CN103214612A - Preparation method of high-barrier-performance vinylidene chloride and acrylonitrile copolymer latex - Google Patents
Preparation method of high-barrier-performance vinylidene chloride and acrylonitrile copolymer latex Download PDFInfo
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- CN103214612A CN103214612A CN2013101605454A CN201310160545A CN103214612A CN 103214612 A CN103214612 A CN 103214612A CN 2013101605454 A CN2013101605454 A CN 2013101605454A CN 201310160545 A CN201310160545 A CN 201310160545A CN 103214612 A CN103214612 A CN 103214612A
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Abstract
The invention relates to a preparation method of high-barrier-performance vinylidene chloride and acrylonitrile copolymer latex. The preparation method is characterized in that the raw material adopted in the preparation method comprises the following components in parts by weight: 90 to 96 parts of vinylidene chloride monomer, 3 to 5 parts of acrylonitrile monomer, 1 to 2 parts of acrylic acid functional monomer, 0.4 to 3 parts of compound emulsifier, 0.05 to 0.3 part of pH (Potential of Hydrogen) modifier, 0.05 to 0.5 part of initiator, 5 to 35 parts of seed latex, 0 to 3.0 parts of stabilizer, 0 to 3.0 parts of antioxidant, and 100 parts of water. The lax shows white color for a long term, cannot be yellowed after being coated, and has high stability; the prepared latex can be directly coated on the surfaces of substrates such as PP (Polypropylene) hard sheets, PET (Polyethylene Terephthalate) hard sheets and PVDC (Polyvinyl Dichloride) hard sheets; a film formed by coating the latex or formed through the coated and dried latex has barrier performance, moisture resistance, fragrance holding performance, resistance to chemical medicines, flame resistance, etc.; and the coated film is transparent and not yellowed for a long time.
Description
Technical field
The present invention relates to the preparation method of a kind of high barrier vinylidene chloride and vinyl cyanide copolymer latex.
Background technology
Polyvinylidene dichloride (PVDC) copolymer latex is to be made through letex polymerization by vinylidene chloride (VDC) and vinyl cyanide, it can directly coat substrate surface, be applied to BOPP, BOPET, the packing of tobacco, food and medicine trades such as the hard sheet of PVC, disposable environmental protection tableware, paper pack internal layer, emulsion has the excellent barrier to oxygen and water (vapour) simultaneously.
The high barrier packing coated film of said polyvinylidene dichloride, also can be used for cigarette and pharmaceutical packing, but the raising and the China of high barrier being packed the coated film cognition degree along with people uses improving constantly of processing technology level, the Application Areas of food-film is in continuous expansion, the market share improves constantly, and the coating PVDC film market that is used for packings such as fried food product, cake, biscuit, fresh milk, snackfoods, dry fruit is increasing.
At present, PVDC latex on the market exists some and makes us dissatisfied part, easy to change, the foaming in coating rear film surface, can not keep the clear, colorless state for a long time, CN1523164A, CN101186666A and CN1294326C: in disclosed technology, mainly solving copolymerization forms, problems such as barrier property, but fail to solve the latex discoloration problem well, PVDC latex can't be applied better in the food product pack field.In addition, present PVDC latex stability is not good enough, place certain hour and occur the part paste easily, and degree of crystallinity is too high, and the normal coating that has influenced it is used.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of vinylidene chloride and acrylonitrile compolymer latex is to overcome the above-mentioned defective that prior art exists.Raw material among the preparation method of the present invention comprises the component of following parts by weight: 90～96 parts of vinylidene, 3～5 parts of acrylonitrile monemers, 1～2 part of acrylate functional monomer, 0.4～3 part of compound emulsifying agent, 0.05～0.3 part of PH conditioning agent, 0.05～0.5 part of initiator, 5～35 parts of seed latexes, 0～3.0 part of stablizer, 0～3.0 part in oxidation inhibitor, 100 parts in water.
