CN103275410B - A kind of permeability type chemical gas protective materials and its preparation method and application - Google Patents
A kind of permeability type chemical gas protective materials and its preparation method and application Download PDFInfo
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- CN103275410B CN103275410B CN201310230623.3A CN201310230623A CN103275410B CN 103275410 B CN103275410 B CN 103275410B CN 201310230623 A CN201310230623 A CN 201310230623A CN 103275410 B CN103275410 B CN 103275410B
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Abstract
The invention discloses a kind of permeability type chemical gas protective materials, it is a kind of organic/inorganic compound film material, by alkaline molecular sieve and the polymer that contains two hydroxy functional groups, poly-(4-(2,3-dihydroxy propoxyl group) styrene) mix, alkaline molecular sieve is embedded in the substrate of the fluoropolymer resin that contains two hydroxy functional groups. This composite membrane is by monomer: 4-(2,3-dihydroxy propoxyl group) styrene, crosslinking agent: p-divinyl benzene, light trigger and alkaline molecular sieve Na56[(AlO2)56(SiO2)136].264H2After O mixes, under ultraviolet lighting solidifies, preparation forms. Permeability type chemical gas protective materials of the present invention can be used for stoping chemical gas, especially seeing through of mustard gas, but allow water vapour to see through simultaneously, can effectively alleviate the problem of traditional protective garment thermic load. The invention also discloses the preparation method and application of above-mentioned permeability type chemical gas protective materials.
Description
Technical field
The present invention relates to a kind of permeability type chemical gas protective materials, particularly a class two hydroxy functional groupsOrganic/inorganic compound film, preparation method and its usage that polymer and alkaline molecular sieve form.
Background technology
Aspect military and civilian national defence, effectively prevent from touching the poisonous chemical warfare agent of vapor form(CWAs) be very important. In CWAs, having a class is vesicant agent, as mustard gas (β β '-Dichloriodiethyl sulfide, DCEES). Their mucous membrane, skin, DNA generation alkylations easy and human body are anti-Should, grievous injury health. Traditional C WA protective garment is based on some fluid-tight, fine and close polymerizationsThing material, as crosslinked butyl rubber etc. It can intercept all steam completely and liquid sees through. But,The shortcoming of this protective garment is airtight, easily causes wearer's heat accumulation, affects personnel's physiological functionAnd operating efficiency. Desirable protective garment should pass through steam in intercepting CWA. Now generally believeThe desirable water vapour percent of pass of chemical protecting suit is 1500-2000gm-2day-1. Some are worked out now saturatingGas type Chemical and biological protective material, great majority are to utilize some unit active or that have an adsorptivity to carry out physical barrierOr chemical degradation CWAs.
Document J.Phys.Chem.B1999,103,325 have reported and utilize oxide catalytic degradation to have poison gasThe method of body, the solid-state MASNMR methods of employing such as author Wagner have been studied under room temperature mustard gas and have been receivedThe reaction of rice MgO, research shows that mustard gas is hydrolyzed on active MgO nano particle, hydrolysis is producedThing has thiodiglycol, and approximately 50% be converted into vinyl thioether,
Document Mater.Res.Soc.Bull.2003,28,574 have reported a vapor-permeable type armored fabric, itThe adsorbable mustard gas of an active carbon layer wherein containing. Shortcoming be charcoal absorption mustard gas steam be one notReversible process, physical absorption does not almost have degradation to mustard gas, after absorption, also need further to process withAvoid mustard gas desorb again to pollute
Document MicroporousMesoporousMater2009,124 (1-3): 232-235 have reported not containing knotThe molecular sieve of the X-type faujasite basket structure of brilliant water, as NaX molecular sieve is passing through mustard gas analogies 2-When chloroethyl ethyl thioether (CEES) gas can with its generation nucleophilic substitution, degradation effect reaches 80%.
US625538 discloses the poly-hydroxy polymer of a kind of separate medium styryl ether. Styryl official energyMore easily there is polymerization, CH in group2=CH2C6H4O-,-O-be on the neighbour or contraposition of alkene, the right canConnect the material of other functional groups.
Summary of the invention
Technical problem: for solving the thermal stress issues of traditional Chemical and biological protective material, the invention provides a kind of based onOrganic/inorganic compound film, has the permeability type chemical gas protective materials of higher water vapour permeability.
