CN103319642B - A kind of heat-sealing type PVDC emulsion possessing anti-fog function and preparation method thereof - Google Patents
A kind of heat-sealing type PVDC emulsion possessing anti-fog function and preparation method thereof Download PDFInfo
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- 229920001328 Polyvinylidene chloride Polymers 0.000 title claims abstract description 101
- 239000000839 emulsion Substances 0.000 title claims abstract description 101
- 239000005033 polyvinylidene chloride Substances 0.000 title claims abstract description 101
- 238000007789 sealing Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 43
- 239000008367 deionised water Substances 0.000 claims abstract description 39
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- -1 acrylic ester Chemical class 0.000 claims abstract description 23
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 239000013530 defoamer Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 73
- 238000003756 stirring Methods 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 238000007599 discharging Methods 0.000 claims description 18
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 10
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 10
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical group [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 10
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 10
- 241001062009 Indigofera Species 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 241000237502 Ostreidae Species 0.000 claims description 9
- 208000002173 dizziness Diseases 0.000 claims description 9
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 9
- 239000011790 ferrous sulphate Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 9
- 235000020636 oyster Nutrition 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 7
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000811 xylitol Substances 0.000 claims description 7
- 229960002675 xylitol Drugs 0.000 claims description 7
- 235000010447 xylitol Nutrition 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229920000223 polyglycerol Polymers 0.000 claims description 6
- 239000005639 Lauric acid Substances 0.000 claims description 5
- 210000000481 breast Anatomy 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 12
- 230000005540 biological transmission Effects 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 11
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000003292 glue Substances 0.000 description 8
- 239000003595 mist Substances 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000004806 packaging method and process Methods 0.000 description 2
- 235000011888 snacks Nutrition 0.000 description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical class ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 235000015220 hamburgers Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 238000007639 printing Methods 0.000 description 1
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- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a kind of heat-sealing type PVDC emulsion possessing anti-fog function, described PVDC emulsion is made up of the raw material of following weight proportioning: PVDC copolymer emulsion 88 ~ 97%, dispersion agent 0.2 ~ 3%, antifogging agent 2 ~ 10%; Described PVDC copolymer emulsion is by vinylidene chloride 35 ~ 45%, acrylic ester monomer 1 ~ 5%, functional monomer 0.1 ~ 3%, oxidized form initiator 0.005 ~ 0.05%, reduced form initiator 0.005 ~ 0.05%, emulsifying agent 0.2 ~ 4%, ionogen 0.01 ~ 0.1%, pH adjusting agent 0.05 ~ 2%, defoamer 0.02 ~ 0.1%, deionized water 42 ~ 55% copolymerization forms.Present invention also offers a kind of preparation method possessing the heat-sealing type PVDC emulsion of anti-fog function.Preparation method's technique of the present invention is simple, is easy to control; Described emulsion property is stablized.
Description
Technical field
The present invention relates to a kind of heat-sealing type PVDC emulsion possessing anti-fog function and preparation method thereof, belong to novel high polymer material field.
Background technology
Snack food product is convenient, fast because of it, receive human consumer greatly to like, and recognize along with more and more people, the harm of the snack food products such as hamburger, it has the trend to dead end development, sandwich because it is healthy, convenient and of all shapes and colorsly will lead the healthy fast food theory of a new round.Need directly to pack after high-temperature sterilization in the production process of circulation of sandwich, then stored refrigerated is carried out, and in order to allow client see product clearly, capital uses window type packaging, but owing to itself containing certain moisture, in package storage process, due to the change of product temperature, be easy to produce one deck water smoke at packing bag internal layer, this has a strong impact on the image appearance of product, makes client to see product clearly and to cut down desire to purchase.
The antifog technology of tradition be by packing plastics film in preparation process by adding antifogging agent and reach anti-fog effect extruding in masterbatch, as patent application CN102285182A, although this invention achievement has bilateral anti-fog function, but without barrier property, the wrap food quality guaranteed period can only reach 3-5 days.Sandwich products production producer, in order to extend haul-cycle time and shelf-lives, packaging film is coated with PVDC barrier material, makes effective period of food quality extend to 15 days.PVDC is a kind of nonpoisonous and tasteless, safe and reliable high resistant oxygen, block water steam material, and also have excellent heat seal strength and printing performance etc., therefore PVDC coated film is widely used in the packaging field such as cake, medicine simultaneously.But existing PVDC does not have anti-fog performance on market, as patent application CN101358054A.
