CN103665244A - Novel network interpenetration coating emulsion and preparation method and application thereof - Google Patents
Novel network interpenetration coating emulsion and preparation method and application thereof Download PDFInfo
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- CN103665244A CN103665244A CN201310601039.4A CN201310601039A CN103665244A CN 103665244 A CN103665244 A CN 103665244A CN 201310601039 A CN201310601039 A CN 201310601039A CN 103665244 A CN103665244 A CN 103665244A
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Abstract
The invention relates to a preparation method for a novel network interpenetration coating emulsion. The preparation method comprises the following steps: (1) adding an emulsifier and deionized water into a reactor and stirring for dissolution; (2) uniformly mixing styrene monomer, acrylate monomer and comonomer X to obtain a dropping liquid A1; uniformly mixing nikasol monomer, acrylate monomer and comonomer Y to obtain a dropping liquid A2, and uniformly mixing an oxidant and deionized water to respectively obtain a dropping liquid B1 and a dropping liquid B2; (3) dropwise adding A1 and B1 simultaneously at a constant speed into the reactor, polymerizing for a period of time, adding A2 and A2 simultaneously at a constant speed into the reactor, and reacting continuously; cooling down after the reaction is completed and emptying. The preparation method has the advantages of simple operation, low cost and the like; the network interpenetration coating emulsion with more stable performance and wider application range can be obtained; when the network interpenetration coating emulsion is used for surface coating of paper, the galling strength and softness of paper surface can be improved, and the paper is endowed with good printing ink absorptivity, water resisting property and the like.
Description
Technical field
The invention belongs to dry strengthening agent used for making papers preparing technical field, be specifically related to a kind of preparation method and application of new network IPN coating emulsion.
Background technology
Coating emulsion is as investment precoat, to use after in process of production last of white board mixes by a certain percentage with the filler such as china clay together, and the quality of white board coating and the height of cost are to have direct relation with coating fluid.The coating emulsion that tradition adopts has two kinds, as relatively low in the styrene-butadiene emulsion cost made from divinyl, but large with the Paper Brittleness of its coating, weathering resistance is poor, the easy deficiency such as yellow of paper.The good coating fluid of quality is to adopt the monomers such as vinylbenzene and vinylformic acid to make at present, although this emulsion property is better than styrene-butadiene emulsion, cost is higher.
IPN is interpenetrating polymer networks structure, is two or more polymer blend, and molecular chain runs through mutually, and the network structure that forms with the mode interlinkage of chemical bond of at least one polymer molecular chain.Because 2 kinds or polymer network of more than two kinds in IPN material tangle mutually, IPN and do not lose the intrinsic characteristic of original copolymer, thus obtain the incomparable special performance of other polymkeric substance.Its maximum feature is can be by the material of the thermodynamics incompatible polymers alloy property that mixed and formation at least can be stable in kinetics mutually, each polymkeric substance that forms the polymer alloy state material of IPN structure itself is external phase, make it can have good Static and dynamic mechanical property concurrently, and wider use temperature scope.Simultaneously owing to there being chemically crosslinked point, IPN can only swelling in any solvent, can not dissolve, and creep can not occur yet and flow, thereby having better bonding force, therefore obtains higher colour fastness.In addition, due to the Tg(second-order transition temperature of each polymkeric substance) be selectable, therefore can select wherein one to have mutually lower Tg, to obtain good elasticity and flexibility, Tg is high for another phase, in order to prevent that emulsion is clamminess.
At present, the coating emulsion that adopts the monomers such as vinylbenzene and vinylformic acid to make is conventional emulsions, does not possess network interpenetrating structure, and range of application is narrow.
Summary of the invention
For the defect existing in prior art, an object of the present invention is to provide a kind of preparation method of new network IPN coating emulsion, simple to operate, low cost and other advantages that the method has, can make that performance is more stable, cohesive force is stronger and the coating emulsion of use temperature a wider range.
