CN103044580A - Preparation method of agglomerated latex - Google Patents
Preparation method of agglomerated latex Download PDFInfo
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- CN103044580A CN103044580A CN2011103145121A CN201110314512A CN103044580A CN 103044580 A CN103044580 A CN 103044580A CN 2011103145121 A CN2011103145121 A CN 2011103145121A CN 201110314512 A CN201110314512 A CN 201110314512A CN 103044580 A CN103044580 A CN 103044580A
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- agglomeration
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- 229920000126 latex Polymers 0.000 title claims abstract description 106
- 239000004816 latex Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 48
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 18
- 238000007127 saponification reaction Methods 0.000 claims abstract description 18
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 10
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 4
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 4
- 239000002174 Styrene-butadiene Substances 0.000 claims abstract description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011115 styrene butadiene Substances 0.000 claims abstract description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract 2
- 238000005054 agglomeration Methods 0.000 claims description 37
- 230000002776 aggregation Effects 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- 235000019394 potassium persulphate Nutrition 0.000 claims description 16
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 15
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 12
- 239000004159 Potassium persulphate Substances 0.000 claims description 9
- 229920002521 macromolecule Polymers 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 230000001804 emulsifying effect Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- ZRIHAIZYIMGOAB-UHFFFAOYSA-N butabarbital Chemical compound CCC(C)C1(CC)C(=O)NC(=O)NC1=O ZRIHAIZYIMGOAB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 19
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229920001059 synthetic polymer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002902 bimodal effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- -1 polyoxyethylene Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a process for the preparation of agglomerated latex; adding deionized water, sodium bicarbonate, sodium dodecyl sulfate, potassium persulfate, dodecyl mercaptan, butyl acrylate and styrene into a reactor to synthesize a polymer agglomerant; adding a compounded emulsifier into the latex to be agglomerated for saponification, and then mixing a polymer agglomerating agent with the saponified latex to be agglomerated; the latex to be agglomerated is polybutadiene latex or styrene-butadiene latex: the small-particle rubber latex to be agglomerated had a d50 of 100nm, solids content: 25-35% and particle size: 70-140 nm and pH value of 8-12; the large-particle rubber latex to be agglomerated was d50 ═ 300nm, solids content: 45-65% and particle size: 280-320 nm and the pH value is 8-12; the particle size distribution of the agglomerated large-particle rubber latex is 260-340 nm; the particle size distribution of the agglomerated rubber latex with the ultra-large particle size is 480-740 nm.
Description
Technical field:
The present invention relates to a kind of preparation method of agglomerating latex, relate in particular to a kind of method of using the polymer agglomeration technique small-particle rubber latex or macroparticle rubber latex to be prepared into large particle diameter or super-size rubber latex.
Background technology:
ABS resin is a kind of very important engineering plastics, uses very extensive.Along with the development of ABS resin production technology and improving constantly of application requiring, also more and more to the demand of the ABS resin of property.
The polymer agglomeration technique is synthetic macromolecule agglomerant at first, and then the polymer agglomerant being added needs to increase in the polymer latex (treating agglomerating latex) of particle diameter the method that latter's particle diameter is increased.Compare with existing chemical agglomeration (such as mineral acid agglomeration, inorganic salt agglomeration etc.), material agglomeration (freezing agglomeration, pressure agglomeration etc.), the polymer agglomeration technique will increase the difficulty of particle diameter to be transferred on synthetic a kind of suitable polymer agglomerant, and can realize that larger particle diameter increases effect.Agglomeration method is simple among the present invention, the agglomeration mild condition, particle diameter increases easily control, latex stability is fabulous after the agglomeration, thereby have very large development potentiality and a practical value, in the production of ABS resin, ACR resin (series modified dose of esters of acrylic acid), MBS resin (methyl methacrylate, divinyl, styrene copolymer) etc., and in the production of rubber toughened resin, be with a wide range of applications.Use the latex after this method agglomeration, centralized particle diameter, and can treat that agglomerating latex Saponification Conditions and polymer agglomerant consumption realize the control to latex particle size by adjustment.Latex after the agglomeration that obtains by the polymer agglomeration technique can also can be used for producing bimodal, multimodal ABS product separately for the production of the ABS product, especially bimodal ABS resin preparation.
