WO2017012458A1 - 一种文物熏蒸方法 - Google Patents

一种文物熏蒸方法 Download PDF

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Publication number
WO2017012458A1
WO2017012458A1 PCT/CN2016/087994 CN2016087994W WO2017012458A1 WO 2017012458 A1 WO2017012458 A1 WO 2017012458A1 CN 2016087994 W CN2016087994 W CN 2016087994W WO 2017012458 A1 WO2017012458 A1 WO 2017012458A1
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WIPO (PCT)
Prior art keywords
fumigation
cultural
fumigant
cultural relics
box
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PCT/CN2016/087994
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English (en)
French (fr)
Inventor
姜标
张琛
陶黎明
周新光
吴来明
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SHANGHAI MUSEUM
Shanghai Institute of Organic Chemistry of CAS
East China University of Science and Technology
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SHANGHAI MUSEUM
Shanghai Institute of Organic Chemistry of CAS
East China University of Science and Technology
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Publication of WO2017012458A1 publication Critical patent/WO2017012458A1/zh
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M13/00—Fumigators; Apparatus for distributing gases

Definitions

  • the invention relates to a method for fumigation of cultural relics, belonging to the technical field of cultural relics preservation.
  • cultural relics can reflect the cultural, scientific and technological level and production status at that time, as well as the life preferences, habits and conditions of people at all levels of society at that time, and have the inheritance of human civilization. There is no substitute for a major role. Therefore, the protection of cultural relics is of great significance.
  • the insecticidal sterilization methods widely used for disinfection of cultural relics mainly include physical insecticidal methods such as aeration (carbon dioxide, nitrogen) deoxidation and chemical control methods using fumigants such as ethylene oxide, methyl bromide and sulfuryl fluoride.
  • aeration carbon dioxide, nitrogen
  • fumigants such as ethylene oxide, methyl bromide and sulfuryl fluoride.
  • a material containing lead oxide forms carbonate in a short time; ethylene oxide is an explosive substance and has a lure Degeneration; the bactericidal ability of methyl bromide is poor, and since the ninth "Convention of the Meeting of the Parties to the Montreal Protocol" in 1997, developed countries have agreed to phase out the use of methyl bromide from 2005, and according to the Montreal Protocol, by 2015, China It is forbidden to use methyl bromide; sulfuryl fluoride is difficult to penetrate into the watery eggs due to its hydrophobicity, so the ability to kill eggs is poor, and the deposition of fluoride is dangerous to human bones.
  • Conditions and fumigation time for example: for paper, bone, ivory materials, the humidity needs to be adjusted at 50-55%; for textile, wood, leather materials, the need to adjust the humidity is 50-60%; generally for black Aspergillus, Aspergillus and other molds need to be fumigated for 20-24 hours; therefore, this patented technology is not only cumbersome to operate, but also can not achieve one-time fumigation treatment of various materials and various bacterial molds under the same environment.
  • the key is that The patented technology does not inform the cultural relics after being treated by the fumigation method, and then placed in the cultural relics collection environment to regenerate the mold.
  • the object of the present invention is to provide a green, safe and effective method for fumigation of cultural relics, which not only achieves safe and effective sterilization, but also does not affect the material and human health of the cultural relics, and does not pollute the environment. It can realize the one-time fumigation treatment of various materials and various bacterial molds under the same environment, and after fumigation treatment, it can be placed in the cultural relics collection environment for at least half a year without regenerating the bacterial mold.
  • a method for fumigation of cultural relics includes the following operations: placing the fumigant and the cultural relics into a fumigation box, fumigation at 25 to 45 ° C for 1 to 36 hours, evacuating under reduced pressure for 1 to 3 hours, opening the fumigation box, and removing the cultural relics.
  • the fumigant is a compound of a thiosulfinate compound and a thiosulfonate compound.
  • the fumigant is supported on a carrier material having an adsorption effect
  • the carrier material may be filter paper, silica gel, filter membrane, cotton, sponge or cloth, or the like.
  • the carrier material loaded with the fumigant is placed in a hollow device having an outwardly diffusing port or mesh surface
  • the hollow device may be a box structure, a box structure, a cage structure, a bag, or the like.
  • the hollow device has a fan and a speed control function.