Another object of the present invention is to provide and adopts the network interpenetrating that above-mentioned preparation method obtains to be coated with the application of emulsion in papermaking.
For reaching above object, the technical solution used in the present invention is: a kind of preparation method of new network IPN coating emulsion, comprises the following steps:
(1) emulsifying agent is added to reactor, then add appropriate amount of deionized water to make bed material, be warming up to 60-65 ℃, stir and make emulsifiers dissolve;
(2) styrene monomer, acrylate monomer, comonomer X are evenly mixed, be made into dropping liquid A1; Vinyl Acetate Monomer, acrylate monomer, comonomer Y are evenly mixed, be made into dropping liquid A2; A part and deionized water in the oxygenant that initiator system is adopted evenly mix, and are made into dropping liquid B1, and residual oxidizing agent and deionized water are evenly mixed, and are made into dropping liquid B2;
(3) dropping liquid A1, B1 are at the uniform velocity added drop-wise in the reactor of step (1) simultaneously, at 80-90 ℃ after polymerization for some time, then dropping liquid A2, B2 are at the uniform velocity added drop-wise in reactor simultaneously, at 80-90 ℃, continue polymerization reaction take place; After completion of the reaction, be cooled to below 50 ℃ blowing.
Further, it is benchmark that raw material per-cent be take total charging capacity (weight), styrene monomer accounts for 12-15%, acrylate monomer accounts for 20-25%, and Vinyl Acetate Monomer accounts for 12-15%, and comonomer X accounts for 0.1-2%, comonomer Y accounts for 0.1-2%, the consumption of the oxygenant of initiator system is the 0.5-2% of aforementioned monomer total amount, and the consumption of emulsifying agent is the 2-4% of aforementioned monomer total amount, and all the other are deionized water.
Further, described acrylate monomer is selected from one or more in methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate and butyl methacrylate.Acrylate monomer in dropping liquid A1, A2 can be identical, also can be different.
Further, described comonomer X and Y are selected from respectively one or more in vinylformic acid, vinyl cyanide, methylpropene sodium sulfonate, maleic anhydride, fumaric acid, methylene-succinic acid and methacrylic acid.
Further, the oxygenant that initiator system adopts is selected from one or both in Sodium Persulfate, ammonium persulphate, hydrogen peroxide, Benzoyl Peroxide and Diisopropyl azodicarboxylate.
Further, in step (2), when preparation dropping liquid A1, B1, add deionized water, and add emulsifying agent to carry out pre-emulsification, the volume ratio of described emulsifying agent and described deionized water is 1:40-50.
Further, emulsifying agent is selected from one or more in polyoxyethylene octylphenol ether (OP-10), polyoxyethylene nonylphenol ether (NP-10), Sodium dodecylbenzene sulfonate and sodium vinyl sulfonate.
Further, in step (3), to adding polymerization reaction take place 1-1.5 hour after dropping liquid A1, B1 in reactor; Add polymerization reaction take place 2-3 hour after dropping liquid A2, B2, total reaction time (containing time for adding) is 4-5 hour again.
First the present invention utilizes dropping liquid A1, B1 to prepare benzene emulsion, and recycling dropping liquid A2, B2 prepare acrylate and vinyl acetate emulsion, by letex polymerization, makes benzene emulsion and acrylate and vinyl acetate emulsion form network interpenetrating structure, finally obtains stable emulsion mixture.In the present invention, selecting to control benzene emulsion is the polymkeric substance that Tg is lower, acrylate and vinyl acetate emulsion is the polymkeric substance that Tg is higher, benzene emulsion can improve the water resisting property of sticking power and the paper of coating layer, and acrylate and vinyl acetate emulsion can improve the smooth slickness of paper, reduces the cost of emulsion simultaneously.