For above problem, if a kind of heat-sealing type PVDC emulsion possessing anti-fog function can be developed, the quality guaranteed period of sandwich product will be extended, make its range of application more extensive.
Summary of the invention
For the above-mentioned shortcoming that PVDC emulsion exists, the object of the present invention is to provide a kind of heat-sealing type PVDC emulsion possessing anti-fog function and preparation method thereof.Described antifog, prevent film surface from hazing exactly and affect its transparency, invent the heat-sealing type PVDC emulsion of this anti-fog function, its innovative point is: one is that acrylate monomer only selects butyl acrylate in PVDC copolymer emulsion building-up process, this can strengthen PVDC polymer chain flexibility greatly, make PVDC coating under low temperature (4 DEG C) environment, be not easy be full of cracks, improve the frost resistance of PVDC barrier material; Two be by the PVDC copolymer emulsion for preparing and antifogging agent blended, due to antifogging agent have can reduce or eliminate frosting and cause because of moisture condensation, the feature such as haze, and PVDC blending emulsion can be made to possess anti-fog performance; Three is by adding functional monomer, making PVDC macromolecular chain to add a lot of hydrophilic radical carboxyl, promotes coating anti-fog function.
Possess a heat-sealing type PVDC emulsion for anti-fog function, described PVDC emulsion is made up of the raw material of following weight proportioning: PVDC copolymer emulsion 88 ~ 97%, dispersion agent 0.2 ~ 3%, antifogging agent 2 ~ 10%; Described PVDC copolymer emulsion is by vinylidene chloride 35 ~ 45%, acrylic ester monomer 1 ~ 5%, functional monomer 0.1 ~ 3%, oxidized form initiator 0.005 ~ 0.05%, reduced form initiator 0.005 ~ 0.05%, emulsifying agent 0.2 ~ 4%, ionogen 0.01 ~ 0.1%, pH adjusting agent 0.05 ~ 2%, defoamer 0.02 ~ 0.1%, deionized water 42 ~ 55% copolymerization forms.
Further technical scheme is, described antifogging agent is one or both arbitrary combination in xylitol ester, lauric acid, polyglycerol fatty acid glyceryl ester.
Further technical scheme is, described dispersion agent is polyoxyethylene glycol.
Further technical scheme is, described acrylic ester monomer is butyl acrylate, and described functional monomer is one or both arbitrary combination in methacrylic acid, vinylformic acid; Described oxidized form initiator is tertbutyl peroxide; Described reduced form initiator is rongalite; Described emulsifying agent is sodium lauryl sulphate; Described ionogen is one or both arbitrary combination in ferrous sulfate, zinc sulfate; Described pH adjusting agent is Glacial acetic acid; Described defoamer is silicone antifoam agent.
The above-mentioned preparation method possessing the heat-sealing type PVDC emulsion of anti-fog function, comprises the following steps:
(1) 35 ~ 45% vinylidene chlorides, 1 ~ 5% acrylic ester monomer and 0.1 ~ 3% functional monomer mix and blend are made into mix monomer A;
(2) by 0.2 ~ 4% emulsifying agent with 20% of the ionized water total amount that accounts for deionized water mix and blend be made into emulsifying agent B;
(3) by the oxidized form initiator of 0.005 ~ 0.05% with 15% of the ionized water total amount that accounts for deionized water dissolving be made into initiator C;
(4) by the reduced form initiator of 0.005 ~ 0.05% with 15% of the ionized water total amount that accounts for deionized water dissolving be made into initiator D;
(5) in polymeric kettle, first add reaction material carry out first time and stir, and at the temperature of nitrogen protection and 50 ~ 52 DEG C reaction 1 ~ 1.5h; Described reaction material comprise 50% of the ionized water total amount that accounts for deionized water, account for mix monomer A total amount 6 ~ 15% mix monomer A, account for emulsifying agent B total amount 1.5 ~ 3.5% emulsifying agent B, account for initiator C total amount 1 ~ 3% the pH adjusting agent of initiator C and 0.05 ~ 2%;
Until described reaction material from oyster white become semi-transparent zone indigo plant dizzy time, continuous dropping residue mix monomer A, residual emulsifier B, residue initiator C and initiator D, continue first time to stir and nitrogen protection, and 8 ~ 10h is reacted at 50 ~ 55 DEG C of temperature, and control residue mix monomer A and residual emulsifier B and first drip off simultaneously, remain initiator C after 1h and initiator D also adds simultaneously; When question response pressure reduces to-0.02MPa from 0.8 ~ 1.2MPa, reaction terminates;
Finally in emulsion, add 0.01 ~ 0.1% ionogen, 0.02 ~ 0.1% defoamer, is cooled to less than 40 DEG C, filters discharging and obtains PVDC copolymer emulsion;
(6) described PVDC copolymer emulsion is joined in another modified-reaction still, under room temperature 25 DEG C of conditions, carry out second time stir, first slowly 0.2 ~ 3% dispersion agent is dripped within the time of 1h, slowly drip the antifogging agent of 2 ~ 10% again, dropwising rear continuation second time to stir after 0.5h through filtering discharging, has the heat-sealing type PVDC emulsion of anti-fog function described in obtained.Further technical scheme is, described first time stirring velocity be 55 ~ 75 revs/min, the stirring velocity that described second time stirs is 30 ~ 50 revs/min.
