技术领域technical field
本发明具体涉及一种工艺简单、可操作性强、无腐蚀、耐热、不粉化、韧性好的利用物理发泡剂制备端异氰酸酯聚醚/酚醛树脂双组份体系泡沫保温材料的方法，属于泡沫保温材料领域。The invention specifically relates to a method for preparing an isocyanate-terminated polyether/phenolic resin two-component system foam insulation material by using a physical foaming agent with simple process, strong operability, no corrosion, heat resistance, no pulverization, and good toughness. It belongs to the field of foam insulation materials.
背景技术Background technique
酚醛泡沫塑料以其绝热性、难燃性、燃烧时低发烟性、低毒性及尺寸稳定性等方面优良的特性，在近二十年来倍受重视，已广泛用做绝热保温材料、隔音材料、包装材料、建筑装饰材料及高吸水性材料等[王军晓，刘新民，潘炯玺，王洪武.夹芯板材用硬质酚醛泡沫性能的研究[J].现代塑料加工应用，2005，17(1)：29-31；马晓雄，何斌，胡新媛、杨勇.抗事故包装箱用酚醛泡沫制备及其性能评价[J].工程塑料，2008，36(7)：60-63；刘新民、郭庆杰，曹长青，王志奇.建筑用酚醛泡沫塑料制备与性能研究[J].中国塑料，2006，20(8)：47-50]。但是，酚醛树脂自身具有多苯环的结构特点，使其表现出脆性大、易粉化的缺点，这极大抑制了酚醛泡沫塑料的发展。因此，改善酚醛树脂的韧性和易粉化现象成为国内外研究的一大热点。酚醛泡沫的增韧，可以通过以下两种途径实现：一种是在体系加入外增韧剂，郭锦棠等通过加入改性剂聚乙烯醇缩丁醛，对酚醛泡沫进行共混改性，得到的酚醛泡沫弯曲强度明显变大，韧性有所增加(郭锦棠，王新英.酚醛树脂的阻燃与增韧研究[J].燃烧科学与技术，2003，87(4)：34-37)；马克明等研究了PVC/NBR-40热塑性弹性体对酚醛泡沫塑料的增韧改性，泡沫的压缩强度有所提高，但泡沫导热系数随之显著升高(马克明，雷渭媛.PVC/NBR-40热塑性弹性体增韧酚醛泡沫塑料的研究[J].沈阳航空工业学院学报，1998，15(1)：25-28)。另一种是化学增韧改性，李少堂等采用腰果油与酚醛树脂共聚，并制备酚醛泡沫，改性后的泡沫密度100kg/m3，拉伸强度和断裂伸长率有所提高，但泡沫的氧指数由40.8降低到35.1，且泡沫尺寸稳定性降低(李少堂，蒋秋云，周丽绘.腰果油增韧酚醛树脂及其泡沫[J].玻璃钢/复合材料，2006，(2)：37-39)；乔冬平等采用环氧树脂改性酚醛泡沫，制备的酚醛泡沫板挠度由未增韧前的8.2mm提高到30mm以上(乔冬平，李为民，淑萍，闻向东，丁利，韩秀丽.柔性环氧树脂增韧酚醛泡沫塑料的研究[J].河南化工，2006，(23)：22-23)；常怀春等对聚丙烯酸正丁酯增韧改性酚醛树脂及酚醛泡沫进行了研究，泡沫的压缩强度由0.2MPa增加到0.4MPa[常怀春，吕通建，杨莹莹.聚丙烯酸正丁酯增韧酚醛泡沫塑料的研究[J].中国塑料，2005，19(12)：53-56；常怀春，平学贞，邱醒宇.PF/PnBA的合成及相容性研究[J].高分子材料科学与工程，1993，9(2)：33-37；常怀春，李冠军.酚醛泡沫塑料的制备方法[P].中国专利：1085576，1994-04-20]。上述研究均取得了一定的增韧效果，但都会带来改性剂与酚醛树脂基体的相容性差，体系粘度过高，导致泡沫体发泡倍率低，并影响了酚醛树脂的固化反应的负面作用。Phenolic foam plastic has been paid more attention in the past two decades due to its excellent characteristics of heat insulation, flame retardancy, low smoke generation, low toxicity and dimensional stability, and has been widely used as heat insulation materials and sound insulation materials. , packaging materials, building decoration materials and high water-absorbing materials, etc. 29-31; Ma Xiaoxiong, He Bin, Hu Xinyuan, Yang Yong. Preparation and performance evaluation of phenolic foam for anti-accident packaging boxes [J]. Engineering Plastics, 2008, 36(7): 60-63; Liu Xinmin, Guo Qingjie, Cao Changqing, Wang Zhiqi. Preparation and Properties of Phenolic Foamed Plastics for Construction [J]. China Plastics, 2006, 20(8): 47-50]. However, phenolic resin itself has the structural characteristics of multiple benzene rings, making it brittle and easy to pulverize, which greatly inhibits the development of phenolic foamed plastics. Therefore, improving the toughness and easy pulverization of phenolic resins has become a hot