WO2017125038A1 - 一种用于防治文物虫霉的熏蒸方法 - Google Patents

一种用于防治文物虫霉的熏蒸方法 Download PDF

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Publication number
WO2017125038A1
WO2017125038A1 PCT/CN2017/071670 CN2017071670W WO2017125038A1 WO 2017125038 A1 WO2017125038 A1 WO 2017125038A1 CN 2017071670 W CN2017071670 W CN 2017071670W WO 2017125038 A1 WO2017125038 A1 WO 2017125038A1
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Prior art keywords
fumigation
group
substituted
fumigant
samples
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PCT/CN2017/071670
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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
Original Assignee
SHANGHAI MUSEUM
Shanghai Institute of Organic Chemistry of CAS
East China University of Science and Technology
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Publication of WO2017125038A1 publication Critical patent/WO2017125038A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/08—Sulfonic acid halides; alpha-Hydroxy-sulfonic acids; Amino-sulfonic acids; Thiosulfonic acids; Derivatives thereof
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Disinfection or sterilisation of materials or objects, in general; Accessories therefor
    • A61L2/16—Disinfection or sterilisation of materials or objects, in general; Accessories therefor using chemical substances
    • A61L2/20—Gaseous substances, e.g. vapours

Definitions

  • the invention relates to a fumigation method for controlling cultural relics, and belongs to the technical field of cultural relic 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.
  • an object of the present invention is to provide a green, environmentally safe, safe and effective fumigation method for controlling and controlling the insects.
  • the invention relates to a fumigation method for controlling a cultural and worm, which comprises the following steps: putting a fumigant and a cultural relic into a fumigation box, fumigation at 25 to 45 ° C for 1 to 36 hours, and then evacuating for 1 to 3 hours under vacuum.
  • the fumigant has the general formula I: Or Formula II: A compound of the chemical structure shown, wherein, in the formula I: X is a halogen or a hydroxyl group; Y 1 and Y 2 are each independently selected from H or F; and R 1 is an R 1 -substituted C 1 -C 10 alkane group, R 3 substituted C 2 -C 10 alkene group, R 3 substituted phenyl group, R 3 substituted benzyl group, R 3 substituted C 3 -C 8 cycloalkyl group, R 3 substituted C 3 -C 8 cycloalkene a group or a R 3 substituted adamantyl group; the R 3 is selected from at least one of hydrogen, a hydroxyl group, a halogen, a C 1 -C 3 alkane group, and a C 2 -C 3 alkene group; in the formula II: X is a halogen
  • X is F, Cl, Br or OH; Y 1 and Y 2 are both F or Y 1 , and Y 2 is F; R 1 is R 3 substituted C 1 -C 10 alkane group, R 3 -substituted C 2 -C 10 alkene group, R 3 -substituted phenyl group, R 3 -substituted benzyl group, R 3 -substituted C 3 -C 6 cycloalkyl group, R 3 -substituted C a 3 -C 6 cycloalkenyl group or an R 3 -substituted adamantyl group; the R 3 being selected from at least one of hydrogen, hydroxy, fluorine, chlorine, bromine, methyl, ethyl, isopropyl, allyl .
  • X is F or Cl; Y 1 and Y 2 are both F; R 1 is a R 3 -substituted C 1 -C 4 alkane group, and R 3 -substituted C 2 -C a olefin group, an R 3 -substituted phenyl group or an R 3 -substituted C 3 -C 6 cycloalkyl group; and the R 3 is at least one selected from the group consisting of hydrogen, a hydroxyl group, fluorine, and chlorine.
  • X is F; Y 1 and Y 2 are both F; R 1 is a C 1 -C 4 alkane group, a C 2 -C 4 alkene group, a phenyl group or a C 3 group ; -C 7 cycloalkyl (ie: R 3 is hydrogen).
  • X is F, Cl, Br or OH
  • R 2 is a R 3 -substituted C 1 -C 4 alkane group, an R 3 -substituted C 2 -C 4 alkene group, R 3 Substituted phenyl, R 3 substituted benzyl, R 3 substituted C 3 -C 7 cycloalkyl, R 3 substituted C 3 -C 7 cycloalkenyl or R 3 substituted adamantyl; said R 3 It is at least one selected from the group consisting of hydrogen, hydroxyl, fluorine, chlorine, bromine, methyl, ethyl, isopropyl, and allyl.
  • X is F or Cl
  • R 2 is a R 3 -substituted C 1 -C 4 alkane group, an R 3 -substituted C 2 -C 4 alkene group, and an R 3 -substituted C a 3- C 7 cycloalkyl group or an R 3 -substituted phenyl group
  • the R 3 is at least one selected from the group consisting of hydrogen, a hydroxyl group, fluorine, and chlorine.
  • X is F
  • R 2 is a C 1 -C 4 alkane group, a C 2 -C 4 alkene group or a phenyl group (ie, R 3 is hydrogen).
  • fumigants of the present invention include, but are not limited to, compounds having the following chemical structural formula:
  • fumigant 1 (abbreviated as fumigant 2), (abbreviated as fumigant 3), (abbreviated as fumigant 4), (abbreviated as fumigant 5), (abbreviated as fumigant 6), (abbreviated as fumigant 7), (abbreviated as fumigant 8), (abbreviated as fumigant 9), (abbreviated as fumigant 10), (abbreviated as fumigant 11), (abbreviated as fumigant 12), (abbreviated as fumigant 13), (abbreviated as fumigant 14), (abbreviated as fumigant 15), (abbreviated as fumigant 16), (abbreviated as fumigant 17), (abbreviated as fumigant 18), (abbreviated as fumigant 19), (abbreviated as fumigant 20), (abbreviated as fumigant 21), (abbreviated as fumigant 22), (abbreviated as fumigant 23); (abbreviated as fumigan
  • the fumigant is supported on a carrier material having an adsorption effect, and the carrier material package
  • a carrier material having an adsorption effect
  • the carrier material package includes, but is not limited to, filter paper, silica gel, filter, cotton, sponge or cloth.