Described acrylate functional monomer is selected from vinylformic acid or methyl acrylate or glycidyl acrylate, and purpose is in order to reduce the degree of crystallinity of latex.
Described compound emulsifying agent is the mixture of anion surfactant and nonionogenic tenside, anion surfactant is selected long-chain benzene sulfonate or hard soap for use, preferred Sodium dodecylbenzene sulfonate or sodium lauryl sulphate, nonionogenic tenside is selected polyoxyethylene nonyl phenyl vinyl ether or octylphenol polyethylene oxyethylene group ether for use.
Described PH conditioning agent is selected acetate for use.
Described initiator is the redox initiator that peroxide compound and reductive agent are formed, and described peroxide compound is selected tertbutyl peroxide for use, and described reductive agent is selected formaldehyde sodium sulfoxylate and solution of ferrous chloride for use.
Described seed latex is the monomeric copolymer latex of vinylidene chloride, vinyl cyanide and acrylate functional.
The present invention is for improving latex stability, makes that its long-term placement does not precipitate, layering, and the present invention also comprises stablizer, and said stablizer is selected from one or more in alkyl-sulphate, alkylbenzene sulfonate, ammonium laurate and the alkylphenol polyoxyethylene thiazolinyl ether.
The present invention deviates from hydrogenchloride for preventing latex under heat, oxygen environment when storing, cause polymkeric substance to produce conjugated double bond, the latex its colour changed into yellow also comprises oxidation inhibitor, oxidation inhibitor is selected from Polyphenols derivative or p-aminophenol derivative, preferably N-cyclohexyl-p-ethoxyaniline.
Preparation method of the present invention is as follows: with water, account for the compound emulsifying agent of gross weight 40～60%, the PH conditioning agent, the seed latex, account for the vinylidene chloride of gross weight 40～60%, the propylene that accounts for gross weight 40～60% is fine, account for the acrylate functional monomer of gross weight 40～60%, in inert atmosphere, pressure is under 0.035～0.15Mp and 45 ℃～55 ℃, drip the redox initiator that peroxide compound and reductive agent are formed, reaction begins to descend as for pressure, this moment, transformation efficiency was 5～35% o'clock, the compound emulsifying agent that adds surplus again, the vinylidene chloride of surplus, the acrylate functional monomer of the vinyl cyanide of surplus and surplus, react when system pressure drops to 0.01～0.035Mpa, add stablizer and oxidation inhibitor, react to system pressure and drop to 0.005～0.01%, from reaction product, collect vinylidene chloride and acrylonitrile compolymer latex then.
Latex of the present invention, color is white in color for a long time, not flavescence after the coating, good stability, gained latex can directly be coated substrate surfaces such as PP, PET, the hard sheet of PVDC, have barrier, moisture resistance, fragrance protectiveness, chemical proofing, flame retardancy etc. by coating or the dry film that forms afterwards of coating, filming is transparent for a long time, not flavescence.
Embodiment
Below, describe technical scheme of the present invention in detail by embodiment.
Embodiment 1
In the 10L still, drop into the 1600g de-salted water, 10.08g sodium lauryl sulphate, 4.0g octyl phenol oxyethylene group ether, the 100g seed latex drops in the still, the nitrogen pressure testing vacuumizes the back and adds the 400g vinylidene chloride, the warm and fine 5g vinylformic acid of 45g propylene mix monomer, be warming up to 50 ℃ after stirring, pressure is 0.035Mpa, drip the 2.0g tertbutyl peroxide, 3.5g formaldehyde sodium sulfoxylate, 0.03g solution of ferrous chloride, the beginning polymerization, polymerisation conversion began to drip the 400g vinylidene chloride at about 30% o'clock, 45g vinyl cyanide and 10g vinylformic acid mix monomer, 8.0g sodium lauryl sulphate and 4.0g octyl phenol oxyethylene group ether mixing and emulsifying agent solution, controlled polymerization transformation efficiency about 70% drips, keep constant ammonium laurate and the N-cyclohexyl-p-ethoxyaniline of when polymerization pressure drops to 0.025Mpa, adding of polymerization temperature, back recovery unreacted monomer stirs, slurry reclaims through stripping, filter, make copolymer latex, the sample analysis test the results are shown in Table 1.