spot of research at home and abroad. The toughening of phenolic foam can be achieved in the following two ways: one is to add an external toughening agent to the system. Guo Jintang et al. blended and modified the phenolic foam by adding modifier polyvinyl butyral to obtain The flexural strength of phenolic foam increases significantly, and the toughness increases (Guo Jintang, Wang Xinying. Research on flame retardancy and toughening of phenolic resin [J]. Combustion Science and Technology, 2003, 87(4): 34-37); Ma Keming, etc. The toughening modification of PVC/NBR-40 thermoplastic elastomer to phenolic foam was studied, and the compressive strength of the foam was improved, but the thermal conductivity of the foam was significantly increased (Ma Keming, Lei Weiyuan. PVC/NBR-40 Research on thermoplastic elastomer toughened phenolic foam [J]. Journal of Shenyang Institute of Aeronautical Industry, 1998, 15(1): 25-28). The other is chemical toughening modification. Li Shaotang et al. used cashew nut oil and phenolic resin to copolymerize, and prepared phenolic foam. The modified foam density was 100kg/m3 , and the tensile strength and elongation at break were improved, but the foam The oxygen index decreased from 40.8 to 35.1, and the dimensional stability of the foam decreased (Li Shaotang, Jiang Qiuyun, Zhou Lihui. Cashew nut oil toughened phenolic resin and its foam [J]. FRP/Composite Materials, 2006, (2): 37-39) ; Qiao Dongping used epoxy resin to modify phenolic foam, and the deflection of the prepared phenolic foam board increased from 8.2 mm before toughening to more than 30 mm (Qiao Dongping, Li Weimin, Shuping, Wen Xiangdong, Ding Li, Han Xiuli. Flexible Research on epoxy resin toughened phenolic foam plastics [J]. Henan Chemical Industry, 2006, (23): 22-23); Chang Huaichun et al. studied the toughened modified phenolic resin and phenolic foam with n-butyl acrylate, The compressive strength of the foam increased from 0.2MPa to 0.4MPa [Chang Huaichun, Lv Tongjian, Yang Yingying. Research on polyacrylic n-butyl ester toughened phenolic foam plastics [J]. China Plastics, 2005, 19(12): 53-56; Chang Huaichun, Ping Xuezhen, Qiu Xingyu. Synthesis and Compatibility of PF/PnBA[J]. Polymer Materials Science and Engineering, 1993, 9(2): 33-37; Chang Huaichun, Li Guanjun. Phenolic Foam Plastics Preparation method [P]. Chinese patent: 1085576, 1994-04-20]. The above studies have achieved a certain toughening effect, but all of them will lead to poor compatibility between the modifier and the phenolic resin matrix, and the system viscosity is too high, resulting in a low expansion ratio of the foam and affecting the curing reaction of the phenolic resin. effect.