  • the hollow device has a self-heating and temperature regulating function.
  • the fumigant is a compound having a volume ratio of 1:1 to 1:5 by a thiosulfinate compound and a thiosulfonate compound.
  • the thiosulfinate compound has the following structural formula: a compound wherein: R 1 and R 2 are the same or different and are each selected from a C 1 -C 4 alkane group (for example, methyl, ethyl, propyl, butyl) or a C 2 -C 4 alkene group. (Example: allyl).
  • R 1 is the same as R 2 .
  • the thiosulfonate compound has the following structural formula: a compound wherein: R 3 and R 4 are the same or different and are each selected from a C 1 -C 4 alkane group (for example, methyl, ethyl, propyl, butyl) or a C 2 -C 4 alkene group. (Example: allyl).
  • R 3 is the same as R 4 .
  • the present invention has the following beneficial effects:
  • the invention adopts a compound of a thiosulfinate compound and a thiosulfonate compound as a fumigant, which not only realizes safe and effective sterilization and disinfection of cultural relics, but also has the lowest environmental pollution and no fumigant residue.
  • the problem does not affect the material material and human health, and has the advantages of green environmental protection; in particular, the invention can realize the one-time treatment of various materials and various bacterial molds in the same fumigation environment, and is subjected to fumigation treatment according to the present invention.
  • the method of the invention has the advantages of simple operation, low cost, wide applicable range of materials and bacterial molds, and long-term preservation of cultural relics. Has important value and far-reaching significance.
  • Methyl methylthiosulfinate and ethyl ethylthiosulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:3; abbreviated as fumigant A; determination of oral LD 50 >500 mg/Kg in mice It belongs to low toxicity.
  • Ethyl ethyl thiosulfinate and methyl methyl sulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:2; abbreviated as fumigant B; determination of oral LD 50 >500 mg/Kg in mice It belongs to low toxicity.
  • Ethyl ethyl thiosulfinate and ethyl thiosulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:1; abbreviated as fumigant C; determination of oral LD 50 >500 mg/Kg in mice It belongs to low toxicity.
  • Methyl methylthiosulfinate and methyl methyl sulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:1.5; abbreviated as fumigant D; the oral LD 50 of the mouse was determined to be >500 mg/Kg. It belongs to low toxicity.
  • the propyl thiosulfinate sulfonate and ethyl ethylthiosulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:2.5; abbreviated as fumigant E; the oral LD 50 of the mouse was determined to be >500 mg/Kg. It belongs to low toxicity.
  • the propyl thiosulfinate propyl ester and allyl thiosulfonic acid allyl ester were stirred and mixed uniformly at room temperature according to a volume ratio of 1:4; abbreviated as fumigant F; the oral LD 50 >500 mg of the mouse was determined. /Kg, which is low in toxicity.
  • Ethyl ethyl thiosulfinate and butyl butyl sulfonate were stirred and mixed uniformly at a volume ratio of 1:5 at room temperature; abbreviated as fumigant G; determination of oral LD 50 >500 mg/Kg in mice It belongs to low toxicity.
  • Ethyl methylthiosulfinate and methyl thiosulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:3; abbreviated as fumigant H; determination of oral LD 50 >500 mg/Kg in mice It belongs to low toxicity.
  • Allyl allysulfinyl sulfinate and allyl methylthiosulfonate were stirred and mixed uniformly at room temperature according to a volume ratio of 1:2.5; abbreviated as fumigant I; determination of oral LD 50 of mice > 500mg/Kg, which is low in toxicity.
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 36 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • Example 3-1 Culture relics fumigation experiment
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 24 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the fumigant is loaded on the filter paper, and then placed in the fumigation box.
  • the fumigation box is placed in the fumigation box together with the cultural relics sample, the fumigation box is closed, and the fumigation box is controlled.
  • the temperature was 25 ° C, after fumigation for 18 hours, the air was depressurized for 2 hours, the fumigation box was opened, and the cultural relic samples were removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the fumigant is loaded on the filter paper, and then placed in the fumigation box.
  • the fumigation box wind level 2 (middle)
  • the fumigating box and the cultural relic sample are placed in the fumigation box, the fumigation box is closed, and the fumigation box is controlled.
