomb composite stone and modified epoxy adhesive. 背景技术:近十年,世界建筑装饰用石材需求量大幅度增长,其中,超薄型石材与铝蜂窝复合的建筑装饰材料发展速度更快。 BACKGROUND: Over the past decade, world architectural stone with a substantial increase in demand, which, ultrathin stone and aluminum honeycomb composite construction materials development faster. 装饰石材表面美观华丽,是高档宾馆、 商场、会展中心及高级住宅内外墙、地面装饰的首选材料。 Beautiful ornate decorative stone surface, the material of choice for high-end hotels, shopping malls, convention centers and senior housing within the external walls, ground decoration. 不过,石材结构7;稳定, 一般作为饰石材料的厚度在20mm左右。 However, the stone structure 7; stable, generally used as decorative stone material thickness of about 20mm. 因石材比重大,增加了建筑物的重量和施工难度,名贵石材价格昂贵,饰面石材厚,用料多,造价也很高。 Due to stone proportion, increasing the weight and the difficulty of construction of the building, expensive precious stone, decorative stone thick, use of materials, the cost is also high. 随着科学技术的进步,市场上推出了厚度5 mm以下的超薄型石材与铝蜂窝复合的饰石材料,单位面积的重量只有原来的1/4或更轻,石材的用量只有原来的1/4~1/10,饰面效果并没有改变,生产成本和施工成本降低了30~50%,深受客户欢迎。 With the progress of science and technology, the market a thickness of less than 5 mm ultrathin stone decorative aluminum honeycomb composite stone material, the weight per unit area or only a quarter of the original lighter, only the original amount of stone 1 / 4 to 1/10, finishes effect has not changed, the cost of production and construction costs by 30 to 50%, welcomed by customers. 石材与铝蜂窝之间是经胶粘剂粘接复合的,这种饰石材料用于室内外装饰, 对材料尺寸的稳定性、强度的保持性、石材表面的美学效果有很高的要求。 Is between stone and aluminum honeycomb composite by adhesive bonding, which decorative stone material for interior decoration, a material for dimensional stability, strength retention, the stone surface aesthetics high demands. 石材与铝蜂窝线膨胀系数差异大、材料尺寸易变形;石材结构疏松,雨水、空气中的腐蚀性物质极易经石材中的裂纹、孔洞向胶层浸蚀。 Aluminum honeycomb stone and large differences in linear expansion coefficient, easily deformable material size; loose stone structure, rainwater, highly corrosive substances in the air to the adhesive layer by etching the stone cracks, holes. 这类装饰材料妇室外使用时,悬挂或粘结在空中,质量不好易发生坠落伤人事故;此外,工程造价高更新不易,因而对胶粘剂的质量要求极为苛刻。 When such women decorative materials for outdoor use, suspension or bonded in the air, poor quality prone to fall injury accidents; in addition, high update project cost is not easy, and thus the quality of the most demanding adhesive. 刚推出的行业标准JC/T 1047-2007《超薄天然石材型复合板》规定了基材为铝蜂窝的复合板物理性能技术指标,其中热处理80°C168小时的粘接强度大亍等于1. 0 MPa,浸水168小时粘接强度大于等于0. 8 MPa,冻融循环25次粘接强度大于等于0.7 MPa。 Just launched industry standard JC / T 1047-2007 "thin natural stone composite panel" defines the substrate is an aluminum honeycomb composite panel physical performance specifications, wherein the heat treatment is 80 ° C168 hours adhesive strength equal to a right foot. 0 MPa, the adhesive strength of greater than 168 hours immersion in water is equal to 0. 8 MPa, 25 cycles of freeze-thaw bonding strength of not less than 0.7 MPa. 该标准的颁发为胶粘剂的使用质量提出了具体要求。 The award criteria put forward specific requirements for the quality of the use of adhesives. 环氧胶粘剂是一种反应型胶粘剂,固化时形成三维化学交联结构,粘接强度高,收縮应力大,石材与铝蜂窝间用环氧胶粘剂结合,极易使复合材料变形报废;同时,环氧胶粘剂耐水性不佳,特别是在粘结超薄型石材时,水逍过石5材的裂缝、孔洞大面积浸入胶层,长期反复作用,易使胶层软化变形而剥离,不能保证超薄型天然石材复合胶的质量。 