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1、精品学习资源二甲醚作为泡沫聚氨酯发泡剂地可行性讨论贾润礼 梁丽华 作为发泡剂替代CFC-11 用于聚氨酯 PU）泡沫地可行性 .DME 毒性极低,化学性质稳固 ,可长期储存而不分解或转化.DME 在大气层中地寿命很短,约 10 天左右 ,在大气层中被降解为二氧化碳和水 ,ODP 值为零 ,因而不会造成环境污染和影响臭氧层.DME沸点低 ,可燃；对极性和非极性有机物质均有高度溶解性,易溶于水 ,与大多数溶剂都能混匀,与一种非燃性溶剂 行业 CFC-11 发泡剂替代行动地实施,一批 CFC-11 替代品及其相关技术得到推广应用 , 一些新型发泡剂在讨论中,但有关二甲醚作为发泡剂用于PU 泡沫尚未见
2、报道 .笔者认为 ,二甲醚DME ）是一种具有特殊性能地物质,特别适合作为PU 发泡剂 .本文分析了 DME 作为 PU 发泡剂地可行性.p1EanqFDPw1 DME 地性能1.1 化学性能DMECH 3OCH 3,相对分子质量 46.10）是乙醇地同分异构体,化学性质稳固 ,只与卤素或卤化氢在低温下反应生成加成化合物,与发烟硫酸或三氧化硫进行气相反应生成硫酸二甲酯,与苯胺蒸汽反应生成N,N- 二甲基苯胺；酷热时分解；可长期储存而不分解或转化,长期储存不易形成过氧化物,不会因氯代物溶剂 而引起氯化 .在大气层中地寿命约10 天左右 ,在大气层中被降解为二氧化碳和水,臭氧消耗潜值 ODP）为零
3、,因而不会造成环境污染和影响臭氧层.DXDiTa9E3d1.2 物理性能DME熔点 138.5 ,沸点 0.1MPa ） 24 , 密度 0.4 MPa,可燃 ,比密度 DME气体/ 空气之密度比值）1.6,蒸发热 484 kJ/kg,比热容 2.37 kJ/kg K, 闪点 5.6, 空气中爆炸极限3.4% 18.6% 下在水中地溶解度为 34%质量分数） .DME 与大多数溶剂如碳氢化合物、卤代烷、醇、醚、酰、胺、酯、醛类等都能混匀,它与一种非燃性溶剂混合就能得到非可燃性混合物.RTCrpUDGiT1.3 毒性DME 地急性、亚急性、慢性吸入毒性极低 .大白鼠暴露 4h 半数致死浓度 时体
4、重增加较少 ,浓度为 1时无变化 .慢性吸入毒性试验 ,大白鼠吸入 30 天,在浓度 0.1、 1时未见毒性；吸入 90 天,浓度为 0.2、1、 2时未见毒性 .当 DME 在空气中地浓度在 20或以上时 ,才有可能形成对人地心脏有作用地浓度.5PCzVD7HxADME 在毒性试验中没有发生过致突变作用,也没有在动物试验中发生过致畸现象.2 用于水发泡体系DME 虽可燃 ,但具有与不燃性物质混合获得不燃性物质地特性,因此可与水、 HFC 等混合而降低或排除其可燃特性 .DME/ 水溶液仍能产生一种零火焰延长性能,对含水 14%、乙醇 6% 和 DME80% 地混合液所作地火焰延长测定结果为零
5、,这一特性大大削减了DME 在储备和使用期间燃烧、爆炸地危急性.jLBHrnAILgDME可与水互溶地特性使其很简单应用于全水发泡路线,DME与少量水混合作为发泡剂,由于削减欢迎下载精品学习资源用水量而导致 CO 2 发气量削减 ,从而有利于改善全水发泡PU 泡沫性脆、强度低、稳固性差、绝热性差地缺陷 ,并可削减多异氰酸酯地用量.DME/ 水混合发泡剂使用成效相当于在CFC-11 替代技术进展初期为减少 CFC-11 地用量而采纳地CFC-11/ 水混合发泡剂 ,其发泡工艺与设备与CFC-11 、HCFC-141b 体系相同 , 泡沫性能包括绝热性能得到各领域认可.在这里 ,由于 DME地强溶
6、剂特性以及与水地互溶性,泡沫性能可能比 CFC-11/ 水混合发泡剂体系要好.xHAQX74J0X由于 DME 地低粘度与低表面张力及强溶剂特性,用于全水发泡体系中可显著降低体系粘度,因而降低了对多元醇粘度地要求 ,即答应使用较高粘度地多元醇,并可提高体系中各组分地混匀性.LDAYtRyKfE虽然 DME 沸点较低 ,但与水互溶后 DME/ 水地共沸点可显著提高,因此在水发泡体系中地各种发泡工艺中应用时仍可使用现行设备.Zzz6ZB2Ltk3 与烷烃发泡剂地比较烷烃类发泡剂有环戊烷、正戊烷、异戊烷统称为戊烷类发泡剂）、正丁烷、异丁烷等,其中戊烷类发泡剂因沸点较高而得到较广泛地应用.戊烷类发泡剂
7、受到重视地缘由是由于其零ODP 值、温室效应很小、无毒、对环境影响微小、常温下为液态、资源丰富、价格低.与 CFC-11 相比,戊烷类发泡剂有三个缺点：易燃、易挥发 ,爆炸极限 1.3% 8%,为保证生产安全 , 必需对现有计量、储存、发泡设备进行较大 改造；戊烷在聚醚多元醇中地溶解性较差,必需使用经改性地多元醇和特殊助剂；戊烷地气相热导率较高,制得地 PU 硬泡绝热性能略差.dvzfvkwMI1DME 同样具有零 ODP 值、温室效应很小、无毒、对环境影响微小、资源丰富、价格低地优点.DME本身在常温下呈气态,但假如与少量高沸点烷烃如庚烷、辛烷）混合可得到常温下液态地混合物.DME爆炸极限比
8、戊烷高一倍,因而安全性相对较高. 与少量 HFC 或 HCFC 混合就可以达到不燃成效, 如以DME 、少量辛烷和HFC 混合成复合发泡剂就可以达到常温下液态及不燃成效,因而完全可以适应现行设备.此外 ,DME 与多元醇地互溶性有利于提高PU 泡沫地发泡效率和尺寸稳固性.rqyn14ZNXI由于 DME表面张力小、粘度低 ,泡沫易显现泡孔直径大而不匀现象,这一点在使用成核剂 如气相二氧化硅）后可完全解决 .EmxvxOtOco4 与氟系发泡剂地比较含氟发泡剂有HCFC 、HFC 、全氟烷烃 PFA ）、氟代醚 :13 142 Jiarunli. Properties and Applicati
9、on of Dimethyl Ether. In: The International Autumn Seminer or Propellant, Explosives and Pyrotechnies. Beijing of China.19960YujCfmUCw3 国家环保总局对外经济合作领导小组办公室等. 聚氨酯硬泡CFC-11 替代技术手册.2002.27 39eUts8ZQVRdThe Feasibility Study of Dimetyl Ether as a Blowing Agent Used for PolyurethaneFoamsQsAEJkW5TJia RunliL
10、iang LihuaPlastics Institute, North China Institute of Technology, Shanxi Taiyuan 030051GMsIasNXkA Union R&D Center , National Engineering Research Center ofTIrRGchYzg Engineering Plastics & North China Institute of Technology7EqZcWLZNXAbstract: The feasibility of dimethyl ether DMEused for polyuret
