CN103044602B - Paper coating water-based emulsion and preparation method and applications thereof - Google Patents
Paper coating water-based emulsion and preparation method and applications thereof Download PDFInfo
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- CN103044602B CN103044602B CN201210571866.9A CN201210571866A CN103044602B CN 103044602 B CN103044602 B CN 103044602B CN 201210571866 A CN201210571866 A CN 201210571866A CN 103044602 B CN103044602 B CN 103044602B
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Abstract
The invention discloses a paper coating water-based emulsion and a preparation method and applications thereof. Aiming at the problem that the barrier property of the current paper coating emulsion is not good, the invention provides the paper coating water-based emulsion. The method comprises the following steps: using a certain amount of vinylidene chloride, acrylonitrile, methacrylate and methacrylic acid as a mixed monomer, selecting a special seed emulsifier and a mixed emulsifier, adopting seed emulsion polymerization, and finally obtaining the paper coating water-based emulsion. The paper coating water-based emulsion has good stability, environmental protection and good barrier property. A vacuum desorption post-processing method is adopted in the later period of emulsion polymerization, so that the monomer residual quantity of the obtained water-based emulsion is low. The prepared coated paper has no foreign smell, cannot pollute food or drugs, and is more beneficial to applications to the package field of food, drugs and the like.
Description
Technical field
The present invention relates to a kind of water-based emulsion, be specifically related to a kind of water-based emulsion for paper coating and its preparation method and application.
Background technology
Current plastics film widely uses at packaging field as wrapping material, plastics film have transparent, cost is low, suitability good, intensity advantages of higher, but plastics film not easily reclaims, non-degradable, printing is poor, a large amount of use can cause the waste of petroleum resources, therefore needs to use other wrapping material to replace.White Board is as a kind of degradation material, and the advantage such as have opaque, glossiness and printing performance is good, may be used for packaging, particularly food, drug packaging etc.CN200410011366 application discloses a kind of completely biological degradation polylactic acid coated material, and it is made up of the plastification polylactic acid composition on ply of paper and ply of paper, may be used for making dixie cup, cutlery box, disposable packaging etc.; But this coated material barrier is bad, can not be used for the packaging of foodstuff.
Summary of the invention
In order to solve the problems referred to above that prior art exists, the object of this invention is to provide a kind of paper coating water-based emulsion, it has satisfactory stability, and barrier property is good, environmental protection.Second object of the present invention is to provide the preparation method of paper coating water-based emulsion.3rd object of the present invention is to provide the application of paper coating water-based emulsion.
Paper coating water-based emulsion of the present invention, it is made up of following feed composition by weight: (1) mix monomer 45-60 part, accounts for the methacrylic acid that the methacrylic ester of mix monomer total amount 0.9 ~ 1.3% and weight percent account for mix monomer total amount 0.1 ~ 0.2% form by the vinyl cyanide that weight percent accounts for the vinylidene chloride of mix monomer total amount 92.5 ~ 93.5%, weight percent accounts for mix monomer total amount 5 ~ 6%, weight percent; (2) initiator: tertbutyl peroxide 0.08 ~ 0.2 part and sodium formaldehyde sulphoxylate 0.075 ~ 0.175 part; (3) seed emulsifying agent: Sodium dodecylbenzene sulfonate 0.05 ~ 0.08 part and MA-800.14 ~ 0.16 part; (4) blending emulsifiers: alkyl sodium sulfonate compounds 0.8 ~ 1 part, 2A-1 emulsifying agent 0.35 ~ 0.4 part and COPS-1 or sodium sulfonate compounds 0.4 ~ 1.5 part; (5) auxiliary agent: ammonium acetate 0.013 ~ 0.017 part.Wherein, alkyl sodium sulfonate compounds is selected from one or more in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate; Sodium sulfonate compounds be selected from vinyl sulfonic acid sodium, sodium allylsulfonate, sodium allyl sulfonate, acrylamide sodium sulfonate one or more.Methacrylic ester be selected from methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate one or more, be preferably methyl methacrylate.MA-80 is sulfo-succinic acid methyl-isobutyl methyl esters salt, and 2A-1 emulsifying agent is alkyl diphenyl ether disulfonate, and COPS-1 is 2-allyl ethers-3-hydroxy propane-1-sodium sulfonate.