Method of the present invention has simple to operate, and low cost and other advantages adopts method of the present invention can make that performance is more stable, cohesive force is stronger and the network interpenetrating coating emulsion of use temperature a wider range.Network interpenetrating prepared by the present invention coating emulsion during for the surface coated of paper, can improve paper surface picking strength, gives ink absorption that paper is good and water tolerance, temperature tolerance etc.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
Preparation method is as follows:
(1) 10.5g OP-10 is added in the reactor with thermometer, condenser and agitator, then add 391g deionized water to make bed material, be warming up to 60-65 ℃, stir OP-10 is dissolved;
(2) 120g vinylbenzene, 80g methyl methacrylate, 2g vinylformic acid are evenly mixed, be made into dropping liquid A1; 135g vinyl acetate, 170g methyl methacrylate, 1g vinyl cyanide are evenly mixed, be made into dropping liquid A2; 4.1g Sodium Persulfate and 40g deionized water are evenly mixed, be made into dropping liquid B1,6g Sodium Persulfate and 40g deionized water are evenly mixed, be made into dropping liquid B2;
(3) dropping liquid A1, B1 are at the uniform velocity added drop-wise in the reactor of step (1) simultaneously, at 80-90 ℃, polymerization is after 1.5 hours, again dropping liquid A2, B2 are at the uniform velocity added drop-wise in reactor simultaneously, at 80-90 ℃, continue polymerization reaction take place 2 hours, total reaction time (containing time for adding) is 5 hours; After completion of the reaction, be cooled to below 50 ℃, blowing, solid content is 50%, viscosity is 50mpa.s.
Embodiment 2
Preparation method is as follows:
(1) 10g NP-10 is added in the reactor with thermometer, condenser and agitator, then add 350g deionized water to make bed material, be warming up to 60-65 ℃, stir NP-10 is dissolved;
(2) 125g vinylbenzene, 100g ethyl propenoate, 5g methylpropene sodium sulfonate and 40g deionized water and 1gNP-10 rapid stirring are formed to pre-emulsion, be made into dropping liquid A1; 120g vinyl acetate, 148g ethyl propenoate, 2g methacrylic acid are evenly mixed, be made into dropping liquid A2; 4.5g hydrogen peroxide (effective content 30%) and 44g deionized water are evenly mixed, be made into dropping liquid B1,5.5g hydrogen peroxide (effective content 30%) and 50g deionized water are evenly mixed, be made into dropping liquid B2;
(3) dropping liquid A1, B1 are at the uniform velocity added drop-wise in the reactor of step (1) simultaneously, at 80-90 ℃, polymerization is after 1 hour, again dropping liquid A2, B2 are at the uniform velocity added drop-wise in reactor simultaneously, at 80-90 ℃, continue polymerization reaction take place 1.5 hours, total reaction time (containing time for adding) is 4 hours; After completion of the reaction, be cooled to below 50 ℃, blowing, solid content is 50%, viscosity is 45mpa.s.
Embodiment 3
Preparation method is as follows:
(1) 12g Sodium dodecylbenzene sulfonate is added in the reactor with thermometer, condenser and agitator, then add 390g deionized water to make bed material, be warming up to 60-65 ℃, stir Sodium dodecylbenzene sulfonate is dissolved;
(2) 150g vinylbenzene, 80g butyl acrylate, 5g maleic anhydride are evenly mixed, be made into dropping liquid A1; 140g vinyl acetate, 123g butyl acrylate, 2g maleic anhydride are evenly mixed, be made into dropping liquid A2; 1.2g Benzoyl Peroxide and 45g deionized water are evenly mixed, be made into dropping liquid B1,1.8g Benzoyl Peroxide and 50g deionized water are evenly mixed, be made into dropping liquid B2;
(3) dropping liquid A1, B1 are at the uniform velocity added drop-wise in the reactor of step (1) simultaneously, at 80-90 ℃, polymerization is after 1.5 hours, again dropping liquid A2, B2 are at the uniform velocity added drop-wise in reactor simultaneously, at 80-90 ℃, continue polymerization reaction take place 2 hours, total reaction time (containing time for adding) is 5 hours; After completion of the reaction, be cooled to below 50 ℃, blowing, solid content is 50%, viscosity is 65mpa.s.
