CN104086123B - Stone-like coating and preparation method thereof - Google Patents

Stone-like coating and preparation method thereof Download PDF

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CN104086123B
CN104086123B CN201410328908.5A CN201410328908A CN104086123B CN 104086123 B CN104086123 B CN 104086123B CN 201410328908 A CN201410328908 A CN 201410328908A CN 104086123 B CN104086123 B CN 104086123B
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coating
parts
starch
stone
monomer
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CN104086123A (en
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田映良
崔芸
郑旺斌
方悦
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GANSU GLDARK NEW MATERIAL Co Ltd
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GANSU GLDARK NEW MATERIAL Co Ltd
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Abstract

The invention discloses a kind of stone-like coating and preparation method thereof, make base-material and there is the slightly poor shortcoming of paint flow levelling to solve existing benzene emulsion for coating, and the problem because easily turning to be yellow containing phenyl ring film.This stone-like coating for aggregate, selects composite modified starch emulsion to be base-material with color sand, adds biomass thickening materials, neutralizing agent, propylene glycol, defoamer, sanitas, softening water and preparing.The present invention obtains stone-like coating, and to have the feature of environmental protection good, and formaldehyde does not detect, and has weathering resistance, water-tolerant, washability (more than 5000 times), the features such as rheological is good.

Description

Stone-like coating and preparation method thereof
Technical field
The invention belongs to paint field, be specifically related to a kind of stone-like coating and preparation method thereof.
Background technology
The developing direction of building external paint is high-decoration, strong contamination resistance, high-durability and saving resource, the saving energy, nuisanceless, pollution-free.From ornamental, that resistant is durable angle, solvent based coating ratio is easier to meet the demands, but its ventilation property and environmental requirement are difficult to reach.From the angle of environmental protection, generally acknowledged approach is Water-borne modification, but the contamination resistance of water-borne coatings, ageing resistance are difficult to usually compared with solvent based coating.
Stone-like coating take resin emulsion as base-material, and with the color sand, stone flour etc. of variable grain for aggregate, spraying or trowelling, on building surface, form the coating with lithotome texture.Stone-like coating has fine weather resistance and contamination resistance, has fine good decorative property simultaneously, can present the texture of similar lithotome, is widely used in the decoration of the various substrate surface of inner-outer wall.Stone-like coating pulp base-material used must have good water tolerance, adhesion strength and ageing resistance, and only in this way guarantee imitates stone coating good over-all properties.Comparatively commonly use as benzene emulsion and pure-acrylic emulsion make base-material, wherein benzene emulsion large usage quantity, has the advantages such as alkali resistance is good, weather resistance is better, but there is the slightly poor shortcoming of paint flow levelling for coating, and because easily turning to be yellow containing phenyl ring film; Pure-acrylic emulsion weathering resistance is good and alkaline good, and hardness of paint film is good, but price is higher.
Summary of the invention
The object of the present invention is to provide a kind of stone-like coating, make base-material and there is the slightly poor shortcoming of paint flow levelling to solve existing benzene emulsion for coating, and the problem because easily turning to be yellow containing phenyl ring film.
Another object of the present invention is the preparation method providing this stone-like coating.
To achieve the above object of the invention, technical scheme of the present invention is, 1. a stone-like coating, comprises the raw material of following masses part: 500-750 parts, color sand, composite modified starch emulsion 100-300 parts, thickening material 1-3 parts, neutralizing agent 1-3 parts, propylene glycol 5-15 parts, defoamer 1-3 parts, sanitas 1-2 parts, softening water 80-200 parts.
Preferably, described thickening material is one or both in Natvosol, carboxymethyl cellulose, carboxymethyl starch or hydroxypropylated starch.
Preferably, described neutralizing agent is the one in amino-2 methyl isophthalic acids-propyl alcohol of sodium hydroxide, potassium hydroxide, ammoniacal liquor, sodium bicarbonate or 2-.
Preferably, described defoamer is one or both in fatty acid metal soap, organophosphate, water drain silica or fatty acid ester.
Preferably, described sanitas is isothiazolinone.
Described composite modified starch emulsion can be purchased, can make by oneself, self-control preferably comprises the raw material of following masses part: Sumstar 190 60-80 parts, acidolysis etherification starch 20-40 parts, swelling inhibitor 0.5-2 parts, linking agent 0.01-0.03 part, emulsifying agent 2-6 parts, initiator 1-5 parts, deionized water 200-400 parts, NaOH 1-2 parts and mix monomer, and mix monomer comprises hard monomer 35-160 parts and soft monomer 65-150 parts.