  • the temperature is 25 ° C, after fumigation for 16 hours, vacuuming for 2 hours, opening the fumigation box, removing the cultural relic samples;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled to be 35° C., after fumigation for 20 hours, the vacuum is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the table below:
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 45 ° C, fumigation is performed for 1 hour, and the vacuum is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the color of the bamboo and wood samples of the cultural relics treated by the above-mentioned fumigation treatment did not change significantly by the color difference meter, and the strength of the bamboo and wood samples subjected to the above fumigation treatment did not change significantly by the tensile test.
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled to 30 ° C, fumigation is carried out for 4 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 24 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • Staphylococcus aureus Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 30 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment of the present embodiment are placed in the cultural relics collection room, and the bacteria tracking test is performed regularly.
  • the test results are shown in the following table:
  • Staphylococcus aureus Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.
  • the fumigant is loaded on the cotton wool sheet, and then placed in the fumigation box.
  • the fumigation box temperature After setting the fumigation box temperature to 45 ° C, the fumigation box and the cultural relic sample are placed in the fumigation box, the fumigation box is closed, and the fumigation box is controlled.
  • the temperature was 25 ° C, after fumigation for 8 hours, the air was depressurized for 2 hours, the fumigation box was opened, and the cultural relic samples were removed;
  • the samples of the cultural relics subjected to the fumigation treatment of the present embodiment are placed in the cultural relics collection room, and the bacteria tracking test is performed regularly.
  • the test results are shown in the following table:
  • Staphylococcus aureus Staphylococcus aureus, Escherichia coli, Bacillus megaterium, Bacillus subtilis, Pseudomonas fluorescens, etc.
  • the fumigant is loaded on the cotton wool sheet, and then placed in the fumigation box.
  • the fumigation box wind level 3 strong
  • the fumigating box and the cultural relic sample are placed in the fumigation box, the fumigation box is closed, and the fumigation box is controlled.
  • the temperature was 25 ° C, after fumigation for 10 hours, the pressure was evacuated for 2 hours, the fumigation box was opened, and the cultural relic samples were removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 24 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the method of the invention can realize one-time treatment of various materials and various bacterial molds in the same fumigation environment.
  • the color, the silk, the linen, the bamboo, the leather, the bone and the bone products of the cultural relic samples after the above-mentioned fumigation treatment were not changed significantly by the color difference meter, and the sample of the cultural relics after the fumigation treatment was obtained by the tensile test.
  • the paper, silk, linen, bamboo and other strengths did not change significantly.
  • the paper folding resistance test showed that the paper folding resistance of the above-mentioned fumigation samples did not change significantly, and the scanning electron microscope was used. It was observed that the fibrous tissue arrangement of the leather and bone products after the above fumigation treatment did not change significantly.
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 24 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 24 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 24 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 24 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • Example 8-6 Culture relics fumigation experiment
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 24 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 24 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, and the temperature in the fumigation box is controlled at 25 ° C. After fumigation for 24 hours, evacuate under reduced pressure for 2 hours, open the fumigation box, and remove the cultural relic samples;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:
  • the fumigant and the cultural relic sample are placed in a fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 25 ° C, fumigation is carried out for 24 hours, and the pressure is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed;
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the mold tracking test is performed regularly.