Compared with prior art, beneficial effect of the present invention is: technique is simple, is easy to control; The emulsion property invented is stablized, and after coating, PVDC coating has good oxygen, vapor water barriers performance, heat seal strength and anti-fog performance.Film after using this emulsion to be coated with is highly suitable for packing needs antifog food, not only improves the illustrative of commodity but also can extend by the shelf-lives of bag food.
Table 1 PVDC emulsion property of the present invention index
By BOPP base material is coated with existing PVDC emulsion and PVDC emulsion of the present invention contrast (as table 2) known, emulsion of the present invention has good vapor water barriers and oxygen barrier property, heat seal strength all can reach 3.5 N/15mm, and has good anti-fog performance.In table 2, described BOPP base material thickness is 19 μm, and PVDC glue spread is 3.0g/m
2; Described cold mist method is respectively used to pack sandwich by the film of BOPP base material film, the film being coated with existing PVDC emulsion, coating PVDC emulsion of the present invention before coating, sealing, first be placed in 90 DEG C, after 20s, let alone Temperature fall, under being then placed in 4 DEG C of environment, refrigerate 30min; Described existing PVDC emulsion refers to the PVDC emulsion that patent CN101358054A mentions; Table 3 is the criterion of anti-fog performance rank.
Table 2 BOPP is coated with existing PVDC emulsion and PVDC emulsion salient features of the present invention contrast
The criterion of table 3 anti-fog performance rank
| Grade | Antifog appearance effect |
| A | Transparency is poor, and face has a lot of little water droplet |
| B | Transparency is general, and face has the large water droplet of part |
| C | Face 70% has water droplet |
| D | Face has part water droplet |
| D/E | Good transparency, face has a small amount of water droplet |
| E | Highly transparent, face is without water droplet |
Embodiment
Below in conjunction with specific embodiment, a kind of heat-sealing type PVDC emulsion with anti-fog function of the present invention and preparation method thereof is described further, but is not limitation of the invention.
Embodiment one
Possesses a heat-sealing type PVDC emulsion for anti-fog function, by following component raw materials (unit: kg)
Above-mentioned a kind of heat-sealing type PVDC emulsion preparation method possessing anti-fog function: 1. first by 30.0kg vinylidene chloride, 0.7kg butyl acrylate, the abundant mix and blend 1h of 0.65kg methacrylic acid, obtains mix monomer A; By the deionized water mix and blend 1h of 0.5kg sodium lauryl sulphate 7.0kg, stirring velocity is 80 revs/min and obtains emulsifying agent B; The deionized water dissolving of the tertbutyl peroxide 5.2kg of 0.02kg is made into initiator C; The deionized water dissolving of the rongalite 5.2kg of 0.02kg is made into initiator D.Remaining deionized water is first added in polymeric kettle; the mix monomer A of 1.95kg; the emulsifying agent B of 0.2kg; the initiator C of 0.1kg, the Glacial acetic acid of 0.8kg, opens and stirs; stirring velocity is 70 revs/min; logical nitrogen protection, is warming up to 50 DEG C of reaction 1h, and it is dizzy that question response material becomes semi-transparent zone indigo plant from oyster white.Continuous dropping remains mix monomer A, residual emulsifier B, residue initiator C and initiator D simultaneously, and keep 53 DEG C to react 8h, and first add the while of controlling mix monomer A and emulsifying agent B, after 1h, initiator C and initiator D also adds simultaneously.Question response pressure reduces to-0.02MPa constantly from 0.8MPa, and reaction terminates.Finally in emulsion, add 0.07kg ferrous sulfate, 0.06kg silicone antifoam agent, be cooled to less than 40 DEG C, filter discharging, obtain the PVDC copolymer emulsion of 67.82kg.