Required large small particle size rubber latex can not make by polyreaction fully in the bimodal ABS resin preparation, generally be to synthesize first required small-particle rubber latex, adopt again the method for agglomeration with the further synthetic required macroparticle rubber latex of small grain size latex, carry out again follow-up production and application.
JP 60112841 discloses by (methyl) vinylformic acid, methylene-succinic acid (or butenoic acid), C1-12 alkyl acrylate and vinyl monomer, adopting the multi-component copolymer latex of two sections letex polymerization preparations is the polymer agglomerant, and agglomeration increases butadiene-propylene acid butyl ester-styrene copolymerized latex.Treat agglomerating latex particle diameter 70nm, agglomeration is particle diameter 290nm after 30 minutes, and agglomeration is particle diameter 310nm after 5 days.
US 2002198309 discloses the method that increases the diolefine latex particle size take butadiene-propylene acetoacetic ester-Sipacril 2739OF latex as the polymer agglomerant.
The synthetic method of the large particle diameter acrylic latex of CN1260352 is: 1) add the emulsifying agent that accounts for reaction monomers total amount 0.0---9.09wt% to polymeric kettle; 2) add the monomer that accounts for reaction monomers total amount 30--60wt% to polymeric kettle; 3) add the initiator that accounts for reaction monomers total amount 0.2--0.8wt% to polymeric kettle; 4) add entry to polymeric kettle; Reinforced complete, add again emulsifying agent and the remaining 40-70wt% monomer that accounts for reaction monomers total amount 0.2-0.8wt% after temperature reaction 15-20 minute, this partial emulsifier and monomer can be once or gradation add the people, reinforced complete, isothermal reaction 3-5 hour, gained latex particle size 200--600nm is aggregated in the same reactor and finishes, and the reaction times is short, cost is low.
CN87104770 is by treating that the latex of agglomeration and a kind of agglomerating latex mix to be selected from the nodulizing of the polymer latex of elastomerics and thermoplastic resin mutually.Agglomerating latex consists of: (A) a kind of polymkeric substance that is selected from elastomerics and thermoplastic resin; (H) a kind of nonionic surface active agent that is comprised of block polymer contains at least one polyoxyethylene segment in the polymkeric substance and at least one is selected from the segment of the polymkeric substance of ethene, diene, acryllic acid or methacrylic ester.By during synthetic (A) polymkeric substance, make a kind of tensio-active agent with (B) and produce above-mentioned agglomerating latex.Be mentioned to polyoxyethylene one polystyrene one polyoxyethylene triblock polymer among the tensio-active agent (H).
CN1730505 the invention belongs to the engineering plastics ABS production technical field, purpose provide a kind of simple, efficient, energy consumption is low, be used for agglomerant and preparation method and agglomeration process that PBL polybutadiene latex particle diameter amplifies.Butyl acrylate, vinylformic acid, de-salted water, Sodium dodecylbenzene sulfonate etc. are put into same container stirring and heating, add Potassium Persulphate and tert-dodecyl mercaptan again, temperature of reaction is controlled at 30-98 ℃, and the reaction times is 2-8 hour, prepares agglomerant.With the agglomeration of this agglomerant for PB latex, in polymeric kettle, add PB latex, stir, heat, again agglomerant, Sodium dodecylbenzene sulfonate, de-salted water are mixed, join in the polymeric kettle after stirring; Add NaOH solution in the polymeric kettle, adjusting the pH value is 9-13 again, obtains that the PB latex particle size is 300-700nm after the agglomeration.Among the present invention, owing to added comonomer, make that thermal discharge reduces in the agglomerant, reaction conditions is gentle, and reaction yield almost 100% does not have environmental pollution.