  • the test results are shown in the following table:

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  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
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Abstract

一种文物熏蒸方法，包括如下步骤，将熏蒸剂与文物放入熏蒸箱内；在25-45℃下熏蒸1-36小时后，减压抽气1-3小时；打开熏蒸箱，移走文物。熏蒸剂为硫代亚硫酸脂类化合物与硫代硫酸脂类化合物的复配物。该方法效果明显、操作简单，适用范围广。

Description

一种文物熏蒸方法 技术领域
本发明是涉及一种文物熏蒸方法，属于文物保存技术领域。
背景技术
文物作为一类具有特殊社会价值的物品，它可以从社会的各个角度反映出当时文化、科学技术水平和生产状况，以及当时人们在社会各个阶层的生活喜好、习惯和状况，对于传承人类文明具有无可替代的重大作用。因此，文物保护工作意义重大。
由于馆藏文物中相当一部分为各种材质的有机质文物，如丝、竹、棉、纸张、毛皮、漆木等，而文物中的有机质成分可以为微生物和害虫的生长、生理代谢等活动提供大量丰富的养料和养分，因此，微生物和害虫对文物造成的危害程度是极为严重的，因而对文物进行防虫防霉处理成为文物保护工作中一项重要内容。
但由于文物本身所具有的不可复制性、不可再生性和唯一性，决定了文物工作者不可能采用常规的防虫防霉方法对其进行保护。因为，一旦使文物受损，将造成无法弥补的巨大损失，文物的保护效果将直接关系到文物的寿命和价值。
目前，广泛用于文物消毒的杀虫灭菌方法主要有充气(二氧化碳、氮气)除氧等物理杀虫法以及采用环氧乙烷、溴甲烷、硫酰氟等熏蒸剂进行熏蒸的化学防治法。虽然现有的这几种方法能在一定程度上达到杀虫灭菌的效果，但各有其不足之处，例如：氮气杀虫时间长，且不同昆虫对高纯度氮气的耐受力差异显著；二氧化碳由于呈弱酸性，在高湿度的条件下对被处理的材料有影响，特别是含氧化铅的材料，短时间即会生成碳酸盐；环氧乙烷属于易爆物质，且具有诱变性；溴甲烷的杀菌能力较差，并且自1997年第九次“蒙特利尔议定书缔约国会议”后开始，发达国家已经约定从2005年起逐步停止使用溴甲烷，而且根据蒙特利尔协议，到2015年，我国也将被禁止使用溴甲烷；硫酰氟由于其疏水性，很难渗透到含水的虫卵中，因而杀卵能力差，且氟化物的沉积对人体骨骼有中毒的危险。另外，硫酰氟温室效应显著，硫酰氟排放造成的温室效应大约是等量的二氧化碳的5000倍！因此，研究开发一种既能有效防虫防霉，又不影响文物材质和人体健康，同时也不污染环境的安全环保的文物保存方法，是摆在世界各国文物保护工作者面前急需解决的一大难题。
虽然中国专利CN201310403788.6公开的文物熏蒸消毒方法，利用植物中的有效成分代替环氯乙烷、溴甲烷等熏蒸剂，解决了易爆性、对环境的破坏性及人体的安全无害性，但 该方法需要将植物熏蒸剂与文物放入熏蒸箱后，熏蒸用的植物精油用量也较大，另外还需通入高纯氮气，而且对不同的霉菌病害类型及文物材质，需要选择特定的湿度条件和熏蒸时间，例如：对于纸张、骨质、象牙材质的文物，需要调节湿度在50-55％；对于纺织品、木质、皮革制品材质的文物，需要调节湿度在50-60％；一般对于黑曲霉、黄曲霉等霉菌，需熏蒸20-24小时；因此，此专利技术不仅操作繁琐，而且不能实现在同一环境下对多种材质的文物和各种细菌霉菌进行一次性熏蒸处理，关键是，该专利技术并未告知文物经过所述的熏蒸消毒方法处理后，再放置在文物馆藏环境下再复生霉菌的情况。
发明内容
针对现有技术存在的上述问题和需求，本发明的目的是提供一种绿色环保安全有效的文物熏蒸方法，不仅实现安全有效杀菌消毒，不影响文物材质和人体健康，同时也不污染环境，而且实现在同一环境下对多种材质的文物和各种细菌霉菌能进行一次性熏蒸处理，并且经过熏蒸处理后能在文物馆藏环境下放置至少半年以上不再复生细菌霉菌。
为实现上述发明目的，本发明采用如下技术方案；
一种文物熏蒸方法，包括如下操作：将熏蒸剂与文物放入熏蒸箱内，在25～45℃下进行熏蒸1～36小时后，减压抽气1～3小时，打开熏蒸箱，移出文物；所述熏蒸剂为硫代亚磺酸酯类化合物与硫代磺酸酯类化合物的复配物。
作为优选方案，将所述熏蒸剂负载在具有吸附作用的载体材料上，所述的载体材料可以为滤纸、硅胶、滤膜、棉花、海绵或布等。
作为优选方案，将负载有熏蒸剂的载体材料放置在具有向外扩散的口或网孔面的中空装置中，所述的中空装置可以是箱式结构、盒式结构、笼式结构、袋子等。
作为进一步优选方案，所述中空装置具有风扇和调速功能。
作为进一步优选方案，所述中空装置具有自加热和调温功能。
作为优选方案，所述熏蒸剂是由硫代亚磺酸酯类化合物与硫代磺酸酯类化合物按体积比为1：1～1：5的复配物。
作为优选方案，所述的硫代亚磺酸酯类化合物是具有如下结构通式：
Figure PCTCN2016087994-appb-000001
的化合物，其中：R1与R2相同或不同，且均选自C1-C4的烷烃基(例如：甲基、乙基、丙基、丁基)或C2-C4的烯烃基(例如：烯丙基)。
作为进一步优选方案，R1与R2相同。
作为优选方案，所述的硫代磺酸酯类化合物是具有如下结构通式：
Figure PCTCN2016087994-appb-000002
的化合物，其中：R3与R4相同或不同，且均选自C1-C4的烷烃基(例如：甲基、乙基、丙基、丁基)或C2-C4的烯烃基(例如：烯丙基)。
作为进一步优选方案，R3与R4相同。
与现有技术相比，本发明具有如下有益效果：
