CN113912880A - Oxygen-enriched film and preparation method thereof - Google Patents
Oxygen-enriched film and preparation method thereof Download PDFInfo
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- CN113912880A CN113912880A CN202110969987.8A CN202110969987A CN113912880A CN 113912880 A CN113912880 A CN 113912880A CN 202110969987 A CN202110969987 A CN 202110969987A CN 113912880 A CN113912880 A CN 113912880A
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- China
- Prior art keywords
- oxygen
- enriched film
- silicone rubber
- methyl vinyl
- vinyl silicone
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 36
- 239000001301 oxygen Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 20
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004945 silicone rubber Substances 0.000 claims abstract description 18
- 239000003292 glue Substances 0.000 claims abstract description 15
- 238000010894 electron beam technology Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 10
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 6
- 229920001971 elastomer Polymers 0.000 claims abstract description 6
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000007480 spreading Effects 0.000 claims abstract description 6
- 238000003892 spreading Methods 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000029058 respiratory gaseous exchange Effects 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/54—Polymerisation initiated by wave energy or particle radiation by X-rays or electrons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses an oxygen-enriched film and a preparation method thereof, wherein the preparation method comprises the following steps: uniformly mixing methyl vinyl silicone rubber and styrene under the condition of nitrogen, heating to 55-65 ℃, dropwise adding benzoyl peroxide into the mixture, reacting for 1-3h under the condition of 85-90 ℃, heating to 100-105 ℃, preserving heat for 20-40min, stopping introducing nitrogen, vacuumizing, and cooling to room temperature to obtain base rubber; spreading the base glue on a substrate, introducing nitrogen gas to the base glue, irradiating electron beams to the base glue for curing, cooling, and demolding to obtain the oxygen-enriched film. The oxygen-enriched film can effectively solve the problems that the existing oxygen-enriched film is easy to generate harmful substances to human bodies after decomposition and has poor mechanical property.
Description
Technical Field
The invention relates to the technical field of oxygen-enriched films, in particular to an oxygen-enriched film and a preparation method thereof.
Background
The food is eaten by people as days, the grains and the vegetables are necessary for three meals a day, and the supply, the storage and the fresh keeping of the foods are important means. Fruits, grains and vegetables are still living bodies after being harvested, oxygen is absorbed and carbon dioxide is exhaled, the respiration effect is based on the premise that nutrients in fruits are consumed, the higher the respiration intensity is, the more the consumed nutrients are, the more the fruits are aged, rotten and deteriorated, and in order to prolong the storage period of the fruits, the scientific method for controlling the respiration effect through temperature reduction and air regulation is needed.
In the middle of the last century, scientific development shows that the organic silicon rubber has good air permeability and air permeability ratio, is an excellent material for modified atmosphere preservation of fruits, vegetables and grains, is simple to operate, economic, environment-friendly, flexible, wide in application range, capable of saving a large amount of mechanical equipment used in the preservation process by adopting a cooling method, and applicable to cities, rural areas, families and the like without consuming electric energy.
With the research of people on the silicon rubber, the existing silicon rubber also has certain defects, such as poor strength and easy aging, the existing silicon rubber is generally prepared by a vulcanization method, and after the residual harmful peroxide in the prepared silicon rubber is decomposed, the prepared silicon rubber has certain damage to the environment, people and livestock and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the oxygen-enriched film and the preparation method thereof, and the oxygen-enriched film can effectively solve the problems that the existing oxygen-enriched film is easy to generate harmful substances to human bodies after decomposition and has poor mechanical property.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of an oxygen-enriched film comprises the following steps:
(1) uniformly mixing methyl vinyl silicone rubber and styrene under the condition of nitrogen, heating to 55-65 ℃, dropwise adding benzoyl peroxide into the mixture, reacting for 1-3h under the condition of 85-90 ℃, heating to 100-105 ℃, preserving heat for 20-40min, stopping introducing nitrogen, vacuumizing, and cooling to room temperature to obtain base rubber;
(2) spreading the base glue on a substrate, introducing nitrogen gas to the base glue, irradiating electron beams to the base glue for curing, cooling, and demolding to obtain the oxygen-enriched film.
Further, the mass ratio of the methyl vinyl silicone rubber, the styrene and the benzoyl peroxide in the step (1) is 80-90:12-20: 1-3.
