CN101701049B - Preparation method of water-soluble acrylic resin - Google Patents
Preparation method of water-soluble acrylic resin Download PDFInfo
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- CN101701049B CN101701049B CN2009100846160A CN200910084616A CN101701049B CN 101701049 B CN101701049 B CN 101701049B CN 2009100846160 A CN2009100846160 A CN 2009100846160A CN 200910084616 A CN200910084616 A CN 200910084616A CN 101701049 B CN101701049 B CN 101701049B
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Abstract
The embodiment of the invention provides a preparation method of water-soluble acrylic resin. The resin comprises the following components according to defined weight percentages: hard monomer, methyl acrylate, acrylic acid, methylacrylic acid, soft monomer, initiator, ethanol, tert-butyl hydroperoxide, sodium formaldehyde sulfoxylate, deionized water, pH regulator, organic amine salt forming agent, nonionic wetting agent and mineral oil defoaming agent. The preparation method comprises the following steps: heating the mixed solution of water and ethanol to 80-84 DEG C, dropping monomer mixed solution and initiator while stirring, then heating to 80-100 DEG C for maturation, reducing the temperature to 70-75 DEG C, adding sodium formaldehyde sulfoxylate and tert-butyl hydroperoxide, keeping the temperature; adding organic amine salt forming agent, wetting agent and defoaming agent in the system while stirring, reducing the temperature, adjusting the pH value, filtrating and discharging to obtain the finished product. In the method of the invention, coating system with excellent coating property, easy film formation, high glossiness and good transparency can be prepared after the polymerization process by controlling the ratio of hydrophilic and hydrophobic monomers, controlling the neutralization process after finishing the reaction.
Description
Technical field
The present invention relates to the preparation of resin coating material, relate in particular to a kind of water soluble acrylic resin's preparation method.
Background technology
In present soft packaging design, mould the overwhelming majority that plastic composite structure has accounted for soft package structure, this complex form needs the two plastic substrates of different purposes, and under the function served as bridge of tackiness agent, being combined with each other reaches final use properties.But because this composite structure technology is complicated; The starting material usage quantity is big, causes the waste of the energy; And the difference of each producer's state of the art causes the quality of this composite structure very different.How reducing raw-material usage quantity, simplify the complicacy of composite structure, reduce the use difficulty of producer, is the developing a kind of trend of soft packaging.
In the seventies and eighties in last century, the laminated film that scribbles coating is developed by U.S. aerochemistry company at first, because huge advantage such as its energy-saving and environmental protection have occupied the very large market share in the soft packaging field.In China because coating technology immature, this technology just began to occur on market up to the beginning of this century, and the coating film forming matter overwhelming majority who uses at present is polyurethane structural, because its higher market value, the coating of this polyurethane structural is only used in some packaging structures than higher gears at home, has had a strong impact on the innovation of composite soft packaging technology.
The domestic market exists at present that a large amount of emulsifying water types is pure third, phenylpropyl alcohol, vinegar third and EVA, VAE emulsion coating system; a lot of technicians are also making great efforts to having protection and the improvement of heat-sealing structure direction concurrently; the basic ideas of its polymer architecture design all are acid coated uses of thermoplastic propene by synthetic high glass transition temperature Tg; but because himself special thin film-forming method of emulsion polymer, determined the limitation of its product self.The easy efflorescence of high glass transition temperature Tg latex particle, self film-forming properties is poor, in order to improve film-forming properties, certainly will need to add the difficult evaporable solvent of high boiling point as film coalescence aid, the existence of a large amount of solvent-borne type film coalescence aid, influenced the glossiness and the film forming continuity of product, required than higher field in some food safety performances, the existence of a large amount of solvent-borne type auxiliary agents makes the packing content thing have bigger potential safety hazard.
Summary of the invention
Based on above-mentioned existing in prior technology problem; the embodiment of the invention provides a kind of water soluble acrylic resin's preparation method, has than high melting temperature, and solvent-free water soluble acrylic resin; but as coating, have provide protection and heat sealability on the laminated film.