Preferably, described mix monomer also comprises function monomer 1-2.5 parts.
Preferably, described swelling inhibitor is sodium-chlor; Described linking agent is the one in epoxy chloropropane, phosphorus oxychloride or Trisodium trimetaphosphate; Described hard monomer is the one in methyl methacrylate, methacrylate ethyl ester or vinyl acetate, and described soft monomer is the one in ethyl propenoate, butyl acrylate or Isooctyl acrylate monomer; Described function monomer be vinylformic acid, methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, vinylformic acid- -hydroxypropyl acrylate or methacrylic acid- one in the different monooctyl ester of-hydroxypropyl acrylate.Preferably, described emulsifying agent is the mixture of anionic emulsifier sodium lauryl sulphate and nonionic emulsifying agent BD-109 1:1.5-2 ratio in mass ratio; Described initiator is the one in Potassium Persulfate or ammonium peroxydisulfate.
The preparation method of above-mentioned stone-like coating, with color sand for aggregate, composite modified starch emulsion is base-material, add multiple auxiliary agent to make, specifically comprise the steps: to get softening water, thickening material, add in dispersion machine, even with the rotating speed dispersed with stirring of 300 ~ 500r/min, add composite modified starch emulsion, color sand, propylene glycol, defoamer, sanitas, neutralizing agent successively by mass fraction, after dispersed with stirring is even, namely obtain stone-like coating.
Beneficial effect of the present invention is: the present invention for aggregate, adopts composite modified starch emulsion to be film forming binder with color sand, and this base-material is prepared after being cross-linked rear and acrylate monomer grafting with Sumstar 190, the mixing of acidolysis etherification starch.This emulsion is used for coating and has the advantage of acrylate and starch emulsion concurrently, and film forming properties is excellent, abrasion resistance is good, good permeability, formaldehydeless and have certain humidity conditioning function.For the preparation of stone-like coating, there is film forming properties excellence, the advantage such as cohesiveness, water-tolerant, environmental protection.Present stage can be improved commonly use benzene emulsion and prepare that water-based stone-like coating rheological is poor, the shortcoming of easily jaundice.The present invention obtains stone-like coating, and to have the feature of environmental protection good, and formaldehyde does not detect, and has weathering resistance, water-tolerant, washability (more than 5000 times), the features such as rheological is good.
" fundamental property test ": carried out fundamental property test (table 1-stone-like coating performance index) according to SAND SLURRY SYNTHETIC EMULSION ARCHITECTURAL COATINGS industry standard (JG/T24-2000).Result shows stone-like coating composite exterior wall coating of the present invention requirement, and excellent property.Require that water-borne coatings industry standard (HJ/T201-2005) carries out detecting (table 2-stone-like coating environmental protection index) according to environmental standard product technology, result shows, this product meets environmentfriendly products requirement simultaneously.
Embodiment
The following examples can further illustrate the present invention, but do not limit the present invention in any way.In following embodiment, not marked raw material is and is purchased.
The Sumstar 190 mentioned in composite modified starch emulsion in following embodiment and acidolysis etherification starch are for raw material adopts following methods to obtain with one or both mixtures in yam starch, waxy corn starch, tapioca (flour), sticky rice flour, W-Gum.
Wherein the preparation method used of embodiment 1-4 Sumstar 190 and acidolysis etherification starch is as follows:
1. Sumstar 190 preparation method is: starch adds deionized water water and is mixed with the starch milk that concentration is 38%, is heated to 55 DEG C, adds the H that concentration is 30% 2o 2solution is as oxygenant, and oxygenant consumption is 6% of starch on dry basis amount, is the CuSO of 0.5% with concentration 4solution is catalyzer, 0.02% of catalyst levels starch on dry basis amount, with mass percent concentration 3% NaOH solution and mass percent concentration 5% HCl for pH adjusting agent, pH is regulated to be 7.3, oxidizing reaction 3-4h, washing, dry, pulverize and obtain Sumstar 190 product.
2. acidolysis etherification starch is that acidolysis sodium starch glycolate and acidolysis hydroxypropylated starch mix, the preparation process of wherein acidolysis carboxymethyl starch is: in acidified starch, add the ethanol of 80%, be mixed with the starch milk of concentration 35%, under whipped state, drip the NaOH ethanol that mass percent concentration is 40%, NaOH ethanol by NaOH and 95% ethanol formulated, alkalization 30min is stirred at the temperature of 30 DEG C, be warming up to 45 DEG C, slowly add sodium chloroacetate ethanol, the ratio that sodium chloroacetate ethanol take mass ratio as 3:1:4 by sodium chloroacetate and sodium hydroxide and 95% ethanol mixes and obtains, reaction 3h, by 5% hydrochloride ethanol liquid adjust ph to 7, filter, by 80% washing with alcohol 3 times, dry, pulverize white or pale yellow powder shape product, be acidolysis carboxymethyl starch.
