CN103059195B - Polyvinyl dichloride (PVDC) latex special for kraft paper used for food packaging and preparation method thereof and application thereof - Google Patents
Polyvinyl dichloride (PVDC) latex special for kraft paper used for food packaging and preparation method thereof and application thereof Download PDFInfo
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- CN103059195B CN103059195B CN201210571789.7A CN201210571789A CN103059195B CN 103059195 B CN103059195 B CN 103059195B CN 201210571789 A CN201210571789 A CN 201210571789A CN 103059195 B CN103059195 B CN 103059195B
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Abstract
The invention discloses a polyvinyl dichloride (PVDC) latex special for kraft paper used for food packaging and a preparation method thereof and application thereof. The kraft paper coated by the PVDC latex can be used for packaging of foods such as peanuts, melon seeds and walnuts. The PVDC latex is obtained by a mixed monomer, an auxiliary, an initiating agent, an emulsifying agent and a seeded emulsifying agent, wherein the mixed monomer contains a certain amount of vinylidene chloride, vinyl cyanide, butyl acrylate and acrylic acid, and the seeded emulsifying agent contains sodium dodecyl benzene sulfonate and a 2A-1 emulsifying agent. The prepared PVDC latex is good in stability and free of emulsification breaking and sediment after placed for 24 months under temperature of 30 DEG C and relative humidity (RH) of 70%. Monomer residual volume in the latex is lower. The kraft paper coated by the PVDC latex has the advantages of being environment-friendly, degradable, good in heat tightness, waterproof, damp proof and the like. When coating amount of the latex is 20g/m2, steam transit amount is less than or equal to 3g/m2.24h and oxygen permeability is less than or equal to 6g/m2.24h, monomer residual amount of the vinylidene chloride is less than or equal to 1ppm or not detected, and heating sealing intensity can reach 3N/15mm.
Description
Technical field
The present invention relates to a kind of PVDC latex, be specifically related to a kind of special PVDC latex of packaging kraft paper for food such as peanut, melon seeds, walnuts and method for making thereof, application, belong to polymeric material field.
Background technology
Plastics film has features such as good toughness, moistureproofness are good, easy to carry and a large amount of for food product pack because of it, but plastics film non-degradable, the white pollution problems that plastics film discarded is in recent years formed is more and more serious.Kraft paper due to its degradable, there is certain thickness and intensity, be applicable to the packaging of opaque material or other particles, sheet, lumpy material, but kraft paper barrier, waterproof, moistureproofness are poor, cracky, and can not seal, make it need the application had in the food product pack of good moistureproofness, heat sealability to be limited at packaging peanut, melon seeds etc.
In order to make kraft paper based packaging material have certain barrier and waterproof, moistureproofness, normally on kraft paper, be coated with barrier layer.Existing barrier layer is multiplex vacuum aluminum-coatedly makes barrier layer, but in production or transport, if run into folding or distortion, easily cause the aluminium foil barrier layer of wrapping material inside to occur the hole of aperture size, can reduce the barriering effect of packaging vessel like this, and vacuum aluminum-coated cost is high.
Polyvinylidene dichloride (PVDC) copolymer latex due to the symmetry of PVDC polymer chain structure high, regularity is high, and degree of crystallinity is high, and polarity is strong, and spread coefficient is little, therefore has the excellent barrier to oxygen and moisture.Current, high barrier coating packing film is if polyvinylidene dichloride latex coating packing film is for the packaging of cigarette and medicine, food.The present invention is based on the feature of kraft paper and PVDC latex, a kind of PVDC latex coating kraft paper is provided, the kraft paper degradable, collapsible of coating PVDC latex, there is good barrier, waterproof and moistureproofness, and can seal, can be used for the food product pack that peanut, melon seeds, walnut etc. need to have good waterproof, moistureproofness.