  • the carrier material loaded with the fumigant is placed in a hollow device having an outwardly diffusing port or mesh face, including but not limited to a box structure, a box structure, a cage structure or Bags, etc.
  • the hollow device has a fan and a speed control function.
  • the hollow device has a self-heating and temperature regulating function.
  • the present invention has the following beneficial effects:
  • the invention not only realizes the safe and effective prevention and control of common insecticidal diseases of the cultural relics, but also has the lowest environmental pollution, no fumigant residue problem, and does not affect the cultural relic material and the human body. It has the advantages of being green and environmentally friendly; in particular, the present invention can realize the one-time treatment of various materials and various cultural relics, bacteria and pests in the same fumigation environment, and the flocked products after the fumigation treatment of the present invention, It can be placed in the cultural relics collection environment for at least half a year without regenerating mold, bacteria and pests. In addition, the method of the invention has the advantages of simple operation, low cost, suitable materials and wide range of molds, bacteria and pests, and the safety of cultural relics. Long-term preservation is of great value and far-reaching significance.
  • the fumigant and the cultural relics sample were placed in a fumigation box, the fumigation box was closed, the temperature in the fumigation box was controlled at 25 ° C, fumigation was carried out for 36 hours, and 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 and bacteria are regularly followed for detection.
  • the test results are shown in the following table:
  • the invention can realize one-time treatment of various materials and various molds and bacteria in the same fumigation environment.
  • Example 3-1 Culture relics fumigation experiment
  • the fumigant and the cultural relics sample were placed in a fumigation box, the fumigation box was closed, the temperature in the fumigation box was controlled at 25 ° C, fumigation was carried out for 24 hours, and the pressure was evacuated for 2 hours, and the fumigation box was opened to 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 and bacteria are regularly followed for detection.
  • the test results are shown in the following table:
  • the invention can realize one-time treatment of various materials and various molds and bacteria in the same fumigation environment.
  • the fumigant is loaded on the filter paper, and then placed in the fumigation box.
  • the fumigation box After setting the fumigation box temperature to 35 ° C, 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, and after fumigation for 18 hours, the air was evacuated for 2 hours, and the fumigation box was opened to 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 and bacteria are regularly tracked and detected.
  • the test results are shown in the table below:
  • the invention can realize one-time treatment of various materials and various molds and bacteria in the same fumigation environment.
  • 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 was 25 ° C, and after fumigation for 16 hours, the pressure was evacuated for 2 hours, and the fumigation box was opened to 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 and bacteria are regularly followed for detection.
  • the test results are shown in the following table:
  • the invention can realize one-time treatment of various materials and various molds and bacteria in the same fumigation environment.
  • 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 and bacteria are regularly followed for detection.
  • the test results are shown in the following table:
  • the invention can realize one-time treatment of various materials and various molds and bacteria in the same fumigation environment.
  • the color samples were observed through the above-mentioned fumigation treatment, and the color was slightly yellowed.
  • the strength of the samples subjected to the above fumigation treatment was slightly deteriorated by the tensile test; According to the test of the temperament, the folding resistance of the paper samples subjected to the above fumigation treatment was slightly deteriorated; and the distribution of the fibrous tissue of the leather and bone products samples after the above fumigation treatment was slightly observed by scanning electron microscopy. change.
  • the fumigant and the cultural relic sample were placed in a fumigation box, the fumigation box was closed, the temperature in the fumigation box was controlled at 45 ° C, and after fumigation for 1 hour, 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 and bacteria are regularly followed for detection.
  • the test results are shown in the following table:
  • the invention can realize one-time treatment of various materials and various molds and bacteria in the same fumigation environment.
  • Fumigant fumigant 27 ( CAS No.: 260417-57-0)
  • the fumigant and the cultural relic sample were placed in a fumigation box, the fumigation box was closed, the temperature in the fumigation box was controlled at 30 ° C, and after fumigation for 4 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 and bacteria are regularly followed for detection.
  • the test results are shown in the following table:
  • the invention can realize one-time treatment of various materials and various molds and bacteria in the same fumigation environment.
  • Fumigant 12 ( CAS number: 1397690-78-6);
  • the invention adopts any one of the above-mentioned fumigant fumigation treatments to realize one-time treatment of various materials and various molds and bacteria in the same fumigation environment.
  • Fumigant fumigant 9 ( CAS No.: 113591-64-3)
  • 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, and after fumigation for 8 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 and bacteria are regularly followed for detection.
  • the test results are shown in the following table:
  • the invention can realize one-time treatment of various materials and various molds and bacteria in the same fumigation environment.
  • 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 and bacteria are regularly followed for detection.
  • the test results are shown in the following table:
  • the invention can realize one-time treatment of various materials and various molds and bacteria in the same fumigation environment.
  • the fumigant and the cultural relic sample are placed in the fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled to 25 ° C, and after fumigation for a certain time, the vacuum is evacuated for 2 hours, the fumigation box is opened, and the cultural relic samples are removed.
  • the pest mortality was monitored and the detailed results are shown in the following table:
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the growth of the pests is regularly tracked.
  • the invention can realize the one-time treatment of various materials and various pests in the same fumigation environment.
