• 屠呦呦与青蒿素 Tu & Arteannuin
  • 石油化工创新简史 A Petrochemistry History
  • 芳烃-改善人们生活 Aromatics Improving the Quality of Your Life
  • 百折不饶聚氨酯 Polyurethene: the Strength of Flexibility
  • 百变百丽有机硅 Silicone: the Art of Flow
  • 氯 这玩意儿 Chlorine Things


  • 强氧化剂的危害
  • 空气的威力
  • 为什么我打不开那个阀门?
  • 氮气的危险及防范
  • 物料错误混装的危害
  • 管帽和堵头-最后的防线
  • 软管破裂泄漏
  • 蒸气云爆炸
  • 危险物料的储存与运输
  • 沸腾液体膨胀蒸气爆炸(BLEVE)
  • 化学品危害性分类与标识
  • 化学品危害性其它标识方法
  • 化学品燃爆反应危害及防范
  • 化学品失控反应危害与防范-失控聚合-苯乙烯
  • 化学品失控反应危害与防范-失控聚合-丙烯酸及酯
  • 化学品遇水反应危害与防范-硅烷
  • 化学品失控反应危害与防范-失控分解-有机过氧化物
  • 工作场所危害与防范-蒸汽
  • 工作场所危害-登高作业

Silicones are an extraordinarily versatile family of products with a striking diversity of applications that make life safer, more pleasant, more exciting and more comfortable. Their flexibility encourages and facilitates innovation and, as silicones are often used to enhance performance, they also help to promote sustainable patterns of resource consumption. Silicones make millions of   products perform better, longer and more reliably. Silicones are sophisticated products that are extremely versatile and can be manufactured in more than 2,000 different forms, within the general categories of silanes, fluids, elastomers and resins. Silicones have important chemical and physical qualities derived from their molecular structure. Depending on requirements, these include longevity, thermostability, chemical, electrical and ultraviolet resistance, enduring elasticity, tensile strength, inertness and microbial resistance. They can be formulated either to resist or absorb water. They are much valued for their purity, especially for advanced electrical devices, and for their cleanliness.



•      Construction

       Conservation & protection 防水防潮

       Sealants 密封

       Other 其它

•      Electrical & electronics Appliances 电气电子设备

       Power, utilities & cables 电力供电线缆

       Other 其它

•      Industrial 工业

       Industrial equipment & moulds 工业设备和模具

       Plastics, auxiliaries & chemicals 注塑,助剂和化学品

       Other 其它

•      Personal & lifestyle 生活时尚

       Health & medical  care       健康医护

       Personal & home care 个人和家居用品

       Other 其它

•      Special systems   特制品

       Adhesives & coatings  黏胶和涂料

       Paper 造纸

       Textiles & leather 纺织和皮革

       Other 其它

•      Transportation 交通

       Automotive 汽车

       General  transportation 通用交通


By definition, silicon-hydrogen products (or“SiH products”in short) are silicon products containing Si-H bonds. These products will liberate hydrogen in some circumstances, presenting a major risk of explosion or fire that is proportional to the rate and/or volume of hydrogen released. The silicon-hydrogen products concerned are:

照定义看,硅 - 氢产物(或简称“SiH产物”)是含有Si-H键的硅产物。这些产物在一定情况下会释放氢,产生与氢的释放速率和/或体积成正比的爆炸或火灾的重大风险。相关的硅 - 氢产品包括:

1. Chlorosilanes containing Si-H bonds such as Me
2HSiCl, MeHSiCl2, HSiCl3 and others which will readily react with water to form corrosive and toxic hydrogen chloride gas and hydrochloric acid.

含有Si-H键的氯硅烷,如Me 2 HSiClMeHSiCl 2HSiCl 3等,它们容易与水反应形成腐蚀性的毒性氯化氢气体和盐酸。

2. SiH silicone fluids such as Me
3Si-O-(Me2Si-O)n-(MeHSi-O)m-SiMe3 and others, generally with a very high SiH content.

SiH硅氧烷液体,例如Me 3 Si-O-Me 2 Si-On - MeHSi-Om -SiMe 3等,通常具有非常高的SiH含量。

3. SiH emulsions SiH

and to a certain extend Compounded elastomers generally RTV2, HTV and LSR based on SiH-SiVinyl curing system


4. Functionalised silicone fluids for their unreacted residual SiH

用于未反应的残余SiH 具功能性的硅氧烷液体


There are 16 commonly used chlorosilanes and more that are known and are used in commerce. 氯硅烷有16种常用的,以及其它一些已知,并商用的。