Summary of the invention
The invention provides a kind of special PVDC latex of kraft paper for food product pack such as peanut, melon seeds, walnuts, it is obtained that the use of this PVDC latex comprises a certain amount of vinylidene chloride, vinyl cyanide, acrylate and acrylic acid mix monomer, initiator, emulsifying agent and seed emulsifying agent; Obtained PVDC latex good stability, has environmental protection, degradable, the feature such as collapsible for food product pack after coating kraft paper, moistureproof, resistance oxygen, block-water effect are good, also have good heat sealability.
The object of the invention is to be achieved through the following technical solutions:
The special PVDC latex of a kind of kraft paper, this PVDC latex by weight, is obtained by mix monomer, auxiliary agent, initiator, emulsifying agent and seed emulsifying agent,
Wherein, mix monomer accounts for 55-65 part, and mix monomer comprises the vinylidene chloride accounting for mix monomer weight percent 80 ~ 86%, the vinyl cyanide accounting for mix monomer weight percent 10.1-17.0%, accounts for the butyl acrylate of mix monomer weight percent 2-4% and account for the vinylformic acid of mix monomer weight percent 0.2-0.5%;
Auxiliary agent; Ammonium acetate 0.012-0.018 part and iron protochloride 0.0004-0.0006 part;
Initiator: tertbutyl peroxide 0.08-0.2 part and sodium formaldehyde sulphoxylate 0.08-0.2 part;
Emulsifying agent: secondary sodium alkanesulfonate 0.4-0.8 part and Sodium dodecylbenzene sulfonate 0.4-0.8 part;
Seed emulsifying agent: Sodium dodecylbenzene sulfonate 0.025-0.07 part and 2A-1 emulsifying agent 0.2-0.25 part; Wherein, 2A-1 emulsifying agent is alkyl diphenyl ether disulfonate.
The present invention also provides a kind of preparation method of above-mentioned PVDC latex, is prepared by seed emulsion polymerization, and concrete preparation process is:
1) preparation of raw material:
(1) preparation of mix monomer, mixes vinylidene chloride, vinyl cyanide, acrylate and vinylformic acid, stirs 2h, obtained mix monomer;
(2) preparation of emulsifying agent, is added to the water secondary sodium alkanesulfonate and Sodium dodecylbenzene sulfonate and makes emulsifier solution;
(3) preparation of initiator, adds tertbutyl peroxide and sodium formaldehyde sulphoxylate respectively in deionized water 4 parts and mixes, and stirs and makes initiator solution;
(4) preparation of seed emulsifying agent, adds in deionized water to carry out being uniformly mixed by described Sodium dodecylbenzene sulfonate and 2A-1 emulsifying agent and makes seed emulsifier solution.
2) seeding polymerization: deionized water or soft water are added reactor, add auxiliary agent ammonium acetate, iron protochloride, seed emulsifying agent, envelope still, with the air in nitrogen replacement reactor three times, vacuumizing, suck seed monomer (3% mix monomer), cold dispersion 0.5h, heats up 47 DEG C, the above-mentioned initiator prepared is pumped into, control 53-57 DEG C with the feed rate of 8kg/48h.When Pressure Drop is to 0.01-0.03MPa, seeded emulsion polymerization terminates, and obtains seed latex.
3) emulsion preparation: pump into the remaining mix monomer of the emulsifying agent prepared in seed latex, 15 hours are reinforced complete, and when Pressure Drop is to 0-0.01MPa, reaction terminates; Add microcrystalline wax 0.05 part, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C, keep 1h, bottom valve is crack, after desorption 2h, adds the water vapor of 0.1MPa, control temperature is 65-70 DEG C, add pH value regulator triethylamine or potassium hydroxide adjust ph 2-2.5, filter, obtain PVDC copolymer emulsion.
The present invention further provides a kind of application by above-mentioned PVDC latex, being used in food product pack aspect for being coated with kraft paper.
The present invention further provides a kind of kraft paper for food product pack, the above-mentioned PVDC latex of this kraft paper is coated with.