The preparation method of paper coating water-based emulsion of the present invention, comprising:
1. the preparation of raw material:
1) mix monomer preparation: vinylidene chloride, vinyl cyanide, methacrylic ester and methacrylic acid are mixed to get mix monomer by formula ratio;
2) initiator preparation: will soluble in waterly for tertbutyl peroxide obtain the tertbutyl peroxide aqueous solution, obtain the sodium formaldehyde sulphoxylate aqueous solution by soluble in water for sodium formaldehyde sulphoxylate;
3) blending emulsifiers preparation: alkyl sodium sulfonate compounds, 2A-1 emulsifying agent and COPS-1 or the mixing of sodium sulfonate compounds are added water and obtains blending emulsifiers;
2. seeding polymerization:
In reactor, add water, add Sodium dodecylbenzene sulfonate, MA-80 and ammonium acetate, envelope still, gas displacement 3 times, vacuumizes, and sucks the mix monomer of formula ratio 3%, cold dispersion 0.5h, be warming up to 47 DEG C, pump into the tertbutyl peroxide aqueous solution and the sodium formaldehyde sulphoxylate aqueous solution that prepare, adding speed is 8kg/48 hour, control temperature 55 DEG C, when Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex;
3. letex polymerization:
In seed latex, pump into the blending emulsifiers prepared, remaining mix monomer, it is constant that initiator adds speed simultaneously, and as Pressure Drop to 0 ~-0.01MPa, reaction terminates; Add microcrystalline wax, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C of 1h, and bottom valve is crack, adds the water vapor of 0.1MPa after desorption 2h, adds potassium hydroxide or triethylamine adjust ph 2 ~ 3, filters and obtains copolymer emulsion.Wherein, the solid content 45-60% of copolymer emulsion.
The application that the present invention also provides water-based emulsion to be coated with for paper.
The present invention also provides a kind of White Board, and it utilizes water-based emulsion of the present invention to be coated with and obtains.
The present invention with a certain amount of vinylidene chloride, vinyl cyanide, methacrylic ester, methacrylic acid for mix monomer, select specific seed emulsifying agent and blending emulsifiers, seeded emulsion polymerization is adopted to obtain paper coating water-based emulsion, its good stability, environmental protection, barrier property is good, can be used for paper coating, obtained White Board free from extraneous odour, can not contaminated food products or medicine, is more conducive to the application at the packaging field such as food, medicine.
The present invention, after letex polymerization completes, adopts the post-treating method of vacuum desorption, and make the aqueous monomer emulsion residual quantity that obtains low, and add microcrystalline wax before vacuumizing, it can play the effect of froth breaking, improves vacuum desorption effect, reduces level of residual monomers; And microcrystalline wax can be recycled by filtration after adding.
Accompanying drawing explanation
Fig. 1 is seeded emulsion polymerization process flow sheet of the present invention.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1:
1. preparation of raw material:
1) mix monomer preparation: by vinylidene chloride 92.5kg, vinyl cyanide 6kg, methyl methacrylate 1.3kg, methacrylic acid 0.2kg is mixed to get mix monomer;
2) initiator preparation: tertbutyl peroxide 160g is dissolved in 8kg water and obtains the tertbutyl peroxide aqueous solution, sodium formaldehyde sulphoxylate 160g is dissolved in 8kg water obtains the sodium formaldehyde sulphoxylate aqueous solution;
3) blending emulsifiers preparation: sodium laurylsulfonate 1.6kg, 2A-1 emulsifying agent 780g and COPS-11.4kg mixing is added water and obtains blending emulsifiers to 20kg;
2. seeding polymerization:
Water 50kg is added in reactor, add Sodium dodecylbenzene sulfonate 100g, MA-80280g, ammonium acetate 30g, envelope still, gas displacement 3 times, vacuumizes, suck the mix monomer of formula ratio 3%, cold dispersion 0.5h, is warming up to 47 DEG C, pumps into the tertbutyl peroxide aqueous solution and the sodium formaldehyde sulphoxylate aqueous solution that prepare, adding speed is 8kg/48 hour, control temperature 55 DEG C; When Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex;
3. letex polymerization:
In seed latex, pump into the blending emulsifiers prepared, remaining mix monomer, it is constant that initiator adds speed simultaneously, and as Pressure Drop to 0 ~-0.01MPa, reaction terminates; Add 100g microcrystalline wax, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C of 1h, and bottom valve is crack, adds the water vapor of 0.1MPa after desorption 2h, adds potassium hydroxide adjust ph 2.5, filters the copolymer emulsion obtaining solid content 50%.
