CN105153449A - High-molecular composite thin film capable of absorbing hydrogen and preparation method of high-molecular composite thin film - Google Patents
High-molecular composite thin film capable of absorbing hydrogen and preparation method of high-molecular composite thin film Download PDFInfo
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- CN105153449A CN105153449A CN201510673143.3A CN201510673143A CN105153449A CN 105153449 A CN105153449 A CN 105153449A CN 201510673143 A CN201510673143 A CN 201510673143A CN 105153449 A CN105153449 A CN 105153449A
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Abstract
The invention discloses a high-molecular composite thin film capable of absorbing hydrogen and a preparation method of the high-molecular composite thin film. The preparation method comprises the steps of dissolving polysiloxane resin into hydrocarbon substances, uniformly mixing the mixture with a catalyst containing noble metals, adding a curing agent for curing, and pressing to form the film, wherein the polysiloxane resin is low-molecular-weight polymethylsiloxane or low-molecular-weight polyphenyl siloxane with a side chain containing vinyl. By virtue of the preparation method, the flame-retardant high-molecular composite thin film capable of absorbing hydrogen can be obtained, the problems that organic molecule low-molecular compounds are difficult to process and form and are inflammable can be solved, the obtained thin film has strong absorption capacity to hydrogen, and the average absorption amount of hydrogen in 24 hours is 7.35mg; and furthermore, the preparation cost is low, and the high-molecular composite thin film is easy to be widely used.
Description
Technical field
The present invention relates to the chemical field of laminated film, particularly, relate to a kind of high score laminated film that can absorb hydrogen and preparation method thereof.
Background technology
In many plant and instrument, due to hydrogen and isotopic existence thereof, various chemistry and galvanic corrosion reaction can be produced.In the good instrument of stopping property, the hydrogen of generation can constantly accumulation, affects the solidification of Embedding Material, thus electronic circuit is exposed in hydrogen be corroded, produce various adverse influence to control panel.In addition, when hydrogen pressure acquires a certain degree, also there is the danger of fire and blast, so need the hydrogen got rid of in time in encloses container.Getting rid of the method that the hydrogen in encloses container commonly uses at present is use to inhale hydrogen agent, namely utilize hydrogen absorber to absorb or with the hydrogen reaction in system, get rid of hydrogen.As far back as the seventies latter stage, this type of material is just brought into use in the sub-laboratory, the Holy Land of the U.S., gets rid of the hydrogen of the generation in Nuclear weapons system.
Current existing suction hydrogen agent material is mainly divided into inorganic and organic materials two kinds.
(1) mineral compound.According to the difference of hydrogen principle of absorption, this type of inhales hydrogen agent can be divided into two classes.The first kind is that precious metal is as Pt, Pd and Rh etc. (U.S.4886048).The water generation reaction of this type of precious metal catalyst hydrogen and oxygen, removes hydrogen.Therefore will have the existence of oxygen in environment for use, and environment for use to there is compatibility to the glassware for drinking water generated.Equations of The Second Kind can generate metal and the metallic compound of hydride with hydrogen reaction.As Mg, U, ZrCo, Mg
2ni etc. (U.S.4512721).But it is very responsive to pollutent, easily poisoning that hydrogen agent inhaled by this metalloid, and inflammable and explosive, and application is restricted.
(2) organic compound.The suction hydrogen principle that organic compound inhales hydrogen agent is that the organic molecule containing unsaturated double-bond and triple bond generates saturated compound with hydrogen generation irreversible reaction under the catalysis of precious metals pd.Conventional unsaturated molecule has tolane base benzene (DEB), 1,6-bis-phenoxy group-2,4-hexadiyne etc. (U.S.3896042, U.S.3963826, U.S.4405487).And being most widely used of DEB.