Embodiment 4
Preparation method is as follows:
(1) 20g sodium vinyl sulfonate is added in the reactor with thermometer, condenser and agitator, then add 385g deionized water to make bed material, be warming up to 60-65 ℃, stir sodium vinyl sulfonate is dissolved;
(2) 125g vinylbenzene, 100g butyl methacrylate, 4g methylene-succinic acid are evenly mixed, be made into dropping liquid A1; 150g vinyl acetate, 116g butyl methacrylate, 5g fumaric acid are evenly mixed, be made into dropping liquid A2; 1.8g Diisopropyl azodicarboxylate and 50g deionized water are evenly mixed, be made into dropping liquid B1,1.2g Diisopropyl azodicarboxylate and 50g deionized water are evenly mixed, be made into dropping liquid B2;
(3) dropping liquid A1, B1 are at the uniform velocity added drop-wise in the reactor of step (1) simultaneously, at 80-90 ℃, polymerization is after 1.5 hours, again dropping liquid A2, B2 are at the uniform velocity added drop-wise in reactor simultaneously, at 80-90 ℃, continue polymerization reaction take place 2 hours, total reaction time (containing time for adding) is 5 hours; After completion of the reaction, be cooled to below 50 ℃, blowing, solid content is 50%, viscosity is 55mpa.s.
Comparative example
Proportioning raw materials is with embodiment 1, different is, benzene feedstock ethene in step (2), methyl methacrylate, vinylformic acid, vinyl acetate, vinyl cyanide, Sodium Persulfate are joined in the lump in the reactor containing OP-10 and water of step (1), make polymerization reaction take place.Consequently, cannot obtain stable emulsion product, occur a large amount of gels, and have more monomer residue.
Application examples
The emulsion applications that embodiment 1-4 is made is in paper technology.Concrete grammar is: emulsion is added to feed chute together with paper grade (stock) base-material and other auxiliary agents, mix, paper per ton is used 5-10kg emulsion.
To being added with the paper strength of the coating emulsion that embodiment 1-4 and comparative example make, test, the results are shown in Table 1.
Table 1
Above-described embodiment just illustrates of the present invention, and the present invention also can implement with other ad hoc fashion or other particular form, and does not depart from main idea of the present invention or essential characteristic.Therefore, the embodiment of description all should be considered as illustrative but not determinate from the viewpoint of any.Scope of the present invention should illustrate by the claim of adding, and any and the intention of claim and the variation of scope equivalence also should be within the scope of the present invention.
Claims (10)
1. new network IPN is coated with a preparation method for emulsion, comprises the following steps:
(1) emulsifying agent is added to reactor, then add appropriate amount of deionized water to make bed material, be warming up to 60-65 ℃, stir and make emulsifiers dissolve;
(2) styrene monomer, acrylate monomer, comonomer X are evenly mixed, be made into dropping liquid A1; Vinyl Acetate Monomer, acrylate monomer, comonomer Y are evenly mixed, be made into dropping liquid A2; A part and deionized water in the oxygenant that initiator system is adopted evenly mix, and are made into dropping liquid B1, and residual oxidizing agent and deionized water are evenly mixed, and are made into dropping liquid B2;
(3) dropping liquid A1, B1 are at the uniform velocity added drop-wise in the reactor of step (1) simultaneously, at 80-90 ℃ after polymerization for some time, then dropping liquid A2, B2 are at the uniform velocity added drop-wise in reactor simultaneously, at 80-90 ℃, continue polymerization reaction take place; After completion of the reaction, be cooled to below 50 ℃ blowing.