采用聚氨酯以及聚氨酯预聚物改性酚醛泡沫是一种有效的增韧方法，由于端异氰酸酯基聚醚预聚物具有很好的链柔顺性，同时端基可以与酚醛树脂反应形成交联网络，近年来引起很多学者的关注。张留城等用甲阶酚醛树脂、聚醚、端异氰酸酯基聚氨酯预聚物、对甲苯磺酸、磷酸、三乙醇胺等复杂体系进行发泡，泡沫的压缩强度有所提高(张留城，台会文.酚醛-聚氨酯复合泡沫塑料的研制[J].塑料工程，1991，(1)：19-23)；周春华等在酚醛树脂体系中添加8％聚氨酯预聚体，以酸做为固化剂制备泡沫，泡沫的冲击强度和压缩强度分别提高了50％和96.5％(周春华，刘威，解竹柏等.酚醛树脂泡沫塑料增韧改性的研究[J].济南大学学报，2004，(18)：243-245)。本研究室曾采用聚氨酯预聚物增韧改性酚醛泡沫，当预聚物的质量分数为3％时，改性泡沫的粉化程度仅为未改性的40％，且泡沫回弹率大于60％(程珏，梁明莉，金光泰.聚氨酯预聚物改性酚醛泡沫塑料脆性的研究[J].塑料工业，2004，(32)：7-9)。上述改性研究均采用在酚醛树脂/酸的体系中添加聚氨酯预聚物的方法，虽然都取得了一定的增韧效果，但聚氨酯预聚物与酚醛树脂相容性差的问题依然存在，允许的添加量很少，并且酚醛树脂体系中有多种含活泼氢物质，与异氰酸酯反应复杂，因此聚氨酯预聚物起不到提高固化交联密度的作用，对泡沫的粉化现象改善不大。Modification of phenolic foam with polyurethane and polyurethane prepolymer is an effective toughening method. Because the isocyanate-terminated polyether prepolymer has good chain flexibility, and the terminal group can react with phenolic resin to form a cross-linked network. In recent years, it has attracted the attention of many scholars. Zhang Liucheng and others used complex systems such as resole phenolic resin, polyether, isocyanate-terminated polyurethane prepolymer, p-toluenesulfonic acid, phosphoric acid, triethanolamine and other complex systems to foam, and the compressive strength of the foam was improved (Zhang Liucheng, Tai Huiwen. Phenolic -The development of polyurethane syntactic foam [J]. Plastic Engineering, 1991, (1): 19-23); Zhou Chunhua etc. added 8% polyurethane prepolymer in the phenolic resin system, prepared foam with acid as curing agent, foam The impact strength and compressive strength have increased by 50% and 96.5% respectively (Zhou Chunhua, Liu Wei, Xie Zhubai, etc. Research on Toughening and Modification of Phenolic Resin Foam Plastics [J]. Journal of Jinan University, 2004, (18): 243- 245). Our laboratory has used polyurethane prepolymer to toughen modified phenolic foam. When the mass fraction of prepolymer is 3%, the pulverization degree of modified foam is only 40% of that of unmodified foam, and the foam rebound rate is greater than 60% (Cheng Jue, Liang Mingli, Jin Guangtai. Study on the Brittleness of Polyurethane Prepolymer Modified Phenolic Foam [J]. Plastic Industry, 2004, (32): 7-9). The above-mentioned modification studies all adopt the method of adding polyurethane prepolymer in the phenolic resin/acid system. Although they have achieved certain toughening effects, the problem of poor compatibility between polyurethane prepolymer and phenolic resin still exists. The addition amount is very small, and there are many kinds of active hydrogen-containing substances in the phenolic resin system, which react complicatedly with isocyanate, so the polyurethane prepolymer cannot improve the cured crosslinking density, and the powdering phenomenon of the foam is not greatly improved.