2. get above-mentioned obtained 67.82kgPVDC copolymer emulsion, be pumped in another modified-reaction still, open and stir, stirring velocity is set as 40 revs/min.First slowly drip 0.78kg polyoxyethylene glycol, more slowly drip the xylitol ester of 1.4kg, time for adding controls, at 1h, to dropwise, and through filtering discharging after continuation stirring reaction 0.5h, obtains the PVDC emulsion that solid content is 50.0%.Obtained PVDC emulsion be coated with, base material is the glue spread of the BOPP of 19 μm, PVDC emulsion is 3.0g/m
2, lower machine solidifies 48h under being placed on 40 DEG C of conditions, records its OTR oxygen transmission rate 14.5cc/m
2.24hr, water vapor transmission rate (WVTR) is 4.0g/m
2.24hr, at 127 DEG C, when 0.14Mpa, 0.75s, the heat seal strength of PVDC coating is 3.5N/15mm, is E level through cold mist method test.
Embodiment two
Possesses a heat-sealing type PVDC emulsion for anti-fog function, by following component raw materials (unit: kg)
Above-mentioned a kind of preparation method possessing the heat-sealing type PVDC emulsion of anti-fog function: 1. first by 48.0kg vinylidene chloride, 5.6kg butyl acrylate, 4.0kg vinylformic acid, abundant mix and blend 1.2h, obtains mix monomer A; By the deionized water mix and blend 1h of 0.28kg sodium lauryl sulphate 15.0kg, stirring velocity is 80 revs/min and obtains emulsifying agent B; The deionized water dissolving of the tertbutyl peroxide 11.0kg of 0.07kg is made into initiator C; The deionized water dissolving of the rongalite 11.0kg of 0.07kg is made into initiator D.Remaining deionized water is first added in polymeric kettle; the mix monomer A of 5.0kg; the emulsifying agent B of 0.3kg; the initiator C of 0.25kg, the Glacial acetic acid of 2.7kg, opens and stirs; stirring velocity is 70 revs/min; logical nitrogen protection, is warming up to 50 DEG C of reaction 1.3h, and it is dizzy that question response material becomes semi-transparent zone indigo plant from oyster white.Continuous dropping remains mix monomer A, residual emulsifier B simultaneously, residue initiator C and initiator D, and keep 55 DEG C to react 10h, and first add the while of controlling mix monomer A and emulsifying agent B, after 1h, initiator C and initiator D also adds simultaneously.Question response pressure reduces to-0.02MPa constantly from 1.2MPa, and reaction terminates.Finally in emulsion, add 0.14kg zinc sulfate, 0.14kg silicone antifoam agent, be cooled to less than 40 DEG C, filter discharging, obtain the PVDC copolymer emulsion of 135.5kg.
2. get above-mentioned obtained 135.5kgPVDC copolymer emulsion, be pumped into another modified-reaction still, open and stir, stirring velocity is set as 40 revs/min.First slowly be added dropwise to 3.0kg polyoxyethylene glycol, more slowly drip the lauric acid of 10.0kg, time for adding controls, at 1h, to dropwise, and through filtering discharging after continuation stirring reaction 0.5h, obtains the PVDC emulsion that solid content is 49.8%.Obtained PVDC emulsion be coated with, base material is the glue spread of the BOPP of 19 μm, PVDC emulsion is 3.0g/m
2, lower machine solidifies 48h under being placed on 40 DEG C of conditions, and recording its OTR oxygen transmission rate is 13cc/m
2.24hr, water vapor transmission rate (WVTR) is 3.8g/m
2.24hr, at 127 DEG C, when 0.14Mpa, 0.75s, the heat seal strength of coating is 3.6N/15mm, is E level through cold mist method test.