Technical scheme: a kind of permeability type chemical gas protective materials of the present invention, comprises alkaline molecular sieve and poly-Compound resin, alkaline molecular sieve is embedded in the substrate of the fluoropolymer resin that contains two hydroxy functional groups, two thingsMatter mass ratio is 1:9～3:7, and wherein fluoropolymer resin is poly-(4-(2,3-dihydroxy propoxyl group) styrene),Molecular structural formula is
The molecular structure of alkaline molecular sieve is Na56[(AlO2)56(SiO2)136].264H2O。
The method of the above-mentioned permeability type chemical gas of preparation of the present invention protective materials, comprises the following steps:
1) by alkaline molecular sieve Na56[(AlO2)56(SiO2)136].264H2O grind up powder, joins 4-In (2,3-dihydroxy propoxyl group) styrene monomer, the two mass ratio is 1:9～3:7, under room temperature, stirs12-24 hour;
2) in the mixture of preparing in step 1), add crosslinking agent and ultraviolet initiator, wherein, 4-(2,3-Dihydroxy propoxyl group) molar ratio of styrene monomer, crosslinking agent and ultraviolet initiator is 100:5:1,Under room temperature, stir more than 20 minutes; Crosslinking agent is p-divinyl benzene, and ultraviolet initiator is arbitrarily followingA kind of: dimethoxybenzoin, 1-hydroxycyclohexylphenylketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-Propyl group) ketone;
3) get described step 2) mixture add in the middle of two polyester film mylar films, ultraviolet lighting is solidChange after at least 1 hour, peel off curing film, obtain permeability type chemical gas protective materials.
The present invention also comprises that above-mentioned permeability type chemical gas protective materials is in shielding mustard gas and mustard gas simulationApplication in thing.
In the present invention, preparation is containing the styryl ether monomer of two hydroxy functional groups, and equation is as follows:
Detailed process is: (a) by a certain amount of parahydroxyben-zaldehyde, NaOH, (C4H9）4N+I-Be dissolved in twoIn methyl sulfoxide (DMSO), slowly drip 3-chlorine-1,2-propylene glycol in 30 minutes. After dropwising,Be warming up to 70 DEG C, reaction 6h. Post processing. (b) get a certain amount of (Ph3PCH3)+Br-Be dissolved in anhydrous tetrahydrochyseneFurans (THF), at 0 DEG C, N2Under protection, add catalyst 18-hat-6 ethers and K+-OC(CH3)3, stir45min. The product of (a) is dissolved in to THF, adds in mixed solution, reaction 3h. Post processing obtains listBody.
Preparation Na56[(AlO2)56(SiO2)136].264H2O molecular sieve, detailed process is: in deionized waterAdd a certain amount of Al3+(-OCH(CH3)2)3(CH3)4N+OH-, stir to clarify. Under high degree of agitationAdd respectively (CH3)4N+Br-, NaOH, then dropwise adds colloidal state SiO2, under this mixture room temperature, stir3 days, then 100 DEG C were stirred 4 days. Centrifugal, pouring liquids, adds deionized water and disperses, and repeats above 3Inferior. Last 600 DEG C of roasting 8h.
The preparation method of organic/inorganic compound film material is as follows:
1) by alkaline molecular sieve Na56[(AlO2)56(SiO2)136].264H2O grind up powder, joins 4-In (2,3-dihydroxy propoxyl group) styrene monomer, the two mass ratio is 1/9～3/7, under room temperature, stirs12-24 hour;
2) in the mixture of preparing in step 1), add crosslinking agent and ultraviolet initiator, wherein, 4-(2,3-Dihydroxy propoxyl group) molar ratio of styrene monomer, crosslinking agent and ultraviolet initiator is 100:5:1,Under room temperature, stir more than 20 minutes; Crosslinking agent is p-divinyl benzene, below described ultraviolet initiator isAny one: dimethoxybenzoin, 1-hydroxycyclohexylphenylketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxylBase-2-propyl group) ketone;
3) get step 2) mixture 100mg add in the middle of two polyester film mylar films, ultraviolet lightingSolidify after at least 1 hour, peel off curing film, obtain permeability type chemical gas protective materials.
The application of permeability type chemical gas protective materials in shielding mustard gas: the laminated film preparing is enteredRow water vapour permeability and mustard gas (DCEES), 2-chloroethyl ethyl thioether (CEES), dipropyl sulfide(DPS), thiodiglycol (TDG) transmission measurement.
