CN103242478A - Acrylate agglomerant and preparation method thereof, and method for modifying ASA (acrylonitrile-styrene-acrylate) resin with agglomerant - Google Patents
Acrylate agglomerant and preparation method thereof, and method for modifying ASA (acrylonitrile-styrene-acrylate) resin with agglomerant Download PDFInfo
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- CN103242478A CN103242478A CN2013101849162A CN201310184916A CN103242478A CN 103242478 A CN103242478 A CN 103242478A CN 2013101849162 A CN2013101849162 A CN 2013101849162A CN 201310184916 A CN201310184916 A CN 201310184916A CN 103242478 A CN103242478 A CN 103242478A
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Abstract
The invention discloses an acrylate agglomerant and a preparation method thereof, and a method for modifying an ASA (acrylonitrile-styrene-acrylate) resin with agglomerant. The acrylate agglomerant is prepared from the following raw materials in parts by mass:12-14 parts of acrylate, 3-4 parts of unsaturated acid, 0.5-0.7 part of compound emulsifier, 80-85 parts of deionized water and 0.05-0.15 part of initiator. The preparation method comprises the following steps: proportionally mixing acrylate, unsaturated acid, compound emulsifier and deionized water, emulsifying by stirring, heating to 70 DEG C, adding the initiator, and keeping the temperature to react for 3 hours to obtain a milk white emulsion which is the agglomerant. The agglomerant disclosed by the invention has the advantages of simple raw material composition and favorable modification effect, can increase the apparent particle size of the basic emulsion particles and ASA resin, and can effectively improve the erosion resistance of the ASA resin.
Description
One, technical field
The present invention relates to esters of acrylic acid agglomerant and application thereof, specifically a kind of esters of acrylic acid agglomerant and preparation method thereof and the method by agglomerant modified ASA resin.
Two, background technology
The ASA resin refers to vinyl cyanide (A), vinylbenzene (S) and acrylate (A) ternary graft copolymer, and ABS resin refers to vinyl cyanide (A), divinyl (B) and vinylbenzene (S) ternary graft copolymer.Discover that when being equipped with ASA or ABS resin material with the emulsion graft polymerization legal system, controlling basic latex particle size is very necessary with the processability good quality production.For many years, relevant for the report that basic latex particle is increased, physical method and chemical process are arranged, these methods all can make latex particle increase always.But reasons such as, the agglomeration cycle undesirable owing to energy consumption height, agglomeration effect is long fail to obtain significant progress and attention always.
In recent years, research and the application report of high score subclass agglomeration method constantly occur, and use the polymer latex method and small grain size latex can be made large grain size latex, and can improve the correlated performance of product.The agglomeration principle of polymer latex method is to utilize the agglomerant partial destruction to treat the tensio-active agent of agglomerant, make it be fused into bigger latex particle, thereby reach the purpose that enlarges particle diameter, enlarge particle diameter the apparent particle size that is dispersed in the rubber phase of resin in is mutually obviously increased, thereby can improve its erosion-resisting characteristics.Therefore the polymer latex agglomeration technique is subjected to common concern when the preparation large grain size latex, and this method agglomeration cycle is short, agglomeration is effective, agglomeration operation is simple and agglomeration process is regulated and control easily.
Show that according to latest information with vinyl monomer or unsaturated acid ester and α, the multipolymer of β unsaturated acid is made agglomerant, can make the particle diameter of small-particle latex increase to 200-700nm.Lin Runxiong etc. have reported with the synthetic big Particle Butadiene-styrene Latex of latex agglomeration technique, can make median size reach 295nm; Reports such as Lin Qingju utilize agglomerant the styrene-butadiene latex of particle diameter for 150nm can be increased to more than the 700nm; Sichuan University and chemical research center, PetroChina Company Limited. Lanzhou report prepare the latex of median size more than 400nm with propylene ester class agglomerant; It is the ABS product of 600nm that Daqing petrochemical company has been produced particle diameter with agglomerant latex.