  • the fumigant is loaded on the filter paper, and then placed in the fumigation box. After setting the fumigation box temperature to 35 ° C, 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. Smoked at 25 ° C After steaming for a certain period of time, evacuate under reduced pressure for 2 hours, open the fumigation box, remove the cultural relic samples, and monitor the death of the pests. The detailed results are shown in the following table:
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the growth of the pests is regularly tracked.
  • the invention can realize the one-time treatment of various materials and various pests in the same fumigation environment.
  • 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 a certain period of time, vacuuming for 2 hours, opening the fumigation box, removing the cultural relic samples, monitoring the death of the pests, the detailed results are shown in the following table:
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the growth of the pests is regularly tracked.
  • the invention can realize the one-time treatment of various materials and various pests in the same fumigation environment.
  • the fumigant and the cultural relics sample are placed in the fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled to be 35 ° C, and after fumigation for a certain time, the vacuum is evacuated for 2 hours, the fumigation box is opened, and the cultural relic samples are removed.
  • the pest mortality was monitored and the detailed results are shown in the following table:
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the growth of the pests is regularly tracked.
  • the invention can realize the one-time treatment of various materials and various pests in the same fumigation environment.
  • the color samples were observed through the above-mentioned fumigation treatment, and the color was slightly yellowed.
  • the strength of the samples subjected to the above fumigation treatment was slightly deteriorated by the tensile test; According to the test of the temperament, the folding resistance of the paper samples subjected to the above fumigation treatment was slightly deteriorated; and the distribution of the fibrous tissue of the leather and bone products samples after the above fumigation treatment was slightly observed by scanning electron microscopy. change.
  • Fumigant fumigant 7 ( CAS No.: 120801-74-3)
  • the fumigant and the cultural relics sample are placed in the fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled at 45 ° C, and after fumigation for a certain time, the vacuum is evacuated for 2 hours, the fumigation box is opened, and the cultural relic samples are removed.
  • the pest mortality was monitored and the detailed results are shown in the following table:
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the growth of the pests is regularly tracked.
  • the test results are shown in the following table:
  • the invention can realize the one-time treatment of various materials and various pests in the same fumigation environment.
  • Fumigant fumigant 5 ( CAS No.: 120801-74-3)
  • the fumigant and the cultural relic sample are placed in the fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled to 30 ° C, and after fumigation for a certain time, the vacuum is evacuated for 2 hours, the fumigation box is opened, and the cultural relic sample is removed.
  • the pest mortality was monitored and the detailed results are shown in the following table:
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the growth of the pests is regularly tracked.
  • the test results are shown in the table below:
  • the invention can realize the one-time treatment of various materials and various pests in the same fumigation environment.
  • 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 is 25 ° C, after fumigation for a certain period of time, vacuuming for 2 hours, opening the fumigation box, removing the cultural relic samples, monitoring the death of the pests, the detailed results are shown in the following table:
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the growth of the pests is regularly tracked.
  • the test results are shown in the following table:
  • the invention can realize the one-time treatment of various materials and various pests in the same fumigation environment.
  • Fumigant fumigant 42 ( CAS No.: 76876-59-0)
  • 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 is 25 ° C, after fumigation for a certain period of time, vacuuming for 2 hours, opening the fumigation box, removing the cultural relic samples, monitoring the death of the pests, the detailed results are shown in the following table:
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the growth of the pests is regularly tracked.
  • the test results are shown in the following table:
  • the invention can realize the one-time treatment of various materials and various pests in the same fumigation environment.
  • Fumigant fumigant 12 ( CAS No.: 1397690-78-6)
  • the fumigant and the cultural relic sample are placed in the fumigation box, the fumigation box is closed, the temperature in the fumigation box is controlled to 25 ° C, and after fumigation for a certain time, the vacuum is evacuated for 2 hours, the fumigation box is opened, and the cultural relic samples are removed.
  • the pest mortality was monitored and the detailed results are shown in the following table:
  • the samples of the cultural relics subjected to the fumigation treatment in this embodiment are placed in the cultural relics collection room, and the growth of the pests is regularly tracked.
  • the test results are shown in the following table:
  • the invention can realize the one-time treatment of various materials and various pests in the same fumigation environment.