Anthony Joseph Papa等用含磷的聚醚多元醇合成了-NCO封端的聚氨酯预聚物，再与酚醛树脂共混发泡，有效地提高了酚醛泡沫的韧性(Anthony J P，Richard L R，Frank E C.phenolic foam modified with phosphorus-containingisocyanate-terminated[P].USP4119584.1978-10-10)；本研究室采用聚氨酯预聚物与碱性酚醛树脂双组份体系制备了新型泡沫材料(程珏，范勇，杨万泰.一种聚氨酯/酚醛泡沫保温材料的制备方法.中国专利，200810105000.2009-10-28)。与以往的添加改性不同，这种改性方法是以聚氨酯预聚物代替酸作为酚醛树脂的固化剂，与酚醛树脂组成双组份体系，二者的相容性好、副反应少、聚氨酯预聚物用量大(30％-60％)，交联反应活性高、交联网络完整，得到一种韧性、不粉化的新型泡沫体。但是，这种体系采用少量酸做发泡剂，导致固化成型速度过快，泡沫体密度高，不容易调节。Anthony Joseph Papa and others synthesized -NCO-terminated polyurethane prepolymer with phosphorus-containing polyether polyol, and then blended and foamed with phenolic resin, which effectively improved the toughness of phenolic foam (Anthony J P, Richard LR, Frank E C.phenolic foam modified with phosphorus-containingisocyanate-terminated[P].USP4119584.1978-10-10); this research laboratory prepared a new type of foam material by using a two-component system of polyurethane prepolymer and basic phenolic resin (Cheng Jue , Fan Yong, Yang Wantai. A preparation method of polyurethane/phenolic foam insulation material. Chinese patent, 200810105000.2009-10-28). Different from the previous addition modification, this modification method uses polyurethane prepolymer instead of acid as the curing agent of phenolic resin, and forms a two-component system with phenolic resin. The two have good compatibility, less side reactions, and polyurethane The amount of prepolymer is large (30%-60%), the cross-linking reaction activity is high, and the cross-linking network is complete, and a new type of foam with toughness and no pulverization is obtained. However, this system uses a small amount of acid as a foaming agent, resulting in too fast curing and molding, high foam density, and difficult adjustment.
发明内容Contents of the invention
本发明目的是提供一种物理发泡剂制备端异氰酸酯聚醚/酚醛树脂泡沫塑料的方法，采用端异氰酸酯聚醚(聚氨酯预聚物)代替传统的固化剂(酸)，与可发性酚醛树脂组成双组份体系制备一种全新的泡沫体，体系中采用物理发泡剂，不再使用有机/无机酸作为发泡剂，副反应少，反应容易控制；采用特种可发性酚醛树脂，解决了聚氨酯预聚物与体形酚醛树脂的相容性差的问题，并且该酚醛树脂与异氰酸酯基团反应速度平稳，制备的泡沫体密度适中，在56kg/m3-109kg/m3之间，泡沫体具有很好的耐温性、韧性和不粉化的特征。The purpose of the invention is to provide a method for preparing isocyanate-terminated polyether/phenolic resin foam by a physical blowing agent, adopting isocyanate-terminated polyether (polyurethane prepolymer) to replace traditional curing agent (acid), and expandable phenolic resin Form a two-component system to prepare a brand-new foam. In the system, a physical blowing agent is used, and organic/inorganic acids are no longer used as a blowing agent. There are few side reactions and the reaction is easy to control; special expandable phenolic resin is used to solve the problem. The problem of poor compatibility between the polyurethane prepolymer and the bulk phenolic resin is solved, and the reaction speed between the phenolic resin and the isocyanate group is stable, and the density of the prepared foam is moderate, between 56kg/m3 -109kg/m3 , the foam It has good temperature resistance, toughness and non-powdering characteristics.
本发明一种端异氰酸酯聚醚/酚醛树脂泡沫塑料的制备方法，其特征在于，包括以下步骤：A kind of preparation method of isocyanate-terminated polyether/phenolic resin foam of the present invention is characterized in that, comprises the following steps:
1)在特种可发性酚醛树脂中加入表面活性剂、发泡剂，搅拌均匀，形成组分A，其中，表面活性剂用量为可发性酚醛树脂质量的4％-12.5％，发泡剂用量为可发性酚醛树脂质量的1-10％；1) Add surfactant and foaming agent to special expandable phenolic resin, stir evenly to form component A, wherein the amount of surfactant is 4%-12.5% of the mass of expandable phenolic resin, foaming agent The dosage is 1-10% of the mass of the expandable phenolic resin;
2)称取端异氰酸酯聚醚预聚体，作为组分B；2) Weigh the isocyanate-terminated polyether prepolymer as component B;
3)将组分A和B混合并搅拌10s-20s搅拌均匀，倒入模具，常温发泡固化，制得端异氰酸酯聚醚/酚醛树脂泡沫保温材料，其中，端异氰酸酯聚醚预聚物中所含-NCO的质量与可发性酚醛树脂的质量比为0.1-0.6∶1，整个发泡过程在室温下进行，操作工艺简单。3) Mix components A and B and stir for 10s-20s, stir evenly, pour into a mold, foam and solidify at room temperature, and obtain an isocyanate-terminated polyether/phenolic resin foam insulation material, wherein, the isocyanate-terminated polyether prepolymer The mass ratio of the -NCO-containing mass to the expandable phenolic resin is 0.1-0.6:1, the entire foaming process is carried out at room temperature, and the operation process is simple.