Reactive adhesive is an epoxy adhesive, a three-dimensional structure of a chemical crosslinking upon curing, high bond strength, large shrinkage stress in combination with an epoxy adhesive between the stone and aluminum honeycomb, scrap easily deformable composite material; the same time, ring oxygen-poor water resistance of the adhesive, particularly when bonding ultrathin stone, Xiao water through crack 5 stone material, the adhesive layer is immersed in a large area of ​​the holes, repeated long-term effect, easy to make and release adhesive layer softening and deformation, can not be guaranteed over lamination adhesive quality of the thin natural stone. 发明内容:针对超薄天然石材型复合板复合用胶粘剂使用特点和质量要求,本发明提供了一种改性环氧胶粘剂。 Summary of the invention: natural stone composite ultrathin composite panels using the adhesive characteristics and quality requirements, the present invention provides a modified epoxy adhesive. 这种胶粘剂使用聚氨酯预聚体来改进环氧胶粘剂胶层的应力应变特性,使其韧性提高弹性模量值降低,当石材与铝蜂窝受热膨胀、 受冷收縮而产生相对变形时,不致于形成过大的内应力而使外形尺寸严重变形失效;还使用了改性胺固化剂,使用脂环族环氧化合物改性脂肪胺合成的固化剂韧性较好,耐温性、耐水性和脂肪胺固化剂比较要好得多。 When this polyurethane prepolymer adhesives to improve the stress strain properties of the epoxy adhesive glue layer, so that toughness decreases elastic modulus, when the thermal expansion of the stone and aluminum honeycomb, produced by cold shrink relative deformation, as not forming excessive stress failure of the dimensions severe deformation; also use the modified amine curing agent, an alicyclic epoxy compound-modified aliphatic amine curing agents synthesized good toughness, heat resistance, water resistance and fatty amines comparison curing agent is much better. 本发明还针对聚氨酯预聚体改性环氧树脂玻璃化温度降低,从而影响耐热性能的缺陷,使用了少量纳米粉体材料,使改性环氧胶粘剂的玻璃化温度比通用环氧胶粘剂的玻璃化温度更高一些。 The present invention is also directed to an epoxy resin modified polyurethane prepolymer glass transition temperature decreases, thus affecting the heat resistance of the defect, the use of a small amount of nano-powder, the glass transition temperature than the general-purpose epoxy adhesive modified epoxy resin adhesive Some higher glass transition temperature. 还要说明的是本发明使用的聚氨酯预聚体是自制的,目的使聚氨酯预聚体在改性环氧胶粘剂固化成形时生成尺寸适当的颗粒,均匀分布亍胶层中,让增韧效果最佳。 It is also noted that the present invention is used in the polyurethane prepolymer is made, the object of the polyurethane prepolymer appropriate particle size generated at the time of forming a cured modified epoxy adhesive, glue uniformly distributed right foot, so that the toughening effect is most good. 本发明具体的技术方案如下:1、 聚氨酯预聚体的制备选择聚醚多元醇、TDI为原料制备聚氨酯预聚体,具体方法如下: 在装有搅拌器、滴液漏斗、回流冷凝器、抽真空管、水浴加热装置的反应器中,加入平均分子质量为600~3000的聚醚多元二醇,开搅拌,升温到'KTC, 抽真空2小时,真空度为0. 092~0. 095MPa,除去聚醚多元醇中的水分,然后消除真空,降温至60。 Particular aspect of the present invention is as follows: 1. Preparation of polyurethane prepolymer of polyether polyol selected, TDI was prepared starting from a polyurethane prepolymer, specifically as follows: equipped with a stirrer, a dropping funnel, a reflux condenser, evacuated the reactor vacuum, water bath heating means added a polyether polyol an average molecular weight of 600 to 3000 diol, open stirring, warmed to 'KTC, evacuated 2 hours, the degree of vacuum of 0. 092 ~ 0. 095MPa, removed polyether polyols in the water, then the vacuum that was cooled to 60. C,经滴液漏斗加入TDI,在60。 C, was added via a dropping funnel TDI, 60. C下反应1小时,升濫.到70 。 The reaction under C 1 hour liter of abuse. 70. C反应l小时,再升温到85'C反应1~3小时,取样测游离异氰酸酯基,游离异氰酸酯基含量为预聚体质量的1~2%为合格。 C-reactive l hour and then heated to 85'C for 1 to 3 hours, the sample measuring free isocyanate groups, free isocyanate group content of the prepolymer of 1 to 2% by mass acceptable. 