  • the fumigation box Place one of the fumigants 2, 3, 4, 6, 8, 13, 14, 16, 17, 18, 19, 20, 21, 22, 23, 24, 26, 45 with the artifact sample in the fumigation box In the middle, the fumigation box is closed, and the temperature in the fumigation box is controlled at 25 ° C. After fumigation for a certain period of time, the air is depressurized for 2 hours, the fumigation box is opened, the cultural relic samples are removed, and the death of the pests is monitored, and the following monitoring is obtained. result:
  • the invention adopts any of the above-mentioned fumigant fumigation treatments to realize one-time treatment of various materials and various pests, mildews and bacteria in the same fumigation environment.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plant Pathology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Insects & Arthropods (AREA)
  • Toxicology (AREA)
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Abstract

本发明公开了一种用于防治文物虫霉的熏蒸方法，其包括如下操作：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；所述熏蒸剂是具有通式I或者通式II所示化学结构的化合物。本发明不仅实现了对文物常见虫霉病害的安全有效防治，而且对环境的污染最低，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文物霉、菌、害虫进行一次性处理，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霉、菌、害虫；另外，本发明方法还具有操作简单，成本低，适用的材质和霉、菌、害虫范围广等优点。

Description

一种用于防治文物虫霉的熏蒸方法 技术领域
本发明是涉及一种用于防治文物虫霉的熏蒸方法，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、安全有效的用于防治文物虫霉的熏蒸方法。
为实现上述发明目的，本发明采用如下技术方案：
一种用于防治文物虫霉的熏蒸方法，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；所述熏蒸剂是具有通式I：
Figure PCTCN2017071670-appb-000001
或者通式II：
Figure PCTCN2017071670-appb-000002
所示化学结构的化合物，其中，所述通式I中：X为卤素或羟基；Y1和Y2各自独立选自H或F；R1为R3取代的C1-C10烷烃基、R3取代的C2-C10烯烃基、R3取代的苯基、R3取代的苄基、R3取代的C3-C8环烷基、R3取代的C3-C8环烯烃基或R3取代的金刚烷基；所述R3选自氢、羟基、卤素、C1-C3烷烃基、C2-C3烯烃基中的至少一种；所述通式II中：X为卤素或羟基；R2为R3取代的C1-C4烷烃基、R3取代的C2-C4烯烃基、R3取代的苯基、R3取代的苄基、R3取代的C3-C8环烷基、R3取代的C3-C8环烯烃基或R3取代的金刚烷基；所述R3选自氢、羟基、卤素、C1-C3烷烃基、C2-C3烯烃基中的至少一种。
作为优选方案，所述通式I中：X为F、Cl、Br或OH；Y1和Y2同时为F或Y1、Y2其中之一为F；R1为R3取代的C1-C10烷烃基、R3取代的C2-C10烯烃基、R3取代的苯基、R3取代的苄基、R3取代的C3-C6环烷基、R3取代的C3-C6环烯烃基或R3取代的金刚烷基；所述R3选自氢、羟基、氟、氯、溴、甲基、乙基、异丙基、烯丙基中的至少一种。
作为进一步优选方案，所述通式I中：X为F或Cl；Y1和Y2同时为F；R1为R3取代的C1-C4烷烃基、R3取代的C2-C4烯烃基、R3取代的苯基或R3取代的C3-C6环烷基；所述R3选自氢、羟基、氟、氯中的至少一种。
作为更进一步优选方案，所述通式I中：X为F；Y1和Y2同时为F；R1为C1-C4烷烃基、C2-C4烯烃基、苯基或C3-C7环烷基(即：R3为氢)。
作为优选方案，所述通式II中：X为F、Cl、Br或OH；R2为R3取代的C1-C4烷烃基、R3取代的C2-C4烯烃基、R3取代的苯基、R3取代的苄基、R3取代的C3-C7环烷基、R3取代的C3-C7环烯烃基或R3取代的金刚烷基；所述R3选自氢、羟基、氟、氯、溴、甲基、乙基、异丙基、烯丙基中的至少一种。
作为进一步优选方案，所述通式II中：X为F或Cl；R2为R3取代的C1-C4烷烃基、R3取代的C2-C4烯烃基、R3取代的C3-C7环烷基或R3取代的苯基；所述R3选自氢、羟基、氟、氯中的至少一种。
作为更进一步优选方案，所述通式II中：X为F；R2为C1-C4烷烃基、C2-C4烯烃基或苯基(即：R3为氢)。
具体说，本发明的熏蒸剂包括但不限于具有下述化学结构式的化合物：
Figure PCTCN2017071670-appb-000003
(简记为熏蒸剂1)、
Figure PCTCN2017071670-appb-000004
(简记为熏蒸剂2)、
Figure PCTCN2017071670-appb-000005
(简记为熏蒸剂3)、
Figure PCTCN2017071670-appb-000006
(简记为熏蒸剂4)、
Figure PCTCN2017071670-appb-000007
(简记为熏蒸剂5)、
Figure PCTCN2017071670-appb-000008
(简记为熏蒸剂6)、
Figure PCTCN2017071670-appb-000009
(简记为熏蒸剂7)、
Figure PCTCN2017071670-appb-000010
(简记为熏蒸剂8)、
Figure PCTCN2017071670-appb-000011
(简记为熏蒸剂9)、
Figure PCTCN2017071670-appb-000012
(简记为熏蒸剂10)、
Figure PCTCN2017071670-appb-000013
(简记为熏蒸剂11)、
Figure PCTCN2017071670-appb-000014
(简记为熏蒸剂12)、
Figure PCTCN2017071670-appb-000015
(简记为熏蒸剂13)、
Figure PCTCN2017071670-appb-000016
(简记为熏蒸剂14)、
Figure PCTCN2017071670-appb-000017
(简记为熏蒸剂15)、
Figure PCTCN2017071670-appb-000018
(简记为熏蒸剂16)、
Figure PCTCN2017071670-appb-000019
(简记为熏蒸剂17)、
Figure PCTCN2017071670-appb-000020
(简记为熏蒸剂18)、
Figure PCTCN2017071670-appb-000021
(简记为熏蒸剂19)、
Figure PCTCN2017071670-appb-000022
(简记为熏蒸剂20)、
Figure PCTCN2017071670-appb-000023
(简记为熏蒸剂21)、
Figure PCTCN2017071670-appb-000024
(简记为熏蒸剂22)、
Figure PCTCN2017071670-appb-000025
(简记为熏蒸剂23)；
Figure PCTCN2017071670-appb-000026
(简记为熏蒸剂24)、
Figure PCTCN2017071670-appb-000027
(简记为熏蒸剂25)、
Figure PCTCN2017071670-appb-000028
(简记为熏蒸剂26)、
Figure PCTCN2017071670-appb-000029
(简记为熏蒸剂27)、
Figure PCTCN2017071670-appb-000030
(简记为熏蒸剂28)、
Figure PCTCN2017071670-appb-000031
(简记为熏蒸剂29)、
Figure PCTCN2017071670-appb-000032
(简记为熏蒸剂30)、
Figure PCTCN2017071670-appb-000033
(简记为熏蒸剂31)、