In the scheme, the methyl vinyl silicone rubber contains a large amount of vinyl, the styrene contains alkenyl and benzene ring structures, after the methyl vinyl silicone rubber is irradiated by electron beams, the vinyl is opened under the action of the electron beams, so that the styrene is grafted to the methyl vinyl silicone rubber to form a three-dimensional network structure, and the benzene ring has certain rigidity, so that the mechanical property of the network structure can be improved after the benzene ring is introduced; by adopting the electron beam irradiation mode, sulfur element can not be introduced, and even if the oxygen-enriched film is subsequently decomposed, harmful substances can not be generated, and the health of a human body can not be influenced.
Further, the viscosity of the methyl vinyl silicone rubber in the step (1) was 15000-22000 mPa.s.
Further, the mass ratio of the vinyl in the methyl vinyl silicone rubber in the step (1) is 50-80%.
Further, the dropping time of the benzoyl peroxide in the step (1) is 40-50 min.
Further, the irradiation intensity of the electron beam in the step (2) is 3X 104-6×104GY。
Further, the curing time in the step (2) is 2 to 4 s.
The invention has the following beneficial effects:
1. according to the invention, the alkenyl in the raw material is promoted to be open-chain by means of electron beam irradiation, the benzene ring is grafted to the silicon rubber to form a three-dimensional cross-linked network structure, and the electron beam mode is adopted, so that sulfur element is not introduced, and further, substances harmful to human bodies are not generated, and the prepared product is green, environment-friendly and pollution-free.
2. Because the benzene ring structure has certain rigidity, the mechanical property of the oxygen-enriched membrane can be greatly improved after the benzene ring structure is introduced into the silicon rubber.
Detailed Description
Example 1
A preparation method of an oxygen-enriched film comprises the following steps:
(1) uniformly mixing methyl vinyl silicone rubber with the viscosity of 15000mPa.s and styrene under the condition of nitrogen, heating to 55 ℃, dropwise adding benzoyl peroxide into the mixture, finishing dropwise adding within 40min, then reacting at 85 ℃ for 1h, heating to 100 ℃, preserving heat for 20min, stopping introducing nitrogen, vacuumizing, and cooling to room temperature to obtain base rubber, wherein the mass ratio of vinyl in the methyl vinyl silicone rubber is 50%;
(2) spreading the base glue on a substrate, introducing nitrogen gas into the base glue, and irradiating electron beam with irradiation intensity of 6 × 10 for 2s4And GY, cooling and demolding to obtain the oxygen-enriched film.
Example 2
A preparation method of an oxygen-enriched film comprises the following steps:
(1) uniformly mixing methyl vinyl silicone rubber with the viscosity of 22000mPa.s and styrene under the condition of nitrogen, heating to 65 ℃, dropwise adding benzoyl peroxide into the mixture, finishing dropwise adding within 50min, then reacting at 90 ℃ for 3h, heating to 105 ℃, preserving heat for 40min, stopping introducing nitrogen, vacuumizing, and cooling to room temperature to obtain base rubber, wherein the mass ratio of vinyl in the methyl vinyl silicone rubber is 80%;
(2) spreading the base glue on a substrate, introducing nitrogen gas into the base glue, and irradiating electron beam with irradiation intensity of 3 × 10 for 4s to cure4And GY, cooling and demolding to obtain the oxygen-enriched film.
Example 3
A preparation method of an oxygen-enriched film comprises the following steps:
(1) uniformly mixing methyl vinyl silicone rubber with viscosity of 20000mPa.s and styrene under the condition of nitrogen, heating to 60 ℃, dropwise adding benzoyl peroxide into the mixture, completing dropwise adding within 45min, then reacting at 88 ℃ for 2h, heating to 103 ℃, preserving heat for 30min, stopping introducing nitrogen, vacuumizing, and cooling to room temperature to obtain base rubber, wherein the mass ratio of vinyl in the methyl vinyl silicone rubber is 70%;
(2) spreading the base glue on a substrate, introducing nitrogen gas into the base glue, and irradiating electron beam with irradiation intensity of 5 × 10 for curing for 3s4And GY, cooling and demolding to obtain the oxygen-enriched film.
Test examples
The gas permeation performance and mechanical properties of the oxygen-rich films prepared in examples 1 to 3 were respectively tested, and the specific test results are shown in tables 1 to 2.
Table 1: gas permeability (gas permeability P ═ x 10)-9ml gas (RTP). cm/cm2·s·Pa)
Gas species | Example 1 | Example 2 | Example 3 | Existing sulfuration oxygen-enriched membrane |
O2 | 0.53 | 0.52 | 0.56 | 0.49 |
CO2 | 0.05 | 0.08 | 0.08 | 0.25 |
As can be seen from the above table, the electron beam cured oxygen-rich films of examples 1 to 3 have higher oxygen permeability and lower carbon dioxide permeability than the conventional vulcanized oxygen-rich films.