11、hane foam as a blowing agent instead of CFC-11 is discussed. DME has very low toxicity and steady chemical properties, it can be stored for a long time without decomposition or inversion. But it has very short lifetime about 10 days in atmosphere and thendegrade s into water and CO 2, and has zero v
12、alue of ODP. So it is considered to be no influence on environmentand ozonosphere. DMEhas lowboilingpointand is ignitable.Animportantproperty ofDMEis its high solubility on polarity and non-polarity organic substance, such as hydrocarbon, alkyl halide, alcohol, ether, acyl, amine, ester, aldehyde an
13、d so on. When mixed witha kindof non-inflammablesolvent such as HFC, the mixtureis non-inflammable. Above properties of DME, can not only insure production safety but also adapt to all production equipment of PU foam, and profit to increase expanding efficiency and dimensional stability. Besides,it
14、is cheap and rich. DME can be used for PU foam as a new blowing agent to substitute CFC-11.lzq7IGf02EKeywords: polyurethane foam ； dimethyl ether ； blowing agent ； CFC-11 ； substitutezvpgeqJ1hk作者简介：贾润礼 华北工学院塑料讨论所所长,联合研发中心主任.主要从事塑料改性及加工工艺讨论 ,发表论文 30 余篇 ,专著 8 部fjnFLDa5Zo Union R&D Center, National Eng
15、ineering Research Center oftfnNhnE6e5 Engineering Plastics & North China Institute of TechnologyHbmVN777sLABSTRACT:Purpose: To studyingthe feasibility of dimethyl ether DMEused for polyurethane foam as a blowing agent instead of CFC-11. Methods:Acording to the properties of DME, the study discusses
16、whether DME can meet the demands of the substitution of CFC-11. DME is the isomer of ethanol , which can react withonly few matters such as halogen or halogen hydride, fuming sulfuric acid or sulfuric trioxide, and aniline vapor欢迎下载精品学习资源due to its steady chemical properties. DME can be stored for a
17、 long time without decomposition or inversion.But it has very short lifetime about 10 days in atmosphere and then degrades into water and CO2 , and has zero value of ODP. So it is considered to be no influence on environment and ozonosphere. It has very low acute, subacute and chronicinhalationtoxic
18、ities,and mightinfluencetopeoplesheart onlywithveryhigh concentration in air. DMEhas low boilingpoint and is ignitable. An important property of DMEis its high solubilityon polarityand non-polarity:soluble easily in water and many other solvents such as hydrocarbon, alkyl halide, alcohol, ether, acy
19、l, amine, ester, aldehyde and so on. When mixed with a kind of non-inflammable solvent, the solution becomes non-inflammable,and if, mixed with high boilingpoint HFC and high boiling point solvent, the mixture becomes liquid and non-inflammable at room temperature.Results: Above properties of DME,ca
20、n not only insure production safety but also adapt to all production equipments of PU foam, and profitto increase expanding efficiencyand dimensional stability.Besides, it is cheap and rich. Conclusion: DME can be used for PU foam as a new blowing agent to substitute CFC-11. V7l4jRB8HsKEYWORDS:polyu