Though about the preparation of esters of acrylic acid agglomerant with use existing documents and materials report, but still be to rest on the experience stage, still not very mature theory can follow.And utilize the esters of acrylic acid agglomerant to prepare the modified ASA resin and improve the resin mechanical property with it and do not appear in the newspapers as yet.
Three, summary of the invention
The present invention aims to provide a kind of esters of acrylic acid agglomerant and preparation method thereof and the method by agglomerant modified ASA resin, and technical problem to be solved is to improve the latex particle size of ASA and improve the mechanical property of ASA resin by the agglomerant agglomeration.
Technical solution problem of the present invention adopts following technical scheme:
Esters of acrylic acid agglomerant of the present invention, its raw material constitutes by mass fraction:
Acrylate 12-14 part, unsaturated acid 3-4 part, composite emulsifier 0.5-0.7 part, deionized water 80-85, initiator 0.05-0.15 part;
More preferably:
13 parts of acrylate, 3.3 parts of unsaturated acid, 0.6 part of composite emulsifier, deionized water 83,0.10 part of initiator.
Described unsaturated acid is vinylformic acid;
Described composite emulsifier is that anionic emulsifier and nonionic emulsifying agent obtain by mass ratio 1:1 is composite;
Described initiator is water soluble starter, preferred Potassium Persulphate.
Described acrylate is butyl acrylate.
The mass ratio of described acrylate and described unsaturated acid is 4:1.
Described anionic emulsifier is sodium lauryl sulphate (SDS), and described nonionic emulsifying agent is triton x-100.
Water-oil ratio is 5:1 in the described agglomerant.Water in the water-oil ratio refers to aqueous phase substance, namely refers to deionized water and initiator potassium persulfate; Oil refers to oil phase substance, namely refers to acrylate, unsaturated acid and composite emulsifier.
The synthetic method of esters of acrylic acid agglomerant of the present invention, be by proportional quantity acrylate, unsaturated acid, composite emulsifier and deionized water to be mixed, stirring and emulsifying is warming up to 70 ℃ after the emulsification, add initiator, insulation reaction obtained milky emulsion in 3 hours and is agglomerant.
Utilize the method for esters of acrylic acid agglomerant modified ASA resin of the present invention, each raw material constitutes by mass fraction:
Butyl acrylate (BA) 6-10 part, vinylbenzene (St) 20-27 part, vinyl cyanide (AN) 7-8 part, esters of acrylic acid agglomerant 2.0-8.0 part, deionized water 50.0-60.0 part, Potassium Persulphate (KPS) 0.08-0.12 part, sodium lauryl sulphate (SDS) 0.2-0.7 part, sodium bicarbonate 0.08-0.16 part, linking agent 0.20-0.40 part, uncle's lauryl mercaptan 0.02-0.08 part;
Described linking agent is selected from tri (propylene glycol) diacrylate (TPGDA) or 1,6 hexanediol diacrylate (HDDA).
Each raw material is preferably by mass fraction:
Butyl acrylate 6-10 part, vinylbenzene 21.32-26.5 part, vinyl cyanide 7.2-7.9 part, esters of acrylic acid agglomerant 2.72-8.0 part, deionized water 52.9-60.0 part, Potassium Persulphate 0.096-0.12 part, sodium lauryl sulphate 0.31-0.7 part, sodium bicarbonate 0.09-0.16 part, linking agent 0.22-0.32 part, uncle's lauryl mercaptan 0.032-0.08 part.