Dimethylchlorosilane                        (CH3)2HSiCl                      二甲基氯硅烷

Trimethylchlorosilane                       (CH3)3SiCl                        三甲基氯硅烷

Methyldichlorosilane                        CH3HSiCl2                        甲基二氯硅烷

Dimethyldichlorosilane                    (CH3)2SiCl2                      二甲基二氯硅烷   

Chloropropylmethyldichlorosilane    C3H6ClCH3SiCl2               氯丙基甲基二氯硅烷

Vinylmethyldichlorosilane                 CH2CHCH3SiCl2               二氯甲基乙烯基硅烷

Diphenyldichlorosilane                     (C6H5)2SiCl2                    二苯基二氯硅烷

Phenylethyldichlorosilane                C6H5C2 H5SiCl2

Methyltrichlorosilane                        CH3SiCl3                           甲基三氯硅烷

Ethyltrichlorosilane                           C2H5SiCl3                         乙基三氯硅烷

Propyltrichlorosilane                        C3H7SiCl3                         丙基三氯硅甲烷

Chloropropyltrichlorosilane                     C3H6ClSiCl3                      氯丙基三氯硅烷

Vinyltrichlorosilane                           CH2CHSiCl3                      乙烯基三氯硅烷

Phenyltrichlorosilane                        C6H5SiCl3                         苯基三氯硅烷

Trichlorosilane                                 HSiC13                              三氯()硅烷

Silicon tetrachloride                         SiC14                                 四氯化硅


The chlorosilanes all react with moisture in the air or water to produce hydrogen chloride, the principal reaction product that can cause acute injury to any body tissue contacted. The major acute health risks are potentially severe corrosive burns of the skin, eyes or respiratory tract.


Except for silicon tetrachloride, all of the chlorosilanes may cause fire hazards.  Chlorosilane vapours are heavier than air, and, except for trimethylchlorosilane, the liquids themselves are heavier than water.

除四氯化硅外,所有氯硅烷都可能引起火灾。 氯硅烷蒸气比空气重,并且除了三甲基氯硅烷,液体本身比水重。

All of the chlorosilanes react vigorously with water, producing hydrogen chloride and, in the case of trichlorosilane and methyldichlorosilane, flammable hydrogen gas and hazardous residues. Trimethylchlorosilane will react with water to also produce hexamethyldisiloxane, which is a flammable liquid itself. 


The chlorosilanes are non-conductors and, therefore, can accumulate static electrical charges when processed, handled or dispensed.




SiH Silicone products are quite stable and not generally considered as hazardous materials, but, under specific conditions, they can generate high volumes of hydrogen gas. Because of its specific physical properties (wide explosive limits, low flammability, ignition energy, etc.) the hydrogen generated by gassing can pose a hazard due to pressure build-up, fire or explosion.


In order to achieve the gassing phenomenon, three conditions are simultaneously required. These conditions are called “the gassing triangle”.



1  SiH source SiH

All chemicals containing a silicon-hydrogen bond can generate hydrogen, and pure polymers or compounded products can be concerned alike.

所有含有硅 - 氢键的化学品都可以产生氢,纯聚合物或化合物亦均属此列。


2  Active hydrogen source活性氢源

All chemicals with an “active hydrogen” can contribute to the gassing phenomenon. The most common is water and can be found in products as an impurity or as an ingredient (emulsion). But other chemicals such as alcohols, amines, acids or alkaline materials used for some processes have the same behaviour and can be a source of “active hydrogen”.



3  Catalyst source

Acids, bases, amines, alkaline or acid salts, metal soaps, products of corrosion and contaminants have a catalytic action on the gassing phenomenon.

The rate of gassing is related to the temperature, acidity and basicity (pH), activity of each component, concentration of the components, their solubility in the system and its viscosity. For example, amines are more active catalysts than alkoxides, which in turn are more active than hydroxides.

酸,碱,胺,碱或酸盐,金属皂(metal soaps),腐蚀和污染产物对放气现象具有催化作用。


It is also important to mention that this phenomenon occurs sometimes with an induction time. Studies showed that, varying within the system studied, the reaction can “wait” for some random time and then occur with a quick evolution. This can explain that the gassing of hydrogen is not always easily predicted.

Nevertheless, if any of the above three conditions is missing, the “triangle” is broken and therefore no gassing occurs. However some products may be both the active hydrogen source and the catalyst (see above).





Chlorosilanes are stable in the absence of air, moisture and catalytic agents. The catalysts that may cause decomposition and rearrangement include bases; Lewis acids, such as aluminium chloride and iron trichloride; and anhydrous bases, such as Grignard reagents, organoalkali compounds and metal hydrides. When it is necessary to mix hydrochlorosilanes with such reagents, allow for the formation of hydrogen and other gases.