2、 改性环氧胶粘剂A组份的制备A组份所用原材料:环氧树脂:包括双酚A环氧树脂E-44、E-51,双酚F环氧树脂6458 、NPf:F-170或者它们的混合物,占A组份重量的20〜4(m。' 活性稀释剂:包括W-95环氧树脂,501、 502、 622、 678活性稀释剂或它们的混合物,占A组份重量的5〜15°/0。 聚氨酯预聚体:自制,占A组份重量的10〜30%。纳米粉体材料:包括纳米Si02,纳米T202,纳米碳酸钙,平均粒径在50~100ra ,占A组份重量的1〜5%。 无机粉状填料:包括硅灰石粉、石英粉、重晶石粉,辉绿岩粉或它们的物理混合物,粒径在400〜1200目之间,占A组份重量的40'、60"5/0。 上述各组份的重量百分数之和为100%。 A组份的制备方法:(1) 在高速分散机中加入活性稀释剂,开动搅拌,调节转速为i()(K::()o转/分,慢慢加入纳米粉体材料,再调节转速至3000~5000转/分,连续搅拌20〜50 分钟,取出纳 Epoxy resin:: 2, parts of a modified epoxy adhesive component A starting material for preparation of the group A include bisphenol A epoxy resin E-44, E-51, a bisphenol F epoxy resin 6458, NPf: F-170 or mixtures thereof, by weight of the component a accounts for 20~4 (m 'reactive diluent: epoxy resin comprising a W-95, 501, 502, 622, 678 reactive diluent or mixtures thereof, by weight of the component a accounts for . the 5~15 ° / 0 polyurethane prepolymer: self, 10~30% a group representing parts by weight of nano-powder: including nano Si02, nano T202, calcium carbonate, average particle size of 50 ~ 100ra, accounting for ~ 5% by weight of component a pulverulent inorganic filler include: wollastonite powder, quartz powder, barite powder, diabase powder or physical mixtures thereof, in the size range 400~1200 mesh, accounting for a 40 parts by weight of a group ', 60 "5/0 the above components were percentages by weight and the sum is 100% of the group a parts preparation: (1) a reactive diluent was added in a high speed dispersing machine, stirring was started, adjusting speed is i () (K: :() o r / min, nano-powder was added slowly, and then adjusted to a rotational speed of 3000 to 5000 r / min, with continuous stirring 20~50 minutes, remove sodium 粉体材料分散液备用。(2) 在反应器中加入环氧树脂,开动搅拌,加入纳米粉体材料分散液,搅拌分散30分钟,加入自制的聚氨酯预聚体,向反应器夹套送蒸汽升温,当温度升至6(TC时,保温反应l小时,再升温至8(TC,保温反应1〜3小时,停送蒸汽, 向反应器中加无机粉状填料,加完填料后,连续搅拌1~3小时至A组份完全混合均匀为止,停搅拌,用80目筛网过滤出料。3、改性环氧胶粘剂B组份的制备B组份由改性胺固化剂、DMP-30促进剂、有机硅偶联剂、玻璃磷片粉、无机粉状填料制得。(1) 改性胺固化剂的制备在反应器中加入lmol 二乙烯基三胺,开动搅拌,慢慢滴加lmol环氧当ll 为84~86,分子中含两个环氧基团的脂环族环氧树脂,加料时间为1小时,加料过程中物料温度自然上升到40〜5(TC。在40〜50'C范围内保温反应1〜3小时,降温到30'C出料得改性胺固化剂。(2) Powder material dispersion liquid for use. (2) added to the epoxy resin in the reactor, stirring was started, dispersion of nano-powder was added and dispersed by stirring for 30 minutes, made of polyurethane prepolymer, feeding steam to the reactor jacket heating, when the temperature was raised to 6 (TC, the reaction was incubated l hour, then warmed to 8 (TC, ~ 3 hours after the reaction incubation, stop sending steam, pulverulent inorganic filler added to the reactor, the filler addition was complete, continuous stirred for 1 to 3 hours until the component a to be thoroughly mixed, stop stirring, filtered off with 80 mesh screen material .3, parts of a modified epoxy adhesive component B preparation B the group consisting of modified amine curing agent, DMP- 30 accelerator, an organic silane coupling agent, a glass flake powder, powdered inorganic filler is prepared. preparation of (1) modified amine curing agent lmol diethylenetriamine was added in a reactor, stirring was started slowly added dropwise when the epoxy plus lmol ll 84 to 86, the molecule containing two alicyclic epoxy resin epoxy groups, addition time was one hour, during the addition the temperature of the material rises to the natural 40~5 (TC. 40 the reaction was kept within the range of 1~3 ~50'C hours, cooled to 30'C to obtain the material modified amine curing agent. (2) 制备B组份所用原材料及用量改性胺固化剂重量份数为20〜30%,改性按固化剂中脂环族环氧树脂是YJ-118型环氧树脂。