Utilizing the method for esters of acrylic acid agglomerant modified ASA resin of the present invention is to operate according to the following steps:
1) at first add butyl acrylate, the deionized water of 10-20%, the sodium lauryl sulphate of 25-35%, the Potassium Persulphate of 30-40% and the whole sodium bicarbonates of 60-70% in the reactor, under nitrogen protection in 65-80 ℃ of reaction 3 hours;
2) in the reaction solution of step 1), add the surplus butyl acrylate, the Potassium Persulphate of the deionized water of 10-20%, the sodium lauryl sulphate of 15-25%, 20-25%, the vinylbenzene of 10-15%, the vinyl cyanide of 6-7% and whole linking agents reacted 3 hours in 65-80 ℃ under nitrogen protection;
3) to step 2) reaction solution in add the esters of acrylic acid agglomerant, under nitrogen protection in 45-65 ℃ of reaction 1 hour;
4) add vinylbenzene, the vinyl cyanide of surplus, the balance of deionized water of surplus in the reaction solution of step 3); the sodium lauryl sulphate of surplus, the Potassium Persulphate of surplus and whole uncle's lauryl mercaptans; under nitrogen protection, reacted 5 hours in 65-80 ℃; breakdown of emulsion after-filtration and in 40-50 ℃ of drying 24 hours obtains modified ASA resin powder.
Described breakdown of emulsion is the sodium chloride aqueous solution that adds mass concentration 2% in reaction solution, and the volume of sodium chloride aqueous solution is 4:1 with the ratio of ASA emulsion volume.
To make the resin batten after the injection moulding of modified ASA resin powder, according to GB/T1040.2-2006 test tensile property, according to GB1843-2008 test impact property.
Preparation method of the present invention is not only applicable to prepared in laboratory (250ml, 500ml reactor), and is amplified to 1000ml and the production of 2000ml reactor also is successful.
The feed composition of agglomerant of the present invention is simple, and the agglomerant modified effect is good, and basic latex particle and ASA resin apparent particle size are increased, and can improve the shock resistance of ASA resin effectively.
Four, specific implementation method
Embodiment 1:
1, the raw material of agglomerant constitutes by mass fraction:
Butyl acrylate: 13 parts,
Vinylformic acid: 3.3 parts,
Composite emulsifier: 0.60 part,
Deionized water: 83 parts,
Initiator potassium persulfate: 0.10 part;
Wherein composite emulsifier is that SDS and triton x-100 obtain by mass ratio 1:1 is composite.
2, the preparation of agglomerant
Press proportional quantity n-butyl acrylate, vinylformic acid, composite emulsifier and deionized water are added stirring and emulsifying in the reactor, be warming up to 70 ℃ after the emulsification, add initiator potassium persulfate, the control temperature obtains oyster white latex and is agglomerant 70 ℃ of insulation reaction 3 hours.
3, the composition of PBA latex and massfraction:
Butyl acrylate: 39.63 parts,
Deionized water: 59.45 parts,
Initiator potassium persulfate: 0.11 part,
Composite emulsifier: 0.79 part.
Wherein composite emulsifier is that SDS and triton x-100 obtain by mass ratio 1:1 is composite.
4, the preparation of PBA latex
1) at first in reactor, adds 0.26 part of composite emulsifier, 19.88 part deionized water, stir fast it is fully dissolved, add 13.21 parts of butyl acrylates again, emulsification half an hour, be warming up to 78 ℃, add 0.04 part of initiator potassium persulfate, question response is warming up to 81 ℃ after proceeding to and not having backflow, insulation reaction is one hour again, makes seed emulsion.
2) drip butyl acrylate, the composite emulsifier of surplus, the initiator potassium persulfate of surplus and the mixing solutions of balance of deionized water of surplus in the reaction solution of step 1), rate of addition control does not have obvious backflow at the reaction flask wall, behind reinforced the end, it is constant that temperature of reaction keeps, react and be warming up to 85 ℃ after 3 hours, slaking half an hour, cooling discharge.
5, the preparation of big particle diameter PBA latex
Be that the ratio of 9:1 adds agglomerant in PBA latex and agglomerant volume ratio in the PBA latex that makes to step 4, the control temperature is 45-65 ℃, and reaction is 1 hour under the nitrogen protection.After the emulsion dilution, adopt the size distribution of Zeta potential analysis-e/or determining latex particle.