3. the preparation process of acidolysis hydroxypropylated starch is: add relative to the swelling inhibitor of starch quality than 13% in deionized water water, add the sodium hydroxide accounting for starch quality 1.0%%, mix to dissolving, add the starch milk of acidified starch furnishing 35% prepared by step (1), stir alkalization 40min, be warming up to 42 DEG C, add the propylene oxide accounting for starch quality 5%, etherification reaction 14h, add the salt acid for adjusting pH to 7.0 of 10%, centrifuge dehydration, drying, sieve after namely obtain acidolysis hydroxypropylated starch;
4. the preparation process of the acidified starch that acidolysis carboxymethyl starch and acidolysis hydroxypropylated starch preparation process are used is: in starch, add mass percent concentration is in the HCl solution of 0.6%, be mixed with the starch milk of concentration 38%, be heated to 50 DEG C of temperature, acidolysis reaction 2h; After acidolysis terminates, the NaOH solution adding mass percent concentration 5% regulates pH to 7, filter, washing, dry acidified starch.
Wherein the preparation method used of embodiment 5-8 Sumstar 190 and acidolysis etherification starch is as follows:
1. Sumstar 190 preparation method is: starch adds the starch milk that deionized water water is mixed with concentration 40%, is heated to 55 DEG C, adds the H that concentration is 30% 2o 2solution is as oxygenant, and oxygenant consumption is 6% of starch on dry basis amount, is the CuSO of 0.5% with concentration 4solution is catalyzer, 0.02% of catalyst levels starch on dry basis amount, with mass percent concentration 3% NaOH solution and mass percent concentration 5% HCl for pH adjusting agent, regulates pH to be 7.3, oxidizing reaction 3h, washing, dry, pulverize and obtain Sumstar 190 product.
2. acidolysis etherification starch is that acidolysis sodium starch glycolate and acidolysis hydroxypropylated starch mix, the preparation process of wherein acidolysis carboxymethyl starch is: in acidified starch, add the ethanol of 90%, be mixed with the starch milk of concentration 38%, under whipped state, drip the NaOH ethanol that mass percent concentration is 40%, NaOH ethanol by NaOH and 95% ethanol formulated, alkalization 40min is stirred at the temperature of 30 DEG C, be warming up to 45 DEG C, slowly add sodium chloroacetate ethanol, the ratio that sodium chloroacetate ethanol take mass ratio as 3:1:6 by sodium chloroacetate and sodium hydroxide and 95% ethanol mixes and obtains, reaction 4h, by 5% hydrochloride ethanol liquid adjust ph to 7.5, filter, by 80% washing with alcohol 3 times, dry, pulverize white or pale yellow powder shape product, be acidolysis carboxymethyl starch.
3. the preparation process of acidolysis hydroxypropylated starch is: add relative to the swelling inhibitor of starch quality than 15% in deionized water water, add the sodium hydroxide accounting for starch quality 1.2%, mix to dissolving, add the starch milk of acidified starch furnishing 38% prepared by step (1), stir alkalization 60min, be warming up to 42 DEG C, add the propylene oxide accounting for starch quality 10%, etherification reaction 18h, add the salt acid for adjusting pH to 7.0 of 10%, centrifuge dehydration, drying, sieve after namely obtain acidolysis hydroxypropylated starch;
4. the preparation process of the acidified starch that acidolysis carboxymethyl starch and acidolysis hydroxypropylated starch preparation process are used is: in starch, add mass percent concentration is in the HCl solution of 0.8%, be mixed with the starch milk of concentration 40%, be heated to 55 DEG C of temperature, acidolysis reaction 3h; After acidolysis terminates, add mass percent concentration be 5% NaOH solution regulate pH to 7, filter, washing, dry acidified starch.
Embodiment 1
Raw material dosage is as follows: color sand (20-120 order) 500kg, composite modified starch emulsion 200 kg, Natvosol 3 kg, sodium hydroxide 1.5 kg, propylene glycol 10 kg, fatty acid metal soap 1 kg, isothiazolinone 1.5 kg, softening water 100 kg.
The preparation method of stone-like coating, comprise the steps: to get softening water, Natvosol, add in dispersion machine, even with the rotating speed dispersed with stirring of 300r/min, add crosslinking-oxidization graft starch emulsion, color sand, propylene glycol, fatty acid metal soap, isothiazolinone, sodium hydroxide successively by mass fraction, after dispersed with stirring is even, namely obtain stone-like coating.