本发明通过选用硫代亚磺酸酯类化合物与硫代磺酸酯类化合物的复配物作为熏蒸剂，不仅实现了对文物的安全有效杀菌消毒，而且对环境的污染最低，没有熏蒸剂残留问题，不影响文物材质和人体健康，具有绿色环保的优点；尤其是，本发明可实现在同一熏蒸环境下对多种材质的文物和各种细菌霉菌进行一次性处理，并且经过本发明熏蒸处理后的文物，能在文物馆藏环境下放置至少半年以上不再复生细菌霉菌；另外，本发明方法还具有操作简单，成本低，适用的材质和细菌霉菌范围广等优点，对文物的安全长久保存具有重要价值和深远意义。
具体实施方式
下面通过实施例对本发明的技术方案做进一步详细说明。
实施例1：熏蒸剂的制备
1、甲基硫代亚磺酸甲酯与乙基硫代磺酸乙酯的复配物：
将甲基硫代亚磺酸甲酯与乙基硫代磺酸乙酯按照体积比1:3在室温下搅拌混合均匀；简记为熏蒸剂A；测定小鼠经口LD50>500mg/Kg，属于低毒。
2、乙基硫代亚磺酸乙酯与甲基硫代磺酸甲酯的复配物：
将乙基硫代亚磺酸乙酯与甲基硫代磺酸甲酯按照体积比1:2在室温下搅拌混合均匀；简记为熏蒸剂B；测定小鼠经口LD50>500mg/Kg，属于低毒。
3、乙基硫代亚磺酸乙酯与乙基硫代磺酸乙酯的复配物：
将乙基硫代亚磺酸乙酯与乙基硫代磺酸乙酯按照体积比1:1在室温下搅拌混合均匀；简记为熏蒸剂C；测定小鼠经口LD50>500mg/Kg，属于低毒。
4、甲基硫代亚磺酸甲酯与甲基硫代磺酸甲酯的复配物：
将甲基硫代亚磺酸甲酯与甲基硫代磺酸甲酯按照体积比1:1.5在室温下搅拌混合均匀；简记为熏蒸剂D；测定小鼠经口LD50>500mg/Kg，属于低毒。
5、丙基硫代亚磺酸丙酯与乙基硫代磺酸乙酯的复配物：
将丙基硫代亚磺酸丙酯与乙基硫代磺酸乙酯按照体积比1:2.5在室温下搅拌混合均匀；简记为熏蒸剂E；测定小鼠经口LD50>500mg/Kg，属于低毒。
6、丙基硫代亚磺酸丙酯与烯丙基硫代磺酸烯丙酯的复配物：
将丙基硫代亚磺酸丙酯与烯丙基硫代磺酸烯丙酯按照体积比1:4在室温下搅拌混合均匀；简记为熏蒸剂F；测定小鼠经口LD50>500mg/Kg，属于低毒。
7、乙基硫代亚磺酸乙酯与丁基硫代磺酸丁酯的复配物：
将乙基硫代亚磺酸乙酯与丁基硫代磺酸丁酯按照体积比1:5在室温下搅拌混合均匀；简记为熏蒸剂G；测定小鼠经口LD50>500mg/Kg，属于低毒。
8、甲基硫代亚磺酸乙酯与乙基硫代磺酸甲酯的复配物：
将甲基硫代亚磺酸乙酯与乙基硫代磺酸甲酯按照体积比1:3在室温下搅拌混合均匀；简记为熏蒸剂H；测定小鼠经口LD50>500mg/Kg，属于低毒。
9、烯丙基硫代亚磺酸烯丙酯与甲基硫代磺酸烯丙酯的复配物：
将烯丙基硫代亚磺酸烯丙酯与甲基硫代磺酸烯丙酯按照体积比1:2.5在室温下搅拌混合均匀；简记为熏蒸剂I；测定小鼠经口LD50>500mg/Kg，属于低毒。
实施例2：文物熏蒸实验
文物材质：纸张
病害：曲霉和青霉等
熏蒸剂：熏蒸剂A
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸36小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上已没有任何霉菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上没有熏蒸剂残留。
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的文物样品的纸张颜色没有发生明显变化，且通过拉力仪测试得知经上述熏蒸处理后的文物样品的纸张强度也没有发生明显变化及通 过纸张耐折度仪测试得知经上述熏蒸处理后的文物样品的纸张耐折度也没有发生明显变化。
实施例3-1：文物熏蒸实验
文物材质：丝绸材料
病害：曲霉和青霉等
熏蒸剂：熏蒸剂C
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸24小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上已没有任何霉菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的文物样品的丝绸颜色没有发生明显变化，且通过拉力仪测试得知经上述熏蒸处理后的文物样品的丝绸强度也没有发生明显变化。
实施例3-2：文物熏蒸实验
文物材质：丝绸材料
病害：曲霉和青霉等
熏蒸剂：熏蒸剂C
先将熏蒸剂负载在滤纸片上，再将其放入熏蒸盒内，设定熏蒸盒温度为35℃后立即将熏蒸盒与文物样品一起置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸18小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上已没有任何霉菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的文物样品的丝绸颜色没有发生明显变化，且通过拉力仪测试得知经上述熏蒸处理后的文物样品的丝绸强度也没有发生明显变化。
实施例3-3：文物熏蒸实验
文物材质：丝绸材料
病害：曲霉和青霉等
熏蒸剂：熏蒸剂C
先将熏蒸剂负载在滤纸片上，再将其放入熏蒸盒内，设定熏蒸盒风力2级(中)后立即将熏蒸盒与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸16小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上已没有任何霉菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的文物样品的丝绸颜色没有发生明显变化，且通过拉力仪测试得知经上述熏蒸处理后的文物样品的丝绸强度也没有发生明显变化。