Embodiment 2:
This enforcement preparation method is with embodiment 1, and different is not use agglomerant that its particle diameter is amplified, and namely omits step 5.After the emulsion dilution, adopt the size distribution of Zeta potential analysis-e/or determining PBA latex particle.
Embodiment 3:
1, the composition of agglomerant and mass fraction thereof are:
Butyl acrylate: 13 parts,
Vinylformic acid: 3.3 parts,
Deionized water: 83 parts,
Initiator potassium persulfate: 0.10 part,
Composite emulsifier: 0.60 part.
Wherein composite emulsifier is that SDS and triton x-100 obtain by mass ratio 1:1 is composite.
2, the preparation of agglomerant:
Press proportional quantity butyl acrylate, vinylformic acid, deionized water and composite emulsifier are added stirring and emulsifying in the reactor, be warming up to 70 ℃ after the emulsification, add initiator potassium persulfate, the control temperature obtains oyster white latex and is agglomerant 70 ℃ of insulation reaction 3 hours.
3, the raw material of modified ASA resin and mass fraction thereof:
Butyl acrylate: 8.4 parts,
Vinylbenzene: 21.32 parts,
Vinyl cyanide: 10.68 parts,
Agglomerant: 2.72 parts,
Deionized water: 60 parts,
Potassium Persulphate: 0.096 part,
Sodium lauryl sulphate: 0.32 part,
Sodium bicarbonate: 0.10 part,
Linking agent HDDA:0.22 part,
Uncle's lauryl mercaptan: 0.048 part.
4, the preparation of modified ASA resin:
1) at first add 67% butyl acrylate, 13% deionized water, 28% sodium lauryl sulphate, 35% Potassium Persulphate and whole sodium bicarbonates in the reactor, under nitrogen protection in 65-80 ℃ of reaction 3 hours;
2) add the butyl acrylate of surplus in the reaction solution of step 1), 13% deionized water, 17% sodium lauryl sulphate, 22% Potassium Persulphate, 12% vinylbenzene, 6.25% vinyl cyanide and whole linking agent HDDA, under nitrogen protection in 65-80 ℃ of reaction 3 hours;
3) to step 2) reaction solution in add agglomerant, control temperature be 45-65 ℃, under the nitrogen protection reaction 1 hour;
4) add vinylbenzene, the vinyl cyanide of surplus, the balance of deionized water of surplus in the reaction solution of step 3), the sodium lauryl sulphate of surplus, the Potassium Persulphate of surplus and whole uncle's lauryl mercaptans, under nitrogen protection, in 65-80 ℃ of reaction 5 hours, obtain the ASA emulsion;
5) add the sodium chloride aqueous solution of the mass concentration 2% of 4 times of volumes in the ASA emulsion of each step 4) preparation, at normal temperatures and pressures to the ASA emulsion breaking, filter back 45 ℃ of dryings and obtain modified ASA resin powder after 24 hours.
To make the resin batten after the injection moulding of modified ASA resin powder, according to GB/T1040.2-2006 test tensile property, according to GB1843-2008 test impact property.
Embodiment 4:
Present embodiment repeats embodiment 3, and different is not add agglomerant, namely omits step 3).
Embodiment 5:
Present embodiment step 1) and step 2) with embodiment 3.
3, the raw material of modified ASA resin and mass fraction thereof:
Butyl acrylate: 6.0 parts,
Vinylbenzene: 23.12 parts,
Vinyl cyanide: 7.68 parts,
Agglomerant: 4.72 parts,
Deionized water: 57.60 parts,
Potassium Persulphate: 0.11 part,
Sodium lauryl sulphate: 0.31 part,
Sodium bicarbonate: 0.09 part,
Linking agent HDDA:0.32 part,
Uncle's lauryl mercaptan: 0.050 part.