The PVDC latex that the present invention obtains, can adopt following evaluation method:
According to above-mentioned testing method, the performance index of measured emulsion are as follows:
Solid content (%): 55-65;
Surface tension (mN/m) :≤40;
Viscosity (mPas) :≤20;
PH value: 2-2.5;
Density (g/cm3) :≤1.27;
The latex stability that the present invention obtains is good, places 24 months not breakdown of emulsion, nothing precipitations at normal temperatures; Microcrystalline wax is recyclable, plays froth breaking effect, makes level of residual monomers in latex lower; Latex can be used for being coated with kraft paper, the kraft paper of coating can be used for food such as packaging peanut, melon seeds etc., there is environmental protection, degradable, collapsible, good heat sealability, the feature such as waterproof, protection against the tide, when being 20g/ ㎡ for being coated with the latex glue spread of kraft paper, water vapor transit dose≤3g/ ㎡ 24h, oxygen transit dose≤30g/ ㎡ 24h, vinylidene chloride monomer residual quantity≤1ppm or do not detect; Heat seal strength can reach 3N/15mm.
Accompanying drawing explanation
Accompanying drawing 1 is preparation technology's skeleton diagram of the special PVDC latex of kraft paper.
Embodiment
Embodiment 1
The special PVDC latex of kraft paper, copolymerization system gross weight is 200kg, and mix monomer accounts for 110kg;
Vinylidene chloride 94.6kg;
Vinyl cyanide 11.11kg;
Butyl acrylate 3.74kg;
Vinylformic acid 0.55kg;
Auxiliary agent; Ammonium acetate 24g and iron protochloride 0.8g;
Initiator: tertbutyl peroxide 160g and sodium formaldehyde sulphoxylate 160g;
Emulsifying agent: secondary sodium alkanesulfonate 800g and Sodium dodecylbenzene sulfonate 800g;
Seed emulsifying agent: Sodium dodecylbenzene sulfonate 50g and 2A-1 emulsifying agent 400g;
Specific operation process is:
1) preparation of raw material:
(1) preparation of mix monomer, mixes the vinylidene chloride of above-mentioned weight, vinyl cyanide, butyl acrylate ester and vinylformic acid, stirs 2h, obtained mix monomer;
(2) preparation of emulsifying agent, secondary sodium alkanesulfonate 800g and Sodium dodecylbenzene sulfonate 800g is added to the water and makes emulsifier solution;
(3) preparation of initiator, adds tertbutyl peroxide 160g and sodium formaldehyde sulphoxylate 160g respectively in deionized water 4 parts and carries out being uniformly mixed making initiator solution;
(4) preparation of seed emulsifying agent, adds in deionized water to carry out being uniformly mixed by the 2A-1 emulsifying agent of Sodium dodecylbenzene sulfonate 50g and 500g and makes seed emulsifier solution;
2) seeding polymerization: deionized water or soft water are added reactor, add auxiliary agent, seed emulsifying agent, envelope still, with the air in nitrogen replacement reactor three times, vacuumize, 3% mix monomer of suction, cold dispersion 0.5h, heat up 47 DEG C, pump into the above-mentioned initiator prepared with the feed rate of 8kg/48h, control 53-57 DEG C.When Pressure Drop is to 0.01-0.03MPa, seeded emulsion polymerization terminates, and obtains seed latex.
3) emulsion preparation: pump into the emulsifying agent prepared, remaining mix monomer in seed latex, 15 hours are reinforced complete, and when Pressure Drop is to 0-0.01MPa, reaction terminates; Add microcrystalline wax 100g, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C, keep 1h, bottom valve is crack, after desorption 2h, adds the water vapor of 0.1MPa, control temperature is 65-70 DEG C, add pH value regulator triethylamine or potassium hydroxide adjust ph 2.2, filter, obtain the PVDC copolymer emulsion that solid content is 55%.
