CN113912880A - Oxygen-enriched film and preparation method thereof - Google Patents

Oxygen-enriched film and preparation method thereof Download PDF

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Publication number
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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oxygen
enriched film
silicone rubber
methyl vinyl
vinyl silicone
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CN202110969987.8A
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Chinese (zh)
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牟六生
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Sichuan Xinda Adhesive Technology Co ltd
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Sichuan Xinda Adhesive Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/54Polymerisation initiated by wave energy or particle radiation by X-rays or electrons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00Characterised 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
    • C08J2351/08Characterised 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

Oxygen-enriched film and preparation method thereof
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
Figure BDA0003225306950000041
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.
CN202110969987.8A 2021-08-23 2021-08-23 Oxygen-enriched film and preparation method thereof Pending CN113912880A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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