CN105254794B - Silicone oil blending and modifying core-shell emulsion and the preparation method of redispersable latex powder and the product of acquisition - Google Patents
Silicone oil blending and modifying core-shell emulsion and the preparation method of redispersable latex powder and the product of acquisition Download PDFInfo
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- CN105254794B CN105254794B CN201510732552.6A CN201510732552A CN105254794B CN 105254794 B CN105254794 B CN 105254794B CN 201510732552 A CN201510732552 A CN 201510732552A CN 105254794 B CN105254794 B CN 105254794B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 135
- 239000000843 powder Substances 0.000 title claims abstract description 67
- 239000004816 latex Substances 0.000 title claims abstract description 58
- 229920000126 latex Polymers 0.000 title claims abstract description 58
- 239000011258 core-shell material Substances 0.000 title claims abstract description 57
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000002156 mixing Methods 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 35
- 239000003921 oil Substances 0.000 claims abstract description 22
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- 239000000084 colloidal system Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- 238000004945 emulsification Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 230000005070 ripening Effects 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- -1 amido silicon Chemical compound 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 210000000481 breast Anatomy 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000000703 high-speed centrifugation Methods 0.000 claims description 4
- 239000006199 nebulizer Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 229940117958 vinyl acetate Drugs 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 2
- XLXGCFTYXICXJF-UHFFFAOYSA-N ethylsilicon Chemical compound CC[Si] XLXGCFTYXICXJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical class CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000004570 mortar (masonry) Substances 0.000 abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 239000003292 glue Substances 0.000 abstract description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract 2
- 238000004064 recycling Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000000945 filler Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- WYRGOSDNPFGZFG-UHFFFAOYSA-K [bis(2-ethylhexoxy)-oxidophosphaniumyl] dihydrogen phosphate [bis(2-ethylhexoxy)-oxidophosphaniumyl] hydrogen phosphate [bis(2-ethylhexoxy)-oxidophosphaniumyl] phosphate propan-2-olate titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP(O)(O)=O.CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP(O)([O-])=O.CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP([O-])([O-])=O WYRGOSDNPFGZFG-UHFFFAOYSA-K 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical compound C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011440 grout Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The preparation method that the invention provides a kind of silicone oil blending and modifying core-shell emulsion and the product obtained by the method, preparation method is first to use emulsion based on ethylene-vinyl acetate copolymer emulsion, by the way of soft core duricrust, ethylene-vinyl acetate copolymer emulsion is made core-shell emulsion, commercially available finished silicon oil product is used to be added directly in core-shell emulsion again, in the presence of particular emulsifier, the water that in core-shell emulsion, self exists is utilized to carry out emulsifying is blended, obtain the core-shell emulsion after silicone oil is blended emulsifying, it is eventually adding coupling agent and carries out mixed and modified, obtain the core-shell emulsion of silicone oil blending and modifying.The present invention also provides for a kind of using the preparation method that above-mentioned silicone oil blending and modifying core-shell emulsion prepares redispersable latex powder as pre-emulsion and the redispersable latex powder obtained by the method; the method is that first in silicon oil modified core-shell emulsion, addition protecting colloid and anti-caking agent make spray-dried emulsion, and recycling drying process with atomizing manufactures re-dispersible glue powder.The redispersable latex powder of the present invention can give mortar and have excellent hydrophobicity and resistance to water.
Description
Technical field
The present invention relates to the preparation method of a kind of aqueous polymer emulsion, particularly relate to a kind of silicone oil blending and modifying nucleocapsid breast
The preparation method of liquid and the product obtained by the method.The invention still further relates to the above-mentioned silicon oil modified blended core-shell emulsion of a kind of employing
The preparation method preparing redispersable latex powder and the product obtained by the method.
Background technology
Redispersable latex powder is the polymer powder obtained by spray drying technology by aqueous polymer emulsion, with water
Emulsion state can be reduced into by rapid dispersion after contact lysis, and there is the performance suitable with former emulsion.Due to redispersion latex powder
After moisture evaporation film forming, rubber powder film has good pliability and high cohesive force, as important the adding of building dry powder mortar industry
Add agent, the adhesion strength of mortar, cohesiveness, wearability, rupture strength, impact resistance, pliability can be effectively improved, also can have
Effect improves the splitting resistance of mortar, moreover it is possible to a certain degree reducing the water absorption rate of mortar, therefore redispersable latex powder is extensively applied
Produce in dry powder and mortars such as ceramic tile bond, inner and external wall putty, anticracking grout, decorative mortar, inorganic heat insulation mortar, gravity flowing levelling mortars
Product field.
The redispersable latex powder mainly employing ethene-vinyl acetate copolymer emulsion process spraying that present stage is the more commonly used
Drying process obtains, and ethene-vinyl acetate copolymer emulsion is from the point of view of self performance, and its resistance to water is relatively low, water absorption rate after film forming
Of a relatively high, further, since the protecting colloid added in production process is the hydroaropic substances such as polyvinyl alcohol, therefore produce
Resistance to water after redispersable latex powder film forming reduces, and the water absorption of film forming self is relatively large, with the sand of this latex powder preparation
Slurry resistance to water is on the low side, and mortar is substantially without hydrophobicity.
Summary of the invention
For overcome with present on problem, it is an object of the invention to provide the preparation of a kind of silicone oil blending and modifying core-shell emulsion
Method.
It is a further object of the present invention to provide a kind of silicone oil blending and modifying core-shell emulsion obtained by said method.