The embodiment of the invention is achieved through the following technical solutions:
The embodiment of the invention provides a kind of water soluble acrylic resin's preparation method, comprising:
Following each component by weight percentage:
Hard monomer 10～30%
Methyl acrylate 5～60%
Vinylformic acid 20～90%
Methacrylic acid 5～30%
Soft monomer 10～30%
Initiator 0.5～5%
Ethanol 10～30%
Tertbutyl peroxide 0.1～0.5%
Rongalite 0.1～0.5%
Deionized water 30～60%
PH conditioning agent 1～10%
Organic amine salt forming agent 0.1～3%
Non-ionic wetting agent 0.05～1.5%
Mineral oil defoaming agent 0.05～1.5%;
The deionized water and the whole ethanol that in container, add the ionized water gross weight 60～75% that accounts for, stir with 80～120 rev/mins speed, be warming up to 80～84 ℃, drip respectively by the monomer mixed solution that forms after hard monomer, methyl acrylate, vinylformic acid and methacrylic acid, the soft monomer mixing and by initiator and mix the initiator system that the back forms with the deionized water of the ion gross weight 1～10% that accounts for, monomer mixed solution drips off at 3.5～4.5h, the dropping time lengthening 10～15min of the dropping time ratio monomer mixed solution of initiator system;
Be warming up to 80～100 ℃ of slaking 1～2h, be cooled to 70～75 ℃, add rongalite and mix the post-treatment agent solution that the back forms, insulation 0.5～1h with the deionized water of the tertbutyl peroxide and the ionized water gross weight 1～10% that accounts for;
Continue to be cooled to below 40 ℃, add the organic amine salt forming agent at whipped state and mix the salt forming agent solution that the back forms with the deionized water of the ion gross weight 5～38% that accounts for the organic amine salt forming agent, non-ionic wetting agent and mineral oil defoaming agent, stir 20～40min, add the PH conditioning agent, discharging is filtered in the pH value to 6.5 of regulation system～7.5, promptly obtains the water soluble acrylic resin.
Described hard monomer comprises:
In vinylbenzene or the methyl methacrylate any or both mixtures.
Described soft monomer comprises the mixture of any or both in butyl acrylate or the ethyl acrylate.
Described initiator adopts the persulphate water soluble starter.
Described persulphate water soluble starter adopts any in Potassium Persulphate, Sodium Persulfate, the ammonium persulfate water soluble starter.
Described PH conditioning agent adopts Ammonia PH conditioning agent.
Described organic amine salt forming agent adopts any in thanomin, diethanolamine, the trolamine.
Described non-ionic wetting agent adopts low EO value to be lower than 10 nonionogenic tenside.
Described mineral oil defoaming agent adopts any in type siloxane, mineral oil base class, the polyalcohols.
The technical scheme that is provided by the invention described above embodiment as can be seen, make the water soluble acrylic resin by the solution polymerization of the bigger water soluble propene's acid system of wetting ability in the embodiment of the invention, by controlling the ratio of hydrophilic hydrophobic monomer, N-process when the control reaction is finished, water soluble acrylic resin's coating system of can obtain the coating excellence, film forming is easy, glossiness is high, the transparency is good.Compare with the supercoat of routine, technology of the present invention is more succinct, uses more convenient.
Embodiment
For ease of understanding, the invention will be further described below in conjunction with specific embodiment.