Although the suction hydrogen agent of having developed at present is of a great variety, but still existing problems in various degree.Compared with the agent of inorganic suction hydrogen, the agent of organic suction hydrogen can play a role under having low fire and explosion hazard, lesser temps, in common atmosphere as advantages such as water vapor, carbonic acid gas etc. still can play a role, therefore the agent of organic suction hydrogen has better applicability.Current organic suction hydrogen agent mostly is the flour that small molecules unsaturated compound mixes as carbon black as DEB etc. and the dispersion catalyzer containing Pd, and because carbon black and organic compound all can burn, therefore the suction hydrogen agent of gained does not also have flame retardant properties.In addition because micromolecular compound is difficult to machine-shaping usually, therefore this kind of final form of suction hydrogen agent is generally powdery, must pack use, cannot with elastomerics, and the forms such as film use, and cannot realize other function.Expensive in addition due to DEB, this type of trace utilization cost inhaling hydrogen agent is higher, also constrains widely using of DEB.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of polymer laminated film that can absorb hydrogen and preparation method thereof, this preparation method is by being dissolved in hydrocarbons by polyorganosiloxane resin, again and containing precious metal catalyst mix evenly after add solidifying agent solidification after suppress film forming, organic micromolecule compound can be solved and be difficult to machine-shaping, the problem such as inflammable, the receptivity of the film obtained to hydrogen is strong, average suction hydrogen in 24 hours is 7.35 ㎎, and prepare cheap, be easy to widely use.
The present invention's adopted technical scheme that solves the problem is:
A kind of preparation method that can absorb the polymer laminated film of hydrogen, polyorganosiloxane resin is dissolved in hydrocarbons, catalyst cured compacting film forming is added after having the carrier of precious metal to mix with precious metal or load again, described polyorganosiloxane resin is the low molecular weight polysiloxane that side chain contains vinyl and silicon hydrogen simultaneously, and concrete structure is:
Or side chain contains the mixture that the polysiloxane a of vinyl and side chain contain the polysiloxane b of silicon hydrogen, and the structure of a and b is as follows:
Precious metal can be Pd, Pt, Rh, and catalyzer is the solution or the powder that contain Pt (0).
Described set time is 2-3 days, and solidification value is room temperature.
According to similar dissolve mutually theory, polyorganosiloxane resin is dissolvable in water in hydrocarbons, and hydrocarbons can be stable hydrocarbon (i.e. alkanes etc.).
Being prepared as of polyorganosiloxane resin: take cyclosiloxane as monomer, initiated polymerization under the effect of ring-opening polymerization initiator, react 5-20 hour under room temperature, obtain low-molecular-weight polysiloxane respectively containing vinyl and silicon hydrogen or the polysiloxane simultaneously containing vinyl and silicon hydrogen.All stoichiometrically proportioning adds each amount participating in the related substances of reaction.
In the preparation of polyorganosiloxane resin, cyclosiloxane monomer can be
R＝CH
3，Ph，H
Arbitrary proportion combination.
In the preparation of polyorganosiloxane resin, initiator can be sulfuric acid or trifluoromethanesulfonic acid.
Load has the carrier of precious metal to be the inorganic powder material of gac or barium sulfate, calcium carbonate and aluminum oxide.
The polymer laminated film of what preparation method described above obtained can absorb hydrogen.The thickness of polymer laminated film is 0.2mm.
To sum up, the invention has the beneficial effects as follows:
1, the present invention can obtain a kind of polymer laminated film of fire-retardant absorption hydrogen, and can solve organic micromolecule compound and be difficult to machine-shaping, the problem such as inflammable, the film obtained is strong to the receptivity of hydrogen, and the average suction hydrogen in 24 hours is 7.35 ㎎;
2, the polymer laminated film of fire-retardant absorption hydrogen prepared of the present invention is with low cost, is easy to widely use.
Embodiment
Below in conjunction with embodiment, to the detailed description further of the present invention's do, but embodiments of the present invention are not limited thereto.
Embodiment 1
The synthesis of polyvinyl siloxane
Measure 40mL t etram-ethyltetravinylcyclotetrasiloxane, add and be equipped with in churned mechanically single port flask, add the 0.5mL vitriol oil afterwards and make catalyzer, stirring at room temperature reaction 5h.Add 100mL n-hexane dissolution reaction product afterwards, the solution of gained uses deionized water wash again three times, organic phase dried over mgso after layering after saturated sodium bicarbonate solution washing, and vacuum removes solvent and low molecular weight volatile thing, obtains target resin.The molecular weight M of resulting polymers
wbe 8 × 10
4g/mol, molecular weight distribution is respectively 1.27.