Embodiment 2
The emulsifying agent kind changes sodium lauryl sulphate and nonyl phenol oxyethylene group ether into when producing copolymer latex, and pressure, consumption are identical with embodiment 1, and other processing condition make copolymer latex with embodiment 1, and the sample analysis test the results are shown in Table 1.
Table 1
Copolymer latex of the present invention as seen from Table 1, color is white in color for a long time, not flavescence after the coating, good stability, gained latex can directly be coated substrate surfaces such as PP, PET, the hard sheet of PVDC, have barrier, moisture resistance, fragrance protectiveness, chemical proofing, flame retardancy etc. by coating or the dry film that forms afterwards of coating, filming is transparent for a long time, not flavescence.
Claims (8)
1. the preparation method of high barrier vinylidene chloride and vinyl cyanide copolymer latex, it is characterized in that: the raw material for preparing this method comprises the component of following parts by weight: 90～96 parts of vinylidene, 3～5 parts of acrylonitrile monemers, 1～2 part of acrylate functional monomer, 0.4～3 part of compound emulsifying agent, 0.05～0.3 part of PH conditioning agent, 0.05～0.5 part of initiator, 5～35 parts of seed latexes, 0～3.0 part of stablizer, 0～3.0 part in oxidation inhibitor, 100 parts in water;
This preparation method is as follows: with water, account for the compound emulsifying agent of gross weight 40～60%, the PH conditioning agent, the seed latex, account for the vinylidene chloride of gross weight 40～60%, the propylene that accounts for gross weight 40～60% is fine, account for the acrylate functional monomer of gross weight 40～60%, in inert atmosphere, pressure is under 0.035～0.15Mp and 45 ℃～55 ℃, drip the redox initiator that peroxide compound and reductive agent are formed, reaction begins to descend as for pressure, this moment, transformation efficiency was 5～35% o'clock, the compound emulsifying agent that adds surplus again, the vinylidene chloride of surplus, the acrylate functional monomer of the vinyl cyanide of surplus and surplus, react when system pressure drops to 0.01～0.035Mpa, add stablizer and oxidation inhibitor, react to system pressure and drop to 0.005～0.01%, from reaction product, collect vinylidene chloride and acrylonitrile compolymer latex then.
2. preparation method according to claim 1 is characterized in that: described acrylate functional monomer is selected from vinylformic acid or methyl acrylate or glycidyl acrylate.
3. preparation method according to claim 1, it is characterized in that: described compound emulsifying agent is the mixture of anion surfactant and nonionogenic tenside, described anion surfactant is selected long-chain benzene sulfonate or hard soap for use, preferred Sodium dodecylbenzene sulfonate or sodium lauryl sulphate, described nonionogenic tenside is selected polyoxyethylene nonyl phenyl vinyl ether or octylphenol polyethylene oxyethylene group ether for use.
4. preparation method according to claim 1 is characterized in that: described PH conditioning agent is selected acetate for use.
5. preparation method according to claim 1, it is characterized in that: described initiator is the redox initiator that peroxide compound and reductive agent are formed, described peroxide compound is selected tertbutyl peroxide for use, and described reductive agent is selected formaldehyde sodium sulfoxylate and solution of ferrous chloride for use.
6. preparation method according to claim 1 is characterized in that: described seed latex is the monomeric copolymer latex of vinylidene chloride, vinyl cyanide and acrylate functional.
7. preparation method according to claim 1 is characterized in that: said stablizer is selected from one or more in alkyl-sulphate, alkylbenzene sulfonate, ammonium laurate and the alkylphenol polyoxyethylene thiazolinyl ether.
8. preparation method according to claim 1 is characterized in that: described oxidation inhibitor is selected from Polyphenols derivative or p-aminophenol derivative, preferably N-cyclohexyl-p-ethoxyaniline.