Embodiment one
Present embodiment provides a kind of water soluble acrylic resin's preparation method, and this method comprises:
This resin comprises following each component by weight percentage:
Following each component by weight percentage:
Hard monomer 10～30%
Methyl acrylate 5～60%
Vinylformic acid 20～90%
Methacrylic acid 5～30%
Soft monomer 10～30%
Initiator 0.5～5%
Ethanol 10～30%
Tertbutyl peroxide 0.1～0.5%
Rongalite 0.1～0.5%
Deionized water 30～60%
PH conditioning agent 1～10%
Organic amine salt forming agent 0.1～3%
Non-ionic wetting agent 0.05～1.5%
Mineral oil defoaming agent 0.05～1.5%;
The deionized water and the whole ethanol that in container, add the ionized water gross weight 60～75% that accounts for, stir with 80～120 rev/mins speed, be warming up to 80～84 ℃, drip respectively by the monomer mixed solution that forms after hard monomer, methyl acrylate, vinylformic acid and methacrylic acid, the soft monomer mixing and by initiator and mix the initiator system that the back forms with the deionized water of the ion gross weight 1～10% that accounts for, monomer mixed solution drips off at 3.5～4.5h, the dropping time lengthening 10～15min of the dropping time ratio monomer mixed solution of initiator system;
Be warming up to 80～100 ℃ of left and right sides slaking 1～2h, be cooled to 70～75 ℃, add rongalite and mix the post-treatment agent solution that the back forms, insulation 0.5～1h with the deionized water of the tertbutyl peroxide and the ionized water gross weight 1～10% that accounts for;
Continue to be cooled to below 40 ℃, add the organic amine salt forming agent at whipped state and mix the organic amine salt forming agent solution that the back forms with the deionized water of the ion gross weight 5～38% that accounts for, non-ionic wetting agent and mineral oil defoaming agent, stir 20～40min, add the PH conditioning agent, discharging is filtered in the pH value to 6.5 of regulation system～7.5, promptly obtains the water soluble acrylic resin.
In above-mentioned preparation water soluble acrylic resin's the prescription, hard monomer comprises: any in vinylbenzene or the methyl methacrylate or both mixtures, the consumption of hard monomer account for 10～30% of acrylic resin formula system gross weight.
Soft monomer comprises the mixture of any or both in butyl acrylate or the ethyl acrylate.The consumption of soft monomer accounts for 10～30% of acrylic resin formula system gross weight.
Initiator adopts the persulphate water soluble starter, and the persulphate water soluble starter can adopt any in Potassium Persulphate, Sodium Persulfate, the ammonium persulfate water soluble starter.
The PH conditioning agent adopts Ammonia PH conditioning agent
The organic amine salt forming agent can adopt any in thanomin, diethanolamine, the trolamine.
Non-ionic wetting agent adopts the EO value to be lower than 10 nonionogenic tenside.
Mineral oil defoaming agent adopts any in type siloxane, mineral oil base class, the polyalcohols.
The water soluble acrylic resin that the embodiment of the invention makes can be used as the coating of film; has environmental protection simple for structure; need not add tackiness agent and carry out compound between the different films; only need coating one deck supercoat on base material film; its thickness and composite structure are similar; need not add composite structure and can reach the over-all properties of composite structure, the composite structure that utilizes this resin coating to make has reduced tackiness agent and has had pollution to environment, has reduced the cost of composite structure.
This composite coating structure; adopt the mode of radical polymerization to synthesize; this coating gloss height; wear resistance and frictional coefficient height, and melt temperature is than higher, after the coating drying; can not only play provide protection attractive in appearance; and this coating can seal under 120～140 ℃ temperature, plays the effect of hot melt adhesive.
Compare with the supercoat of routine, technology of the present invention is more succinct, uses more conveniently, has carried out Promethean breakthrough in the following aspects:
(1) embodiment of the invention adopts water-soluble propenoic-acids to be listed as high molecular form to make fully, and it is composite to have abandoned traditional alkali swelling property polymer and emulsion system, mixes film forming and plays a protective role; In preparation method's of the present invention system formulation, the consumption of Acrylic Acid Monomer accounts for more than 50% of system monomer total amount in the guarantee system, and carry out other monomers of suitable allotment according to its water miscible difference, used water-soluble high slightly monomers such as methyl acrylate, ethyl propenoate, methyl methacrylate, guaranteed
(2) reaction system of the embodiment of the invention is directly made the water insoluble thermoplastic polymer when molecular designing, by the melt temperature of control unitary system, has reached the heat sealability under corresponding temperature and pressure condition.The synthetic of water soluble propene's acid system of the embodiment of the invention has the membrane formation mechanism of solvent-based system and the environment-friendly function of aqueous high molecular concurrently, makes it have the good and cheap market competition advantage of film-forming properties simultaneously concurrently;
(3) reaction system of the embodiment of the invention, just be directed to corresponding system in the molecular designing stage and carry out the auxiliary agent match selection, like this in later stage composite, floating oil, flocculation etc. neither can occur influences the stable and outward appearance phenomenon of system, the not good phenomenons of outward appearance such as pin hole, white point can not occur again in coating.