Above-mentioned composite modified starch emulsion materials consumption is as follows: Sumstar 190 60kg, acidolysis etherification starch 40 kg, swelling inhibitor 2 kg, linking agent 0.03 kg, hard monomer 35 kg, soft monomer 65 kg, function monomer 1 kg, emulsifying agent 2 kg, initiator 1 kg, deionized water 200 kg, NaOH are 1.2 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, add Sumstar 190 and acidolysis etherification starch (be that the acidolysis sodium starch glycolate of 0.4 with the acidolysis hydroxypropylated starch of substitution value 0.1 with the ratio of 1:2 mix by substitution value) in deionized water in mass fraction, form certain density starch milk;
(2) in the swelling inhibitor sodium-chlor of step (1) gained starch milk additional proportion, starch milk pH to 10.5 is adjusted with the sodium hydroxide solution that volumetric concentration is 5%;
(3) add the linking agent phosphorus oxychloride of affiliated mass fraction in step (2) gained starch milk, reaction 1h, adds the salt acid for adjusting pH to 8.5 that volumetric concentration is 10%;
(4) 80 DEG C of abundant gelatinizations 30 minutes are warming up in step (3) gained starch milk;
(5) take initiator (Potassium Persulfate), add deionized water and be mixed with solution and the initiator solution that mass concentration is 5%;
(6) emulsifying agent that additional proportion is mixed by the ratio of sodium lauryl sulphate and BD-109 1:2 in mass ratio in step (4) gained starch milk, then 1/4 amount of step (5) initiator solution is added, 1/10 amount of mix monomer (methyl methacrylate, butyl acrylate, vinylformic acid mix), reacts 20 minutes; At the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer with constant pressure funnel again, after adding, be warming up to 80 DEG C, reaction 2h;
(7) reaction system is down to room temperature, and volumetric concentration is the NaOH aqueous solution adjustment pH to 6 of 20%, obtains coating emulsion.
Embodiment 2
Raw material dosage is as follows: color sand (20-120 order) 550 kg, composite modified starch emulsion 150 kg, carboxymethyl cellulose 2.5 kg, ammoniacal liquor 1 kg, propylene glycol 5 kg, organophosphate 1.5 kg, isothiazolinone 2 kg, softening water 150 kg.
The preparation method of stone-like coating, comprises the steps:
Get softening water, carboxymethyl cellulose, add in dispersion machine, even with the rotating speed dispersed with stirring of 500r/min, add crosslinking-oxidization graft starch emulsion, color sand, propylene glycol, organophosphate, isothiazolinone, ammoniacal liquor successively by mass fraction, after dispersed with stirring is even, namely obtain stone-like coating.
Above-mentioned composite modified starch emulsion materials consumption is as follows: Sumstar 190 70 kg, acidolysis etherification starch 30 kg, swelling inhibitor 1.5 kg, linking agent 0.02 kg, hard monomer 80 kg, soft monomer 120 kg, emulsifying agent 4 kg, initiator 2.5 kg, deionized water 300 kg, NaOH are 1.5 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, add Sumstar 190 and acidolysis etherification starch (be that the acidolysis sodium starch glycolate of 0.8 with the acidolysis hydroxypropylated starch of substitution value 0.08 with the ratio of 1:4 mix by substitution value) in deionized water in mass fraction, form certain density starch milk;
(2) in the swelling inhibitor sodium-chlor of step (1) gained starch milk additional proportion, starch milk pH to 11 is adjusted with the sodium hydroxide solution that volumetric concentration is 5%;
(3) add the linking agent Trisodium trimetaphosphate of affiliated mass fraction in step (2) gained starch milk, reaction 2h, adds the salt acid for adjusting pH to 9 that volumetric concentration is 10%;
(4) 85 DEG C of abundant gelatinizations 30 minutes are warming up in step (3) gained starch milk;
(5) take initiator (ammonium peroxydisulfate), add deionized water and be mixed with solution and the initiator solution that mass concentration is 8%;
(6) emulsifying agent that additional proportion is mixed by the ratio of sodium lauryl sulphate and OP-10 1:1.5 in mass ratio in step (4) gained starch milk, then that add 1/4 amount of step (5) initiator solution with mix monomer (methacrylate ethyl ester mixes with ethyl propenoate) 1/10 amount, react 30 minutes; At the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer with constant pressure funnel again, after adding, be warming up to 85 DEG C, reaction 2.5h;
(7) reaction system is down to room temperature, and volumetric concentration is the NaOH aqueous solution adjustment pH to 7 of 20%, obtains coating emulsion.
