CN1054899C - Macromolecular composite for deodorization and fresh keeping and its prepn. method - Google Patents
Macromolecular composite for deodorization and fresh keeping and its prepn. method Download PDFInfo
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- CN1054899C CN1054899C CN95106186A CN95106186A CN1054899C CN 1054899 C CN1054899 C CN 1054899C CN 95106186 A CN95106186 A CN 95106186A CN 95106186 A CN95106186 A CN 95106186A CN 1054899 C CN1054899 C CN 1054899C
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- acrylic monomer
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- deodorizing
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Abstract
The present invention relates to a macromolecular composite for deodorization and preservation and a production method thereof, which has the technical scheme that acrylic acid and alkali salt thereof are used as main components; a monomer which can have crosslinking copolymerization and graft copolymerization with acrylic monomers is used as an auxiliary component; the main components, the auxiliary component and modified fiber base material which can have graft copolymerization with the acrylic monomers have graft copolymerization under the action of an initiator in order to form the macromolecular composite. The macromolecular composite has the advantage of good ventilation property and has a certain function of regulating dry-wet balance in limited enclosed space; thus, the macromolecular composite has the functions of preserving garden stuff and removing odor obviously; for example, 95% of water-solubility abnormal smell in a refrigerator can be removed when the macromolecular composite is put in a storage chamber of the refrigerator for 36 hours, and the production method of the macromolecular composite has the advantage of good repeatability.
Description
Deodorizing and fresh-keeping belongs to fine chemical product and production technology thereof with polymer composite and manufacture method thereof.
Existing food, fruit and vegetable fresh-keeping agent and deodorant mostly are independently products of difference, do not have the product that two kinds of functions can be rolled into one.The antistaling agent great majority are to be Main Ingredients and Appearance with inorganic salts or organic salt, form with addition of various natural or artificial mildew-resistant, preservative agent again.As food antioxidant, preservative agent, drier, fruits and vegetables are protected ripe antistaling agent or its spray liniment, flower antistaling agent etc.Though these antistaling agents have the different fresh-keeping function of degree, all there is the side effect of medicine in they and to the pollution problem of fruit-vegetable food.And the use troublesome poeration, even some antistaling agent is not used, arriving certain time limit itself also can be mouldy.Existing deodorant or odor removal effect are all not obvious again.
The objective of the invention is to develop a kind of it not only should have tangible fresh-keeping effect, and also should have the polymer composite of obvious deodorization functions simultaneously.This material also should possess without any side effects, use simple to operation, the performance that the long-term storage of material own can be not mouldy yet.For reach this purpose again respective design its manufacture method.
Polymer composite of the present invention is a major constituent with acrylic acid and its alkali metal salt, with acrylic monomer copolymerzation with cross-linking and the monomer that connects the skill copolymerization be helper component, the modified fibre base-material that connects the skill copolymerization with acrylic monomer under action of evocating connects the skill copolymerization and forms.Connect in the acrylic monomer solution of skill copolymerization, the alkali metal salt (by weight percentage) of acrylic acid and it accounts for 20～90, with the acrylic monomer copolymerzation with cross-linking with connect that the skill comonomer accounts for 0.01～5, initator accounts for 0.01～6.The modified fibre base-material is not done requirement as carrier to its percentage by weight, but the thickness of base-material should be selected 0.01mm～2mm for use, and base-material should have the gas permeability micropore.The high molecular polymer thickness on base-material surface is 0.01mm～0.2mm.
Base-material can be selected polyvinyl alcohol modification fabric nonwoven cloth, vinal film, starch starching modified fibre gauze, starch starching modified fibre film, hydroxylated cellulose modified fibre cloth, hydroxylated cellulose modified fibre film etc. for use.
Also include the azanol reductant in being connect the acrylic monomer solution of skill copolymerization, the azanol reductant accounts for 0.01～6 by weight percentage.Initator adopts water-soluble peroxide.As potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate etc.The combination that can select a kind of in N.N acid amide type crosslinking agent, acrylic acid ethylene glycol or its polyethylene glycol compounds or two kinds for use with the monomer (being crosslinking agent) of acrylic monomer copolymerzation with cross-linking.
The manufacture method of polymer composite of the present invention is: the acrylic acid and the NaOH aqueous solution are carried out the part neutralization, and the initator that adds crosslinking agent and 1/3rd amounts then fully dissolves and forms acrylic monomer solution, is blown into nitrogen and catches up with except that dissolved oxygen.The initiator solution of preparation residue separately 2/3rds feeds nitrogen and catches up with except that dissolved oxygen in addition.In the closed dipping reactive tank that the acrylic monomer solution for preparing and initiator solution are put into nitrogen protection respectively; to be placed in the reactive tank through the fiber base-material that modification is handled again and flood; be placed in the plastic bag that is filled with nitrogen after taking out base-material; catch up with and remove nitrogen rear enclosed sack in the bag; place 65 ℃ ± 5 ℃ constant-temperature hot water solution to carry out polymerisation, the reaction back is incubated 3～6 hours under 65 ℃ ± 5 ℃ conditions.Take out the back it is carried out the dry shaping of vacuum drawn.