Above technology treats that agglomerating latex does not all have saponification before agglomeration is synthetic, the present invention adopts the technology for the treatment of the front first saponification of agglomerating latex agglomeration to prepare the high stability agglomerating latex, latex particle size, surface tension, mechanical stability etc. are not too large variation substantially, and the agglomerating latex of this method preparation can be easy to prepare the ABS resin with superior physical properties percentage of grafting control within the required range in the grafting process of preparation ABS resin.
Summary of the invention:
(1) purpose of the present invention
The present invention adopts the polymer agglomeration technique, with unsaturated organic acid ester-unsaturated organic acid-aryl ethylene latex as the polymer agglomerant, with the rubber latex of the rubber latex of Dn50=100nm or Dn50=300nm as treating agglomerating latex, the large particle diameter of preparation particle diameter Dn50=300nm or the rubber latex of Dn50=600nm super-size, and use the method prepares the large particle diameter of particle diameter Dn50=300nm or the rubber latex of Dn50=600nm super-size has goodish stability, latex particle size behind the placement first quarter moon, surface tension, mechanical stabilities etc. are not too large variation substantially, still can be used as the basic latex of preparation ABS resin grafting, and guarantee in the grafting process, can control at an easy rate percentage of grafting within the required range, the ABS resin of preparation has excellent physicals.
(2) technical scheme of the present invention
1) synthetic macromolecule agglomerant
With deionized water, sodium bicarbonate (NaHCO
3), sodium lauryl sulphate (SDS), Potassium Persulphate (KPS), lauryl mercaptan (TDDM), butyl acrylate (BA) and vinylbenzene (ST) joins in the reactor, use nitrogen replacement after starting stirring and emulsifying, heat up, temperature is controlled at 50～70 ℃, polymerase 10 .5-1 hour, then drip mix monomer, comprise BA, methacrylic acid (MMA), ST, emulsifier op-10, reacted 1～4 hour, temperature is increased to 70-85 ℃, reaction in restir 0.5-2 hour finishes, cooling, filtration.
The mass fraction of polymer agglomerant is:
2) will treat the agglomerating latex saponification:
Add composite good emulsifying agent in treating agglomerating latex, additional proportion treats to add in the agglomerating latex 0.01～0.10 part for 100 parts take the butt quality as benchmark, stirs at normal temperatures 5～25 minutes.
Composite emulsifier component by mass parts is:
1.5～3.5 parts of OP-10
3.0～6.5 parts in nilox resin acid potassium
100 parts of deionized waters
3) agglomeration
To treat the agglomerating latex saponification, and again the polymer agglomerant be added good the treating in the agglomerating latex of saponification by the butt mass ratio, the limit edged slowly stirred 1-60 minute, discharging.
The synthetic components in mass portion number of agglomerating latex is:
Treat 100 parts of agglomerating latex
0.01～15 part of polymer agglomerant
4) the used agglomerating latex for the treatment of is polybutadiene latex or styrene-butadiene latex:
Treat that agglomeration small-particle rubber latex is d50=100nm, solid content: 25～35%, particle diameter: 70～140nm, pH value are 8～12;
Or treat that agglomeration macroparticle rubber latex is d50=300nm, solid content: 45～65%, particle diameter: 280～320nm, pH value are 8～12;
Macroparticle rubber latex size distribution after the agglomeration: 260～340nm;
Super-size rubber latex size distribution: 480～740nm after the agglomeration.
(3) effect of the present invention
Technique of the present invention is simple, the agglomeration mild condition is controlled, no matter be that small-particle latex agglomerates into macroparticle latex or large grain size latex agglomerates into super-size latex, latex after the agglomeration all has extraordinary stability, the basic not too large variations such as latex particle size, surface tension, mechanical stability behind the placement first quarter moon, still can be used as the basic latex of preparation ABS resin grafting, and guarantee in the grafting process, can control at an easy rate percentage of grafting within the required range, the ABS resin of preparation has excellent physicals.