Embodiment 3
Raw material dosage is as follows: color sand (20-120 order) 600 kg, composite modified starch emulsion 300 kg, amino-2 methyl isophthalic acids-propyl alcohol 2 kg of carboxymethyl starch 2 kg, 2-, propylene glycol 8 kg, fatty acid ester 2 kg, isothiazolinone 1 kg, softening water 80 kg.
The preparation method of stone-like coating, comprises the steps:
Get softening water, carboxymethyl starch, add in dispersion machine, even with the rotating speed dispersed with stirring of 400r/min, add crosslinking-oxidization graft starch emulsion, color sand, propylene glycol, fatty acid ester, isothiazolinone, amino-2 methyl isophthalic acids-propyl alcohol of 2-successively by mass fraction, after dispersed with stirring is even, namely obtain stone-like coating.
Above-mentioned composite modified starch emulsion materials consumption is as follows: Sumstar 190 80 kg, acidolysis etherification starch 20 kg, swelling inhibitor 1 kg, linking agent 0.01 kg, hard monomer 160 kg, soft monomer 100 kg, emulsifying agent 6 kg, initiator 5 kg, deionized water 350 kg, NaOH1.8 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, add Sumstar 190 and acidolysis etherification starch (be that the acidolysis sodium starch glycolate of 0.1 with the acidolysis hydroxypropylated starch of substitution value 0.12 with the ratio of 1:3 mix by substitution value) in deionized water in mass fraction, form certain density starch milk;
(2) in the swelling inhibitor sodium-chlor of step (1) gained starch milk additional proportion, starch milk pH to 11 is adjusted with the sodium hydroxide solution that volumetric concentration is 5%;
(3) add the linking agent epoxy chloropropane of affiliated mass fraction in step (2) gained starch milk, reaction 3h, adds the salt acid for adjusting pH to 9 that volumetric concentration is 10%;
(4) 90 DEG C of abundant gelatinizations 30 minutes are warming up in step (3) gained starch milk;
(5) take initiator (Potassium Persulfate), add deionized water and be mixed with solution and the initiator solution that mass concentration is 6%;
(6) emulsifying agent that additional proportion is mixed by the ratio of sodium lauryl sulphate and BD-109 1:1.6 in mass ratio in step (4) gained starch milk, then that add 1/4 amount of step (5) initiator solution with mix monomer (vinyl acetate, butyl acrylate mix) 1/10 amount, react 25 minutes; At the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer with constant pressure funnel again, after adding, be warming up to 80 DEG C, reaction 3h;
(7) reaction system is down to room temperature, and volumetric concentration is the NaOH aqueous solution adjustment pH to 6 of 20%, obtains coating emulsion.
Embodiment 4
Raw material dosage is as follows: color sand (20-120 order) 700 kg, composite modified starch emulsion 250 kg, hydroxypropylated starch 1.5 kg, sodium bicarbonate 3 kg, propylene glycol 12 kg, water drain silica 2.5 kg, isothiazolinone 1.5 kg, softening water 160 kg.
The preparation method of stone-like coating, comprises the steps:
Get softening water, hydroxypropylated starch, add in dispersion machine, even with the rotating speed dispersed with stirring of 500r/min, add crosslinking-oxidization graft starch emulsion, color sand, propylene glycol, water drain silica, isothiazolinone, sodium bicarbonate successively by mass fraction, after dispersed with stirring is even, namely obtain stone-like coating.
Above-mentioned composite modified starch emulsion materials consumption is as follows: Sumstar 190 60 kg, acidolysis etherification starch 40 kg, swelling inhibitor 2 kg, linking agent 0.03 kg, hard monomer 148 kg, soft monomer 150 kg, function monomer 2 kg, emulsifying agent 5 kg, initiator 4 kg, deionized water 400 kg, NaOH2 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, add Sumstar 190 and acidolysis etherification starch (be that the acidolysis sodium starch glycolate of 0.2 with the acidolysis hydroxypropylated starch of substitution value 0.15 with the ratio of 1:4 mix by substitution value) in deionized water in mass fraction, form certain density starch milk;
(2) in the swelling inhibitor sodium-chlor of step (1) gained starch milk additional proportion, starch milk pH to 10.5 is adjusted with the sodium hydroxide solution that volumetric concentration is 5%;
(3) add the linking agent Trisodium trimetaphosphate of affiliated mass fraction in step (2) gained starch milk, reaction 2h, adds the salt acid for adjusting pH to 8.5 that volumetric concentration is 10%;
(4) 85 DEG C of abundant gelatinizations 30 minutes are warming up in step (3) gained starch milk;
(5) take initiator (Potassium Persulfate), add deionized water and be mixed with solution and the initiator solution that mass concentration is 7%;
(6) emulsifying agent that additional proportion is mixed by the ratio of sodium lauryl sulphate and OP-10 1:1.7 in mass ratio in step (4) gained starch milk, then add 1/4 amount of step (5) initiator solution and 1/10 amount of mix monomer (methyl methacrylate, ethyl propenoate, Hydroxyethyl acrylate mix), react 20 minutes; At the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer with constant pressure funnel again, after adding, be warming up to 90 DEG C, reaction 3h;
(7) reaction system is down to room temperature, and volumetric concentration is the NaOH aqueous solution adjustment pH to 7 of 20%, obtains coating emulsion.