Figure PCTCN2017071670-appb-000034
(简记为熏蒸剂32)、
Figure PCTCN2017071670-appb-000035
(简记为熏蒸剂33)、
Figure PCTCN2017071670-appb-000036
(简记为熏蒸剂33)、
Figure PCTCN2017071670-appb-000037
(简记为熏蒸剂35)、
Figure PCTCN2017071670-appb-000038
(简记为熏蒸剂36)、
Figure PCTCN2017071670-appb-000039
(简记为熏蒸剂37)、
Figure PCTCN2017071670-appb-000040
(简记为熏蒸剂38)、
Figure PCTCN2017071670-appb-000041
(简记为熏蒸剂39)、
Figure PCTCN2017071670-appb-000042
(简记为熏蒸剂40)、
Figure PCTCN2017071670-appb-000043
(简记为熏蒸剂41)、
Figure PCTCN2017071670-appb-000044
(简记为熏蒸剂42)、
Figure PCTCN2017071670-appb-000045
(简记为熏蒸剂43)、
Figure PCTCN2017071670-appb-000046
(简记为熏蒸剂44)、
Figure PCTCN2017071670-appb-000047
(简记为熏蒸剂45)、
Figure PCTCN2017071670-appb-000048
(简记为熏蒸剂46)、
Figure PCTCN2017071670-appb-000049
(简记为熏蒸剂47)、
Figure PCTCN2017071670-appb-000050
(简记为熏蒸剂48)、
Figure PCTCN2017071670-appb-000051
(简记为熏蒸剂49)、
Figure PCTCN2017071670-appb-000052
(简记为熏蒸剂50)、
Figure PCTCN2017071670-appb-000053
(简记为熏蒸剂51)、
Figure PCTCN2017071670-appb-000054
(简记为熏蒸剂52)、
Figure PCTCN2017071670-appb-000055
(简记为熏蒸剂53)、
Figure PCTCN2017071670-appb-000056
(简记为熏蒸剂54)。
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，所述的载体材料包 括但不限于滤纸、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，所述的中空装置包括但不限于箱式结构、盒式结构、笼式结构或袋子等。
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。
与现有技术相比，本发明具有如下有益效果：
本发明通过选用具有通式I或II结构的化合物作为熏蒸剂，不仅实现了对文物常见虫霉病害的安全有效防治，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文物霉、菌以及害虫进行一次性处理，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霉、菌和害虫；另外，本发明方法还具有操作简单，成本低，适用的材质和霉、菌、害虫范围广等优点，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、熏蒸剂15(2,2-二氟-2-(磺酰氟基)乙酸环丙酯)的制备：
Figure PCTCN2017071670-appb-000057
取环丙醇(58mg)加入二氯甲烷(10mL)，在冰水浴冷却下滴加全氟磺酸酯(1mL)，滴毕，自然升至室温，反应完全后，加水淬灭反应，用二氯甲烷萃取(100mL×2)，水洗(10mL×2)，饱和食盐水洗(10mL×2)，无水硫酸钠干燥，加压蒸除溶剂，得到粗品熏蒸剂15(2,2-二氟-2-(磺酰氟基)乙酸环丙酯)，摩尔收率90％；1HNMR(CDCl3)δ(ppm)2.70(m,1H),0.60(m,2H),0.35(m,2H).LR-ESI:[M+H]+218.99.
2、熏蒸剂16、17、18、19、20、21、22、23的制备：
参照1中熏蒸剂15的制备方法，分别将环丁醇、环戊醇、薄荷醇、异胡薄荷醇、二氢香芹醇、香芹醇、香茅醇、柠檬醇与全氟磺酸酯进行反应，从而可制得相对应的熏蒸剂：
Figure PCTCN2017071670-appb-000058
1HNMR(CDCl3)δ(ppm)4.23(m,1H),2.30(m,2H),1.91-2.08(m,4H).LR-ESI:[M+H]+233.0；
Figure PCTCN2017071670-appb-000059
1HNMR(CDCl3)δ(ppm)4.12(m,1H),1.92(m,2H),1.46-1.63(m,6H).LR-ESI:[M+H]+247.02；
Figure PCTCN2017071670-appb-000060
1HNMR(CDCl3)δ(ppm)4.03(m,1H),1.85-1.98(m,2H),1.50-1.62(m,5H),1.20-1.29(m,2H),0.97(d,J＝5.6Hz,3H),0.89(d,J＝6.0Hz,6H).LR-ESI:[M+H]+317.10；
Figure PCTCN2017071670-appb-000061
1HNMR(CDCl3)δ(ppm)5.10(s,1H),4.90(s,1H),4.04(m,1H),2.65(m,1H),1.90(s,3H),1.55-1.69(m,5H),1.25-1.35(m,2H),0.95(d,J＝5.6Hz,3H).LR-ESI:[M]+314.08；
Figure PCTCN2017071670-appb-000062
1HNMR(CDCl3)δ(ppm)5.11(s,1H),4.87(s,1H),4.08(m,1H),2.20(m,1H),2.10(m,1H),1.88(s,3H),1.56-1.72(m,4H),1.22-1.34(m,2H),0.94(d,J＝5.6Hz,3H).LR-ESI:[M]+314.08；
Figure PCTCN2017071670-appb-000063
1HNMR(CDCl3)δ(ppm)5.32(m,1H),5.15(s,1H),4.93(s,1H),4.32(m,1H),2.30(m,1H),1.75-1.90(m,4H),1.86(s,3H),1.82(s,3H).LR-ESI:[M+1]+313.06；
Figure PCTCN2017071670-appb-000064
1HNMR(CDCl3)δ(ppm)5.22(s,1H),4.07(m,2H),2.01(m,2H),1.85(s,3H),1.73(s,3H),1.50-1.61(m,5H),0.98(d,J＝6.0Hz,3H).LR-ESI:[M+1]+ 317.10；
Figure PCTCN2017071670-appb-000065
1HNMR(CDCl3)δ(ppm)5.38(m,1H),5.22(m,1H),4.45(m,2H),2.10(m,2H),2.04(m,2H),1.90(s,3H),1.88(s,3H),1.80(s,3H).LR-ESI:[M+1]+315.08。
3、其余熏蒸剂的制备：
由于其余熏蒸剂均是已知化合物，均可按照各自公开的制备方法制备得到。
实施例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24(
Figure PCTCN2017071670-appb-000066
CAS号：677-25-8)
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；由气相色谱与质谱联用仪检测分析得知：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
说明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，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例3-1：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24(
Figure PCTCN2017071670-appb-000067
CAS号：677-25-8)
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；由气相色谱与质谱联用仪检测分析得知：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
说明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，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例3-2：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24(
Figure PCTCN2017071670-appb-000068