(4) analyzing and testing
Latex regularly detects mechanical stability after the agglomeration, the change of granularity scope, and surface tension variations is analysed the glue amount, determines the stability of latex.
Mechanical stability detects
Adopt the steady instrument of the central physics and chemistry UP-2 of Co., Ltd. machine to measure the mechanical stability of latex.
Granularity Detection
Adopt the U.S. Brooker Hai Wen 90Plus of company particle diameter tester to measure.
Surface tension detects
Adopt BZY-1 Full-automatic tension instrument to measure.
The pH pH-value determination pH
The intelligent acidity tester SevenEasy laboratory pH meter that adopts plum Teller-Tuo benefit Instr Ltd. to produce is measured.
Embodiment:
Embodiment 1:
(1) synthetic macromolecule agglomerant
With deionized water, sodium bicarbonate (NaHCO
3), sodium lauryl sulphate (SDS), Potassium Persulphate (KPS), lauryl mercaptan (TDDM), butyl acrylate (BA) and vinylbenzene (ST) add with agitator, reflux exchanger, in the four-hole bottle of thermometer, put into water-bath, use nitrogen replacement after starting stirring and emulsifying, heat up, temperature reaches 55 ℃, the beginning timing, polymerization dripped mix monomer after 1 hour, comprise BA, methacrylic acid (MMA), ST, OP-10, reacted 2 hours, temperature is increased to 75 ℃, and restir reaction in 1 hour finishes cooling, filter.
(2) emulsifying agent is composite
5 parts in nilox resin acid potassium, 2.5 parts of OP-10, deionized water 100 parts (butt umbers) are stirred at normal temperatures and be uniformly emulsify liquid in 10 minutes.
(3) treat the agglomerating latex saponification
The composite emulsifier for the treatment of to add in the attached latex 0.05 part (butt umber) at 100 parts of median size 130nm slowly stirred 9 minutes while dripping.
(4) treat in the agglomerating latex, slowly stir discharging in 10 minutes for 100 parts that 1 part of synthetic polymer agglomerant (dried portion rate) are added saponification.
Test result
| Particle diameter (nm) | The pH value | Mechanical stability | Surface tension | |
| After the discharging 1 hour | 320 | 11.5 | 0.042 | 28.5 |
| 8 hours | 343 | 11.5 | 0.051 | 28.7 |
| 24 hours | 353 | 11.6 | 0.062 | 28.7 |
| 72 hours | 356 | 11.5 | 0.079 | 28.7 |
| 3 days | 359 | 11.5 | 0.083 | 29.9 |
| 7 days | 342 | 11.6 | 0.10 | 33.6 |
| 15 days | 348 | 11.5 | 0.19 | 35.5 |
Embodiment 2:
(1) synthetic macromolecule agglomerant
With deionized water, sodium bicarbonate (NaHCO
3), sodium lauryl sulphate (SDS), Potassium Persulphate (KPS), lauryl mercaptan (TDDM), butyl acrylate (BA) and vinylbenzene (ST) add with agitator, reflux exchanger, in the four-hole bottle of thermometer, put into water-bath, use nitrogen replacement after starting stirring and emulsifying, heat up, temperature reaches 55 ℃, the beginning timing, polymerization dripped mix monomer after 1 hour, comprise BA, methacrylic acid (MMA), ST, OP-10, reacted 2 hours, temperature is increased to 75 ℃, and restir reaction in 1 hour finishes cooling, filter.
(2) emulsifying agent is composite
5 parts in nilox resin acid potassium, 2.5 parts of OP-10, deionized water 100 parts (butt umbers) are stirred at normal temperatures and be uniformly emulsify liquid in 10 minutes.
(3) treat the agglomerating latex saponification
The composite emulsifier for the treatment of to add in the attached latex 0.10 part (butt umber) at 100 parts of median size 265nm slowly stirred 10 minutes while dripping.