B组份中所用促进剂是2, 4, 6-(甲氨基甲基)苯酚,商品名称为:DMP-30, 重量份数为1~5%。B组份中所用有机硅偶联剂,包括KH-550、 KH-560或它们的混合物,重量份数为1~5%。B组份中所用玻璃磷片为中碱玻璃,厚度《Sum,过200目筛网,重量份数为5~10%。 Preparation of Component B parts by weight of the raw materials and the modified amine curing agent is used in an amount of 20 to 30%, by modifying the curing agent is a cycloaliphatic epoxy resin parts Epoxy type YJ-118 .B group accelerator used 2, 4, 6- (methylaminomethyl) phenol, trade name: DMP-30, parts by weight of 1 ~ 5% .B component used in the organosilicon coupling agent, comprising KH-550, KH- 560, or mixtures thereof, parts by weight of 1 ~ 5% .B component as a glass flake as alkali glass, the thickness of the "Sum use, through a 200 mesh screen, parts by weight of 5 to 10%. B组份中所用无机粉状填料是硅微粉、石英粉、滑石粉、重晶石粉、辉绿岩粉或它们的混合物,细度在400-1200目之间,重量份数为40〜60%。 B component as the inorganic filler used is pulverulent silica powder, quartz powder, talc, barite powder, diabase powder or mixtures thereof, the fineness of between 400-1200 mesh, parts of 40~60% by weight . B组份中各组份的重量百分数之和为100%。 Each group B component parts and percentages by weight sum to 100%. (3) B组份的制备将改性胺固化剂输入反应器,开动搅拌,分别加入促进剂和偶联剂,,逐渐升温至60〜8(TC,保温反应1-2小时,停止加热,加入玻璃鳞片,搅拌分散30 分钟,加入无机粉料填料,搅拌l-3小时,过滤出料。具体实施方式本发明通过下面的实施例更详细地予以说明:实施例1(1)聚氨酯预聚体的制备聚氨酯预聚体制备时投料量和预聚体游离异氰酸酯基含量见表1,表l聚氨酯预聚体的制备<table>table see original document page 9</column></row> <table>'制备方法:在装有搅拌器、滴液漏斗、抽真空管、水浴加热装置的反应器中加入100g聚醚多元醇,升温至9(TC,抽真空2小时,真空度为0. 092-0. 095MPa, 降温至60"C,消除真空,经滴液漏斗滴加TDI,在6(TC下反应1小时,升温至7(TC反应1小时,再升温至85'C反应1小时,降至常温,取样测预聚体游离异(2)改性环氧胶粘剂中A组份的配 (3) B Component Preparation of modified amine curing agent into the reactor, stirring was started, promoters and coupling agents were added gradually warmed to ,, 60~8 (TC, reaction was incubated for 1-2 hours, heating was stopped, glass flake was added and dispersed by stirring for 30 minutes, the inorganic powder filler, stirred for l-3 hours, filtered and the material embodiment of the present invention dETAILED be described in more detail by the following examples: Example 1 (1) a polyurethane prepolymer preparation of preparing polyurethane precursor prepolymerized system feeding amount and the isocyanate group content of free prepolymer shown in table 1 was prepared table l polyurethane prepolymer of the <table> table see original document page 9 </ column> </ row> <table > 'preparation: equipped with a stirrer, a dropping funnel, a vacuuming water bath reactor apparatus was charged 100g of polyether polyols, warmed to 9 (TC, vacuum for 2 hours and the degree of vacuum of 0. 092- 0. 095MPa, cooled to 60 "C, the vacuum that via a dropping funnel TDI, the reaction (the TC 6 1 h, allowed to warm to 7 (TC 1 hour, then heated to 85'C for 1 hour, reducing to room temperature, sampled for divorced travel prepolymer (2) a modified epoxy adhesive component feature 制配料:环氧树脂E-44 15g 6458 14g 活性稀释剂W-95 10g 聚氨酯预聚体16g 纳米粉体材料Si02 3g无机粉状填料硅灰石粉20g石英粉15g重晶石粉7g 制备方法:在高速分散机中加入活性稀释剂,开动搅拌,转速为100-200转/分,加入纳米粉体材料,升速至3000~5000转/分,连续搅拌30分钟,停搅拌,取出在带搅拌和加料加热装置的反应器中加入环氧树脂,开动搅拌,加入纳X粉体材料分散液,搅拌分散30分钟,加入自制的聚氨酯预聚体,开启加热装置, 使物料升温至6(TC保温反应1小时,再升温至8(TC,保温反应1小时,停止加热。向反应器内加无机粉状填料,加完填料后连续搅拌2小时至A组份完全混合均匀为止,停搅拌,出料得A组份。