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| CN2013101605454A CN103214612A (en) | 2013-05-06 | 2013-05-06 | Preparation method of high-barrier-performance vinylidene chloride and acrylonitrile copolymer latex |
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| CN2013101605454A CN103214612A (en) | 2013-05-06 | 2013-05-06 | Preparation method of high-barrier-performance vinylidene chloride and acrylonitrile copolymer latex |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482572A (en) * | 2014-10-09 | 2016-04-13 | 南通瑞普埃尔生物工程有限公司 | Preparation method of PVDC latex for egg freshness retaining coating |
| WO2017049695A1 (en) * | 2015-09-25 | 2017-03-30 | 南通瑞普埃尔生物工程有限公司 | Method for preparing pvdc emulsion for water-based environmentally-friendly tableware |
| CN109206797A (en) * | 2018-08-30 | 2019-01-15 | 奚正华 | It is a kind of based on vinylidene chloride-ethylene-propylene lonitrile copolymer preservative film and preparation method thereof |
| CN110437684A (en) * | 2019-08-15 | 2019-11-12 | 安徽大学 | Aniline tripolymer modified water-soluble polyvinylidene chloride anticorrosive paint and preparation method |
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| CN101033276A (en) * | 2007-03-27 | 2007-09-12 | 中山大学 | Self-deposition coating based on vinylidene chloride-acrylate copolymer latex and preparing method |
| JP2012197391A (en) * | 2011-03-23 | 2012-10-18 | Asahi Kasei Chemicals Corp | Coating material for pottery-based siding material and pottery-based siding material |
| CN102936309A (en) * | 2012-10-29 | 2013-02-20 | 浙江巨化股份有限公司电化厂 | Boiling-resistant PVDC (polyvinyl dichloride) water-based emulsion |
| CN103059193A (en) * | 2012-12-26 | 2013-04-24 | 海南必凯水性涂料有限公司 | Polyvinyl dichloride (PVDC) coating latex special for cigarette films and preparation method and application thereof |
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2013
- 2013-05-06 CN CN2013101605454A patent/CN103214612A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101033276A (en) * | 2007-03-27 | 2007-09-12 | 中山大学 | Self-deposition coating based on vinylidene chloride-acrylate copolymer latex and preparing method |
| JP2012197391A (en) * | 2011-03-23 | 2012-10-18 | Asahi Kasei Chemicals Corp | Coating material for pottery-based siding material and pottery-based siding material |
| CN102936309A (en) * | 2012-10-29 | 2013-02-20 | 浙江巨化股份有限公司电化厂 | Boiling-resistant PVDC (polyvinyl dichloride) water-based emulsion |
| CN103059193A (en) * | 2012-12-26 | 2013-04-24 | 海南必凯水性涂料有限公司 | Polyvinyl dichloride (PVDC) coating latex special for cigarette films and preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482572A (en) * | 2014-10-09 | 2016-04-13 | 南通瑞普埃尔生物工程有限公司 | Preparation method of PVDC latex for egg freshness retaining coating |
| WO2017049695A1 (en) * | 2015-09-25 | 2017-03-30 | 南通瑞普埃尔生物工程有限公司 | Method for preparing pvdc emulsion for water-based environmentally-friendly tableware |
| CN109206797A (en) * | 2018-08-30 | 2019-01-15 | 奚正华 | It is a kind of based on vinylidene chloride-ethylene-propylene lonitrile copolymer preservative film and preparation method thereof |
| CN110437684A (en) * | 2019-08-15 | 2019-11-12 | 安徽大学 | Aniline tripolymer modified water-soluble polyvinylidene chloride anticorrosive paint and preparation method |
| CN110437684B (en) * | 2019-08-15 | 2021-11-26 | 安徽大学 | Aniline trimer modified aqueous polyvinylidene chloride heavy-duty anticorrosive paint and preparation method thereof |
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Application publication date: 20130724 |