实施例3-4：文物熏蒸实验
文物材质：丝绸材料
病害：曲霉和青霉等
熏蒸剂：熏蒸剂C
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为35℃，进行熏蒸20小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上已没有任何霉菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测， 检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
但通过色差仪观察发现：经上述熏蒸处理后的文物样品的丝绸颜色会略微变黄及丝绸强度会略微变差。
通过比较实施例3-1和3-2可见：通过将熏蒸剂先负载在滤纸片上，然后放入熏蒸盒内，并使熏蒸盒具有加热功能，可实现在较短熏蒸时间内达到相同熏蒸效果，而且对文物材质不会产生任何伤害。
通过比较实施例3-1和3-3可见：通过将熏蒸剂先负载在滤纸片上，然后放入熏蒸盒内，并使熏蒸盒具有风扇功能，可实现在较短熏蒸时间内达到相同熏蒸效果，而且对文物材质不会产生任何伤害。
通过比较实施例3-1和3-4可见：在同等条件下，虽然直接调节熏蒸箱内的温度对熏蒸效果没有影响，但温度的升高会对置入熏蒸箱内的文物材质的颜色及其它性能产生一定的影响。
实施例4：文物熏蒸实验
文物材质：竹木
病害：曲霉和青霉等
熏蒸剂：熏蒸剂F
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为45℃，进行熏蒸1小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上已没有任何霉菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的文物样品的竹木颜色没有发生明显变化，且通过拉力仪测试得知经上述熏蒸处理后的文物样品的竹木强度也没有发生明显变化。
实施例5：文物熏蒸实验
文物材质：棉织品
病害：蜡叶芽枝霉、根霉和木霉等
熏蒸剂：熏蒸剂G
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为30℃，进行熏蒸4小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上已没有任何霉菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的文物样品的颜色没有发生明显变化，且通过拉力仪测试得知经上述熏蒸处理后的文物样品的强度也没有发生明显变化。
实施例6：文物熏蒸实验
文物材质：皮革和骨制品
病害：毛壳霉和木霉等
熏蒸剂：熏蒸剂H
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸24小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上已没有任何霉菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
霉菌生长情况 无任何霉菌 无任何霉菌 无任何霉菌 无任何霉菌
另外，通过色差仪观察经上述熏蒸处理后的文物样品的颜色没有发生明显变化，且通过扫描电镜观察发现经上述熏蒸处理后的皮革和骨制品的纤维组织排列也没有发生明显变化。
实施例7-1：文物熏蒸实验
文物材质：麻织品
病害：金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂B
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸30小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上已没有任何细菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行细菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
细菌生长情况 无任何细菌 无任何细菌 无任何细菌 无任何细菌
另外，通过色差仪观察经上述熏蒸处理后的文物样品的颜色没有发生明显变化，且通过拉力仪测试得知经上述熏蒸处理后的麻织品强度也没有发生明显变化。
实施例7-2：文物熏蒸实验
文物材质：麻织品
病害：金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂B
熏蒸方法：
先将熏蒸剂负载在脱脂棉片上，再将其放入熏蒸盒内，设定熏蒸盒温度为45℃后立即将熏蒸盒与文物样品一起置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸8小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上已没有任何细菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品 上没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行细菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
细菌生长情况 无任何细菌 无任何细菌 无任何细菌 无任何细菌
另外，通过色差仪观察经上述熏蒸处理后的文物样品的颜色没有发生明显变化，且通过拉力仪测试得知经上述熏蒸处理后的麻织品强度也没有发生明显变化。