其中，步骤1)中所述的特种可发性酚醛树脂为碱性可发性酚醛树脂，含水量为3.5％-6.7％，粘度为0.9Pa.S-4.8Pa.S，25℃。Wherein, the special expandable phenolic resin described in step 1) is an alkaline expandable phenolic resin with a water content of 3.5%-6.7%, a viscosity of 0.9Pa.S-4.8Pa.S, and 25°C.
步骤1)中所述的表面活性剂为吐温系列或者硅油系列中的一种或者几种，表面活性剂的优选用量为可发性酚醛树脂质量的8％-10％。The surfactant described in step 1) is one or more of Tween series or silicone oil series, and the preferred amount of surfactant is 8%-10% of the mass of the expandable phenolic resin.
步骤1)中所述的发泡剂为低沸点类物理发泡剂；优选HFCs(氢氟烃)、戊烷类、液态CO2中的一种或者几种；优选用量为可发性酚醛树脂质量的1.5％-6.5％。通过调节发泡剂用量来控制泡沫的密度。The foaming agent described in step 1) is a low-boiling point physical foaming agent; preferred HFCs (hydrofluorocarbons), pentanes, liquid CO in one ormore ; the preferred amount is expandable phenolic resin 1.5%-6.5% of mass. The density of the foam is controlled by adjusting the amount of blowing agent.
步骤2)中所述的端异氰酸酯聚醚预聚物为聚醚氧化丙烯二醇(PPG1000)和二苯甲烷二异氰酸酯(MDI)按一定比例采用常规方法制备或者市售的均可，-NCO基团含量为18.5％-19.5％(质量分数)，粘度为0.15Pa.S-0.65Pa.S(25℃)。The isocyanate-terminated polyether prepolymer described in step 2) is polyether oxide propylene glycol (PPG1000) and diphenylmethane diisocyanate (MDI) prepared by conventional methods or commercially available in a certain proportion, and -NCO group The lump content is 18.5%-19.5% (mass fraction), and the viscosity is 0.15Pa.S-0.65Pa.S (25°C).
步骤3)中所述的端异氰酸酯聚醚/酚醛树脂泡沫保温材料中，加入体系中的-NCO与酚醛树脂的质量比优选0.2-0.5∶1。In the isocyanate-terminated polyether/phenolic resin foam insulation material described in step 3), the mass ratio of -NCO to the phenolic resin added to the system is preferably 0.2-0.5:1.
本发明具有以下有益效果：The present invention has the following beneficial effects:
1)本发明所制备的端异氰酸酯聚醚/酚醛树脂泡沫保温材料，综合了酚醛泡沫和聚氨酯泡沫各自的优点，既解决了酚醛泡沫的韧性差、易粉化缺点，同时也改善了聚氨酯泡沫的耐热性差的缺点。1) The isocyanate-terminated polyether/phenolic resin foam insulation material prepared by the present invention combines the respective advantages of phenolic foam and polyurethane foam, which not only solves the shortcomings of poor toughness and easy pulverization of phenolic foam, but also improves the performance of polyurethane foam. The disadvantage of poor heat resistance.
2)本发明采用特种可发性酚醛树脂，与普通酚醛树脂相比，这种可发性酚醛树脂采用碱性催化剂催化，含水量低、粘度低，与聚氨酯预聚物完全互容，没有团聚现象出现，解决了酚醛树脂与聚氨酯预聚物相容性差的缺点。2) The present invention adopts a special expandable phenolic resin. Compared with ordinary phenolic resins, this expandable phenolic resin is catalyzed by an alkaline catalyst, has low water content and low viscosity, and is completely compatible with polyurethane prepolymers without agglomeration The phenomenon appeared, which solved the disadvantage of poor compatibility between phenolic resin and polyurethane prepolymer.