Embodiment 5
Raw material dosage is as follows: color sand (20-120 order) 750 kg, composite modified starch emulsion 100 kg, Natvosol: carboxymethyl starch (1:1) is totally 1 kg, potassium hydroxide 2.5 kg, propylene glycol 15kg, organophosphate: fatty acid ester (2:1) is totally 3 kg, isothiazolinone 2 kg, softening water 200 kg.
The preparation method of stone-like coating, comprises the steps:
Get softening water, Natvosol and carboxymethyl starch mixture, add in dispersion machine, even with the rotating speed dispersed with stirring of 300r/min, add crosslinking-oxidization graft starch emulsion, color sand, propylene glycol, organophosphate and fatty acid ester blends, isothiazolinone, potassium hydroxide successively by mass fraction, after dispersed with stirring is even, namely obtain stone-like coating.
Above-mentioned composite modified starch emulsion materials consumption is as follows: Sumstar 190 70 kg, acidolysis etherification starch 30 kg, swelling inhibitor 1 kg, linking agent 0.02 kg, hard monomer 80 kg, soft monomer 120 kg, function monomer 2.5 kg, emulsifying agent 4 kg, initiator 3 kg, deionized water 300 kg, NaOH1 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, add Sumstar 190 and acidolysis etherification starch (be that the acidolysis sodium starch glycolate of 0.6 with the acidolysis hydroxypropylated starch of substitution value 0.08 with the ratio of 1:3.5 mix by substitution value) in deionized water in mass fraction, form certain density starch milk;
(2) in the swelling inhibitor sodium-chlor of step (1) gained starch milk additional proportion, starch milk pH to 11.5 is adjusted with the sodium hydroxide solution that volumetric concentration is 5%;
(3) add the linking agent epoxy chloropropane of affiliated mass fraction in step (2) gained starch milk, reaction 3h, adds the salt acid for adjusting pH to 9.5 that volumetric concentration is 10%;
(4) 80 DEG C of abundant gelatinizations 30 minutes are warming up in step (3) gained starch milk;
(5) take initiator (Potassium Persulfate), add deionized water and be mixed with solution and the initiator solution that mass concentration is 8%;
(6) emulsifying agent that additional proportion is mixed by the ratio of sodium lauryl sulphate and OP-10 1:1.8 in mass ratio in step (4) gained starch milk, then add 1/4 amount of step (5) initiator solution and 1/10 amount of mix monomer (methyl methacrylate, Isooctyl acrylate monomer, Rocryl 410 mix), react 20-30 minutes; At the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer with constant pressure funnel again, after adding, be warming up to 85 DEG C, reaction 2.5h;
(7) reaction system is down to room temperature, and volumetric concentration is the NaOH aqueous solution adjustment pH to 6 of 20%, obtains coating emulsion.
The present embodiment obtains emulsion and has good alcohol resistance, water tolerance, and has hydroxy functional monomer and can be used for interior wall and exterior coating, also can be used for two-component coating.