Polymer composite of the present invention also can adopt following manufacture method to finish.Acrylic acid and NaOH solution are carried out the part neutralization, add monomer, azanol reductant and initator with the acrylic monomer copolymerzation with cross-linking again, to form the acrylic monomer aqueous solution.This solution is removed dissolved oxygen with nitrogen bubbling law.The acrylic monomer aqueous solution is put into the closed dipping reactive tank of nitrogen protection; to be placed in the reactive tank through the fiber base-material that modification is handled again and flood; be placed in the plastic bag that is filled with nitrogen after taking out base-material; catch up with and remove nitrogen rear enclosed sack in the bag; place 65 ℃ ± 5 ℃ constant-temperature hot water solution to carry out polymerisation, the reaction back is incubated 3～6 hours under 65 ℃ ± 5 ℃ conditions.Take out the back it is carried out the dry shaping of vacuum drawn.
Polymer composite of the present invention has air permeability and good, and certain regulatory function is arranged to doing wet balance in the limited enclosure space, so it has the effect of freshness-retaining vegetable, melon and fruit, as vegetables, melon and fruit being placed in the container of sealing, pack into behind this polymer composite, the average fate of freshness-retained vegetables did not go rotten at 15～50 days to moisture bigger vegetables (as Chinese cabbage) fresh keeping time greater than 7 days.It also has tangible deodorization functions, as the storeroom of putting into refrigerator is after 24 hours, and water-soluble peculiar smell can be removed after 80%, 36 hour and just can remove peculiar smell 95% in the case.Itself can not go mouldy this composite long-term storage yet, use simple to operate, without any side effects to vegetables, meet state health standards.This material also can be used for waterproofing and leakage-stopping.Its manufacture method advanced person, good reproducibility is easy to suitability for industrialized production, and the thickness of compound copolymer is even.
Embodiment one: add 105.3g, purity in the 500ml taper triangle cup and be 95% acrylic acid, slowly add 46.7g, concentration and be 25% the NaOH aqueous solution under continuous cooling and neutralize.Add 0.46g crosslinking agent and 0.59g initator and 0.3g azanol reductant then, and adjust the monomer concentration in the aqueous solution, make monomer concentration thus and be 28% the acrylic monomer aqueous solution.It is stand-by to remove dissolved oxygen with nitrogen bubbling law again.The polyvinyl alcohol nonwoven fabric of handling well (specification is 15 meters long, 11cm is wide, 0.09mm thick) is rolled into volume.The acrylic monomer aqueous solution input for preparing is provided with in the closed dipping reactive tank of nitrogen protection.Nonwoven fabric with continuous impregnating at the uniform velocity, is batched nonwoven fabric behind the dipping with synchronizing speed simultaneously, treat whole nonwoven fabric soaked take out after, put into the plastic bag that is filled with nitrogen in advance immediately, catch up with remove bag in nitrogen rear enclosed sack.Place 65 ℃ of constant-temperature hot water solution to carry out polymerisation, the time of polymerisation is 10～30 minutes, then 65 ℃ of condition insulations 4 hours, has so far made the macromolecular compound cloth band of macromolecule graft copolymers.Flatten through cut-out, vacuum drawn drying, shaping, make the polymer composite of 15 meters of length, wide 11cm.Be about 110g by compound suction graft copolymers, the thickness of compound copolymer is 0.01～0.03mm.
Embodiment two: add 105.3g, purity in the 500ml taper triangle cup and be 95% acrylic acid, slowly to add 52.6g, purity under the cooling be that 95% NaOH, concentration are that 25% the aqueous solution neutralizes constantly stirring, obtain acrylic acid that 90% (mole) hydroxyl is neutralized and its alkali metal salt soln thus, add 0.59g crosslinking agent, 0.16g initator again, it is fully dissolved, and adjustment solution concentration, make concentration and be 38% acrylic monomer solution, be blown into nitrogen catch up with except that dissolved oxygen stand-by.The initiator solution of preparation 0.34g in addition separately, also feed in this initiator solution nitrogen catch up with except that dissolved oxygen stand-by.In the closed dipping reactive tank that the acrylic monomer solution for preparing respectively and initiator solution input are provided with nitrogen protection.The dipping operation and the condition of modified fibre nonwoven fabric are identical with embodiment one, just repeat no more.