4, the preparation of modified ASA resin:
1) at first add 67% butyl acrylate, 13% deionized water, 28% sodium lauryl sulphate, 35% Potassium Persulphate and whole sodium bicarbonates in the reactor, under nitrogen protection in 65-80 ℃ of reaction 3 hours;
2) in the reaction solution of step 1), add the surplus butyl acrylate, 13% deionized water, 17% sodium lauryl sulphate, 22% Potassium Persulphate, 12% vinylbenzene, 6.25% vinyl cyanide and whole linking agent HDDA, under nitrogen protection in 65-80 ℃ of reaction 3 hours;
3) to step 2) reaction solution in add agglomerant, under nitrogen protection in 45-65 ℃ the reaction 1 hour;
4) add vinylbenzene, the vinyl cyanide of surplus, the balance of deionized water of surplus in the reaction solution of step 3), the sodium lauryl sulphate of surplus, the Potassium Persulphate of surplus and whole uncle's lauryl mercaptans, under nitrogen protection, in 65-80 ℃ of reaction 5 hours, obtain the ASA emulsion;
5) add the sodium chloride aqueous solution of the mass concentration 2% of 4 times of volumes in the ASA emulsion of each step 4) preparation, at normal temperatures and pressures to the ASA emulsion breaking, filter back 45 ℃ of dryings and obtain modified ASA resin powder after 24 hours.
To make the resin batten after the injection moulding of modified ASA resin powder, according to GB/T1040.2-2006 test tensile property, according to GB1843-2008 test impact property.
Embodiment 6:
Present embodiment repeats embodiment 5, and different is not add agglomerant, namely omits step 3).
Embodiment 7:
Present embodiment step 1) and step 2) with embodiment 3.
3, the raw material of modified ASA resin and mass fraction thereof:
Butyl acrylate: 10.0 parts,
Vinylbenzene: 23.2 parts,
Vinyl cyanide: 7.2 parts,
Agglomerant: 6.5 parts,
Deionized water: 56.0 parts,
Potassium Persulphate: 0.096 part,
Sodium lauryl sulphate: 0.42 part,
Sodium bicarbonate: 0.12 part,
Linking agent HDDA:0.22 part,
Uncle's lauryl mercaptan: 0.048 part.
4, the preparation of modified ASA resin:
1) at first add 67% butyl acrylate, 13% deionized water, 28% sodium lauryl sulphate, 35% Potassium Persulphate and whole sodium bicarbonates in the reactor, under nitrogen protection in 65-80 ℃ of reaction 3 hours;
2) in the reaction solution of step 1), add the surplus butyl acrylate, 13% deionized water, 17% sodium lauryl sulphate, 22% Potassium Persulphate, 12% vinylbenzene, 6.25% vinyl cyanide and whole linking agent HDDA, under nitrogen protection in 65-80 ℃ of reaction 3 hours;
3) to step 2) reaction solution in add agglomerant, under nitrogen protection in 45-65 ℃ the reaction 1 hour;
4) add vinylbenzene, the vinyl cyanide of surplus, the balance of deionized water of surplus in the reaction solution of step 3), the sodium lauryl sulphate of surplus, the Potassium Persulphate of surplus and whole uncle's lauryl mercaptans, under nitrogen protection, in 65-80 ℃ of reaction 5 hours, obtain the ASA emulsion;
5) add the sodium chloride aqueous solution of the mass concentration 2% of 4 times of volumes in the ASA emulsion of each step 4) preparation, at normal temperatures and pressures to the ASA emulsion breaking, filter back 45 ℃ of dryings and obtain modified ASA resin powder after 24 hours.
To make the resin batten after the injection moulding of modified ASA resin powder, according to GB/T1040.2-2006 test tensile property, according to GB1843-2008 test impact property.
Embodiment 8:
Present embodiment repeats embodiment 7, and different is not add agglomerant, namely omits step 3).
Embodiment 9:
Present embodiment step 1 and step 2 are with embodiment 3.