(4) treat in the agglomerating latex, slowly stir discharging in 10 minutes for 100 parts that 11 parts of synthetic polymer agglomerants (dried portion rate) are added saponification.
Test result
| Particle diameter (nm) | The pH value | Mechanical stability | Surface tension | |
| After the discharging 1 hour | 586 | 11.8 | 0.062 | 23.8 |
| 8 hours | 596 | 11.7 | 0.064 | 23.7 |
| 24 hours | 608 | 11.8 | 0.083 | 23.9 |
| 72 hours | 628 | 11.7 | 0.095 | 24.2 |
| 3 days | 632 | 11.9 | 0.17 | 25.1 |
| 7 days | 638 | 11.8 | 0.22 | 26.3 |
| 15 days | 642 | 11.6 | 0.38 | 29.9 |
Embodiment 3:
(1) synthetic macromolecule agglomerant
With deionized water, sodium bicarbonate (NaHCO
3), sodium lauryl sulphate (SDS), Potassium Persulphate (KPS), lauryl mercaptan (TDDM), butyl acrylate (BA) and vinylbenzene (ST) add with agitator, reflux exchanger, in the four-hole bottle of thermometer, put into water-bath, use nitrogen replacement after starting stirring and emulsifying, heat up, temperature reaches 55 ℃, the beginning timing, polymerization dripped mix monomer after 1 hour, comprise BA, methacrylic acid (MMA), ST, OP-10, reacted 2 hours, temperature is increased to 75 ℃, and restir reaction in 1 hour finishes cooling, filter.
(2) emulsifying agent is composite
3.0 parts in nilox resin acid potassium, 1.8 parts of OP-10, deionized water 100 parts (butt umbers) are stirred at normal temperatures and be uniformly emulsify liquid in 10 minutes.
(3) treat the agglomerating latex saponification
The composite emulsifier for the treatment of to add in the attached latex 0.5 part (butt umber) at 100 parts of median size 260nm slowly stirred 15 minutes while dripping.
(4) treat in the agglomerating latex, slowly stir discharging in 10 minutes for 100 parts that 8.5 parts of synthetic polymer agglomerants (dried portion rate) are added saponification.
Test result
| Particle diameter (nm) | The pH value | Mechanical stability | Surface tension | |
| After the discharging 1 hour | 559 | 11.8 | 0.062 | 23.9 |
| 8 hours | 590 | 11.7 | 0.074 | 24.0 |
| 24 hours | 609 | 11.8 | 0.093 | 24.9 |
| 72 hours | 623 | 11.7 | 0.15 | 25.2 |
| 3 days | 632 | 11.9 | 0.18 | 27.1 |
| 7 days | 641 | 11.8 | 0.22 | 28.3 |
| 15 days | 649 | 11.6 | 0.29 | 31.9 |
Embodiment 4:
(1) synthetic macromolecule agglomerant
With deionized water, sodium bicarbonate (NaHCO
3), sodium lauryl sulphate (SDS), Potassium Persulphate (KPS), lauryl mercaptan (TDDM), butyl acrylate (BA) and vinylbenzene (ST) add with agitator, reflux exchanger, in the four-hole bottle of thermometer, put into water-bath, use nitrogen replacement after starting stirring and emulsifying, heat up, temperature reaches 55 ℃, the beginning timing, polymerization dripped mix monomer after 1 hour, comprise BA, methacrylic acid (MMA), ST, OP-10, reacted 2 hours, temperature is increased to 75 ℃, and restir reaction in 1 hour finishes cooling, filter.
(2) emulsifying agent is composite
3.0 parts in nilox resin acid potassium, 1.8 parts of OP-10, deionized water 100 parts (butt umbers) are stirred at normal temperatures and be uniformly emulsify liquid in 12 minutes.
(3) treat the agglomerating latex saponification
The composite emulsifier for the treatment of to add in the attached latex 0.5 part (butt umber) at 100 parts of median size 143nm slowly stirred 10 minutes while dripping.