Chlorosilanes, except for silicon tetrachloride, are flammable and can form explosive mixtures with air. Moisture in air causes hydrolysis; hydrogen chloride fumes will be generated.

Water reacts vigorously with chlorosilanes, forming large volumes of hydrogen chloride. Trichlorosilane and methyldichlorosilane reacted with water can also produce hydrogen. Hydrogen can further be generated when hydrochloric acid reacts with some metals.

Primary alcohols react with chlorosilanes almost as rapidly as does water, forming hydrogen chloride; secondary and tertiary alcohols react less rapidly.

Ammonia and the aliphatic amines react rapidly with chlorosilanes, generating heat and solids (ammonium and amine salts).

Bases react violently with chlorosilanes, generating heat and potentially generating hydrogen with hydrogen-containing chlorosilanes.

Chlorine will react violently with any hydrogen-containing chlorosilane.

氯硅烷在没有空气,水分和催化剂的情况下是稳定的。可能引起分解和重组的催化剂包括碱; 路易斯酸,如氯化铝和三氯化铁; 和无水碱,例如格氏试剂,有机碱化合物和金属氢化物。 当需要将氢氯硅烷与这些试剂混合时,要充分考虑氢气和其它气体的产生。

氯硅烷,除四氯化硅外,都是易燃的,可与空气形成爆炸性混合物。空气中的水汽会引起水解; 会产生氯化氢烟雾。

氯硅烷与水会剧烈反应,形成大量氯化氢。三氯硅烷和甲基二氯硅烷与水反应则会产生氢。 而盐酸与一些金属反应时也可进一步产生氢。







It should be pointed out that even in the absence of an active hydrogen source, SiH products themselves may pose additional hazards. Polymerisation, de-polymerisation and equilibration processes can lead to side reactions producing dangerous volatile and highly flammable gases other than hydrogen.

In the presence of acid or basic catalysts (Lewis acids or bases, clays etc.) and - even in the absence of humidity – restructuring of the siloxane chain has been observed in association with the formation of highly flammable, gaseous by-products like for example Me3SiH, Me2SiH2, MeSiH3, depending on the nature of substituents (Me = Methyl, CH3) present on the siloxane backbone.

In extreme cases (H-Siloxane) where tri-functional HSiO1.5 units are present, the formation of SiH4 has been reported. SiH4 is a highly volatile (b.p. –112 °C) and self-ignitable gas on air.

Incompatibility: account should be taken of very severe reactions with peroxides and oxidizers leading to temperature increase and fire.


在酸或碱性催化剂(路易斯酸或碱,粘土等)存在时,并且 - 即使在没有湿气的情况下 - 观察到硅氧烷链的重构,从而形成高度易燃的气态副产物,例如Me 3 SiHMe 2 SiH 2MeSiH 3,这取决于存在于硅氧烷主链上的取代基(Me =甲基,CH 3)的性质。

极端情况下(H-硅氧烷),即存在三官能HSiO1.5 单元时,已有报道能形成SiH 4 SiH 4是高挥发性(沸点-112℃)和自燃气体。




As mentioned previously, build-up, fire or explosion can be generated by hydrogen gassing. 

Stored in an inappropriate closed container, products can release enough hydrogen to develop a substantial pressure. The sudden release of overpressure can propel any loose part of the container as a dangerous projectile potentially causing serious injuries to people around. That’s why venting devices are needed for storage for “Control of Hazards” and closed glass bottles are not recommended for samples storage.



The release of hydrogen is also hazardous as hydrogen has exploding properties even at low concentrations (explosive limits for hydrogen in air are generally mentioned in literature between 4% and 74%). Exposed to an electric spark, heat or open flame, a hydrogen/air mixture burns with a very hot flame and can be source of bigger fires. All the necessary precautions for the safe handling of flammable gases should, therefore, be observed as mentioned in MSDS.


Sometimes, for viscous products, hydrogen gassing can bring out foaming and overflowing of containers due to build-up.

Reaction of SiH containing products may also form – besides hydrogen gas - solid/resinous products capable to block pipes, exhausts or safety valves which may lead to a rise of pressure in the manufacturing system.




EMULSIONS  Emulsions are the most sensitive potential gassers because they usually contain a fairly high SiH level and have an unlimited supply of active hydrogen in the form of water. So they are therefore very sensitive to catalyst pollution.