(3) 改性环氧胶粘剂B组份的制备改性胺固化剂的制备在带搅拌器、加料漏斗和加热装置的反应器中加入lmol二乙烯基三胺,开启搅拌,经滴液漏斗滴 Ingredients prepared: epoxy resin E-44 15g 6458 14g reactive diluent W-95 10g 16g polyurethane prepolymer Si02 3g nano inorganic filler is wollastonite powder powdered quartz powder 15g 20g 7g barite powder material preparation method thereof: high-speed reactive diluent was added in a dispersing machine, stirring speed of 100-200 rev / min, nano-powder was added, increases the speed to 3000 to 5000 rev / min, stirring was continued for 30 minutes, stop stirring and extracted in a stirred addition the reactor was charged with an epoxy resin heating apparatus, stirring Jia Runa X powder material dispersion, the dispersion was stirred for 30 minutes, made of polyurethane prepolymer, the heating means is turned on, so that the material temperature was raised to 6 (TC incubated for 1 h, then warmed to 8 (TC, incubated for 1 hour, heating was stopped. pulverulent inorganic filler is added into the reactor, continuous stirred 2 hours after the addition of filler to component A thoroughly mixed up, stop stirring, the material obtained a component. preparation of (3) parts of a modified epoxy adhesive group B preparation of modified amine curing agent is added in a reactor with a stirrer, addition funnel and heating device lmol diethylenetriamine, open stirring, dried dropping funnel 加lmol的YJ-118型环氧树脂,加料时间为1小时,物料温度上升至4(K5(TC 。在40〜5(TC温度下保温反应2小时,降温至30°C出料。B组份的配料改性胺固化剂32g促进剂DMP-30 4g偶联剂KH-550 3g 玻璃鳞片10g无机粉状填料硅灰石粉30g滑石粉10g重晶石粉llg B组份制备方法:在带搅拌器、加料加热装置的反应器中加入改性胺固化剂,开启搅梓,加入促进剂、偶联剂,升温至75'C,保温反应2小时,停止加热,加入玻璃鳞片, 搅拌分散30分钟,加入无机粉状填料,搅拌分散2小时,过滤出料。 The YJ-118 plus lmol type epoxy resin, an addition time of 1 hour, the slurry temperature was raised to 4 (K5 (TC. Incubation at 40~5 (TC temperature for 2 hours, cooled to 30 ° C the material .B group parts of a modified amine hardener ingredient 32g accelerator DMP-30 4g coupling agent KH-550 3g pulverulent inorganic filler is glass flakes wollastonite powder 10g 30g 10g talc barite powder llg component B preparation: stirrer the reactor feed heating device modified amine curing agent was added, stirred open Zi, the addition of promoters, coupling agents, warmed to 75'C, incubated for 2 hours, heating was stopped, the glass flakes were added, dispersed for 30 minutes with stirring, adding an inorganic pulverulent filler and dispersed by stirring for 2 hours the material was filtered. (4) 改性环氧胶粘剂的配制和使用在使用前,将A组份、B组份以重量比2.5〜3.5: l的比例称取,混合均匀, 即可使用。 (4) Preparation and use of modified epoxy adhesive prior to use, the component A, component B in a weight ratio of 2.5~3.5: l ratio weighed, mixed, can be used. 在粘接面上刷胶要做到胶层厚薄均匀,叠合压力不小于0. 1MPl営温下固化时间为24小时,6(TC固化时间为6小时。以此胶粘剂用于超薄石材和铝蜂窝复合,制得了基材为铝蜂窝的复合板,其性能技术指标见表2。10实施例2 A组份配料为:环氧树脂E-44 10g E-51 8g 6458 14g 活性稀释剂622 6g 678 2g 聚氨酯预聚体19g无机粉状填料硅灰石粉20g石英粉10g 重晶石粉llg 其余同实施例1制备方法同实施例l,产品用于薄型石材与铝蜂窝复合,测试结果见表2。实施例3B组份配料为:改性胺固化剂38g促进剂DMP-30 5g偶联剂KH-560 4g 玻璃鳞片8g无机粉状填料硅灰石粉25g滑石粉15g重晶石粉5g其余同实施例2比较例A组份配料为:环氧树脂E-44 12g E-51 10g 6458 15g 活性稀释剂W-95 8g 622 6g无机粉状填料硅灰石粉18g石英粉18g重晶石粉13g 制备方法是将环氧树脂、活性稀释剂加入反应器中,开搅拌,升温至50'C, To achieve the bonding surface a uniform adhesive layer thickness gluing, laminating under pressure not less than 0. 