Embodiment two
Present embodiment provides a kind of water soluble acrylic resin's preparation method, is undertaken by following step:
At first get each raw material by the weight of following prescription:
Water 200 grams
Vinylformic acid 70 grams
Methacrylic acid 15 grams
Methyl acrylate 15 grams
Methyl methacrylate 15 grams
Butyl acrylate 35 grams
Ammonium persulfate 2.5 grams
Thanomin 5 grams
Ethanol 100 grams
Nonionogenic tenside 0.3 gram
Type siloxane defoamer 0.2 gram
Tertbutyl peroxide 0.8 gram
Rongalite 0.8 gram
Ammonia 3.2 grams
In there-necked flask, add 120 gram water and whole ethanol, under 80～120 rev/mins speed whipped state, in water-bath, be warming up to 80～82 ℃, drip subsequently by vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate and butyl acrylate and mix the monomer mixed solution that the back forms, drip H simultaneously
2O/APS (deionized water/ammonium persulfate) ratio is 20/2.5 initiator system 22.5g, the control rate of addition, and 3～4h drips off, and initiator system drips about time lengthening 15min than monomer system;
Be warming up to 80 ℃ of left and right sides slaking 1h, be cooled to 70 ℃, the deionized water that adds rongalite, tertbutyl peroxide and 20g mixes the post-treatment agent solution that the back forms, insulation 1h;
Be cooled to below 40 ℃, under whipped state, add by H respectively
2Organic amine salt forming agent solution, nonionogenic tenside master type siloxane defoamer that O/DMEA (deionized water/thanomin) forms by 40/5 mixed, stir about 30min, in system, add ammonia, the pH value of regulation system is 7.5, promptly obtains the water soluble acrylic resin after the filtration discharging.
When using this water soluble acrylic resin; used water or water and alcoholic acid mixed solution are diluted to system 10～15% solid content; last machine coating can obtain the good supercoat of luster performance, and this coating obtains the heat sealability of sealing strength excellence under 120～140 ℃ of suitable pressure.
Embodiment three
Present embodiment provides a kind of water soluble acrylic resin's preparation method, is undertaken by following step:
At first get each raw material by the weight of following prescription:
Water 250 grams
Vinylformic acid 85 grams
Methacrylic acid 15 grams
Methyl acrylate 15 grams
Vinylbenzene 10 grams
Methyl methacrylate 5 grams
Ethyl acrylate 20 grams
Potassium Persulphate 1.5 grams
Diethanolamine 5 grams
Ethanol 100 grams
Nonionogenic tenside 0.3 gram
Mineral oil based defoamer 0.2 gram
Tertbutyl peroxide 0.8 gram
Rongalite 0.6 gram
Ammonia 4.5 grams
In there-necked flask, add 180 gram water and whole ethanol, under 80～120 rev/mins speed whipped state, in water-bath, be warming up to 80～82 ℃, drip subsequently by vinylformic acid, methacrylic acid, methyl acrylate, vinylbenzene, methyl methacrylate and ethyl acrylate and mix the monomer mixed solution that the back forms, drip H simultaneously
2O/APS (deionized water/Potassium Persulphate) ratio is 15/1.5 initiator system 16.5g, the control rate of addition, and 3～4h drips off, and initiator system drips about time lengthening 15min than monomer system;
Be warming up to 100 ℃ of left and right sides slaking 1h, be cooled to 75 ℃, the deionized water that adds rongalite, tertbutyl peroxide and 15g mixes the post-treatment agent solution that the back forms, insulation 1h;
Be cooled to below 40 ℃, under whipped state, add by H respectively
2Organic amine salt forming agent solution, nonionogenic tenside and mineral oil based defoamer that O/DMEA (deionized water/diethanolamine) forms by 40/5 mixed, stir about 30min, in system, add ammonia, the pH value of regulation system is 6.5, promptly obtains the water soluble acrylic resin after the filtration discharging.