COMPOUNDED ELASTOMERS  Some RTV, HTV and LSR silicone products contain more SiH compounds. Moisture from fillers, polymerization catalyst residues from polymers and contamination during repackaging may cause reaction and gassing. If viscosity is high, foaming and overflowing could happen.


SiH SILICONE FLUIDS  Hydrogen siloxane fluids can have a very high SiH content. Used and processed under “clean” conditions, they are quite insensitive to gassing. With no active hydrogen content and catalyst, they are stable products, but it remains imperative that water, acids and bases be excluded.



FUNCTIONALISED SILICONE FLUIDS  Functionalised silicone fluids can generate gassing problems due to unreacted residual SiH.  Depending on process conditions, some active hydrogen products can remain. Specific analysis for catalyst contamination should be done.




There are many ways in which these conditions can arise as mentioned in the following examples. 



Generally, equipment cleanout includes both solvent and water flushing followed by drying. When inadequate cleanouts occur, trace amounts of catalyst and active hydrogen compounds (water for example) may be left behind completing the gassing triangle for the following batch. Caustic cleaning will cause the same phenomena.




If an active hydrogen compound (water, alcohol, amine, etc) is used during the manufacturing process of the SiH fluid or compound, and incompletely separated after, the active hydrogen left behind could later complete the gassing triangle if a catalyst is also present. 




Poor container liners or unprotected storage conditions can cause moisture (water is an active hydrogen source) contamination due to cracking of liners or bad water tightness of venting devices.




Rusting in containers occurs due to damage such as denting, rupturing, or cracking of container liners, thereby allowing moisture to enter the container and to cause chemical corrosion. The by-products of the corrosion process often have a catalytic action on the gassing phenomenon.  Also, accidental introduction of rust or of other contaminants during container filling operations can have the same consequences.


容器生锈常由于诸如容器内衬凹陷,破裂或裂纹等各种损伤而产生,从而使水分进入容器并引起化学腐蚀。 腐蚀过程的副产物通常对放气现象有催化作用。此外,在容器灌装操作期间意外引入的锈污或其它污染物可能具有相同的结果。



In some cases, hydrogen evolution may be caused by the chemical breakdown of a product due to ageing. Most products have recommended shelf lives which should be safely observed.



The total equipment, such as lines, pumps, valves, vessels, etc., must be thoroughly dried with no trace of water remaining before introducing any SiH product unless SiH emulsions and dispersions are produced.


Prior to operation, the system should be tested for leaks at or above operating pressure with dry inert gas (nitrogen) and each joint painted with soap solution and checked for bubbles.


Whenever necessary, totally enclosed systems should be used. Atmospheric openings or vents will allow moisture to enter the system causing the generation of hydrogen under unfavourable conditions and causing the generation of hydrogen chloride (for chlorosilane), which will attack the equipment.


Use only dry inert gas (nitrogen), when any of the following must be done: pressurising vessels, priming pumps, blanketing tanks, and filling or withdrawing of tank contents.



Storage and filtration equipment

All storage tanks for SiH products should be ‘blanketed’ or ‘padded’ with nitrogen. Grounding and bonding must be provided for tanks and ancillary transfer equipment, and when filling drums and IBCs. Free-fall or splash filling of vessels and containers should be avoided by the use of, for example, dip pipes. 

High levels of static electricity can be generated when filtering SiH materials. Care should be taken to ensure that effective grounding is in place, and that lines are purged with nitrogen prior to and after filtration, particularly if the equipment is to be subsequently opened up.


SiH产品的所有储罐应采用氮气“氮封”或“填充”。 必须对储罐和辅助输送设备以及在装桶和装IBC时进行接地连接。应通过使用例如浸没管来避免落体式或飞溅式充装槽罐容器。




Pure SiH fluids show a very low electrical conductivity in general. Thus SiH fluids are extremely prone to accumulation of static electricity.

Static electricity discharges can ignite flammable SiH product vapour. It is therefore essential to inert the whole system in which flammable SiH products or mixtures are present. Dry inert gas (nitrogen) should be used for transfer operations.


Static electricity may be generated when SiH products flow through or are discharged from a pipe or fall freely through space. Splash filling is particularly hazardous and should be avoided. Unless a dip tube is installed, vessels, tanks should be filled from the bottom.
To eliminate static charges and avoid spark discharges, a continuous path from the point of generation to ground must be provided. This is best accomplished by electrically interconnecting (bonding) all vessels, piping and related flanges, and grounding all equipment.
Fill lines should be conductively bonded to provide a path to ground externally. 

Ground wiring should be designed to provide reasonable protection against physical wear. Periodic checks of continuity to ground should be made.