3)采用物理发泡剂发泡，酚醛树脂与异氰酸酯基团反应速度平稳，泡沫体密度适中(56kg/m3-109kg/m3)，可通过发泡剂用量调节。3) The physical foaming agent is used for foaming, the reaction speed between the phenolic resin and the isocyanate group is stable, and the foam density is moderate (56kg/m3 -109kg/m3 ), which can be adjusted by the amount of foaming agent.
4)组分A与B混合发泡阶段均在常温下进行，操作工艺简单，无需加热、添加助剂等其他手段，污染性小4) The mixing and foaming stages of components A and B are carried out at room temperature, the operation process is simple, no heating, additives and other means are required, and the pollution is small
5)制备的端异氰酸酯聚醚/酚醛树脂保温材料形成了完整的网络结构，体积稳定性好。5) The prepared isocyanate-terminated polyether/phenolic resin insulation material forms a complete network structure and has good volume stability.
具体实施方式Detailed ways
碱性可发性酚醛树脂(市售)，含水量为3.5％-6.7％，粘度为0.9Pa.S-4.8Pa.S(25℃)，平均聚合度为2-3；端异氰酸酯聚醚预聚物(市售)，-NCO基团含量为18.5％-19.5％(质量分数)，粘度为0.15Pa.S-0.65Pa.S(25℃)。Alkaline expandable phenolic resin (commercially available), with a water content of 3.5%-6.7%, a viscosity of 0.9Pa.S-4.8Pa.S (25°C), and an average degree of polymerization of 2-3; Polymer (commercially available), -NCO group content is 18.5%-19.5% (mass fraction), viscosity is 0.15Pa.S-0.65Pa.S (25°C).
下述实施例中所述的份数均为质量份数。The parts described in the following examples are all parts by mass.
实施例1Example 1
1)容器中称取20份碱性可发性酚醛树脂(含水量4.9％，粘度为2.8Pa.S，25℃)，依次加入2.0份吐温60，0.3份HFCs，混合搅拌30s，得到组分A；1) Weigh 20 parts of alkaline expandable phenolic resin (water content 4.9%, viscosity 2.8 Pa.S, 25°C) in a container, add 2.0 parts of Tween 60 and 0.3 parts of HFCs in sequence, and mix and stir for 30 seconds to obtain the composition Point A;
2)称取48份端异氰酸酯聚醚预聚物，作为组分B；2) Weigh 48 parts of isocyanate-terminated polyether prepolymer as component B;
3)将组分B倒入组分A中，机械搅拌10s，倒入模具中进行发泡，得到端异氰酸酯聚醚/酚醛树脂泡沫保温材料。3) Pour component B into component A, mechanically stir for 10 seconds, pour into a mold for foaming, and obtain an isocyanate-terminated polyether/phenolic resin foam insulation material.
得到的泡沫致密均匀，泡沫表面不粉化，体积稳定性好；泡沫材料密度为109.24Kg/m3，达到屈服点时弯曲应变为21％，最大弯曲应力为0.42MPa，150℃环境下烘烤2小时质量损失率为2.47％。The obtained foam is dense and uniform, the surface of the foam is not pulverized, and the volume stability is good; the density of the foam material is 109.24Kg/m3 , the bending strain is 21% when reaching the yield point, the maximum bending stress is 0.42MPa, and it is baked at 150°C The 2-hour mass loss rate was 2.47%.
实施例2Example 2
1)容器中称取20份碱性可发性酚醛树脂(含水量3.5％，粘度为0.9Pa.S，25℃)，依次加入1.8份吐温80，0.5份环戊烷，混合搅拌45s，使之混合均匀，得到组分A；1) Weigh 20 parts of alkaline expandable phenolic resin (water content 3.5%, viscosity 0.9 Pa.S, 25°C) in a container, add 1.8 parts of Tween 80 and 0.5 parts of cyclopentane in turn, mix and stir for 45 seconds, Mix it evenly to obtain component A;
2)称取40份端异氰酸酯聚醚预聚物，作为组分B；2) Weigh 40 parts of isocyanate-terminated polyether prepolymer as component B;
3)将组分B倒入组分A中，机械搅拌15s，倒入模具中进行发泡，得到端异氰酸酯聚醚/酚醛树脂泡沫保温材料。3) Pour component B into component A, stir mechanically for 15 seconds, pour into a mold for foaming, and obtain an isocyanate-terminated polyether/phenolic resin foam insulation material.