Table 2: mechanical Properties
As can be seen from the above table, the electron cured oxygen-rich films of examples 1 to 3 have better mechanical properties than the conventional oxygen-rich films obtained by vulcanization.
Claims (8)
1. The preparation method of the oxygen-enriched film is characterized by comprising the following steps:
(1) uniformly mixing methyl vinyl silicone rubber and styrene under the condition of nitrogen, heating to 55-65 ℃, dropwise adding benzoyl peroxide into the mixture, reacting for 1-3h under the condition of 85-90 ℃, heating to 105 ℃ again, preserving heat for 20-40min, stopping introducing nitrogen, vacuumizing, and cooling to room temperature to obtain base rubber;
(2) spreading the base glue on a substrate, introducing nitrogen gas to the base glue, irradiating electron beams to the base glue for curing, cooling, and demolding to obtain the oxygen-enriched film.
2. The method of preparing an oxygen-enriched membrane according to claim 1, wherein the mass ratio of the methyl vinyl silicone rubber, the styrene and the benzoyl peroxide in the step (1) is 80-90:12-20: 1-3.
3. The method for preparing an oxygen-rich membrane according to claim 1, wherein the viscosity of the methyl vinyl silicone rubber in the step (1) is 15000-22000 mpa.s.
4. The method for producing an oxygen-rich membrane according to claim 1, wherein the mass ratio of vinyl groups in the methyl vinyl silicone rubber of the step (1) is 50 to 80%.
5. The method of preparing an oxygen-rich membrane according to claim 1, wherein the dropping time of the benzoyl peroxide in the step (1) is 40-50 min.
6. The method of claim 1, wherein the electron beam in step (2) is appliedThe irradiation intensity was 3X 104-6×104GY。
7. The method of claim 1, wherein the curing time in step (2) is 2-4 s.
8. An oxygen-rich membrane produced by the production method according to any one of claims 1 to 7.
Priority Applications (1)
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CN202110969987.8A CN113912880A (en) | 2021-08-23 | 2021-08-23 | Oxygen-enriched film and preparation method thereof |
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CN202110969987.8A CN113912880A (en) | 2021-08-23 | 2021-08-23 | Oxygen-enriched film and preparation method thereof |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20010050000A1 (en) * | 1999-08-26 | 2001-12-13 | Jae-Jin Hong | Novel oxygen enriching membrane |
CN1485126A (en) * | 2002-09-23 | 2004-03-31 | 暨南大学 | Oxygen enrichment film made of modified silicon rubber including cobalt(II) and the preparation process thereof |
KR20050119375A (en) * | 2004-06-16 | 2005-12-21 | 실로켐 주식회사 | Oxygen enriching membrane made of metallosiloxane and process preparing the same |
CN110204906A (en) * | 2019-06-25 | 2019-09-06 | 汤姆森电气有限公司 | A kind of compound anti-bird umbrella cover of macromolecule and preparation method thereof |
CN112717641A (en) * | 2020-12-24 | 2021-04-30 | 上海氧隆科技有限公司 | Oxygen-enriched membrane with excellent gas separation capacity and preparation method thereof |
-
2021
- 2021-08-23 CN CN202110969987.8A patent/CN113912880A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20010050000A1 (en) * | 1999-08-26 | 2001-12-13 | Jae-Jin Hong | Novel oxygen enriching membrane |
CN1485126A (en) * | 2002-09-23 | 2004-03-31 | 暨南大学 | Oxygen enrichment film made of modified silicon rubber including cobalt(II) and the preparation process thereof |
KR20050119375A (en) * | 2004-06-16 | 2005-12-21 | 실로켐 주식회사 | Oxygen enriching membrane made of metallosiloxane and process preparing the same |
CN110204906A (en) * | 2019-06-25 | 2019-09-06 | 汤姆森电气有限公司 | A kind of compound anti-bird umbrella cover of macromolecule and preparation method thereof |
CN112717641A (en) * | 2020-12-24 | 2021-04-30 | 上海氧隆科技有限公司 | Oxygen-enriched membrane with excellent gas separation capacity and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
周剑 等: "硅橡胶富氧膜材料研究进展", 《化工新型材料》, vol. 40, no. 2, pages 31 - 34 * |
张可达 等: "改性硅橡胶富氧膜的制备", 《应用化学》, no. 1, pages 92 - 94 * |
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Application publication date: 20220111 |