1MPl ei curing temperature and time is 24 hours, 6 (TC curing time was 6 hours. In this adhesive for the thin stone and composite aluminum honeycomb, was prepared substrate is an aluminum honeycomb composite panel, its technical performance indicators in Table 2 a 2.10 cases of embodiment of the component ingredients: epoxy resin E-44 10g E-51 8g 6458 14g reactive diluent 622 6g 678 2g polyurethane prepolymer pulverulent inorganic filler wollastonite powder 19g 20g 10g barite llg quartz powder with the remaining procedure of Example 1 was prepared as in Example L, for the thin stone products complex with aluminum honeycomb, the test results shown in Table 2 Example 3B ingredients as components: 38g modified amine curing agent accelerator DMP-30 5g coupling agent KH-560 4g 8g glass flake inorganic filler is wollastonite powder 25g talc powder 15g barite powder remaining in Example 5g Comparative Example 2 ingredients for the component A: an epoxy resin E-44 12g 10g 6458 15g reactive diluent W-95 8g 622 6g pulverulent inorganic filler quartz powder wollastonite powder 18g 13g 18g barite prepared is E-51 epoxy resin, reactive diluent added to the reactor, the open stirring, warmed to 50'C, 加入无机粉状填料,加完料后,停止加热,搅拌2小时,过滤出料。 B组份制备: 聚酰胺固化剂34g促进剂DMP-30 4g偶联剂KH-550 3g 玻璃鳞片9g无机粉状填料硅灰石粉20g滑石粉15g重晶石粉15g 制备方法同实施例1。改性环氧胶粘剂的配制和使用同实施例l,用于超薄石材与铝蜂窝复合,其复合板性能技术指标见表2。表2基材为铝蜂窝的薄型石材复合板物理性能技术指标<table>table see original document page 12</column></row> <table> Adding an inorganic powder filler, after completion of the addition, heating was stopped, stirring for 2 hours, the material was filtered Preparation B component: polyamide curing agent accelerator 34g DMP-30 4g coupling agent KH-550 3g glass flake inorganic powder 9g fillers like talc wollastonite powder 20g 15g 15g barite prepared using the same method of Example 1. the modified formulation and the epoxy adhesive in Example L, for the thin stone aluminum honeycomb composite, which composite board performance specifications See table 2. table 2 substrate is an aluminum honeycomb thin stone composite board physical performance specifications <table> table see original document page 12 </ column> </ row> <table>

Claims (9)

  1. 1、一种超薄型石材与铝蜂窝复合的改性环氧胶粘剂,其特征是由A、B两组份组成,A组份由重量份数为20~40%的环氧树脂,重量份数为5~15%的活性稀释剂,重量份数为10~30%的聚氨酯预聚体,重量份数为1~5%的纳米粉体材料,重量份数为40~60%的无机粉状填料配制,各组份的重量百分数为100%;B组份由重量份数为20~30%的改性胺固化剂,重量份数为1~5%的促进剂,重量份数为1~5%的偶联剂,重量份数为5~10%的玻璃鳞片,重量份数为40~60%的无机粉状填料配制,各组份的重量份数之和为100%。 An ultra-thin aluminum honeycomb composite stone and epoxy adhesive is modified, characterized in that the two parts A, B composition, A component of 20 to 40% by weight of the epoxy resin, parts by weight number of 5 to 15% of reactive diluents, 10 parts by weight to 30% polyurethane prepolymer, by weight of 1 to 5% nano-powder, 40 parts by weight of the inorganic powder to 60% shaped filler formulation, percent of each component is 100% by weight; parts by weight of component B is 20 to 30% of modified amine hardener, 1-5 parts by weight of 1% of the promoting agent, 1 parts by weight of to 5% of coupling agent, 5 parts by weight to 10% glass flake, 40 parts by weight to 60% of an inorganic filler powder formulation, parts by weight of each component is 100%.
  2. 2、 根据权利要求1所述的改性环氧胶粘剂,其特征在于A组份与B组份按重量比为2. 5~3.5:1混合而成。 2. The modified epoxy adhesive according to claim 1, characterized in that component A and component B at a weight ratio of 2.5 to 3.5: 1 are mixed.
  3. 3、 根据权利要求1所述的改性环氧胶粘剂,其特征是聚氨酯预聚体由聚醚多元醇N210或N220与TDI反应制得,预聚体的游离异氰酸酯基为预聚体质量的1~2%。 3. The modified epoxy adhesive according to claim 1, characterized in that the polyurethane prepolymer of a polyether polyol and TDI N210 or N220 prepared by the reaction, free isocyanate groups of the prepolymer is a prepolymer mass to 2%.