实施例7-3：文物熏蒸实验
文物材质：麻织品
病害：金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂B
熏蒸方法：
先将熏蒸剂负载在脱脂棉片上，再将其放入熏蒸盒内，设定熏蒸盒风力3级(强)后立即将熏蒸盒与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸10小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上已没有任何细菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
存放时间 0个月 1个月 3个月 6个月
细菌生长情况 无任何细菌 无任何细菌 无任何细菌 无任何细菌
另外，通过色差仪观察经上述熏蒸处理后的文物样品的颜色没有发生明显变化，且通过拉力仪测试得知经上述熏蒸处理后的麻织品强度也没有发生明显变化。
实施例8-1：文物熏蒸实验
文物材质：纸张、丝绸、麻布、竹木、皮革和骨制品等
病害：曲霉、青霉、木霉、金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂C
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸24小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上均已没有任何霉菌和细菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
Figure PCTCN2016087994-appb-000003
说明本发明方法可实现在同一熏蒸环境下对多种材质的文物和各种细菌霉菌进行一次性处理。
另外，通过色差仪观察经上述熏蒸处理后的文物样品的纸张、丝绸、麻布、竹木、皮革和骨制品等颜色均没有发生明显变化，通过拉力仪测试得知经上述熏蒸处理后的文物样品纸张、丝绸、麻布、竹木等强度也均没有发生明显变化，通过纸张耐折度仪测试得知经上述熏蒸处理后的文物样品的纸张耐折度也均没有发生明显变化，且通过扫描电镜观察发现经上述熏蒸处理后的皮革和骨制品的纤维组织排列也没有发生明显变化。
实施例8-2：文物熏蒸实验
文物材质：纸张、丝绸、麻布、竹木、皮革和骨制品等
病害：曲霉、青霉、木霉、金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂A
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸24小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上均已没有任何霉菌和细菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上均没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
Figure PCTCN2016087994-appb-000004
实施例8-3：文物熏蒸实验
文物材质：纸张、丝绸、麻布、竹木、皮革和骨制品等
病害：曲霉、青霉、木霉、金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂B
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸24小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上均已没有任何霉菌和细菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上均没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
Figure PCTCN2016087994-appb-000005
实施例8-4：文物熏蒸实验
文物材质：纸张、丝绸、麻布、竹木、皮革和骨制品等
病害：曲霉、青霉、木霉、金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂D
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸24小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上均已没有任何霉菌和细菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上均没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
Figure PCTCN2016087994-appb-000006
实施例8-5：文物熏蒸实验
文物材质：纸张、丝绸、麻布、竹木、皮革和骨制品等
病害：曲霉、青霉、木霉、金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂E
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸24小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上均已没有任何霉菌和细菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上均没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