 (绑接所有容器,管道和相关法兰,以及接所有设备接地。 灌料管线应导电绑接以便在外部提供接地通路。

接地线应设计能提供合理保护,防止物理磨损。 应定期检查对地的连续导通性。



The SiH containing materials cause a particular hazard for fire and explosion, as these have the potential to develop hydrogen. Hydrogen is lighter than air, has a very low Lower Explosion Limit of 4 vol. % in air (the Higher Explosive Limit is 74 vol. %). The hydrogen/air mixture burns with a very hot, non-luminous flame that is extremely difficult to see during the daylight.

Particular SiH products, with a relatively high flashpoint, but sensitive to gassing, can create unexpected fire and explosion hazards, for example SiH containing emulsions.

SiH物料具有火灾和爆炸的特殊危险,因为它们具有产生氢的潜力。氢气比空气轻,具有非常低的爆炸极限,爆炸下限4 %体积、爆炸上限为74%体积。氢/空气混合物燃烧,h产生极热无色火焰,在日光下极难看到。




Due to its reactivity with chlorosilanes, water should NOT be used as an extinguishing agent for chlorosilane fires, except for very small fires. Water can also be used to protect exposures and personnel and on the vapour cloud to disperse and dilute the HCl vapour. (Care should be taken, however, to prevent any over-spray or runoff from contacting the chlorosilane.)
Prevent extinguishing agents from entering a container or vessel that contains chlorosilane. The resulting release of hydrogen chloride vapours may over-pressurise the container or vessel, resulting in a sudden rupture of the container or vessel.
Sodium- and potassium-bicarbonate-based dry chemical fire extinguishers have proven effective to extinguish small chlorosilane fires, except those involving hydrogen-containing chlorosilanes such as trichlorosilane and methyldichlorosilane, where success has been marginal at best. Expect to use much larger quantities of dry chemical than would be required to extinguish a similar hydrocarbon fire. Dry chemical is generally not effective on large fires because an adequate amount of agent cannot be delivered quickly enough. Use of dry chemical on hydrogen-containing chlorosilanes will release hydrogen, which may ignite explosively.


Foam is the most effective agent overall for use on chlorosilane fires. However, a number of variables, most notably the chlorosilane involved, the foam concentrate, the concentration of the foam, the expansion ratio (final foam volume versus initial solution volume), the application equipment and the fire conditions, can have a significant impact on the effectiveness of foam on chlorosilane fires. Certain combinations of these variables can in fact produce less than satisfactory (and even adverse) results.
In general, though, alcohol-(polar) compatible AFFF (Aqueous Film Forming Foam) has proven to be an extremely effective foam type, and medium-expansion foam has been found to be the most effective foam expansion. Other foam types and expansions, however, can produce satisfactory results, especially on fires involving dimethyldichlorosilane, trimethylchlorosilane and other heavily organic substituted chlorosilanes. For chlorosilanes containing Si-H (silicon-hydrogen) bonds, e.g., trichlorosilane and methyldichlorosilane, alcohol-compatible AFFF and medium-expansion foam are highly recommended for maximum effectiveness.

– (极性)相容的AFFF(水性成膜泡沫)已证明是非常有效的泡沫类型,而中度膨胀泡沫已发现是最有效的泡沫膨胀物。当然其它一些泡沫类型和膨胀物也可得到令人满意的结果,特别是在涉及二甲基二氯硅烷,三甲基氯硅烷和其它重有机化氯硅烷燃烧方面。 对于含有Si-H(硅 - 氢)键的氯硅烷,例如三氯硅烷和甲基二氯硅烷,强烈建议使用醇容性AFFF和中度膨胀泡沫以达到最佳效果。

Since foam solutions contain water, reaction with the chlorosilane will normally be observed when foam is applied. Be aware that application of foam will release significant amounts of corrosive vapours. In addition, hydrogen vapours can he released from hydrogen-containing chlorosilanes and may be trapped under the foam blanket. Extreme care should be taken not to disturb the foam blanket during and after foam application.
Other extinguishing agents that may be effective on small fires include dry sand and carbon dioxide. (Caution: When using carbon dioxide in enclosed spaces without adequate ventilation, an asphyxiation hazard can be created.)

泡沫溶液含水,使用泡沫时通常观察到其与氯硅烷的反应。请注意,施用泡沫会释放大量的腐蚀性蒸气。 此外,氢气可以从含氢的氯硅烷释放并且可以被封堵在泡沫覆盖层下。泡沫施用期间和之后,应当非常小心不要扰动泡沫层。

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