CAS号：677-25-8)
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；由气相色谱与质谱联用仪检测分析得知：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
说明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，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例3-3：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24(
Figure PCTCN2017071670-appb-000069
CAS号：677-25-8)
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；由气相色谱与质谱联用仪检测分析得知：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
说明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，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例3-4：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24(
Figure PCTCN2017071670-appb-000070
CAS号：677-25-8)
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；由气相色谱与质谱联用仪检测分析得知：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
说明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，发现颜色均有略微变黄；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均有略微变差；通过纸张耐折度仪测试得知，经上述熏蒸处理后的纸张文物样品的耐折度均也略微变差；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文物样品的纤维组织排列发生略微改变。
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：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25(
Figure PCTCN2017071670-appb-000071
CAS号：754-03-0)
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；由气相色谱与质谱联用仪检测分析得知：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
说明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，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例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27(
Figure PCTCN2017071670-appb-000072
CAS号：260417-57-0)
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；由气相色谱与质谱联用仪检测分析得知：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
说明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，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例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1(
Figure PCTCN2017071670-appb-000073
CAS号：680-15-9)；
熏蒸剂10(
Figure PCTCN2017071670-appb-000074
CAS号：CAS:309-21-7)；
熏蒸剂12(
Figure PCTCN2017071670-appb-000075
CAS号：1397690-78-6)；
将熏蒸剂1、10、12中的任意一种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：经上述任意一种熏蒸剂熏蒸处理后的文物样品上，均已没有任何霉、菌生长；由气相色谱与质谱联用仪检测分析得知：经上述任意一种熏蒸剂熏蒸处理后的文物样品上均没有熏蒸剂残留。
将经过本实施例上述任意一种熏蒸剂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，均具有如下检测结果：
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
说明本发明采用上述任意一种熏蒸剂熏蒸处理可实现在同一熏蒸环境下对多种材质的文物和各种霉、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，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例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9(
Figure PCTCN2017071670-appb-000076
CAS号：113591-64-3)
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霉、菌生长；由气相色谱与质谱联用仪检测分析得知：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
说明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，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例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15
Figure PCTCN2017071670-appb-000077
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霉、菌生长；由气相色谱与质谱联用仪检测分析得知：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
说明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，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例9-1：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：黑皮蠹、小圆皮蠹、衣鱼、袋衣蛾、烟草甲、书虱、蟑螂和白蚁等
熏蒸剂：熏蒸剂24(
Figure PCTCN2017071670-appb-000078
CAS号：677-25-8)
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℃，进行熏蒸一定时间后，减压抽气2小时，打开熏蒸箱，移出文物样品，对其中的害虫死亡情况进行监测，详细结果如下表所示：
Figure PCTCN2017071670-appb-000079
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，定期跟踪害虫生长情况，
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
害虫存活和生长情况 无任何害虫 无任何害虫 无任何害虫 无任何害虫
说明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害虫进行一次性处理。
另外，通过色差仪观察经上述熏蒸处理后的文物样品，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例9-2：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：黑皮蠹、小圆皮蠹、衣鱼、袋衣蛾、烟草甲、书虱、蟑螂和白蚁等
熏蒸剂：熏蒸剂24(
Figure PCTCN2017071670-appb-000080
CAS号：677-25-8)
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 蒸一定时间后，减压抽气2小时，打开熏蒸箱，移出文物样品，对其中的害虫死亡情况进行监测，详细结果如下表所示：
Figure PCTCN2017071670-appb-000081