Embodiment three
Possesses a heat-sealing type PVDC emulsion for anti-fog function, by following component raw materials (unit: kg)
Above-mentioned a kind of preparation method possessing the heat-sealing type PVDC emulsion of anti-fog function: 1. first by 70.0kg vinylidene chloride, 9.5kg butyl acrylate, 0.4kg vinylformic acid, 1.5kg methacrylic acid, abundant mix and blend 1h, obtains mix monomer A; By the deionized water mix and blend 1h of 7.5kg sodium lauryl sulphate 20.0kg, stirring velocity is 80 revs/min and obtains emulsifying agent B; By the tertbutyl peroxide of 0.03kg be made into initiator C with the deionized water dissolving of 15.0kg; The deionized water dissolving of the rongalite 15.0kg of 0.03kg is made into initiator D.Remaining deionized water is first added in polymeric kettle; the mix monomer of 6.2kg; the emulsifying agent B of 0.58kg; the initiator C of 0.35kg, the Glacial acetic acid of 1.4kg, opens and stirs; stirring velocity is 70 revs/min; logical nitrogen protection, is warming up to 50 DEG C of reaction 1h, and it is dizzy that question response material becomes semi-transparent zone indigo plant from oyster white.Continuous dropping remains mix monomer A, residual emulsifier B, residue initiator C and initiator D simultaneously, and keep 55 DEG C to react 8h, and first add the while of controlling mix monomer A and emulsifying agent B, after 1h, initiator C and initiator D also adds simultaneously.Question response pressure reduces to-0.02MPa constantly from 1MPa, and reaction terminates.Finally in emulsion, add 0.1kg ferrous sulfate, 0.4kg silicone antifoam agent, be cooled to less than 40 DEG C, filter discharging, obtain the PVDC copolymerization breast of 190.5kg.
2. get above-mentioned obtained 190.5kg PVDC copolymer emulsion, be pumped in another modified-reaction still, open and stir, stirring velocity is set as 40 revs/min.First slowly drip 1.2kg polyoxyethylene glycol, more slowly drip the xylitol ester of 3.0kg and the lauric acid of 6.5kg, time for adding controls, at 1h, to dropwise, and through filtering discharging after continuation stirring reaction 0.5h, obtains the PVDC emulsion that solid content is 50.1%.Obtained PVDC emulsion be coated with, base material is the glue spread of the BOPP of 19 μm, PVDC emulsion is 3.0g/m
2, lower machine solidifies 48h under being placed on 40 DEG C of conditions, and recording its OTR oxygen transmission rate is 14.2cc/m
2.24hr, water vapor transmission rate (WVTR) is 3.2g/m
2.24hr, at 127 DEG C, when 0.14Mpa, 0.75s, the heat seal strength of coating is 3.6N/15mm, is E level through cold mist method test.
Embodiment four
Possesses a heat-sealing type PVDC emulsion for anti-fog function, by following component raw materials (unit: kg)
Above-mentioned a kind of preparation method possessing the heat-sealing type PVDC emulsion of anti-fog function: 1. first by 22.0kg vinylidene chloride, 2.5kg butyl acrylate, 0.03kg vinylformic acid, 0.03kg methacrylic acid, abundant mix and blend 1h, obtains mix monomer A; By the deionized water mix and blend 1h of 0.2kg sodium lauryl sulphate 5.8kg, stirring velocity is 80 revs/min and obtains emulsifying agent B; By the tertbutyl peroxide of 0.025kg be made into initiator C with the deionized water dissolving of 4.4kg; The deionized water dissolving of the rongalite 4.4kg of 0.025kg is made into initiator D.Remaining deionized water is first added in polymeric kettle; the mix monomer A of 2.8kg; the emulsifying agent B of 0.15kg; the initiator C of 0.1kg, the Glacial acetic acid of 0.03kg, opens and stirs; stirring velocity is 70 revs/min; logical nitrogen protection, is warming up to 50 DEG C of reaction 1.5h, and it is dizzy that question response material becomes semi-transparent zone indigo plant from oyster white.Continuous dropping remains mix monomer A, residual emulsifier B, residue initiator C and initiator D simultaneously, and keep 54 DEG C to react 9h, and first add the while of controlling mix monomer A and emulsifying agent B, after 1h, initiator C and initiator D also adds simultaneously.Question response pressure reduces to-0.02MPa constantly from 0.9MPa, and reaction terminates.Finally in emulsion, add 0.04kg ferrous sulfate, 0.02kg silicone antifoam agent, be cooled to less than 40 DEG C, filter discharging, obtain the PVDC copolymerization breast of 54.9kg.