21、rethane foam, dimethyl ether, blowing agent, CFC-11, substitute.83lcPA59W9With the substitution action of CFC-11 blowing agent in the field of polyurethanePU foam, a number of substitutes of CFC-11 have been used, and some new blowing agents are exploring. But there are not reportages about DME bein
22、g blowing agent used for PU foam. It is considered that dimethyl ether is a kind of matter which has special properties, and is very suit to be a blowing agent of PU. The study discusses the feasibility of DMEas blowing agent of PU. mZkklkzaaP1 Properties of DME1.1 Chemical propertiesDMECH 3OCH 3, r
23、elative molecular weight 46.10 is the isomer of ethanol. It has stable chemical propertiesand only few reactions can take place: reacting with halogen or halogen hydride at low temperature to form addition compound, with fuming sulfuric acid or sulfuric trioxide in gas phase to form dimethyl sulfate
24、, withaniline vapor to formN,N-dimethyl aniline, and disintegrating when red heated. DME can be stored for a long time without decomposition and inversion and peroxide formation. DME can not be chloridized by chlorination solvent. It can just exist ten days in atmosphere and then will degrade into C
25、O2 and water. Its ODP value is zero, so can not endanger to environment and ozonosphere.AVktR43bpw1.2 Physical propertiesDME has melt point -138.5 ,boiling point0.1MPa-24 ,densityliquid state 20 666kg/m 3 , manometer pressure 20 0.4MPa,specificdensity,firepoint 235,spontaneous ignition temperature 3
26、50 . DME is colorlessness, flavorness and odorless. It has very low viscosity and surface tension, and is highly soluble in polarity and non-polarity. It is easily soluble in water andthe solubility is 34%W at 1 atm. DME can also be homogeneously mixed with most solvents such as hydrocarbon, alkyl h
27、alide, alcohol, ether, acyl, amine, ester and aldehyde etc. If mixed with a kind of non- inflammable solvent, the mixture becomes non-inflammable. ORjBnOwcEd1.3 ToxitiesThe acute, subacute and chronic inhalation toxicity tests on rats showed that DME is very low toxic: the rats exposed, for four hou
28、rs half the pieces lethal concentration LC50 was 16.4%, for 30min LC50 was 39%； ten days subacute tests on rats, rats gained a few weight at exposed concentration 5 104ppm, and gained zeroweight at 1 104ppm； chronic inhalation tests, rats had not been found toxity for30days at 1 103ppm,1104ppm, and
29、for 90days at 2 103ppm,1 104 ppm,2 104ppm. Only when the concentration of DME in air up to 2 105ppm or above, it might influence peoples hearts. 2MiJTy0dTTDuring the toxity tests, mutation and teratogenicity phenomenon about DME were not find.gIiSpiue7A欢迎下载精品学习资源2 Application in water expanding syst
30、emsAlthoughDMEis inflammable,it may become non-inflammablematter by mixingwith non-inflammable matter. That is to say its inflammable performance can be eliminated or reduced by mixed with water or HFC.The mixture of DME/water has a important property of“ zero fire elongation” , and test result of f
31、irefora mixturewhich contents 14% water, 6% alcoholand 80% DMEshowed zero value. Aboveproperty decreases greatly flammable or explosive danger of DME during storage and usage period. uEh0U1YfmhThe mutual solution property of DME with water makes it easy to be used for water expanding system of PU fo