Embodiment 6
The raw material dosage of stone-like coating and preparation method are with embodiment 1, and difference is that composite modified starch emulsion materials consumption is as follows: Sumstar 190 80 kg, acidolysis etherification starch 20 kg, swelling inhibitor 0.5 kg, linking agent 0.01 kg, hard monomer 35 kg, soft monomer 65 kg, function monomer 1 kg, emulsifying agent 3 kg, initiator 2 kg, deionized water 200 kg, NaOH1.2 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, add Sumstar 190 and acidolysis etherification starch (be that the acidolysis sodium starch glycolate of 0.3 with the acidolysis hydroxypropylated starch of substitution value 0.05 with the ratio of 1:2 mix by substitution value) in deionized water in mass fraction, form certain density starch milk;
(2) in the swelling inhibitor sodium-chlor of step (1) gained starch milk additional proportion, starch milk pH to 11.5 is adjusted with the sodium hydroxide solution that volumetric concentration is 5%;
(3) add the linking agent phosphorus oxychloride of affiliated mass fraction in step (2) gained starch milk, reaction 1h, adds the salt acid for adjusting pH to 9.5 that volumetric concentration is 10%;
(4) 90 DEG C of abundant gelatinizations 30 minutes are warming up in step (3) gained starch milk;
(5) take initiator (ammonium peroxydisulfate), add deionized water and be mixed with solution and the initiator solution that mass concentration is 5%;
(6) emulsifying agent that additional proportion is mixed by the ratio of sodium lauryl sulphate and OP-10 1:1.9 in mass ratio in step (4) gained starch milk, then add 1/4 amount of step (5) initiator solution and mix monomer (methyl methacrylate, butyl acrylate, vinylformic acid- -hydroxypropyl acrylate mix) 1/10 amount, react 30 minutes; At the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer with constant pressure funnel again, after adding, be warming up to 80 DEG C, reaction 2h;
(7) reaction system is down to room temperature, and volumetric concentration is the NaOH aqueous solution adjustment pH to 7 of 20%, obtains coating emulsion.
The present embodiment obtains emulsion and has good adjustable wet, and has hydroxy functional monomer, can be used for humidity controlling coating, also can be used for two-component coating.
Embodiment 7
The raw material dosage of stone-like coating and preparation method are with embodiment 2, and difference is that composite modified starch emulsion materials consumption is as follows: Sumstar 190 70 kg, acidolysis etherification starch 30 kg, swelling inhibitor 1.5 kg, linking agent 0.02 kg, hard monomer 70 kg, soft monomer 130 kg, function monomer 1 kg, emulsifying agent 4 kg, initiator 2.5 kg, deionized water 300 kg, NaOH1.5 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, add Sumstar 190 and acidolysis etherification starch (be that the acidolysis sodium starch glycolate of 0.8 with the acidolysis hydroxypropylated starch of substitution value 0.08 with the ratio of 1:4 mix by substitution value) in deionized water in mass fraction, form certain density starch milk;
(2) in the swelling inhibitor sodium-chlor of step (1) gained starch milk additional proportion, starch milk pH to 11 is adjusted with the sodium hydroxide solution that volumetric concentration is 5%;
(3) add the linking agent Trisodium trimetaphosphate of affiliated mass fraction in step (2) gained starch milk, reaction 2h, adds the salt acid for adjusting pH to 9 that volumetric concentration is 10%;
(4) 85 DEG C of abundant gelatinizations 30 minutes are warming up in step (3) gained starch milk;
(5) take initiator (ammonium peroxydisulfate), add deionized water and be mixed with solution and the initiator solution that mass concentration is 6%;
(6) emulsifying agent that additional proportion is mixed by the ratio of sodium lauryl sulphate and OP-10 1:1.5 in mass ratio in step (4) gained starch milk, then add 1/4 amount of step (5) initiator solution with mix monomer (methyl methacrylate, ethyl propenoate, methacrylic acid- the mixing of-hydroxypropyl acrylate different monooctyl ester) 1/10 amount, react 30 minutes; At the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer with constant pressure funnel again, after adding, be warming up to 85 DEG C, reaction 2.5h;
(7) reaction system is down to room temperature, and volumetric concentration is the NaOH aqueous solution adjustment pH to 7 of 20%, obtains coating emulsion.
The present embodiment obtains emulsion and has good weathering resistance, can be used for interior wall and exterior coating, and has hydroxy functional monomer, can be used for two-component coating.
Embodiment 8
The raw material dosage of stone-like coating and preparation method are with embodiment 3, and difference is that composite modified starch emulsion materials consumption is as follows: Sumstar 190 60 kg, acidolysis etherification starch 40 kg, swelling inhibitor 2 kg, linking agent 0.03 kg, hard monomer 130 kg, soft monomer 140 kg, function monomer 2 kg, emulsifying agent 5 kg, initiator 4 kg, deionized water 400 kg, NaOH are 2 kg.