Claims (9)
1, deodorizing and fresh-keeping polymer composite, it is characterized in that it is a major constituent with acrylic acid and its alkali metal salt, with acrylic monomer copolymerzation with cross-linking and the monomer that connects the skill copolymerization be helper component, the modified fibre base-material that connects the skill copolymerization with acrylic monomer under action of evocating connects the skill copolymerization and forms; Connect in the acrylic monomer solution of skill copolymerization, the alkali metal salt (by weight percentage) of acrylic acid and it accounts for 20～90, account for 0.01～5 with acrylic monomer copolymerzation with cross-linking and the monomer that connects the skill copolymerization, initator 0.01～6; The modified fibre base-material should have the gas permeability micropore.
2, the deodorizing and fresh-keeping manufacture method of polymer composite, it is characterized in that the acrylic acid and the NaOH aqueous solution are carried out the part neutralization, the initator that adds crosslinking agent and 1/3rd amounts then fully dissolves and forms acrylic monomer solution, is blown into nitrogen and catches up with except that dissolved oxygen; The initiator solution of preparation residue separately 2/3rds; feeding nitrogen catches up with except that dissolved oxygen; in the closed dipping reactive tank that the acrylic monomer solution for preparing and initiator solution are put into nitrogen protection respectively; to be placed in the reactive tank through the fiber base-material that modification is handled again and flood; be placed in the plastic bag that is filled with nitrogen after taking out base-material; catch up with and remove nitrogen rear enclosed sack in the bag; place 65 ℃ ± 5 ℃ constant-temperature hot water solution to carry out polymerisation; the reaction back is incubated 3～6 hours under 65 ℃ ± 5 ℃ conditions, take out the back it is carried out the dry shaping of vacuum drawn.
3, deodorizing and fresh-keeping polymer composite according to claim 1 is characterized in that the modified fibre base-material can select polyvinyl alcohol modification fabric nonwoven cloth, vinal film, starch starching modified fibre gauze, starch starching modified fibre film, hydroxylated cellulose modified fibre cloth, hydroxylated cellulose modified fibre film for use.
4, deodorizing and fresh-keeping polymer composite according to claim 1 is characterized in that can selecting for use with the monomer of acrylic monomer copolymerzation with cross-linking the combination of a kind of in N.N acid amide type crosslinking agent, acrylic acid ethylene glycol or its polyethylene glycol compounds or two kinds.
5, the deodorizing and fresh-keeping according to claim 2 manufacture method of polymer composite, it is characterized in that the acrylic acid and the NaOH aqueous solution are carried out the part neutralization, add monomer and azanol reductant and initator again with the acrylic monomer copolymerzation with cross-linking, to form the acrylic monomer aqueous solution, this solution is removed dissolved oxygen with nitrogen bubbling law; The acrylic monomer aqueous solution is put into the closed dipping tank of nitrogen protection; to be placed in the reactive tank through the fiber base-material that modification is handled again and flood; be placed in the plastic bag that is filled with nitrogen after taking out base-material; catch up with and remove nitrogen rear enclosed sack in the bag; place 65 ℃ ± 5 ℃ constant-temperature hot water solution to carry out polymerisation; under 65 ℃ ± 5 ℃ conditions, be incubated 3～6 hours, take out the back it is carried out the dry shaping of vacuum drawn.
6, deodorizing and fresh-keeping polymer composite according to claim 1, the thickness that it is characterized in that base-material is 0.01mm～2mm.
7, deodorizing and fresh-keeping polymer composite according to claim 1, the thickness that it is characterized in that the high molecular polymer on base-material surface is 0.01mm～2mm.
8, deodorizing and fresh-keeping polymer composite according to claim 1 is characterized in that being connect in the acrylic monomer solution of skill copolymerization and also includes the azanol reductant, and the azanol reductant accounts for 0.01～6 by weight percentage.
9, deodorizing and fresh-keeping polymer composite according to claim 1 is characterized in that initator adopts water-soluble peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95106186A CN1054899C (en) | 1995-06-05 | 1995-06-05 | Macromolecular composite for deodorization and fresh keeping and its prepn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95106186A CN1054899C (en) | 1995-06-05 | 1995-06-05 | Macromolecular composite for deodorization and fresh keeping and its prepn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1120614A CN1120614A (en) | 1996-04-17 |
| CN1054899C true CN1054899C (en) | 2000-07-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95106186A Expired - Fee Related CN1054899C (en) | 1995-06-05 | 1995-06-05 | Macromolecular composite for deodorization and fresh keeping and its prepn. method |
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| CN (1) | CN1054899C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005039968A1 (en) * | 2005-08-23 | 2007-03-08 | Basf Ag | Improved moisture-regulating composites |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101290A (en) * | 1993-10-05 | 1995-04-12 | 蒋晶洁 | Freshing agent |
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1995
- 1995-06-05 CN CN95106186A patent/CN1054899C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101290A (en) * | 1993-10-05 | 1995-04-12 | 蒋晶洁 | Freshing agent |
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| Publication number | Publication date |
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| CN1120614A (en) | 1996-04-17 |
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