3, the raw material of modified ASA resin and mass fraction thereof:
Butyl acrylate: 9.4 parts,
Vinylbenzene: 26.5 parts,
Vinyl cyanide: 7.9 parts,
Agglomerant latex: 8.0 parts,
Deionized water: 52.9 parts,
Potassium Persulphate: 0.12 part,
Sodium lauryl sulphate: 0.7 part,
Sodium bicarbonate: 0.16 part,
Linking agent HDDA:0.24 part,
Uncle's lauryl mercaptan: 0.08 part.
4, the preparation of modified ASA resin:
1) at first add 67% butyl acrylate, 13% deionized water, 28% sodium lauryl sulphate, 35% Potassium Persulphate and whole sodium bicarbonates in the reactor, under nitrogen protection in 65-80 ℃ of reaction 3 hours;
2) in the reaction solution of step 1), add the surplus butyl acrylate, 13% deionized water, 17% sodium lauryl sulphate, 22% Potassium Persulphate, 12% vinylbenzene, 6.25% vinyl cyanide and whole linking agent HDDA, under nitrogen protection in 65-80 ℃ of reaction 3 hours;
3) to step 2) reaction solution in add agglomerant, under nitrogen protection in 45-65 ℃ the reaction 1 hour;
4) add vinylbenzene, the vinyl cyanide of surplus, the balance of deionized water of surplus in the reaction solution of step 3), the sodium lauryl sulphate of surplus, the Potassium Persulphate of surplus and whole uncle's lauryl mercaptans, under nitrogen protection, in 65-80 ℃ of reaction 5 hours, obtain the ASA emulsion;
5) add the sodium chloride aqueous solution of the mass concentration 2% of 4 times of volumes in the ASA emulsion of each step 4) preparation, at normal temperatures and pressures to the ASA emulsion breaking, filter back 45 ℃ of dryings and obtain modified ASA resin powder after 24 hours.
To make the resin batten after the injection moulding of modified ASA resin powder, according to GB/T1040.2-2006 test tensile property, according to GB1843-2008 test impact property.
Embodiment 10:
Present embodiment repeats embodiment 9, and different is not add agglomerant, namely omits step 3).
Table 1 is PBA latex and ASA graft latex and the particle diameter test result that is equipped with PBA latex and ASA graft latex by the agglomerating latex legal system by the preparation of conventional emulsion polymerization method.Can obviously be found out by table 1, after esters of acrylic acid agglomerant latex agglomeration modification, the particle diameter of PBA latex will increase 109% than the latex particle particle diameter of conventional emulsion polymerization method preparation, and after the grafting, the apparent particle size of both grafting ASA latex differs also bigger, and the ASA latex particle size that the agglomeration technique modification makes will increase nearly 50%.
The latex particle size contrast of table 1 agglomeration/not agglomeration
| Model | Particle diameter | Remarks |
| Embodiment 2-PBA latex | 133nm | Do not add agglomerant |
| Embodiment 4-ASA latex | 208nm | Do not add agglomerant |
| Embodiment 1-PBA latex | 278nm | Add agglomerant |
| Embodiment 3-ASA latex | 304nm | Add agglomerant |
Table 2 is the Mechanics Performance Testing result of the ASA resin of conventional emulsion polymerization method preparation; Table 3 is the stretching mechanical property testing result of agglomerant modified ASA resin of the present invention.The tensile mechanical properties result who is surveyed by table 2 and table 3 can know that the tensile strength of the ASA resin of process latex agglomeration technique preparation will be higher than the ASA resin of conventional emulsion polymerization method preparation.
Table 2
Table 3
Table 4 is that the ASA resin of process agglomerant modification preparation and the notched Izod impact strength of passing through the ASA resin of conventional emulsion polymerization method preparation contrast.As shown in Table 4, the ASA resin that the notched Izod impact strength of modified ASA resin of the present invention makes apparently higher than the conventional emulsion polymerization method, notched Izod impact strength can improve 42.5% after the agglomerant modification.