2. a kind of new network IPN according to claim 1 is coated with the preparation method of emulsion, it is characterized in that, it is benchmark that raw material per-cent be take total charging capacity (weight), and styrene monomer accounts for 12-15%, and acrylate monomer accounts for 20-25%, Vinyl Acetate Monomer accounts for 12-15%, comonomer X accounts for 0.1-2%, and comonomer Y accounts for 0.1-2%, and the consumption of the oxygenant of initiator system is the 0.5-2% of aforementioned monomer total amount, the consumption of emulsifying agent is the 2-4% of aforementioned monomer total amount, and all the other are deionized water.
3. a kind of new network IPN according to claim 1 and 2 is coated with the preparation method of emulsion, it is characterized in that, described acrylate monomer is selected from one or more of methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate and butyl methacrylate.
4. a kind of new network IPN according to claim 3 is coated with the preparation method of emulsion, it is characterized in that, described comonomer X and Y are selected from respectively one or more in vinylformic acid, vinyl cyanide, methylpropene sodium sulfonate, maleic anhydride, fumaric acid, methylene-succinic acid and methacrylic acid.
5. a kind of new network IPN according to claim 1 and 2 is coated with the preparation method of emulsion, it is characterized in that, the oxygenant that initiator system adopts is selected from one or both in Sodium Persulfate, ammonium persulphate, hydrogen peroxide, Benzoyl Peroxide and Diisopropyl azodicarboxylate.
6. the preparation method of a kind of new network IPN coating emulsion according to claim 1, is characterized in that, in step (2), when preparation dropping liquid A1, B1, add deionized water, and add emulsifying agent to carry out pre-emulsification, the volume ratio of described emulsifying agent and described deionized water is 1:40-50.
7. according to the preparation method of a kind of new network IPN coating emulsion described in claim 1 or 6, it is characterized in that, emulsifying agent is selected from one or more in polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, Sodium dodecylbenzene sulfonate and sodium vinyl sulfonate.
8. according to the preparation method of a kind of new network IPN coating emulsion described in claim 1,2 or 6, it is characterized in that, in step (3), to adding polymerization reaction take place 1-1.5 hour after dropping liquid A1, B1 in reactor; Add polymerization reaction take place 2-3 hour after dropping liquid A2, B2, total reaction time is 4-5 hour again.
9. the application of the network interpenetrating coating emulsion being obtained by the arbitrary described preparation method of claim 1-7 in papermaking.
10. application according to claim 8, is characterized in that, is network interpenetrating is coated with to emulsion as the surface coated emulsion of paper.
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Cited By (3)
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| CN104673009A (en) * | 2015-03-24 | 2015-06-03 | 中国化工株洲橡胶研究设计院有限公司 | Emulsion for water-based sound-insulation anticorrosive paint and preparation method thereof |
| CN105255298A (en) * | 2015-10-17 | 2016-01-20 | 佛山市顺德区巴德富实业有限公司 | VAc/St/BA (vinyl acetate-styrene-butyl acrylate) stone paint emulsion and preparation method |
| CN111303333A (en) * | 2018-12-11 | 2020-06-19 | 万华化学集团股份有限公司 | Quick-drying water-based acrylic polymer emulsion and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104673009A (en) * | 2015-03-24 | 2015-06-03 | 中国化工株洲橡胶研究设计院有限公司 | Emulsion for water-based sound-insulation anticorrosive paint and preparation method thereof |
| CN105255298A (en) * | 2015-10-17 | 2016-01-20 | 佛山市顺德区巴德富实业有限公司 | VAc/St/BA (vinyl acetate-styrene-butyl acrylate) stone paint emulsion and preparation method |
| CN105255298B (en) * | 2015-10-17 | 2017-10-10 | 佛山市顺德区巴德富实业有限公司 | A kind of true mineral varnish emulsion of vinegar phenylpropyl alcohol and preparation method |
| CN111303333A (en) * | 2018-12-11 | 2020-06-19 | 万华化学集团股份有限公司 | Quick-drying water-based acrylic polymer emulsion and preparation method and application thereof |
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