2. get above-mentioned obtained 54.9kg PVDC copolymer emulsion, be pumped in another modified-reaction still, open and stir, stirring velocity is set as 40 revs/min.First slowly drip 1.8kg polyoxyethylene glycol, more slowly drip the polyglycerol fatty acid glyceryl ester of 4.3kg, time for adding controls, at 1h, to dropwise, and through filtering discharging after continuation stirring reaction 0.5h, obtains the PVDC emulsion that solid content is 50.8%.Obtained PVDC emulsion be coated with, base material is the glue spread of the BOPP of 19 μm, PVDC emulsion is 3.0g/m
2, lower machine solidifies 48h under being placed on 40 DEG C of conditions, and recording its OTR oxygen transmission rate is 13.5cc/m
2.24hr, water vapor transmission rate (WVTR) is 3.5g/m
2.24hr, at 127 DEG C, when 0.14Mpa, 0.75s, the heat seal strength of coating is 3.8N/15mm, is E level through cold mist method test.
Embodiment five
Possesses a heat-sealing type PVDC emulsion for anti-fog function, by following component raw materials (unit: kg)
Above-mentioned a kind of preparation method possessing the heat-sealing type PVDC emulsion of anti-fog function: 1. first by 48.0kg vinylidene chloride, 3.5kg butyl acrylate, 2.0kg vinylformic acid, 1.0kg methacrylic acid, abundant mix and blend 1h, obtains mix monomer A; By the deionized water of 3.2kg sodium lauryl sulphate 15.0kg, mix and blend 1h, stirring velocity is 80 revs/min and obtains emulsifying agent B; By the tertbutyl peroxide of 0.01kg be made into initiator C with the deionized water dissolving of 11.0kg; The deionized water dissolving of the rongalite 11.0kg of 0.01kg is made into initiator D.Remaining deionized water is first added in polymeric kettle; the mix monomer A of 4.8kg; the emulsifying agent B of 0.5kg; the initiator C of 0.3kg; the Glacial acetic acid of 0.9kg is opened and is stirred, and stirring velocity is 70 revs/min, logical nitrogen protection; be warming up to 50 DEG C of reaction 1.5h, it is dizzy that question response material becomes semi-transparent zone indigo plant from oyster white.Continuous dropping remains mix monomer A, residual emulsifier B, residue initiator C and initiator D simultaneously, and keep 55 DEG C to react 10h, and first add the while of controlling mix monomer A and emulsifying agent B, after 1h, initiator C and initiator D also adds simultaneously.Question response pressure reduces to-0.02MPa constantly from 1.1MPa, and reaction terminates.Finally in emulsion, add 0.1kg ferrous sulfate, 0.08kg silicone antifoam agent, be cooled to less than 40 DEG C, filter discharging, obtain the PVDC copolymerization breast of 132.8kg.
2. get above-mentioned obtained 132.8kg PVDC copolymer emulsion, be pumped in another modified-reaction still, open and stir, stirring velocity is set as 40 revs/min.First slowly drip 2.2kg polyoxyethylene glycol, more slowly drip the xylitol ester of 7.0kg and the polyglycerol fatty acid glyceryl ester of 8.0kg, time for adding controls, at 1h, to dropwise, and through filtering discharging after continuation stirring reaction 0.5h, obtains the PVDC emulsion that solid content is 50.7%.Obtained PVDC emulsion be coated with, base material is the glue spread of the BOPP of 19 μm, PVDC emulsion is 3.0g/m
2, lower machine solidifies 48h under being placed on 40 DEG C of conditions, and recording its OTR oxygen transmission rate is 12.5cc/m
2.24hr, water vapor transmission rate (WVTR) is 3.2g/m
2.24hr, at 127 DEG C, when 0.14Mpa, 0.75s, the heat seal strength of coating is 3.7N/15mm, is E level through cold mist method test.