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，定期跟踪害虫生长情况，
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
害虫存活和生长情况 无任何害虫 无任何害虫 无任何害虫 无任何害虫
说明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害虫进行一次性处理。
另外，通过色差仪观察经上述熏蒸处理后的文物样品，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例9-3：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：黑皮蠹、小圆皮蠹、衣鱼、袋衣蛾、烟草甲、书虱、蟑螂和白蚁等
熏蒸剂：熏蒸剂24(
Figure PCTCN2017071670-appb-000082
CAS号：677-25-8)
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℃，进行熏蒸一定时间后，减压抽气2小时，打开熏蒸箱，移出文物样品，对其中的害虫死亡情况进行监测，详细结果如下表所示：
Figure PCTCN2017071670-appb-000083
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，定期跟踪害虫生长情况，
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
害虫存活和生长情况 无任何害虫 无任何害虫 无任何害虫 无任何害虫
说明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害虫进行一次性处理。
另外，通过色差仪观察经上述熏蒸处理后的文物样品，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例9-4：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：黑皮蠹、小圆皮蠹、衣鱼、袋衣蛾、烟草甲、书虱、蟑螂和白蚁等
熏蒸剂：熏蒸剂24(
Figure PCTCN2017071670-appb-000084
CAS号：677-25-8)
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℃，进行熏蒸一定时间后，减压抽气2小时，打开熏蒸箱，移出文物样品，对其中的害虫死亡情况进行监测，详细结果如下表所示：
Figure PCTCN2017071670-appb-000085
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，定期跟踪害虫生长情况，
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
害虫存活和生长情况 无任何害虫 无任何害虫 无任何害虫 无任何害虫
说明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害虫进行一次性处理。
另外，通过色差仪观察经上述熏蒸处理后的文物样品，发现颜色均有略微变黄；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均有略微变差；通过纸张耐折度仪测试得知，经上述熏蒸处理后的纸张文物样品的耐折度均也略微变差；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文物样品的纤维组织排列发生略微改变。
通过比较实施例9-1和9-2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9-1和9-3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9-1和9-4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的颜色及其它性能产生一定的影响。
实施例10：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：黑皮蠹、小圆皮蠹、衣鱼、袋衣蛾、烟草甲、书虱、蟑螂和白蚁等
熏蒸剂：熏蒸剂7(
Figure PCTCN2017071670-appb-000086
CAS号：120801-74-3)
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℃，进行熏蒸一定时间后，减压抽气2小时，打开熏蒸箱，移出文物样品，对其中的害虫死亡情况进行监测，详细结果如下表所示：
Figure PCTCN2017071670-appb-000087
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，定期跟踪害虫生长情况，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
害虫存活和生长情况 无任何害虫 无任何害虫 无任何害虫 无任何害虫
说明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害虫进行一次性处理。
另外，通过色差仪观察经上述熏蒸处理后的文物样品，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例11：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：黑皮蠹、小圆皮蠹、衣鱼、袋衣蛾、烟草甲、书虱、蟑螂和白蚁等
熏蒸剂：熏蒸剂5(
Figure PCTCN2017071670-appb-000088
CAS号：120801-74-3)
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℃，进行熏蒸一定时间后，减压抽气2小时，打开熏蒸箱，移出文物样品，对其中的害虫死亡情况进行监测，详细结果如下表所示：
Figure PCTCN2017071670-appb-000089
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，定期跟踪害虫生长情况， 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
害虫存活和生长情况 无任何害虫 无任何害虫 无任何害虫 无任何害虫
说明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害虫进行一次性处理。
另外，通过色差仪观察经上述熏蒸处理后的文物样品，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例12：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：黑皮蠹、小圆皮蠹、衣鱼、袋衣蛾、烟草甲、书虱、蟑螂和白蚁等
熏蒸剂：熏蒸剂43(
Figure PCTCN2017071670-appb-000090
CAS号：139631-62-2)
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℃，进行熏蒸一定时间后，减压抽气2小时，打开熏蒸箱，移出文物样品，对其中的害虫死亡情况进行监测，详细结果如下表所示：
Figure PCTCN2017071670-appb-000091
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，定期跟踪害虫生长情况，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
害虫存活和生长情况 无任何害虫 无任何害虫 无任何害虫 无任何害虫
说明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害虫进行一次性处理。
另外，通过色差仪观察经上述熏蒸处理后的文物样品，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例13：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：黑皮蠹、小圆皮蠹、衣鱼、袋衣蛾、烟草甲、书虱、蟑螂和白蚁等
熏蒸剂：熏蒸剂42(
Figure PCTCN2017071670-appb-000092
CAS号：76876-59-0)
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℃，进行熏蒸一定时间后，减压抽气2小时，打开熏蒸箱，移出文物样品，对其中的害虫死亡情况进行监测，详细结果如下表所示：
Figure PCTCN2017071670-appb-000093
Figure PCTCN2017071670-appb-000094
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，定期跟踪害虫生长情况，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