When using this water soluble acrylic resin; used water or water and alcoholic acid mixed solution are diluted to 10～15% with system; last machine coating can obtain the good supercoat of luster performance, and this coating obtains the heat sealability of sealing strength excellence under 120～140 ℃ of suitable pressure.
In use, water or water and alcoholic acid mixed solution are diluted to 10～15% with system, and higher level's coating can obtain the good supercoat of luster performance, and this coating obtains the heat sealability of sealing strength excellence under 120～140 ℃ of suitable pressure.
Embodiment four
Present embodiment provides a kind of water soluble acrylic resin's preparation method, is undertaken by following step:
At first get each raw material by the weight of following prescription:
Water 320 grams
Vinylformic acid 90 grams
Methacrylic acid 15 grams
Methyl acrylate 15 grams
Vinylbenzene 15 grams
Butyl acrylate 5 grams
Ethyl acrylate 10 grams
Sodium Persulfate 4 grams
Trolamine 5 grams
Ethanol 100 grams
Nonionogenic tenside 0.3 gram
Polyalcohols defoamer 0.2 gram
Tertbutyl peroxide 1.4 grams
Rongalite 1.1 grams
Ammonia 5.5 grams
In there-necked flask, add 210 gram water and whole ethanol, under 80～120 rev/mins speed whipped state, in water-bath, be warming up to 80～82 ℃, drip subsequently by vinylformic acid, methacrylic acid, methyl acrylate, vinylbenzene, butyl acrylate and ethyl acrylate and mix the monomer mixed solution that the back forms, drip H simultaneously
2O/APS (deionized water/Sodium Persulfate) ratio is 30/4 initiator system 34g, the control rate of addition, and 3～4h drips off, and initiator system drips about time lengthening 15min than monomer system;
Be warming up to 90 ℃ of left and right sides slaking 1h, be cooled to 73 ℃, the deionized water that adds rongalite, tertbutyl peroxide and 30g mixes the post-treatment agent solution that the back forms, insulation 1h;
Be cooled to below 40 ℃, under whipped state, add by H respectively
2Organic amine salt forming agent solution, nonionogenic tenside and polyalcohols defoamer that O/DMEA (deionized water/trolamine) forms by 50/5 mixed, stir about 30min, in system, add ammonia, the pH value of regulation system is 7, promptly obtains the water soluble acrylic resin after the filtration discharging.
When using this water soluble acrylic resin; used water or water and alcoholic acid mixed solution are diluted to 10～15% with system; higher level's coating can obtain the good supercoat of luster performance, and this coating obtains the heat sealability of sealing strength excellence under 120～140 ℃ of suitable pressure.
In use, water or water and alcoholic acid mixed solution are diluted to 10～15% with system, and higher level's coating can obtain the good supercoat of luster performance, and this coating obtains the heat sealability of sealing strength excellence under 110～130 ℃ of suitable pressure.
In sum; the water soluble acrylic resin that the embodiment of the invention makes is as coating structure; has succinct environmental protection; need not add tackiness agent and carry out compound between the different films; only need coating one deck supercoat on base material film; its thickness and composite structure are similar; the composite structure that need not add can reach the over-all properties of composite structure; the appearance of this composite structure; reduced the pollution of tackiness agent existence to environment; reduced the cost of composite structure, accepted and use by More and more factories.This composite coating structure; adopt the mode of radical polymerization to synthesize; this coating gloss height; wear resistance and frictional coefficient height, and melt temperature is than higher, after the coating drying; can not only play provide protection attractive in appearance; and this coating can seal under 120～140 ℃ temperature, plays the effect of hot melt adhesive.