Embodiment six
Possesses a heat-sealing type PVDC emulsion for anti-fog function, by following component raw materials (unit: kg)
Above-mentioned a kind of preparation method possessing the heat-sealing type PVDC emulsion of anti-fog function: 1. first by 40.0kg vinylidene chloride, 1.8kg butyl acrylate, 0.5kg vinylformic acid, 0.8kg methacrylic acid, abundant mix and blend 1h, obtains mix monomer A; By the deionized water of 1.0kg sodium lauryl sulphate 11.2kg, mix and blend 1h, stirring velocity is 80 revs/min and obtains emulsifying agent B; By the tertbutyl peroxide of 0.02kg be made into initiator C with the deionized water dissolving of 8.4kg; The deionized water dissolving of the rongalite 8.4kg of 0.02kg is made into initiator D.Remaining deionized water is first added in polymeric kettle; the mix monomer A of 4.0kg; the emulsifying agent B of 0.3kg; the initiator C of 0.15kg; the Glacial acetic acid of 1.2kg is opened and is stirred, and stirring velocity is 70 revs/min, logical nitrogen protection; be warming up to 50 DEG C of reaction 1.5h, it is dizzy that question response material becomes semi-transparent zone indigo plant from oyster white.Continuous dropping remains mix monomer A, residual emulsifier B, residue initiator C and initiator D simultaneously, and keep 55 DEG C to react 9h, and first add the while of controlling mix monomer A and emulsifying agent B, after 1h, initiator C and initiator D also adds simultaneously.Question response pressure reduces to-0.02MPa constantly from 1.15MPa, and reaction terminates.Finally in emulsion, add 0.08kg ferrous sulfate, 0.08kg silicone antifoam agent, be cooled to less than 40 DEG C, filter discharging, obtain the PVDC copolymerization breast of 100.5kg.
2. get above-mentioned obtained 100.5kgPVDC copolymer emulsion, be pumped in another modified-reaction still, open and stir, stirring velocity is set as 40 revs/min.First slowly drip the polyoxyethylene glycol of 5.0kg, more slowly drip the lauric acid of 5.0kg and the polyglycerol fatty acid glyceryl ester of 3.0kg, time for adding controls, at 1h, to dropwise, and through filtering discharging after continuation stirring reaction 0.5h, obtains the PVDC emulsion that solid content is 49.5%.Obtained PVDC emulsion be coated with, base material is the glue spread of the BOPP of 19 μm, PVDC emulsion is 3.0g/m
2, lower machine solidifies 48h under being placed on 40 DEG C of conditions, and recording its OTR oxygen transmission rate is 13.6cc/m
2.24hr, water vapor transmission rate (WVTR) is 3.7g/m
2.24hr, at 127 DEG C, when 0.14Mpa, 0.75s, the heat seal strength of coating is 3.8N/15mm, is E level through cold mist method test.
Embodiment seven
Possesses a heat-sealing type PVDC emulsion for anti-fog function, by following component raw materials (unit: kg)
Above-mentioned a kind of preparation method possessing the heat-sealing type PVDC emulsion of anti-fog function: 1. first by 26.0kg vinylidene chloride, 3.0kg butyl acrylate, 1.02kg methacrylic acid, abundant mix and blend 1h, obtain mix monomer A, by the deionized water of 0.42kg sodium lauryl sulphate 6.4kg, mix and blend 1h, stirring velocity is 80 revs/min and obtains emulsifying agent B; By the tertbutyl peroxide of 0.01kg be made into initiator C with the deionized water dissolving of 4.8kg; The deionized water dissolving of the rongalite 4.8kg of 0.01kg is made into initiator D.Remaining deionized water is first added in polymeric kettle; the mix monomer A of 3.2kg; the emulsifying agent B of 0.2kg; the initiator C of 0.1kg, the Glacial acetic acid of 1.3kg, opens and stirs; stirring velocity is 70 revs/min; logical nitrogen protection, is warming up to 50 DEG C of reaction 1.5h, and it is dizzy that question response material becomes semi-transparent zone indigo plant from oyster white.Continuous dropping remains mix monomer A, residual emulsifier B, residue initiator C and initiator D simultaneously, and keep 55 DEG C to react 8h, and first add the while of controlling mix monomer A and emulsifying agent B, after 1h, initiator C and initiator D also adds simultaneously.Question response pressure reduces to-0.02MPa constantly from 0.85MPa, and reaction terminates.Finally in emulsion, add 0.04kg ferrous sulfate, 0.07kg silicone antifoam agent, be cooled to less than 40 DEG C, filter discharging, obtain the PVDC copolymer emulsion of 66.85kg.
2. get above-mentioned obtained 66.85kg PVDC copolymer emulsion, be pumped in another modified-reaction still, open and stir, stirring velocity is set as 40 revs/min.First slowly drip the polyoxyethylene glycol of 0.15kg, more slowly drip the xylitol ester of 2.0kg, time for adding controls, at 1h, to dropwise, and through filtering discharging after continuation stirring reaction 0.5h, obtains the PVDC emulsion that solid content is 50.7%.Obtained PVDC emulsion be coated with, base material is the glue spread of the BOPP of 19 μm, PVDC emulsion is 3.0g/m
2, lower machine solidifies 48h under being placed on 40 DEG C of conditions, and recording its OTR oxygen transmission rate is 14.3cc/m
2.24hr, water vapor transmission rate (WVTR) is 3.6g/m
2.24hr, at 127 DEG C, when 0.14Mpa, 0.75s, the heat seal strength of coating is 4.0N/15mm, is E level through cold mist method test.