The table 4 agglomeration/not notched Izod impact strength contrast of agglomeration ASA resin
| Model | Angle ( o） | Absorb merit (J) | Toughness (KJ/m 2?） |
| Embodiment 4-ASA resin | -150.12 | 0.120 | 3.764 |
| Embodiment 6-ASA resin | -150.03 | 0.207 | 6.483 |
| Embodiment 8-ASA resin | -150.12 | 0.246 | 7.709 |
| Do not add agglomerant-average | -150.09 | 0.191 | 5.985 |
| Embodiment 3-ASA resin | -150.12 | 0.426 | 6.293 |
| Embodiment 5-ASA resin | -150.12 | 0.201 | 9.379 |
| Embodiment 7-ASA resin | -150.12 | 0.272 | 13.317 |
| Add agglomerant-average | -150.12 | 0.300 | 8.526 |
Table 5 is the shock strength contrast of modified ASA resin of the present invention and the ASA resin that passes through the preparation of conventional emulsion polymerization method.By table 5 measured result as can be known, the ASA resin that the shock strength of modified ASA resin of the present invention makes apparently higher than the conventional emulsion polymerization method, non-notched Izod impact strength can improve 81.7% after the agglomeration modification.
The table 5 agglomeration/not shock strength contrast of agglomeration ASA resin
| Model | Angle ( o） | Absorb merit (J) | Toughness (KJ/m 2?） |
| Embodiment 4-ASA resin | -150.?03 | 1.991 | 49.775 |
| Embodiment 6-ASA resin | -150.03 | 0.877 | 21.925 |
| Embodiment 8-ASA resin | -150.12 | 1.317 | 32.925 |
| Do not add agglomerant-average | -150.06 | 1.395 | 34.875 |
| Embodiment 3-ASA resin | -150.?21 | 1.731 | 41.730 |
| Embodiment 5-ASA resin | -150.12 | 3.066 | 76.650 |
| Embodiment 7-ASA resin | -150.03 | 2.867 | 71.675 |
| Add agglomerant-average | -150.12 | 2.555 | 63.352 |
Claims (10)
1. esters of acrylic acid agglomerant is characterized in that its raw material constitutes by mass fraction:
Acrylate 12-14 part, unsaturated acid 3-4 part, composite emulsifier 0.5-0.7 part, deionized water 80-85, initiator 0.05-0.15 part;
Described unsaturated acid is vinylformic acid;
Described composite emulsifier is that anionic emulsifier and nonionic emulsifying agent obtain by mass ratio 1:1 is composite;
Described initiator is water soluble starter.
2. esters of acrylic acid agglomerant according to claim 1 is characterized in that its raw material constitutes by mass fraction:
13 parts of acrylate, 3.3 parts of unsaturated acid, 0.6 part of composite emulsifier, deionized water 83,0.10 part of initiator.
3. esters of acrylic acid agglomerant according to claim 1 and 2 is characterized in that:
Described acrylate is butyl acrylate; The mass ratio of described acrylate and described unsaturated acid is 4:1.
4. esters of acrylic acid agglomerant according to claim 1 and 2 is characterized in that:
Described anionic emulsifier is sodium lauryl sulphate, and described nonionic emulsifying agent is triton x-100.
5. esters of acrylic acid agglomerant according to claim 1 and 2 is characterized in that:
Described initiator is Potassium Persulphate.
6. esters of acrylic acid agglomerant according to claim 1 and 2 is characterized in that:
Water-oil ratio is 5:1 in the described agglomerant.
7. the synthetic method of esters of acrylic acid agglomerant according to claim 1 and 2 is characterized in that:
Press proportional quantity acrylate, unsaturated acid, composite emulsifier and deionized water are mixed, stirring and emulsifying is warming up to 70 ℃ after the emulsification, adds initiator, and insulation reaction obtained milky emulsion in 3 hours and is agglomerant.