The synthesis of the polysiloxane of siliceous hydrogen and the synthesis of polyvinyl siloxane similar.
Embodiment 2
The preparation of the polyvinyl siloxane containing silicon hydrogen group
Measure 40mL t etram-ethyltetravinylcyclotetrasiloxane, add and be equipped with in churned mechanically single port flask, add 5mL tetramethyl-ring tetrasiloxane afterwards.Add the 0.5mL vitriol oil after stirring and make catalyzer, stirring at room temperature reaction 20h.Add 100mL n-hexane dissolution reaction product afterwards, the solution of gained uses deionized water wash again three times, organic phase dried over mgso after layering after saturated sodium bicarbonate solution washing, and vacuum removes solvent and low molecular weight volatile thing, obtains target resin.
The molecular weight M of resulting polymers
wbe 3 × 10
4g/mol, molecular weight distribution is respectively 1.16.
Embodiment 3
Take the hydrogeneous polyvinyl siloxane resin of 3.6g, add 3mL normal heptane, stirring and dissolving, add 1.4gPd/C (5wt%Pd) catalyzer afterwards, add the agent of 30mg cassette catalyzer after being uniformly dispersed and stir.Here the solution of cassette catalyzer namely containing pt (0), afterwards the solution of gained is molded on vulkameter the film with 0.2mm thickness in room temperature, self-vulcanizing 3 days, obtains the Elastic Film of black.The black thin film of gained is placed in the encloses container being filled with 146KPa pure hydrogen and tests under room temperature, and the hydrogen－sucking amount of different time is as shown in the table:
| Time/hour | 2 | 6 | 10 | 16 | 24 | 48 | 96 |
| Hydrogen－sucking amount/mg | 2.6 | 5.6 | 6.7 | 7.3 | 8.0 | 8.2 | 8.2 |
Embodiment 4
Take 3.0g siliceous hydrogen polyvinyl siloxane resin, the hydrogeneous phenyl silicone oil of 1.0g, adds 3mL octane, stirring and dissolving.Add 1.4gPd/C (5wt%Pd) catalyzer afterwards, after adding 30mg cassette catalyzer after stirring, the solution of gained is molded into the film with 0.2mm thickness or other desired thickness on vulkameter in room temperature, cured at room temperature two days, obtains black Elastic Film.The black thin film of gained is placed in the encloses container being filled with 146KPa pure hydrogen and tests under room temperature, and the hydrogen－sucking amount of different time is as shown in the table:
| Time/hour | 2 | 6 | 10 | 16 | 24 | 48 | 96 |
| Hydrogen－sucking amount/mg | 1.8 | 4.3 | 5.0 | 5.9 | 6.4 | 6.7 | 6.8 |
Embodiment 5
Take 3.0g siliceous hydrogen polyvinyl siloxane resin, 1.0g polyisoprene, adds 3mL normal hexane, stirring and dissolving.Add 1.4gPd/C (5wt%Pd) catalyzer afterwards, after stirring, add 30mg cassette catalyzer.Afterwards the solution of gained is molded on vulkameter the film with 0.2mm thickness or other desired thickness in room temperature, cured at room temperature two days, obtains black Elastic Film.The black thin film of gained is placed in the encloses container being filled with 146KPa pure hydrogen and tests under room temperature, and the hydrogen－sucking amount of different time is as shown in the table:
| Time/hour | 2 | 6 | 10 | 16 | 24 | 48 | 96 |
| Hydrogen－sucking amount/mg | 3.5 | 4.9 | 5.8 | 7.0 | 7.9 | 8.3 | 8.5 |
Embodiment 6
Take 3.0g siliceous hydrogen polyvinyl siloxane resin, 1.0g polyhutadiene, adds 3mL Skellysolve A, stirring and dissolving.Add 1.4gPd/C (5wt%Pd) catalyzer afterwards, after stirring, add the agent of 30mg cassette catalyst.Afterwards the solution of gained is molded on vulkameter the film with 0.2mm thickness or other desired thickness in room temperature, cured at room temperature two days, obtains black Elastic Film.The black thin film of gained is placed in the encloses container being filled with 146KPa pure hydrogen and tests under room temperature, and the hydrogen－sucking amount of different time is as shown in the table:
| Time/hour | 2 | 6 | 10 | 16 | 24 | 48 | 96 |
| Hydrogen－sucking amount/mg | 2.0 | 4.0 | 5.3 | 6.5 | 7.1 | 7.4 | 7.5 |
As mentioned above, the present invention can be realized preferably.