Claims (5)
1. possess a heat-sealing type PVDC emulsion for anti-fog function, it is characterized in that: described PVDC emulsion is made up of the raw material of following weight: PVDC copolymer emulsion 132.8kg, dispersion agent 2.2kg, antifogging agent 15kg; Described PVDC copolymer emulsion by vinylidene chloride 48kg, acrylic ester monomer 3.5kg, functional monomer 3.0kg, oxidized form initiator 0.01kg, reduced form initiator 0.01kg, emulsifying agent 3.2kg, ionogen 0.1, pH adjusting agent 0.9kg, defoamer 0.08kg, deionized water 74kg copolymerization forms.
2. a kind of heat-sealing type PVDC emulsion possessing anti-fog function according to claim 1, is characterized in that: described antifogging agent is one or both arbitrary combination in xylitol ester, lauric acid, polyglycerol fatty acid glyceryl ester.
3. a kind of heat-sealing type PVDC emulsion possessing anti-fog function according to claim 2, is characterized in that: described dispersion agent is polyoxyethylene glycol.
4. a kind of heat-sealing type PVDC emulsion possessing anti-fog function according to claim arbitrary in claims 1 to 3, it is characterized in that: described acrylic ester monomer is butyl acrylate, described functional monomer is one or both arbitrary combination in methacrylic acid, vinylformic acid; Described oxidized form initiator is tertbutyl peroxide; Described reduced form initiator is rongalite; Described emulsifying agent is sodium lauryl sulphate; Described ionogen is one or both arbitrary combination in ferrous sulfate, zinc sulfate; Described pH adjusting agent is Glacial acetic acid; Described defoamer is silicone antifoam agent.
5. the preparation method possessing the heat-sealing type PVDC emulsion of anti-fog function according to claim 4, is characterized in that: comprise the following steps:
(1) first by 48.0kg vinylidene chloride, 3.5kg butyl acrylate, 2.0kg vinylformic acid, 1.0kg methacrylic acid, abundant mix and blend 1h, obtains mix monomer A; By the deionized water of 3.2kg sodium lauryl sulphate 15.0kg, mix and blend 1h, stirring velocity is 80 revs/min and obtains emulsifying agent B; The deionized water dissolving of the tertbutyl peroxide 11.0kg of 0.01kg is made into initiator C; The deionized water dissolving of the rongalite 11.0kg of 0.01kg is made into initiator D; Remaining deionized water is first added in polymeric kettle, the mix monomer A of 4.8kg, the emulsifying agent B of 0.5kg, the initiator C of 0.3kg, the Glacial acetic acid of 0.9kg is opened and is stirred, and stirring velocity is 70 revs/min, logical nitrogen protection, be warming up to 50 DEG C of reaction 1.5h, it is dizzy that question response material becomes semi-transparent zone indigo plant from oyster white; Continuous dropping remains mix monomer A, residual emulsifier B, residue initiator C and initiator D simultaneously, and keep 55 DEG C to react 10h, and first add the while of controlling mix monomer A and emulsifying agent B, after 1h, initiator C and initiator D also adds simultaneously; Question response pressure reduces to-0.02MPa constantly from 1.1MPa, and reaction terminates; Finally in emulsion, add 0.1kg ferrous sulfate, 0.08kg silicone antifoam agent, be cooled to less than 40 DEG C, filter discharging, obtain the PVDC copolymerization breast of 132.8kg;
(2) get above-mentioned obtained 132.8kg PVDC copolymer emulsion, be pumped in another modified-reaction still, open and stir, stirring velocity is set as 40 revs/min; First slowly drip 2.2kg polyoxyethylene glycol, slowly drip the xylitol ester of 7.0kg and the polyglycerol fatty acid glyceryl ester of 8.0kg again, time for adding controls, at 1h, to dropwise, through filtering discharging after continuation stirring reaction 0.5h, obtain the PVDC emulsion that solid content is 50.7%.
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| CN101358054A (en) * | 2008-09-04 | 2009-02-04 | 葛飞雄 | High barrier food package coated membrane latexes by thermal sealing at low temperature and preparation method |
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