Obtained PVDC latex performance perameter is as follows:
Solid content (%): 55
Surface tension (mN/m): 36
Viscosity (mPas): 15
PH value: 2.2
Density (g/cm
3): 1.25
Embodiment 2
The special PVDC latex of kraft paper, copolymerization system gross weight is 200kg, and mix monomer accounts for 120kg;
Vinylidene chloride 96kg;
Vinyl cyanide 20.4kg;
Butyl acrylate 3.36kg;
Vinylformic acid 0.24kg;
Auxiliary agent; Ammonium acetate 30g and iron protochloride 1g;
Initiator: tertbutyl peroxide 320g and sodium formaldehyde sulphoxylate 320g;
Emulsifying agent: secondary sodium alkanesulfonate 1.2kg and Sodium dodecylbenzene sulfonate 1.2kg;
Seed emulsifying agent: Sodium dodecylbenzene sulfonate 90g and 2A-1 emulsifying agent 460g;
Specific operation process is:
1) preparation of raw material: the preparation of mix monomer, seed emulsifying agent, emulsifying agent and initiator is as embodiment 1.
2) seeding polymerization: deionized water or soft water are added reactor, add auxiliary agent, seed emulsifying agent, envelope still, with the air in nitrogen replacement reactor three times, vacuumize, suck the mix monomer of 3%, cold dispersion 0.5h, heat up 47 DEG C, pump into the above-mentioned initiator prepared with the feed rate of 8kg/48h, control 53-57 DEG C.When Pressure Drop is to 0.01-0.03MPa, seeded emulsion polymerization terminates, and obtains seed latex.
3) emulsion preparation: pump into the emulsifying agent prepared, remaining mix monomer in seed latex, 15 hours are reinforced complete, and when Pressure Drop is to 0-0.01MPa, reaction terminates; Add microcrystalline wax 100g, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C, keep 1h, bottom valve is crack, after desorption 2h, adds the water vapor of 0.1MPa, control temperature is 65-70 DEG C, add pH value regulator triethylamine adjust ph 2.2, filter, obtain the PVDC copolymer emulsion that solid content is 60%.
Embodiment 3
The special PVDC latex of kraft paper, copolymerization system gross weight is 200kg, and mix monomer accounts for 130kg;
Vinylidene chloride 106.6kg;
Vinyl cyanide 20.15kg;
Butyl acrylate 2.6kg;
Vinylformic acid 0.65kg;
Auxiliary agent; Ammonium acetate 36g and iron protochloride 1.2g;
Initiator: tertbutyl peroxide 400g and sodium formaldehyde sulphoxylate 400g;
Emulsifying agent: secondary sodium alkanesulfonate 1.6kg and Sodium dodecylbenzene sulfonate 1.6kg;
Seed emulsifying agent: Sodium dodecylbenzene sulfonate 140g and 2A-1 emulsifying agent 500g;
Specific operation process is:
1) preparation of raw material: the preparation of mix monomer, seed emulsifying agent, emulsifying agent and initiator is as embodiment 1.
2) seeding polymerization: deionized water or soft water are added reactor, add auxiliary agent, seed emulsifying agent, envelope still, with the air in nitrogen replacement reactor three times, vacuumize, suck the mix monomer of 3%, cold dispersion 0.5h, pump into the above-mentioned initiator prepared with the feed rate of 8kg/48h, heat up 47 DEG C, control 53-57 DEG C.When Pressure Drop is to 0.01-0.03MPa, seeded emulsion polymerization terminates, and obtains seed latex.
3) emulsion preparation: pump into the emulsifying agent prepared in seed latex, remaining mix monomer feeds in raw material complete in 15 hours, when Pressure Drop is to 0-0.01MPa, reaction terminates; Add microcrystalline wax 100g, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C, keep 1h, bottom valve is crack, after desorption 2h, adds the water vapor of 0.1MPa, control temperature is 65-70 DEG C, add pH value regulator potassium hydroxide adjust ph 2.3, filter, obtain the PVDC copolymer emulsion that solid content is 65%.