(4) treat in the agglomerating latex, slowly stir discharging in 10 minutes for 100 parts that 9 parts of synthetic polymer agglomerants (dried portion rate) are added saponification.
Test result
| Particle diameter (nm) | The pH value | Mechanical stability | Surface tension | |
| After the discharging 1 hour | 320 | 11.5 | 0.042 | 28.5 |
| 8 hours | 343 | 11.5 | 0.051 | 28.7 |
| 24 hours | 353 | 11.6 | 0.052 | 28.7 |
| 72 hours | 356 | 11.5 | 0.059 | 28.7 |
| 3 days | 359 | 11.5 | 0.063 | 29.9 |
| 7 days | 342 | 11.6 | 0.085 | 33.6 |
| 15 days | 348 | 11.5 | 0.11 | 35.5 |
The comparative example 1:
(1) synthetic macromolecule agglomerant
With deionized water, sodium bicarbonate (NaHCO
3), sodium lauryl sulphate (SDS), Potassium Persulphate (KPS), lauryl mercaptan (TDDM), butyl acrylate (BA) and vinylbenzene (ST) add with agitator, reflux exchanger, in the four-hole bottle of thermometer, put into water-bath, use nitrogen replacement after starting stirring and emulsifying, heat up, temperature reaches 55 ℃, the beginning timing, polymerization dripped mix monomer after 1 hour, comprise BA, methacrylic acid (MMA), ST, OP-10, reacted 2 hours, temperature is increased to 75 ℃, and restir reaction in 1 hour finishes cooling, filter.
(2) 8 parts of synthetic polymer agglomerants (dried portion rate) being added 100 parts of median sizes is treating in the agglomerating latex of 100nm, slowly stirs discharging in 10 minutes.
Test result
| Particle diameter (nm) | The pH value | Mechanical stability | Surface tension | |
| After the discharging 1 hour | 376 | 11.6 | 0.082 | 25.6 |
| 8 hours | 396 | 11.7 | 0.78 | 26.4 |
| 24 hours | 398 | 11.5 | 1.96 | 29.3 |
| 72 hours | 402 | 11.3 | 2.25 | 32.6 |
| 3 days | 409 | 11.2 | 4.69 | 35.5 |
| 7 days | 415 | 11.3 | 6.89 | 55.6 |
| 15 days | 418 | 11.3 | 10.96 | 65.8 |
The comparative example 2:
(1) synthetic macromolecule agglomerant
With deionized water, sodium bicarbonate (NaHCO
3), sodium lauryl sulphate (SDS), Potassium Persulphate (KPS), lauryl mercaptan (TDDM), butyl acrylate (BA) and vinylbenzene (ST) add with agitator, reflux exchanger, in the four-hole bottle of thermometer, put into water-bath, use nitrogen replacement after starting stirring and emulsifying, heat up, temperature reaches 55 ℃, the beginning timing, polymerization dripped mix monomer after 1 hour, comprise BA, methacrylic acid (MMA), ST, OP-10, reacted 2 hours, temperature is increased to 75 ℃, and restir reaction in 1 hour finishes cooling, filter.
(2) 15 parts of synthetic polymer agglomerants (dried portion rate) being added 100 parts of median sizes is treating in the agglomerating latex of 297nm, slowly stirs discharging in 10 minutes.