Beneficial effect: the present invention compared with prior art, has the following advantages:
The invention provides a permeability type organic/inorganic composite material that can be used for chemical gas protection. PassButyl rubber, the halogenated butyl rubber class chemical gas protective materials of system have high densification, air-locked feature,Although it can shield chemical substance effectively, its water vapour permeability is too low, causes utilizing such materialThe wearing comfortableness of the personnel protection clothes of preparation is poor, weak heat-dissipating, and personnel's thermic load is high; Material of the present inventionExpect that maximum advantage is that a fluoropolymer resin with o-dihydroxy functional group, o-dihydroxy have been invented in designFunctional group can make vaporous water molecule rapidly by fluoropolymer resin by hydrogen bond action, makes whole materialHave higher water vapour permeability, in material, the alkaline molecular sieve of doping can be realized chemistry poison simultaneouslyGas, especially mustard gas (DCEES), monochloro for diethyl thioether (CEES), dipropyl sulfide (DPS),The degraded of thiodiglycol (TDG). Say from preparation technology, whole material can solidify by ultraviolet lightingThe method preparation of film forming, simple, be convenient to industrialized production.
Detailed description of the invention
Below by embodiment, the present invention is done further and illustrated.
The preparation of I organic/inorganic compound film
I1:Na56[(AlO2)56(SiO2)136]264H2The preparation of O molecular sieve
In 40.15g deionized water, add 6.88gAl3+(-OCH(CH3)2)3(98wt%) and 29.83g(CH3)4N+OH-(the 25wt% aqueous solution) stirs to clarify. Under high degree of agitation, add respectively 2.39g(CH3)4N+Br-(98wt%), 0.0648gNaOH (98wt%), stirs to clarify. Then under high degree of agitation byBe added dropwise to 11.03gLudoxAS-40 colloidal state SiO2, under this mixture room temperature, stir 3 days then 100 DEG CStir 4 days. By the solution centrifugal 20min(8000rpm of last milk shape), pour out supernatant liquid, thenAdd deionized water dispersing molecule sieve particle again, this process repeats 3 times. Last 600 DEG C of roasting 8h.I2:4-(2,3-dihydroxy propoxyl group) preparation of styrene monomer
(1) by 6g parahydroxyben-zaldehyde, 2.4mgNaOH, 0.15g(C4H9）4N+I-Be dissolved in 5mlDMSOIn, slowly drip 13.3g3-chlorine-1,2-propylene glycol in 30 minutes. After dropwising, be warming up to 70 DEG C, anti-Answer 6h. After solution is cooling, join in 80ml water. Separatory, collects organic phase, water ether(3*20ml) washing, organic phase saturated common salt water washing, finally spends the night with anhydrous magnesium sulfate drying. RevolveSteaming desolventizes, and obtains product liquid.
(2) get 5.4g (Ph3PCH3)+Br-Be dissolved in anhydrous THF25ml, at 0 DEG C, N2Under protection, add 0.1gCatalyst 18-hat-6 ethers and 1.8gK+-OC(CH3)3, stir 45min. The product 2.5g that gets previous step is moltenIn 10mlTHF, add in mixed solution 0 DEG C of reaction 3h to. The centrifugal KBr that removes, revolves and steams to obtain oilyMaterial, is dissolved in ether and phosphine oxide, is placed in refrigerator overnight, filters, and revolves steaming, drying at room temperature,Obtain yellow liquid product.
I3: the preparation of permeability type chemical gas protective materials
First by the alkaline molecular sieve Na of grind up powder56[(AlO2)56(SiO2)136].264H2O, joins listIn body, molecular sieve is 1:9～3:7 with monomer mass ratio, stirring at room temperature 12-24h. In mixture, add againAccount for the crosslinking agent and the 1mol% ultraviolet initiator that accounts for amount of monomer of the 5mol% of amount of monomer, select peace hereinCease fragrant dimethyl ether as light trigger, stirring at room temperature 20min. The mixture that takes a morsel is added in the middle of two mylar films,Ultraviolet lighting solidifies at least 1h. While noting illumination, need anhydrous and oxygen-free condition. Finally carefully scrape thin with scraperFilm. The formula of institute's made membrane is as shown in the table:
The water vapour permeability of II permeability type chemical gas protective materials and mustard gas (DCEES) and mustard seedGas analogies monochloro sees through for diethyl thioether (CEES), dipropyl sulfide (DPS), thiodiglycol (TDG)Rate test:
(1) water vapour permeability test: utilize water vapor permeation rate tester, film sample is clamped in to testBetween chamber, have the nitrogen of stable relative humidity in a side flow of film, drying nitrogen is at another of filmSide flow, due to the existence of moist gradient, steam can pass film diffusion to low humidity side from high humidity side,Low humidity side, the drying nitrogen that the steam seeing through is flowed is carried into sensor, while entering sensor, can produceThe signal of telecommunication in proportion, by the analytical calculation to sensor electrical signal, thereby show that the steam of sample is saturatingCross the parameters such as rate.