得到的泡沫致密均匀，泡沫表面不粉化，体积稳定性好；泡沫材料密度为89.11Kg/m3，达到屈服点时弯曲应变为22％，最大弯曲应为0.35MPa，150℃环境下烘烤2小时质量损失率为3.12％。The obtained foam is dense and uniform, the surface of the foam is not pulverized, and the volume stability is good; the density of the foam material is 89.11Kg/m3 , the bending strain is 22% when it reaches the yield point, and the maximum bending should be 0.35MPa. Baking at 150°C The 2-hour mass loss rate was 3.12%.
实施例3Example 3
1)容器中称取40份碱性可发性酚醛树脂(含水量6.7％，粘度为4.8Pa.S，25℃)，依次加入4.5份硅油，1.5份正戊烷，混合搅拌65s，使之混合均匀，得到组分A；1) Weigh 40 parts of basic expandable phenolic resin (water content 6.7%, viscosity 4.8 Pa.S, 25°C) in the container, add 4.5 parts of silicone oil and 1.5 parts of n-pentane in sequence, and mix and stir for 65 seconds to make it Mix evenly to obtain component A;
2)称取78份端异氰酸酯聚醚预聚物，作为组分B；2) Weigh 78 parts of isocyanate-terminated polyether prepolymer as component B;
3)将组分B倒入组分A中，机械搅拌12s，倒入模具中进行发泡，得到端异氰酸酯聚醚/酚醛树脂泡沫保温材料。3) Pour component B into component A, mechanically stir for 12 seconds, pour into a mold for foaming, and obtain an isocyanate-terminated polyether/phenolic resin foam insulation material.
得到的泡沫致密均匀，泡沫表面不粉化，体积稳定性好；泡沫材料密度为80.37Kg/m3，达到屈服点时弯曲应变为25％，最大弯曲应力为0.32MPa，150℃环境下烘烤2小时质量损失率为3.91％。The obtained foam is dense and uniform, the surface of the foam is not pulverized, and the volume stability is good; the density of the foam material is 80.37Kg/m3 , the bending strain is 25% when reaching the yield point, the maximum bending stress is 0.32MPa, and it is baked at 150°C The 2-hour mass loss rate was 3.91%.
实施例4Example 4
1)容器中称取10份碱性可发性酚醛树脂(含水量5.5％，粘度为3.2Pa.S，25℃)，依次加入1份硅油，0.7份环戊烷，混合搅拌50s，使之混合均匀，得到组分A；1) Weigh 10 parts of alkaline expandable phenolic resin (water content 5.5%, viscosity 3.2 Pa.S, 25°C) in the container, add 1 part of silicone oil and 0.7 part of cyclopentane in sequence, mix and stir for 50 seconds, and make it Mix evenly to obtain component A;
2)称取23份端异氰酸酯聚醚预聚物，作为组分B；2) Weigh 23 parts of isocyanate-terminated polyether prepolymer as component B;
3)将组分B倒入组分A中，机械搅拌16s，倒入模具中进行发泡，得到端异氰酸酯聚醚/酚醛树脂泡沫保温材料。3) Pour component B into component A, mechanically stir for 16 seconds, pour into a mold for foaming, and obtain an isocyanate-terminated polyether/phenolic resin foam insulation material.
得到的泡沫致密均匀，泡沫表面不粉化，体积稳定性好；泡沫材料密度为56.42Kg/m3，达到屈服点时弯曲应变为26％，最大弯曲应力为0.19MPa，150℃环境下烘烤2小时质量损失率为4.98％。The obtained foam is dense and uniform, the surface of the foam is not pulverized, and the volume stability is good; the density of the foam material is 56.42Kg/m3 , the bending strain is 26% when reaching the yield point, the maximum bending stress is 0.19MPa, and it is baked at 150°C The 2-hour mass loss rate was 4.98%.