The preparation method of composite modified starch emulsion, comprises the steps:
(1) under whipped state, add Sumstar 190 and acidolysis etherification starch (be that the acidolysis sodium starch glycolate of 0.2 with the acidolysis hydroxypropylated starch of substitution value 0.15 with the ratio of 1:4 mix by substitution value) in deionized water in mass fraction, form certain density starch milk;
(2) in the swelling inhibitor sodium-chlor of step (1) gained starch milk additional proportion, starch milk pH to 10.5 is adjusted with the sodium hydroxide solution that volumetric concentration is 5%;
(3) add the linking agent Trisodium trimetaphosphate of affiliated mass fraction in step (2) gained starch milk, reaction 2h, adds the salt acid for adjusting pH to 8.5 that volumetric concentration is 10%;
(4) 85 DEG C of abundant gelatinizations 30 minutes are warming up in step (3) gained starch milk;
(5) take initiator (Potassium Persulfate), add deionized water and be mixed with solution and the initiator solution that mass concentration is 8%;
(6) emulsifying agent that additional proportion is mixed by the ratio of sodium lauryl sulphate and OP-10 1:1.7 in mass ratio in step (4) gained starch milk, then add 1/4 amount of step (5) initiator solution and 1/10 amount of mix monomer (β-dimethyl-aminoethylmethacrylate, ethyl propenoate, methacrylate mix), react 20 minutes; At the uniform velocity drip all the other 3/4 amounts of step (5) initiator solution and all the other 9/10 amounts of mix monomer with constant pressure funnel again, after adding, be warming up to 90 DEG C, reaction 3h;
(7) reaction system is down to room temperature, and volumetric concentration is the NaOH aqueous solution adjustment pH to 7 of 20%, obtains coating emulsion.

Claims (9)

1. a stone-like coating, is characterized in that it comprises the raw material of following masses part: 500-750 parts, color sand, composite modified starch emulsion 100-300 parts, thickening material 1-3 parts, neutralizing agent 1-3 parts, propylene glycol 5-15 parts, defoamer 1-3 parts, sanitas 1-2 parts, softening water 80-200 parts;
Described composite modified starch emulsion comprises the raw material of following masses part: Sumstar 190 60-80 parts, acidolysis etherification starch 20-40 parts, swelling inhibitor 0.5-2 parts, linking agent 0.01-0.03 part, emulsifying agent 2-6 parts, initiator 1-5 parts, deionized water 200-400 parts, NaOH 1-2 parts and mix monomer, and mix monomer comprises hard monomer 35-160 parts and soft monomer 65-150 parts.
2. stone-like coating according to claim 1, is characterized in that: described thickening material is one or both in Natvosol, carboxymethyl cellulose, carboxymethyl starch or hydroxypropylated starch.
3. stone-like coating according to claim 1, is characterized in that: described neutralizing agent is the one in amino-2 methyl isophthalic acids-propyl alcohol of sodium hydroxide, potassium hydroxide, ammoniacal liquor, sodium bicarbonate or 2-.
4. stone-like coating according to claim 1, is characterized in that: described defoamer is one or both in fatty acid metal soap, organophosphate, water drain silica or fatty acid ester.
5. stone-like coating according to claim 1, is characterized in that: described sanitas is isothiazolinone.
6. stone-like coating according to claim 1, is characterized in that: described mix monomer also comprises function monomer 1-2.5 parts.
7. stone-like coating according to claim 6, is characterized in that: described swelling inhibitor is sodium-chlor; Described linking agent is the one in epoxy chloropropane, phosphorus oxychloride or Trisodium trimetaphosphate; Described hard monomer is the one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate or vinyl acetate, and described soft monomer is the one in ethyl propenoate, butyl acrylate or Isooctyl acrylate monomer; Described function monomer is the one in vinylformic acid, methacrylic acid, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, vinylformic acid-β-hydroxypropyl acrylate or the different monooctyl ester of methacrylic acid-β-hydroxypropyl acrylate.
8. stone-like coating according to claim 6, is characterized in that: described emulsifying agent is the mixture of anionic emulsifier sodium lauryl sulphate and nonionic emulsifying agent BD-109 1:1.5-2 ratio in mass ratio; Described initiator is the one in Potassium Persulfate or ammonium peroxydisulfate.
9. the preparation method of stone-like coating described in claim 1, it is characterized in that: it with color sand for aggregate, composite modified starch emulsion is base-material, add multiple auxiliary agent to make, specifically comprise the steps: to get softening water, thickening material, add in dispersion machine, even with the rotating speed dispersed with stirring of 300 ~ 500r/min, add composite modified starch emulsion, color sand, propylene glycol, defoamer, sanitas, neutralizing agent successively by mass fraction, after dispersed with stirring is even, namely obtain stone-like coating.
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CN1154391A (en) * 1996-01-12 1997-07-16 北京安顺达装饰材料有限公司 method for prepn. and application of powder-like construction coatings
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