Test result
| Particle diameter (nm) | The pH value | Mechanical stability | Surface tension | |
| After the discharging 1 hour | 636 | 10.8 | 0.069 | 26.5 |
| 8 hours | 645 | 10.7 | 0.36 | 29.7 |
| 24 hours | 649 | 10.9 | 1.96 | 31.3 |
| 72 hours | 653 | 10.9 | 3.58 | 36.7 |
| 3 days | 682 | 11.0 | 4.89 | 42.5 |
| 7 days | 692 | 10.9 | 8.63 | 57.9 |
| 15 days | 698 | 10.8 | 10.36 | 66.5 |
Claims (1)
1. the preparation method of an agglomerating latex is characterized in that: may further comprise the steps:
1) synthetic macromolecule agglomerant
Deionized water, sodium bicarbonate, sodium lauryl sulphate, Potassium Persulphate, lauryl mercaptan, butyl acrylate and vinylbenzene are joined in the reactor, use nitrogen replacement after starting stirring and emulsifying, heat up, temperature is controlled at 50～70 ℃, polymerase 10 .5-1 hour, then drip mix monomer, comprise BA, methacrylic acid, ST, emulsifier op-10, reacted 1～4 hour, temperature is increased to 70-85 ℃, reaction in restir 0.5-2 hour finishes, cooling, filtration;
The mass fraction of polymer agglomerant is:
2) will treat the agglomerating latex saponification:
Add composite good emulsifying agent in treating agglomerating latex, additional proportion treats to add in the agglomerating latex 0.01～0.10 part for 100 parts take the butt quality as benchmark, stirs at normal temperatures 5～25 minutes;
Composite emulsifier component by mass parts is:
1.5～3.5 parts of OP-10
3.0～6.5 parts in nilox resin acid potassium
100 parts of deionized waters;
3) agglomeration
To treat the agglomerating latex saponification, and again the polymer agglomerant be added good the treating in the agglomerating latex of saponification by the butt mass ratio, the limit edged slowly stirred 1-60 minute, discharging;
The synthetic components in mass portion number of agglomerating latex is:
Treat 100 parts of agglomerating latex
0.01～15 part of polymer agglomerant;
4) the used agglomerating latex for the treatment of is polybutadiene latex or styrene-butadiene latex:
Treat that agglomeration small-particle rubber latex is d50=100nm, solid content: 25～35%, particle diameter: 70～140nm, pH value are 8～12;
Or treat that agglomeration macroparticle rubber latex is d50=300nm, solid content: 45～65%, particle diameter: 280～320nm, pH value are 8～12.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103756604A (en) * | 2014-01-22 | 2014-04-30 | 九洲生物技术（苏州）有限公司 | Novel biological latex as well as preparation method and application thereof |
| CN104628964A (en) * | 2015-01-29 | 2015-05-20 | 天津大学 | Early-strength type salt-tolerant toughening styrene-butadiene latex as well as preparation method and application |
| CN105504174A (en) * | 2015-12-29 | 2016-04-20 | 成都新柯力化工科技有限公司 | Spherical styrene-butadiene rubber for 3D printing and preparation method thereof |
| CN108250519A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | Large-particle-size styrene-isoprene-butadiene latex and preparation method thereof |
| CN113754797A (en) * | 2021-08-27 | 2021-12-07 | 北方华锦化学工业股份有限公司 | Preparation method and application technology of polymer agglomerated latex |
| CN117024659A (en) * | 2023-09-11 | 2023-11-10 | 河南大树实业有限公司 | Preparation method of large-particle-size high-solid-content styrene-butadiene latex |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104628964B (en) * | 2015-01-29 | 2017-02-22 | 天津大学 | Early-strength type salt-tolerant toughening styrene-butadiene latex as well as preparation method and application |
| CN105504174A (en) * | 2015-12-29 | 2016-04-20 | 成都新柯力化工科技有限公司 | Spherical styrene-butadiene rubber for 3D printing and preparation method thereof |
| CN108250519A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | Large-particle-size styrene-isoprene-butadiene latex and preparation method thereof |
| CN113754797A (en) * | 2021-08-27 | 2021-12-07 | 北方华锦化学工业股份有限公司 | Preparation method and application technology of polymer agglomerated latex |
| CN117024659A (en) * | 2023-09-11 | 2023-11-10 | 河南大树实业有限公司 | Preparation method of large-particle-size high-solid-content styrene-butadiene latex |
| CN117024659B (en) * | 2023-09-11 | 2024-05-31 | 河南大树实业有限公司 | Preparation method of large-particle-size high-solid-content styrene-butadiene latex |
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