Figure PCTCN2016087994-appb-000007
实施例8-6：文物熏蒸实验
文物材质：纸张、丝绸、麻布、竹木、皮革和骨制品等
病害：曲霉、青霉、木霉、金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂F
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸24小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上均已没有任何霉菌和细菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上均没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
Figure PCTCN2016087994-appb-000008
实施例8-7：文物熏蒸实验
文物材质：纸张、丝绸、麻布、竹木、皮革和骨制品等
病害：曲霉、青霉、木霉、金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂G
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸24小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上均已没有任何霉菌和细菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上均没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
Figure PCTCN2016087994-appb-000009
实施例8-8：文物熏蒸实验
文物材质：纸张、丝绸、麻布、竹木、皮革和骨制品等
病害：曲霉、青霉、木霉、金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂H
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行 熏蒸24小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上均已没有任何霉菌和细菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上均没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
Figure PCTCN2016087994-appb-000010
实施例8-9：文物熏蒸实验
文物材质：纸张、丝绸、麻布、竹木、皮革和骨制品等
病害：曲霉、青霉、木霉、金黄色葡萄球菌、大肠杆菌、巨大芽孢杆菌、枯草杆菌和荧光假单孢杆菌等
熏蒸剂：熏蒸剂I
熏蒸方法：
将熏蒸剂与文物样品置入熏蒸箱中，封闭熏蒸箱，控制熏蒸箱内的温度为25℃，进行熏蒸24小时后，减压抽气2小时，打开熏蒸箱，移出文物样品；
由显微镜检测得知：经上述熏蒸处理后的文物样品上均已没有任何霉菌和细菌生长；
并由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述熏蒸处理后的文物样品上均没有熏蒸剂残留；
将经过本实施例熏蒸处理后的文物样品放置在文物馆藏室，定期进行霉菌跟踪检测，检测结果见下表所示：
Figure PCTCN2016087994-appb-000011
最后有必要在此说明的是，以上所述仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。

Claims (10)

  1. 一种文物熏蒸方法，其特征在于，包括如下操作：将熏蒸剂与文物放入熏蒸箱内，在25～45℃下进行熏蒸1～36小时后，减压抽气1～3小时，打开熏蒸箱，移出文物；所述熏蒸剂为硫代亚磺酸酯类化合物与硫代磺酸酯类化合物的复配物。
  2. 根据权利要求1所述的文物熏蒸方法，其特征在于：将所述熏蒸剂负载在具有吸附作用的载体材料上。
  3. 根据权利要求2所述的文物熏蒸方法，其特征在于：将负载有熏蒸剂的载体材料放置在具有向外扩散的口或网孔面的中空装置中。
  4. 根据权利要求3所述的文物熏蒸方法，其特征在于：所述中空装置具有风扇和调速功能。
  5. 根据权利要求3或4所述的文物熏蒸方法，其特征在于：所述中空装置具有自加热和调温功能。
  6. 根据权利要求1或2所述的文物熏蒸方法，其特征在于：所述熏蒸剂是由硫代亚磺酸酯类化合物与硫代磺酸酯类化合物按体积比为1：1～1：5的复配物。
  7. 根据权利要求6所述的文物熏蒸方法，其特征在于：所述的硫代亚磺酸酯类化合物是具有如下结构通式：
    Figure PCTCN2016087994-appb-100001
    的化合物，其中：R1与R2相同或不同，且均选自C1-C4的烷烃基或C2-C4的烯烃基。
  8. 根据权利要求7所述的文物熏蒸方法，其特征在于：R1与R2相同。
  9. 根据权利要求6所述的文物熏蒸方法，其特征在于：所述的硫代磺酸酯类化合物是具有如下结构通式：
    Figure PCTCN2016087994-appb-100002
    的化合物，其中：R3与R4相同或不同，且均选自C1-C4的烷烃基或C2-C4的烯烃基。
  10. 根据权利要求9所述的文物熏蒸方法，其特征在于：R3与R4相同。
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