8. method with the described esters of acrylic acid agglomerant of claim 1 modified ASA resin is characterized in that each raw material constitutes by mass fraction:
Butyl acrylate 6-10 part, vinylbenzene 20-27 part, vinyl cyanide 7-8 part, esters of acrylic acid agglomerant 2.0-8.0 part, deionized water 50.0-60.0 part, Potassium Persulphate 0.08-0.12 part, sodium lauryl sulphate 0.2-0.7 part, sodium bicarbonate 0.08-0.16 part, linking agent 0.20-0.40 part, uncle's lauryl mercaptan 0.02-0.08 part;
Described linking agent is selected from tri (propylene glycol) diacrylate or 1,6 hexanediol diacrylate.
9. method according to claim 8 is characterized in that each raw material constitutes by mass fraction:
Butyl acrylate 6-10 part, vinylbenzene 21.32-26.5 part, vinyl cyanide 7.2-7.9 part, esters of acrylic acid agglomerant 2.72-8.0 part, deionized water 52.9-60.0 part, Potassium Persulphate 0.096-0.12 part, sodium lauryl sulphate 0.31-0.7 part, sodium bicarbonate 0.09-0.16 part, linking agent 0.22-0.32 part, uncle's lauryl mercaptan 0.032-0.08 part.
10. method according to claim 8 is characterized in that operating according to the following steps:
1) at first in reactor, adds the butyl acrylate of 60-70%, the deionized water of 10-20%, the sodium lauryl sulphate of 25-35%, Potassium Persulphate and the sodium bicarbonate of 30-40%, under nitrogen protection, reacted 3 hours in 65-80 ℃;
2) in the reaction solution of step 1), add the surplus butyl acrylate, vinyl cyanide and the linking agent of the Potassium Persulphate of the deionized water of 10-20%, the sodium lauryl sulphate of 15-25%, 20-25%, the vinylbenzene of 10-15%, 6-7% reacted 3 hours in 65-80 ℃ under nitrogen protection;
3) to step 2) reaction solution in add the esters of acrylic acid agglomerant, under nitrogen protection in 45-65 ℃ of reaction 1 hour;
4) add vinylbenzene, the vinyl cyanide of surplus, the balance of deionized water of surplus in the reaction solution of step 3); the sodium lauryl sulphate of surplus, the Potassium Persulphate of surplus and whole uncle's lauryl mercaptans; in 65-80 ℃ of reaction 5 hours, breakdown of emulsion after-filtration and drying obtained modified ASA resin powder under nitrogen protection.
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| CN103570882A (en) * | 2013-11-01 | 2014-02-12 | 杭州华创实业有限公司 | ASA (acrylonitrile styrene acrylate) graft copolymerization resin rubber powder and preparation method thereof |
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| CN111363109A (en) * | 2020-04-26 | 2020-07-03 | 安徽金喜龙新型建材有限公司 | Uvioresistant ASA synthetic resin tile |
| CN112661909A (en) * | 2019-05-05 | 2021-04-16 | 淮安市博彦土木工程科学研究院有限公司 | Preparation method of flame-retardant agglomerating agent for building material field |
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| CN103570882A (en) * | 2013-11-01 | 2014-02-12 | 杭州华创实业有限公司 | ASA (acrylonitrile styrene acrylate) graft copolymerization resin rubber powder and preparation method thereof |
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| CN112661909A (en) * | 2019-05-05 | 2021-04-16 | 淮安市博彦土木工程科学研究院有限公司 | Preparation method of flame-retardant agglomerating agent for building material field |
| CN112661909B (en) * | 2019-05-05 | 2022-01-07 | 淮安市博彦土木工程科学研究院有限公司 | Preparation method of flame-retardant agglomerating agent for building material field |
| CN111363109A (en) * | 2020-04-26 | 2020-07-03 | 安徽金喜龙新型建材有限公司 | Uvioresistant ASA synthetic resin tile |
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