  4. 4、 根据权利要求l所述的改性环氧胶粘剂,其特征是改性胺固化剂由二乙烯基三胺与YJ-118型环氧树脂等摩尔反应制得。 4. The modified epoxy adhesive according to claim l, wherein the modified amine curing agent is prepared from diethylenetriamine and YJ-118 type epoxy equimolar reaction.
  5. 5、 根据权利要求l所述的改性环氧胶粘剂,其特征是A组份中的环氧树脂是双酚A环氧树脂E-44或E-51,双酚F环氧树脂6458或NPEF-170,或者是它们的混合物;活性稀释剂是W-95环氧树脂,501、 502、 622、 678活性稀释剂或它们的混合物;纳米粉体材料是纳米Si02、纳米Ti02、纳米碳酸钙,平均粒径在50〜100nm;无机粉状填料是硅灰石粉、石英粉、重晶石粉、辉绿岩粉或它们的混合物,粒径在400-1200目之间。 5, modified epoxy adhesive according to claim according to claim l, characterized in that component A is an epoxy group of bisphenol A epoxy resin E-44 or E-51, 6458 or bisphenol F epoxy resins NPEF -170, or a mixture thereof; reactive diluent is an epoxy resin W-95, 501, 502, 622, 678 reactive diluent or mixtures thereof; nano-powder is Si02 nano, nano Titania and, calcium carbonate, the average particle size of 50~100nm; pulverulent inorganic filler is wollastonite powder, quartz powder, barite powder, diabase powder or a mixture thereof, the particle size between 400-1200 mesh.
  6. 6、 根据权利要求1所述的改性环氧胶粘剂,其特征是B组份中的促进剂是DMP-30;偶联剂是有机硅氧烷KH-550、 KH-560或它们的混合物;玻璃鳞片是^ 碱玻璃,厚度《8um,过200目筛网;无机粉状填料是硅灰石粉、石英粉、滑石粉、重晶石粉、辉绿岩粉或它们的混合物,细度在400~1200目之间。 6. The modified epoxy adhesive according to claim 1, characterized in that component B is in the accelerators DMP-30; organosiloxane coupling agent KH-550, KH-560, or mixtures thereof; ^ alkali glass is glass flakes, the thickness "8um, 200-mesh sieve; pulverulent inorganic filler is wollastonite powder, quartz powder, talc, barite powder, diabase powder or mixtures thereof, at 400 to fineness between 1200 mesh.
  7. 7、 根据权利要求2所述的改性环氧胶粘剂,其特征是聚氨酯预聚体的合成方法为:在配备搅拌器、滴液漏斗、抽真空管、加热装置的反应器中加入聚醚多元醇,开搅拌,升温到9(TC抽真空2小时,真空度为0. 092〜0. 095MPa,除去聚謎多元醇中的水份,然后清除真空,降温至60"C,加入TDI,在6(TC反应]小时, 升温至7(TC反应1小时,再升温至85T:反应l-3小时,取样测游离异ff:,酸酯为预聚体质量的1-2%为合格。 7, modified epoxy adhesive according to claim 2, characterized in that the synthesis of polyurethane prepolymer: equipped with a stirrer, a dropping funnel, a vacuuming pipe reactor, the heating apparatus was charged with a polyether polyol open stirring, warmed to 9 (TC vacuum for 2 hours and the degree of vacuum of 0. 092~0. 095MPa, poly puzzle polyols removed moisture, then remove in vacuo, cooled to 60 "C, was added TDI, 6 (TC reaction] h, allowed to warm to. 7 (TC 1 hour, then warmed to 85T: l-3 hours the reaction, sampled for travel divorced prepolymerized ff :, esters 1-2% of body weight is acceptable.
  8. 8、 根据权利要求3所述的改性环氧胶粘剂,其特征是改性胺固化剂的合成方法为:在配备有搅拌器、滴液漏斗、加热装置的反应器中按重量比加入二乙烯基三胺,开搅拌,按重量比滴加环氧树脂,加料时间为l小时,然后在40〜5CTC范围内反应l-3小时,冷却后出料。 8, modified epoxy adhesive according to claim 3, characterized in that the synthesis method is a modified amine curing agent: equipped with a stirrer, a dropping funnel, a heating apparatus is added in a weight ratio of diethylenetriamine triamine, open stirring, the weight ratio of the epoxy resin was added dropwise, the addition time of l hour, then the reaction in the range of 40~5CTC l-3 hours. after cooling the material.