害虫存活和生长情况 无任何害虫 无任何害虫 无任何害虫 无任何害虫
说明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害虫进行一次性处理。
另外，通过色差仪观察经上述熏蒸处理后的文物样品，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例14：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：黑皮蠹、小圆皮蠹、衣鱼、袋衣蛾、烟草甲、书虱、蟑螂和白蚁等
熏蒸剂：熏蒸剂12(
Figure PCTCN2017071670-appb-000095
CAS号：1397690-78-6)
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℃，进行熏蒸一定时间后，减压抽气2小时，打开熏蒸箱，移出文物样品，对其中的害虫死亡情况进行监测，详细结果如下表所示：
Figure PCTCN2017071670-appb-000096
Figure PCTCN2017071670-appb-000097
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，定期跟踪害虫生长情况，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
害虫存活和生长情况 无任何害虫 无任何害虫 无任何害虫 无任何害虫
说明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害虫进行一次性处理。
另外，通过色差仪观察经上述熏蒸处理后的文物样品，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
实施例15：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、荧光假单孢杆菌、黑皮蠹、小圆皮蠹、衣鱼、袋衣蛾、烟草甲、书虱、蟑螂和白蚁等
熏蒸剂：
熏蒸剂2(
Figure PCTCN2017071670-appb-000098
CAS号：815-36-1)；
熏蒸剂3(
Figure PCTCN2017071670-appb-000099
CAS号：18225-68-8)；
熏蒸剂4(
Figure PCTCN2017071670-appb-000100
CAS号：756-21-8)；
熏蒸剂8(
Figure PCTCN2017071670-appb-000101
CAS号：2927-22-2)；
熏蒸剂13(
Figure PCTCN2017071670-appb-000102
CAS号：1536468-56-0)；
熏蒸剂14(
Figure PCTCN2017071670-appb-000103
CAS号：1536468-56-0)；
熏蒸剂16
Figure PCTCN2017071670-appb-000104
熏蒸剂17
Figure PCTCN2017071670-appb-000105
熏蒸剂18
Figure PCTCN2017071670-appb-000106
熏蒸剂19
Figure PCTCN2017071670-appb-000107
熏蒸剂20
Figure PCTCN2017071670-appb-000108
熏蒸剂21
Figure PCTCN2017071670-appb-000109
熏蒸剂22
Figure PCTCN2017071670-appb-000110
熏蒸剂23
Figure PCTCN2017071670-appb-000111
熏蒸剂24(
Figure PCTCN2017071670-appb-000112
CAS号：677-25-8)；
熏蒸剂26(
Figure PCTCN2017071670-appb-000113
CAS号：154264-08-1)；
熏蒸剂45(
Figure PCTCN2017071670-appb-000114
CAS号：2674-37-5)
将熏蒸剂2、3、4、6、8、13、14、16、17、18、19、20、21、22、23、24、26、45中的任意一种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℃，进行熏蒸一定时间后，减压抽气2小时，打开熏蒸箱，移出文物样品，对其中的害虫死亡情况进行监测，均得到如下监测结果：
Figure PCTCN2017071670-appb-000115
另外：由显微镜检测得知：经上述任意一种熏蒸剂熏蒸处理后的文物样品上均已没有任何霉、菌生长；由气相色谱与质谱联用仪(GC-Ms)检测分析得知：经上述任意一种熏蒸剂熏蒸处理后的文物样品上均没有熏蒸剂残留。
将经过本实施例上述任意一种熏蒸剂熏蒸处理后的文物样品放置在文物馆藏室，定期跟踪霉、菌、害虫生长情况，均得到如下检测结果：
存放时间 0个月 1个月 3个月 6个月
害虫存活和生长情况 无任何害虫 无任何害虫 无任何害虫 无任何害虫
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
说明本发明采用上述任意一种熏蒸剂熏蒸处理都可实现在同一熏蒸环境下对多种材质的文物和各种害虫及霉、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，发现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的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纸张文物样品的耐折度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文物样品的纤维组织排列也没有发生明显变化。
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. 一种用于防治文物虫霉的熏蒸方法，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；所述熏蒸剂是具有通式I：
    Figure PCTCN2017071670-appb-100001
    或者通式II：
    Figure PCTCN2017071670-appb-100002
    所示化学结构的化合物，其中，所述通式I中：X为卤素或羟基；Y1和Y2各自独立选自H或F；R1为R3取代的C1-C10烷烃基、R3取代的C2-C10烯烃基、R3取代的苯基、R3取代的苄基、R3取代的C3-C8环烷基、R3取代的C3-C8环烯烃基或R3取代的金刚烷基；所述R3选自氢、羟基、卤素、C1-C3烷烃基、C2-C3烯烃基中的至少一种；所述通式II中：X为卤素或羟基；R2为R3取代的C1-C4烷烃基、R3取代的C2-C4烯烃基、R3取代的苯基、R3取代的苄基、R3取代的C3-C8环烷基、R3取代的C3-C8环烯烃基或R3取代的金刚烷基；所述R3选自氢、羟基、卤素、C1-C3烷烃基、C2-C3烯烃基中的至少一种。
  2. 根据权利要求1所述的熏蒸方法，其特征在于，所述通式I中：X为F、Cl、Br或OH；Y1和Y2同时为F或Y1、Y2其中之一为F；R1为R3取代的C1-C10烷烃基、R3取代的C2-C10烯烃基、R3取代的苯基、R3取代的苄基、R3取代的C3-C6环烷基、R3取代的C3-C6环烯烃基或R3取代的金刚烷基；所述R3选自氢、羟基、氟、氯、溴、甲基、乙基、异丙基、烯丙基中的至少一种。
  3. 根据权利要求2所述的熏蒸方法，其特征在于，所述通式I中：X为F或Cl；Y1和Y2同时为F；R1为R3取代的C1-C4烷烃基、R3取代的C2-C4烯烃基、R3取代的苯基或R3取代的C3-C6环烷基；所述R3选自氢、羟基、氟、氯中的至少一种。
  4. 根据权利要求1所述的熏蒸方法，其特征在于，所述通式II中：X为F、Cl、Br或OH；R2为R3取代的C1-C4烷烃基、R3取代的C2-C4烯烃基、R3取代的苯基、R3取代的苄基、R3取代的C3-C7环烷基、R3取代的C3-C7环烯烃基或R3取代的金刚烷基；所述R3选自氢、羟基、氟、氯、溴、甲基、乙基、异丙基、烯丙基中的至少一种。
  5. 根据权利要求4所述的熏蒸方法，其特征在于，所述通式II中：X为F或Cl；R2为R3取代的C1-C4烷烃基、R3取代的C2-C4烯烃基、R3取代的C3-C7环烷基或R3取代的苯基；所述R3选自氢、羟基、氟、氯中的至少一种。
  6. 根据权利要求3或5所述的熏蒸方法，其特征在于：所述R3为氢。
  7. 根据权利要求1所述的熏蒸方法，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，所述的载体材料包括但不限于滤纸、硅胶、滤膜、棉花、海绵或布。
  8. 根据权利要求7所述的熏蒸方法，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，所述的中空装置包括但不限于箱式结构、盒式结构、笼式结构或袋子。
  9. 根据权利要求8所述的熏蒸方法，其特征在于：所述中空装置具有风扇和调速功能。
  10. 根据权利要求8或9所述的熏蒸方法，其特征在于：所述中空装置具有自加热和调温功能。
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