32、am. Using the mixture of DME and a few water as blowing agent. because of water reduction, can improve shortcomings of water expanded PU foam of brittleness, low strength, low stability and low thermal insulation due to water reduction, so as to reduce quantities of polyisocyanate. In the first deve
33、lopment stage of CFC-11 substitute technique, CFC-11/water mixture was used as blowing agent in PU foam for reducing CFC-11, theexpanding process and used equipments were same as that of CFC-11 or HCFGC-141b, and the foam properties of PU including thermal insulation were accepted. Herein, the usage
34、 effectiveness of mixing blowing agent of DME/watercorresponds with that of CFC-11/water, and the foam may be better than CFC-11/water system because DME has strong solvent property and compatibility with water.IAg9qLsgBXBecause of the low viscosity, low surface tension and strong solvent property,
35、DME can remarkably decrease the viscosity of water expanding system, and decreases request to viscosity of polyol, in other words, allows to use higher viscosity polyol, and raises mixing homogenization of components.WwghWvVhPEAlthough DME has lower boiling point, the azeotropic point of DME/water w
36、ill be higher than DME. So thecurrent equipments of any kindofexpanding process in water blowingsystem can stillbe used without reformation when DME is used. asfpsfpi4k3 Comparing with paraffin blowing agentsParaffin blowingagents contain cyclopentane, n-pentane and isopentane generally called penta
37、ne blowing agents, n-butane, isobutene etc., withinwhich, pentane has found more applications. The reason of pentane attached importance to be blowing agents are zero value of ODP, very little greenhouse effect, non-toxic, verysmall influence on environment, liquid state at normal temperature, rich
38、resources and lower price. Comparing with CFC-11, there are three disadvantages over pentane: first, it is ignitable and volatile, its explosion limit is 1.3%8%. To insure production safety, all meterage, storage and expanding equipments must be modified large scale； second, pentane has lower solubi
39、lity in polyether polyol, so it is must to use modified polyether polyoland special assistants. Third, gaseous pentane has higher heat conductivity, so thermal insulation property of PUfoam expanded by it is not so good. ooeyYZTjj1Similarly, DME has zero ODP, very little greenhouse effect, non-toxic
40、, very small influence to environment,rich resources and lower price. Though DMEis gaseous at normal temperature, if mixedwith some higher boiling point paraffin such as hexane or octane the mixture can change into liquid state at normal temperature.Its explosion limit is double times as pentane, so the safety is relative higher than pentane. Non-inflammability can be reached by mixing with some HFC or HCFC, and if mixed with some octane and HFC, the mixture willbe liquidat normal temperature and non-inflammable.So DMEcan completely suit to current