  9. 9、 根据权利要求1所述的改性环氧胶粘剂,其特征是改性环氧胶粘剂的制备方法是:(1) A组份的制备在高速分散机中按重量比加入活性稀释剂,开动搅拌,转速为10()〜200转/ 分,按重量比加入纳米粉体材料,升速至3000-5000转/分,连续搅拌20《)0分钟,停搅拌,取出纳米粉体材料分散液。 9. The modified epoxy adhesive according to claim 1, wherein the preparation is a modified epoxy adhesive: Preparation (1) A group of parts in a high speed disperser is added in a weight ratio of reactive diluents, start stirring speed was 10 () ~ 200 r / min, by weight 比加入纳米 material powder, increases the speed to 3000-5000 revolutions / min, with continuous stirring 20 ") to 0 minutes, stop stirring, remove nano-powder dispersion . 在带搅拌和加料、加热装置的反应器中,按重量比加入环氧树脂,开动搅拌,加入纳米粉体材料分散液,搅拌分散30分钟,按重量比加入自制的聚氨酯预聚体,开启加热装置,使物料升温至6(TC,保温反应l小时,再升温至80T〕 保温反应1-3小时,停止加热,向反应器内按重量比加无机粉状填料,加完填料后,连续搅拌l-3小时,至A组份完全混合均匀为止,停搅拌,出料。(2) B组份的制备将改性胺固化剂按重量比加入反应器,开动搅拌,按重量比分别加入促註剂和偶联剂,逐渐升温至60〜80"C,保温反应l-2小时,停止加热,按重量比加入玻璃鳞片,搅拌分散30分钟,按重量比加入无机粉状填料,搅拌].-3小时, 过滤出料。(3) 改性环氧胶粘剂的制备按A组份与B组份重量比2. 5~3. 5:1称取A组份、B组份,两者充分混合均匀,涂刷于被粘物表面,然后将两被粘物对齐、 In a stirred reactor and addition, a heating device, a weight ratio of epoxy resin was added, stirring was started, dispersion of nano-powder was added, dispersed for 30 minutes with stirring, is added at a weight ratio of polyurethane prepolymer made, turn the heating It means the material was warmed to 6 (TC, the reaction incubated l hour, the reaction was warmed to 80T] incubated for 1-3 hours, heating was stopped, the weight ratio of the inorganic powder filler is added, the addition was complete filling reactor, continuous stirred l-3 hours until the component a to be thoroughly mixed, with stirring stopped, the material. (2) preparation of component B is the modified amine curing agent weight ratio added to the reactor, stirring was started, were added to promote weight ratio injection and a coupling agent, was gradually warmed to 60~80 "C, the reaction was kept l-2 hours, the heating was stopped, the weight ratio of the glass flakes were added, dispersed for 30 minutes with stirring, the weight ratio of the inorganic powder filler is added, with stirring]. 3 hours, the filtered material (3) preparation of modified epoxy adhesive component by component a and B weight ratio of 2.5 to 3. 5: 1. Weigh the component a, component B group, both fully mixed, brushing the surface of the adherend, and then the two adherends aligned, 合、加压,改性环氧胶粘剂胶层经化学反应固化,将被粘物粘接好。 Bonding, pressing, modified epoxy adhesive subbing layer by chemical cure, good adhesion to an adherend.
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CN101475788B (en) 2009-01-15 2012-08-15 湖南神力实业有限公司 High strength polyurethane modified epoxy construction structure glue and manufacturing method thereof
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CN101948667B (en) 2010-10-13 2012-10-03 湖南神力铃胶粘剂制造有限公司 Adhesive for compounding marble veneer with base material and preparation method thereof
CN102070873A (en) * 2010-12-21 2011-05-25 中国建筑科学研究院 Environmentally-friendly flexible epoxy resin grouting material
WO2012088693A1 (en) * 2010-12-30 2012-07-05 Dow Global Technologies Llc Exterior thermal insulation system
CN102898993A (en) * 2012-09-11 2013-01-30 苏州市胶粘剂厂有限公司 High strength epoxy pouring sealant composition and application thereof
CN102898993B (en) 2012-09-11 2013-12-18 苏州市胶粘剂厂有限公司 High strength epoxy pouring sealant composition and application thereof
CN103756614A (en) * 2014-01-14 2014-04-30 湖南柯盛新材料有限公司 Modified epoxy stone back mesh adhesive and preparation method thereof
CN103756614B (en) * 2014-01-14 2015-03-11 湖南柯盛新材料有限公司 Modified epoxy stone back mesh adhesive and preparation method thereof
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CN105885759A (en) * 2016-04-07 2016-08-24 主义 Epoxy resin polymer daub and preparation method thereof
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