The above; only be the preferable embodiment of the present invention; but protection scope of the present invention is not limited thereto; the present invention is not had any impact because of the succession of each embodiment yet; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (3)
1. a water soluble acrylic resin preparation method is characterized in that, is undertaken by following step:
At first get each raw material by the weight of following prescription:
In there-necked flask, add 120 gram water and whole ethanol, under 80～120 rev/mins speed whipped state, in water-bath, be warming up to 80～82 ℃, drip subsequently by vinylformic acid, methacrylic acid, methyl acrylate, methyl methacrylate and butyl acrylate and mix the monomer mixed solution that the back forms, drip deionized water/ammonium persulphate ratio simultaneously and be 20/2.5 initiator system 22.5g, the control rate of addition, 3～4h drips off, and initiator system drips time lengthening 15min than monomer system;
Be warming up to 80 ℃ of slaking 1h, be cooled to 70 ℃, the deionized water that adds rongalite, tertbutyl peroxide and 20g mixes the post-treatment agent solution that the back forms, insulation 1h;
Be cooled to below 40 ℃, under whipped state, add the organic amine salt forming agent solution, nonionogenic tenside and the type siloxane defoamer that form by 40/5 mixed by deionized water/thanomin respectively, stir 30min, in system, add ammonia, the pH value of regulation system is 7.5, promptly obtains the water soluble acrylic resin after the filtration discharging.
2. a water soluble acrylic resin preparation method is characterized in that, is undertaken by following step:
At first get each raw material by the weight of following prescription:
In there-necked flask, add 180 gram water and whole ethanol, under 80～120 rev/mins speed whipped state, in water-bath, be warming up to 80～82 ℃, drip subsequently by vinylformic acid, methacrylic acid, methyl acrylate, vinylbenzene, methyl methacrylate and ethyl acrylate and mix the monomer mixed solution that the back forms, drip deionized water/Potassium Persulphate ratio simultaneously and be 15/1.5 initiator system 16.5g, the control rate of addition, 3～4h drips off, and initiator system drips time lengthening 15min than monomer system;
Be warming up to 100 ℃ of slaking 1h, be cooled to 75 ℃, the deionized water that adds rongalite, tertbutyl peroxide and 15g mixes the post-treatment agent solution that the back forms, insulation 1h;
Be cooled to below 40 ℃, under whipped state, add the organic amine salt forming agent solution, nonionogenic tenside and the mineral oil based defoamer that form by 40/5 mixed by deionized water/diethanolamine respectively, stir 30min, in system, add ammonia, the pH value of regulation system is 6.5, promptly obtains the water soluble acrylic resin after the filtration discharging.
3. a water soluble acrylic resin preparation method is characterized in that, is undertaken by following step:
At first get each raw material by the weight of following prescription:
In there-necked flask, add 210 gram water and whole ethanol, under 80～120 rev/mins speed whipped state, in water-bath, be warming up to 80～82 ℃, drip subsequently by vinylformic acid, methacrylic acid, methyl acrylate, vinylbenzene, butyl acrylate and ethyl acrylate and mix the monomer mixed solution that the back forms, drip deionized water/Sodium Persulfate ratio simultaneously and be 30/4 initiator system 34g, the control rate of addition, 3～4h drips off, and initiator system drips time lengthening 15min than monomer system;
Be warming up to 90 ℃ of slaking 1h, be cooled to 73 ℃, the deionized water that adds rongalite, tertbutyl peroxide and 30g mixes the post-treatment agent solution that the back forms, insulation 1h;
Be cooled to below 40 ℃, under whipped state, add the organic amine salt forming agent solution, nonionogenic tenside and the polyalcohols defoamer that form by 50/5 mixed by deionized water/trolamine respectively, stir 30min, in system, add ammonia, the pH value of regulation system is 7, promptly obtains the water soluble acrylic resin after the filtration discharging.
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| CN2009100846160A CN101701049B (en) | 2009-05-22 | 2009-05-22 | Preparation method of water-soluble acrylic resin |
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| CN104449036A (en) * | 2014-12-12 | 2015-03-25 | 天津市侨阳印刷有限公司 | Preparation method of water-based ink |
| CN115627108B (en) * | 2022-10-25 | 2023-12-01 | 福建长塑实业有限公司 | Barrier coating liquid, heat-sealable barrier coated polylactic acid film and preparation method thereof |
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Effective date of registration: 20181219 Address after: 226407 Yangkou Chemical Industrial Park, Rudong Coastal Economic Development Zone, Nantong City, Jiangsu Province Patentee after: Nantong Gaomeng New Material Co., Ltd. Address before: 102502 No. 8, Yanshan Industrial Zone, Beijing, Fangshan District Patentee before: Beijing Comens New Materials Co., Ltd. |
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