Claims (8)
1. one kind can absorb the preparation method of the polymer laminated film of hydrogen, it is characterized in that, polyorganosiloxane resin is dissolved in hydrocarbons, catalyst cured compacting film forming is added after having the carrier of precious metal to mix with precious metal or load again, described polyorganosiloxane resin is the low molecular weight polysiloxane that side chain contains vinyl and silicon hydrogen simultaneously, and concrete structure is:
Or side chain contains the mixture that the polysiloxane a of vinyl and side chain contain the polysiloxane b of silicon hydrogen, and the structure of polysiloxane a and polysiloxane b is as follows:
Precious metal can be Pd, Pt, Rh, and catalyzer is the solution or the powder that contain Pt (0).
2. preparation method according to claim 1, is characterized in that, described set time is 2-3 days, and solidification value is room temperature.
3. preparation method according to claim 1, it is characterized in that, being prepared as of polyorganosiloxane resin: take cyclosiloxane as monomer, initiated polymerization under the effect of ring-opening polymerization initiator, in room temperature reaction 5-20 hour, obtain low-molecular-weight polysiloxane containing vinyl and silicon hydrogen or side chain and contain the polysiloxane b that the polysiloxane a of vinyl and side chain contain silicon hydrogen.
4. preparation method according to claim 3, is characterized in that, described cyclosiloxane monomer can be
In arbitrary proportion combination.
5. preparation method according to claim 3, is characterized in that, ring-opening polymerization initiator can be sulfuric acid or trifluoromethanesulfonic acid.
6. the preparation method according to any one of claim 1-5, is characterized in that, load has the carrier of precious metal to be the inorganic powder material of gac or barium sulfate, calcium carbonate and aluminum oxide.
7. the polymer laminated film that can absorb hydrogen that obtains of preparation method as claimed in claim 6.
8. can absorb the polymer laminated film of hydrogen as claimed in claim 7, it is characterized in that, the thickness of polymer laminated film is 0.2mm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110951262A (en) * | 2019-11-25 | 2020-04-03 | 中国工程物理研究院总体工程研究所 | Preparation method of novel polysiloxane type hydrogen-absorbing polymer film material |
| CN112321830A (en) * | 2020-11-09 | 2021-02-05 | 中国工程物理研究院总体工程研究所 | Organic silicon resin with hydrogen absorption function and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3896042A (en) * | 1974-02-15 | 1975-07-22 | Us Energy | Low temperature, low pressure hydrogen gettering |
| US4886048A (en) * | 1987-03-31 | 1989-12-12 | Labaton Isaac J | Hydrogen pump |
| CN101121116A (en) * | 2007-05-29 | 2008-02-13 | 中国工程物理研究院总体工程研究所 | Irreversible hydrogen-absorbing material, product and preparation method |
-
2015
- 2015-10-13 CN CN201510673143.3A patent/CN105153449B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3896042A (en) * | 1974-02-15 | 1975-07-22 | Us Energy | Low temperature, low pressure hydrogen gettering |
| US4886048A (en) * | 1987-03-31 | 1989-12-12 | Labaton Isaac J | Hydrogen pump |
| CN101121116A (en) * | 2007-05-29 | 2008-02-13 | 中国工程物理研究院总体工程研究所 | Irreversible hydrogen-absorbing material, product and preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110951262A (en) * | 2019-11-25 | 2020-04-03 | 中国工程物理研究院总体工程研究所 | Preparation method of novel polysiloxane type hydrogen-absorbing polymer film material |
| CN110951262B (en) * | 2019-11-25 | 2022-02-22 | 中国工程物理研究院总体工程研究所 | Preparation method of polysiloxane type hydrogen-absorbing polymer film material |
| CN112321830A (en) * | 2020-11-09 | 2021-02-05 | 中国工程物理研究院总体工程研究所 | Organic silicon resin with hydrogen absorption function and preparation method thereof |
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