The physical index of the paper coating water-based emulsion obtained is:
Embodiment 2:
1. preparation of raw material:
1) mix monomer preparation: by vinylidene chloride 111kg, vinyl cyanide 7.2kg, methyl methacrylate 1.56kg, methacrylic acid 0.24kg is mixed to get mix monomer;
2) initiator preparation: tertbutyl peroxide 240g is dissolved in 8kg water and obtains the tertbutyl peroxide aqueous solution, sodium formaldehyde sulphoxylate 240g is dissolved in 8kg water obtains the sodium formaldehyde sulphoxylate aqueous solution;
3) blending emulsifiers preparation: sodium laurylsulfonate 1.8kg, 2A-1 emulsifying agent 780g and COPS-12kg mixing is added water and obtains blending emulsifiers to 20Kg;
2. seeding polymerization:
Water 30kg is added in reactor, add Sodium dodecylbenzene sulfonate 130g, MA-80300g, ammonium acetate 30g, envelope still, gas displacement 3 times, vacuumizes, suck the mix monomer of formula ratio 3%, cold dispersion 0.5h, is warming up to 47 DEG C, pumps into the tertbutyl peroxide aqueous solution and the sodium formaldehyde sulphoxylate aqueous solution that prepare, adding speed is 8kg/48 hour, control temperature 55 DEG C; When Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex;
3. letex polymerization:
In seed latex, pump into the blending emulsifiers prepared, remaining mix monomer, it is constant that initiator adds speed simultaneously, and as Pressure Drop to 0 ~-0.01MPa, reaction terminates; Add 100g microcrystalline wax, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C of 1h, and bottom valve is crack, adds the water vapor of 0.1MPa after desorption 2h, adds potassium hydroxide adjust ph 2, filters the copolymer emulsion obtaining solid content 60%.
Embodiment 3:
1. preparation of raw material:
1) mix monomer preparation: by vinylidene chloride 92.5kg, vinyl cyanide 6kg, β-dimethyl-aminoethylmethacrylate 1.3kg, methacrylic acid 0.2kg is mixed to get mix monomer;
2) initiator preparation: tertbutyl peroxide 160g is dissolved in 8kg water and obtains the tertbutyl peroxide aqueous solution, sodium formaldehyde sulphoxylate 160g is dissolved in 8kg water obtains the sodium formaldehyde sulphoxylate aqueous solution;
3) blending emulsifiers preparation: Sodium dodecylbenzene sulfonate 1.6kg, 2A-1 emulsifying agent 780g and vinyl sulfonic acid sodium 1.4kg mixing is added water and obtains blending emulsifiers to 20kg;
2. seeding polymerization:
Water 50kg is added in reactor, add Sodium dodecylbenzene sulfonate 100g, MA-80280g, ammonium acetate 30g, envelope still, gas displacement 3 times, vacuumizes, suck the mix monomer of formula ratio 3%, cold dispersion 0.5h, is warming up to 47 DEG C, pumps into the tertbutyl peroxide aqueous solution and the sodium formaldehyde sulphoxylate aqueous solution that prepare, adding speed is 8kg/48 hour, control temperature 55 DEG C; When Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex;
3. letex polymerization:
In seed latex, pump into the blending emulsifiers prepared, remaining mix monomer, it is constant that initiator adds speed simultaneously, and as Pressure Drop to 0 ~-0.01MPa, reaction terminates; Add 100g microcrystalline wax, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C of 1h, and bottom valve is crack, adds the water vapor of 0.1MPa after desorption 2h, adds triethylamine adjust ph 2.5, filters the copolymer emulsion obtaining solid content 50%.