实施例5Example 5
1)容器中称取30份碱性可发性酚醛树脂(含水量4.6％，粘度为2.4Pa.S，25℃)，依次加入3.5份吐温60，1.6份液态CO2，混合搅拌58s，使之混合均匀，得到组分A；1) Weigh 30 parts of alkaline expandable phenolic resin (water content 4.6%, viscosity 2.4 Pa.S, 25°C) in a container, add 3.5 parts of Tween 60, 1.6 parts of liquid CO2 in sequence, mix and stir for 58 seconds, Mix it evenly to obtain component A;
2)称取57份端异氰酸酯聚醚预聚物，作为组分B；2) Weigh 57 parts of isocyanate-terminated polyether prepolymer as component B;
3)将组分B倒入组分A中，机械搅拌17s，倒入模具中进行发泡，得到端异氰酸酯聚醚/酚醛树脂泡沫保温材料。3) Pour component B into component A, stir mechanically for 17 seconds, pour into a mold for foaming, and obtain an isocyanate-terminated polyether/phenolic resin foam insulation material.
得到的泡沫致密均匀，泡沫表面不粉化，体积稳定性好；泡沫材料密度为62.89Kg/m3，达到屈服点时弯曲应变为29％，最大弯曲应力为0.23MPa，150℃环境下烘烤2小时质量损失率为4.63％。The obtained foam is dense and uniform, the surface of the foam is not pulverized, and the volume stability is good; the density of the foam material is 62.89Kg/m3 , the bending strain is 29% when it reaches the yield point, the maximum bending stress is 0.23MPa, and it is baked at 150°C The 2-hour mass loss rate was 4.63%.
实施例6Example 6
1)容器中称取20份碱性可发性酚醛树脂(含水量4.0％，粘度为1.6Pa.S，25℃)，依次加入2.5份吐温80，0.5份HFCs，混合搅拌34s，使之混合均匀，得到组分A；1) Weigh 20 parts of alkaline expandable phenolic resin (water content 4.0%, viscosity 1.6 Pa.S, 25°C) in the container, add 2.5 parts of Tween 80 and 0.5 parts of HFCs in sequence, and mix and stir for 34s to make Mix evenly to obtain component A;
2)称取49份端异氰酸酯聚醚预聚物，作为组分B；2) Weigh 49 parts of isocyanate-terminated polyether prepolymer as component B;
3)将组分B倒入组分A中，机械搅拌18s，倒入模具中进行发泡，得到端异氰酸酯聚醚/酚醛树脂泡沫保温材料。3) Pour component B into component A, mechanically stir for 18 seconds, pour into a mold for foaming, and obtain an isocyanate-terminated polyether/phenolic resin foam insulation material.
得到的泡沫致密均匀，泡沫表面不粉化，体积稳定性好；泡沫材料密度为78.26Kg/m3，达到屈服点时弯曲应变为24％，最大弯曲应力为0.29MPa，150℃环境下烘烤2小时质量损失率为3.35％。The obtained foam is dense and uniform, the surface of the foam is not pulverized, and the volume stability is good; the density of the foam material is 78.26Kg/m3 , the bending strain is 24% when reaching the yield point, the maximum bending stress is 0.29MPa, and it is baked at 150°C The 2-hour mass loss rate was 3.35%.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102251097ACN101885856B (en) | 2010-07-02 | 2010-07-02 | Method for preparing isocyanate terminated polyether/phenolic resin foamed plastic |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102251097ACN101885856B (en) | 2010-07-02 | 2010-07-02 | Method for preparing isocyanate terminated polyether/phenolic resin foamed plastic |
| Publication Number | Publication Date |
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| CN101885856A CN101885856A (en) | 2010-11-17 |
| CN101885856Btrue CN101885856B (en) | 2012-07-04 |
| Application Number | Title | Priority Date | Filing Date |
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| CN2010102251097AExpired - Fee RelatedCN101885856B (en) | 2010-07-02 | 2010-07-02 | Method for preparing isocyanate terminated polyether/phenolic resin foamed plastic |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731961B (en)* | 2011-10-18 | 2014-03-19 | 蓝云飞 | Phenolic foam composite insulation material and production method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003246673A (en)* | 2002-02-27 | 2003-09-02 | Nisshinbo Ind Inc | Glassy carbon foam and method for producing the same |
| CN101565541B (en)* | 2008-04-25 | 2010-12-08 | 北京化工大学 | A kind of preparation method of polyurethane/phenolic foam insulation material |
| Publication number | Publication date |
|---|---|
| CN101885856A (en) | 2010-11-17 |
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