Claims (3)
1. a preparation method for the special PVDC latex of kraft paper, is characterized in that, this PVDC latex by weight, is obtained by mix monomer, auxiliary agent, initiator, emulsifying agent and seed emulsifying agent,
Wherein, mix monomer accounts for 55-65 part, and mix monomer comprises the vinylidene chloride accounting for mix monomer weight percent 80 ~ 86%, the vinyl cyanide accounting for mix monomer weight percent 10.1-17.0%, accounts for the butyl acrylate of mix monomer weight percent 2-4% and account for the vinylformic acid of mix monomer weight percent 0.2-0.5%;
Auxiliary agent; Ammonium acetate 0.012-0.018 part and iron protochloride 0.0004-0.0006 part;
Initiator: tertbutyl peroxide 0.08-0.2 part and sodium formaldehyde sulphoxylate 0.08-0.2 part;
Emulsifying agent: secondary sodium alkanesulfonate 0.4-0.8 part and Sodium dodecylbenzene sulfonate 0.4-0.8 part;
Seed emulsifying agent: Sodium dodecylbenzene sulfonate 0.025-0.07 part and 2A-1 emulsifying agent 0.2-0.25 part;
It is prepared by seed emulsion polymerization, and concrete preparation process is:
1) preparation of expecting:
(1) preparation of mix monomer, mixes described vinylidene chloride, vinyl cyanide, acrylate and vinylformic acid, stirs 2h, obtained mix monomer;
(2) preparation of emulsifying agent, is added to the water described secondary sodium alkanesulfonate and Sodium dodecylbenzene sulfonate and makes emulsifier solution;
(3) preparation of initiator, adds tertbutyl peroxide and sodium formaldehyde sulphoxylate respectively in deionized water 4 parts and mixes, and stirs and makes initiator solution;
(4) preparation of seed emulsifying agent, adds in deionized water to carry out being uniformly mixed by described Sodium dodecylbenzene sulfonate and 2A-1 emulsifying agent and makes seed emulsifier solution;
2) seeding polymerization: deionized water or soft water are added reactor, add auxiliary agent ammonium acetate, iron protochloride, seed emulsifying agent Sodium dodecylbenzene sulfonate and 2A-1 emulsifying agent, envelope still, with the air in nitrogen replacement reactor three times, vacuumize, the mix monomer of suction seed monomer, namely 3%, cold dispersion 0.5h, heats up 47 DEG C, pumps into the above-mentioned initiator prepared with the feed rate of 8kg/48h, control 53-57 DEG C, when Pressure Drop is to 0.01-0.03MPa, seeded emulsion polymerization terminates, and obtains seed latex;
3) emulsion preparation: pump into the emulsifying agent prepared and remaining mix monomer in seed latex, 15 hours are reinforced complete, and when Pressure Drop is to 0-0.01MPa, reaction terminates; Add microcrystalline wax 0.05 part, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C, keep 1h, bottom valve is crack, after desorption 2h, adds the water vapor of 0.1MPa, control temperature is 65-70 DEG C, adds pH value regulator potassium hydroxide adjust ph 2-2.5, filters, obtains PVDC copolymer emulsion.
2. an application for the PVDC latex obtained by preparation method of the special PVDC latex of a kind of kraft paper as claimed in claim 1, is characterized in that, PVDC latex is used for food packaging kraft paper.
3. a food packaging kraft paper, is characterized in that, uses the PVDC latex obtained by preparation method of the special PVDC latex of a kind of kraft paper to be as claimed in claim 1 coated with this kraft paper.
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| CN103275260B (en) * | 2013-05-13 | 2015-03-25 | 浙江科冠聚合物有限公司 | Preparation method of acrylic plastic-plastic composite latex |
| CN103275262A (en) * | 2013-05-13 | 2013-09-04 | 浙江科冠聚合物有限公司 | Ultra-high blocking latex for food packaging |
| CN112252084B (en) * | 2020-09-16 | 2023-06-06 | 齐鲁工业大学 | Heat-sealable filter base paper based on natural plant fibers and preparation method thereof |
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