Claims (2)
1. a paper coating water-based emulsion, is characterized in that: described paper coating water-based emulsion is made up of the raw material containing following weight: (1) mix monomer: vinylidene chloride 92.5kg, vinyl cyanide 6kg, methyl methacrylate 1.3kg, methacrylic acid 0.2kg; (2) initiator: tertbutyl peroxide 160g and sodium formaldehyde sulphoxylate 160g; (3) seed emulsifying agent: Sodium dodecylbenzene sulfonate 100g and MA-80280g; (4) blending emulsifiers: sodium laurylsulfonate 1.6kg, 2A-1 emulsifying agent 780g and COPS-11.4kg; (5) auxiliary agent: ammonium acetate 30g.
2. paper coating water-based emulsion preparation method as claimed in claim 1, is characterized in that, comprise the steps:
(1) preparation of raw material:
1) mix monomer preparation: by vinylidene chloride 92.5kg, vinyl cyanide 6kg, methyl methacrylate 1.3kg, methacrylic acid 0.2kg is mixed to get mix monomer;
2) initiator preparation: tertbutyl peroxide 160g is dissolved in 8kg water and obtains the tertbutyl peroxide aqueous solution, sodium formaldehyde sulphoxylate 160g is dissolved in 8kg water obtains the sodium formaldehyde sulphoxylate aqueous solution;
3) blending emulsifiers preparation: sodium laurylsulfonate 1.6kg, 2A-1 emulsifying agent 780g and COPS-11.4kg mixing is added water and obtains blending emulsifiers to 20kg;
(2) seeding polymerization:
Water 50kg is added in reactor, add Sodium dodecylbenzene sulfonate 100g, MA-80280g, ammonium acetate 30g, envelope still, gas displacement 3 times, vacuumizes, suck the mix monomer of formula ratio 3%, cold dispersion 0.5h, is warming up to 47 DEG C, pumps into the tertbutyl peroxide aqueous solution and the sodium formaldehyde sulphoxylate aqueous solution that prepare, adding speed is 8kg/48 hour, control temperature 55 DEG C; When Pressure Drop is to 0.01-0.03MPa, seeding polymerization terminates, and obtains seed latex;
(3) letex polymerization:
In seed latex, pump into the blending emulsifiers prepared, remaining mix monomer, it is constant that initiator adds speed simultaneously, and when Pressure Drop is to 0-0.01MPa, reaction terminates; Add 100g microcrystalline wax, vacuumize, bottom valve does not open desorption 1h, and temperature rises to 70 DEG C of 1h, and bottom valve is crack, adds the water vapor of 0.1MPa after desorption 2h, adds potassium hydroxide adjust ph 2.5, filters the copolymer emulsion obtaining solid content 50%.
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| CN104109988B (en) * | 2013-11-21 | 2016-03-30 | 海南必凯水性涂料有限公司 | A kind of environmental protection coating internal lining paper and manufacture method thereof |
| CN105295582B (en) * | 2015-11-26 | 2017-11-07 | 海南赛诺实业有限公司 | A kind of non-sticky lid special-purpose latex of Yoghourt and its preparation method and application |
| WO2017223551A1 (en) * | 2016-06-24 | 2017-12-28 | Corning Incorporated | Zirconia-toughened glass ceramics |
| CN113389060A (en) * | 2021-06-10 | 2021-09-14 | 海南必凯水性新材料有限公司 | Coating cloth for food packaging |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102650111A (en) * | 2012-05-10 | 2012-08-29 | 海南必凯水性涂料有限公司 | High-solid coating containing polyvinylidene chloride for paper coating and preparation method of coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102650111A (en) * | 2012-05-10 | 2012-08-29 | 海南必凯水性涂料有限公司 | High-solid coating containing polyvinylidene chloride for paper coating and preparation method of coating |
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Address after: 571152, No. 18, North Light Road, Lion Industrial Park, Haikou national hi tech Zone, Hainan Applicant after: Hainan Bikai Waterborne Coatings Co., Ltd. Address before: 570125 Hainan city in Haikou Province, North Longkun Road No. 2 Park building 19 floor Applicant before: Hainan Bikai Waterborne Coatings Co., Ltd. |
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Address after: 571152, No. 18, North Light Road, Lion Industrial Park, Haikou national hi tech Zone, Hainan Patentee after: Hainan Kai Kai Shui New Material Co., Ltd. Address before: 571152, No. 18, North Light Road, Lion Industrial Park, Haikou national hi tech Zone, Hainan Patentee before: Hainan Bikai Waterborne Coatings Co., Ltd. |