(2) mustard gas (DCEES) transmission measurement: DCEES drop drops in a glass of film topOn fiber filter paper, filter paper below is supported with a stainless steel cloth. Film (2.8cm2) and its top is notBetween rust steel mesh, have a little space, obstructed water vapour in this space, can be used as test liquid DCEES(3ml) saturated air body source. It is 80% that film below passes into a humidity, and temperature is the air of 30 DEG C, streamSpeed is 100cm3/ min. After 24h, detect away the content of DCEES in air with flame ionization detector.
(3) monochloro is for diethyl thioether (CEES) transmission measurement: CEES drop drops in of film topOn glass fibre filter paper, filter paper below is supported with a stainless steel cloth. Film (2.8cm2) and its topStainless (steel) wire between there is a little space, in this space, obstructed water vapour, can be used as test liquidCEES(3ml) saturated air body source. It is 80% that film below passes into a humidity, and temperature is the air of 30 DEG C,Flow velocity is 100cm3/ min. After 24h, detect away the content of CEES in air with flame ionization detector.
(4) dipropyl sulfide (DPS) transmission measurement: DPS drop drops in a glass fibre of film topOn filter paper, filter paper below is supported with a stainless steel cloth. Film (2.8cm2) with its top stainless steelBetween net, have a little space, obstructed water vapour in this space, can be used as test liquid DPS(3ml)Saturated air body source. It is 80% that film below passes into a humidity, and temperature is the air of 30 DEG C, and flow velocity is100cm3/ min. After 24h, detect away the content of DPS in air with flame ionization detector.
(5) thiodiglycol (TDG) transmission measurement: TDG drop drops in a glass fibre mistake of film topOn filter paper, filter paper below is supported with a stainless steel cloth. Film (2.8cm2) with its top stainless (steel) wireBetween there is a little space, obstructed water vapour in this space, can be used as test liquid TDG(3ml)Saturated air body source. It is 80% that film below passes into a humidity, and temperature is the air of 30 DEG C, and flow velocity is100cm3/ min. After 24h, detect away the content of TDG in air with flame ionization detector.
Carry out water transmitance and DCEES, CEES, DPS, TDG transmission measurement, the following institute of its resultShow:
Claims (2)
1. a permeability type chemical gas protective materials, it is characterized in that, this material comprises alkaline molecular sieve and fluoropolymer resin, described alkaline molecular sieve is embedded in the substrate of the fluoropolymer resin that contains two hydroxy functional groups, two material masses are than being 1:9～3:7, described fluoropolymer resin is poly-(4-(2,3-dihydroxy propoxyl group) styrene), and molecular structural formula is
The molecular structure of described alkaline molecular sieve is Na56[(AlO2)56(SiO2)136]·264H2O。
2. a method of preparing permeability type chemical gas protective materials claimed in claim 1, is characterized in that, the method comprises the following steps:
1) by alkaline molecular sieve Na56[(AlO2)56(SiO2)136]·264H2O grind up powder, joins in 4-(2,3-dihydroxy propoxyl group) styrene monomer, and the two mass ratio is 1:9～3:7, under room temperature, stirs 12-24 hour;
2) in described step 1) add crosslinking agent and ultraviolet initiator in the mixture prepared, wherein, the molar ratio of 4-(2,3-dihydroxy propoxyl group) styrene monomer, crosslinking agent and ultraviolet initiator is 100:5:1, stirs more than 20 minutes under room temperature; Described crosslinking agent is p-divinyl benzene, described ultraviolet initiator be following any one: dimethoxybenzoin, 1-hydroxycyclohexylphenylketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone;
3) get described step 2) mixture add in the middle of two polyester film mylar films, ultraviolet lighting solidify after 1 hour, peels off curing film, obtain permeability type chemical gas protective materials.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6255385B1 (en) * | 1996-02-20 | 2001-07-03 | Jan Ericsson | Polyhydroxy polymers substituted with styryl ether groups and gels and surfaces prepared from them |
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| US6255385B1 (en) * | 1996-02-20 | 2001-07-03 | Jan Ericsson | Polyhydroxy polymers substituted with styryl ether groups and gels and surfaces prepared from them |
Non-Patent Citations (1)
| Title |
|---|
| A highly breathable organic/inorganic barrier material that blocks the passage of mustard agent simulants;Yeny C.Hudiono et aL;《Industrial & Engineering Chemistry Research》;20120517;第51卷;p7453-7456 * |
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