Third object of the present invention is to provide a kind of employing silicone oil blending and modifying core-shell emulsion and prepares Redispersable latex
The preparation method of powder.
Fourth object of the present invention also resides in a kind of redispersable latex powder obtained by said method of offer.
For realizing above first purpose, the preparation method of a kind of silicone oil blending and modifying core-shell emulsion of the present invention, successively
Comprise the steps:
(1) preparation of core-shell emulsion: weigh core emulsion based on a certain amount of ethene-vinyl acetate copolymer emulsion, will
Core emulsion is entirely within reaction unit, adds the emulsifying agent of shell monomer amount 2%-8%, stirs and be warming up to 35-45 DEG C,
Weigh the shell monomer of core emulsion amount 50%-70%, weigh the initiator of shell monomer amount 2%-6% simultaneously, be slowly added dropwise respectively into reaction
In device, and make both be added dropwise to complete with the identical time, keep reaction temperature at 35-45 DEG C and to start to shear while dropping
Emulsifying 1-1.5 hour, obtains the core-shell emulsion of stable and uniform；
Above-mentioned shell monomer is one or more in vinylacetate, acrylate or methyl methacrylate；Emulsifying agent
For one or more in NPE NP series, OPEO OP series or alkylbenzenesulfonate；
Initiator is Ammonium persulfate. or potassium peroxydisulfate；
(2) silicone oil is blended emulsifying core-shell emulsion: weigh the silicone oil of core-shell emulsion amount 8-10%, is slowly added dropwise and obtains into step (1)
To core-shell emulsion in, keep reaction temperature at 35-45 DEG C, weigh the emulsifying agent of silicone oil amount 60-65%, disposably join core
In shell emulsion, stirring, be to start emulsification pretreatment after 6-6.5 with the pH value of pH adjusting agent regulation system, emulsification times is 1-
1.5h, takes a small amount of emulsion droplets and is added to the water, and observes and occurs without oil slick, lamination, i.e. obtains the nucleocapsid after silicone oil is blended emulsifying
Emulsion；
Above-mentioned silicone oil is containing hydrogen silicone oil, hydroxy silicon oil, amido silicon oil, methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, methyl
One or more in chlorphenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil or methyl vinyl silicon oil；PH adjusts
Joint agent is phosphoric acid, acetic acid or citric acid；Emulsifying agent is NPE NP series, OPEO OP system
One or more in row, alkylbenzenesulfonate, isomery alcohol ether E-1300 series or fatty alcohol-polyoxyethylene ether AEO series；
(3) silicone oil that step (2) obtains is blended emulsifying core-shell emulsion stand ripening, be cooled to room temperature after, add silicone oil
The coupling agent of core-shell emulsion amount 1-6% emulsifying after is blended, and low rate mixing to after uniformly, stands ripening and i.e. obtains silicone oil and be blended and change
Property core-shell emulsion；Coupling agent is one or both in silane coupler KH series or titanate coupling agent NDZ series.
In order to more accurately judge that silicone oil is the most abundant to the blended emulsifying of core-shell emulsion, above-mentioned steps (2) is anti-in emulsifying
After should carrying out 1h, constantly take a small amount of emulsion droplets and be added to the water, seen whether that oil slick, layering occur, if not having oil slick, being layered out
Existing, take 5ml blending emulsion and separate 20min with 3000r/min high speed centrifugation in high speed centrifuge, if layering, breakdown of emulsion do not occur
I.e. judge emulsifying is blended etc. phenomenon.
In the preparation method of above-mentioned emulsion, shell monomer and the initiator of step (1) preferably drip off in 25-35min.
In the preparation method of above-mentioned emulsion, the preferred 800r/min of mulser rotating speed of step (1) emulsification pretreatment, step (2)
The preferred 1000r/min of mulser rotating speed of emulsification pretreatment.
Present invention also offers a kind of silicone oil blending and modifying core-shell emulsion obtained by said method.
For realizing above 3rd purpose, the employing silicone oil blending and modifying core-shell emulsion of the present invention prepares Redispersable latex
The preparation method of powder, in turn includes the following steps:
(1) spray-dried emulsion prepares: weigh the silicone oil blending and modifying core-shell emulsion work that any of the above-described preparation method obtains
For pre-emulsion, after the protecting colloid of pre-emulsion amount 5%-10% is dissolved in water into the solution that solid content is 20%, join pre-emulsion
In, it is simultaneously introduced proper quantity of defoaming agent, stirs 10-15min, add the anti-caking agent of pre-emulsion amount 5%-20%, stir 10-
20min, the final emulsion before being spray-dried；
(2) preparation of redispersable latex powder: setting spray drying tower inlet temperature as 160 ± 5 DEG C, feed rate is
11.5ml/min, outlet temperature is 70 ± 5 DEG C, nebulizer rotating speed 250rpm；By the pumping input of final emulsion to centrifugal atomizer
It is spray-dried, through redispersable latex powder prepared by cyclone collection, obtains final products.
In above-mentioned preparation method, the protecting colloid preferably polyethylene alcohol of step (1)；The preferred ground calcium carbonate of anti-caking agent,
One or both in silicon dioxide.
Present invention also offers a kind of redispersable latex powder obtained by said method.
The present invention has the advantage that compared to existing technology
1, breast based on the main raw material(s) ethene-vinyl acetate copolymer emulsion of existing redispersable latex powder is utilized
Liquid, uses the mode of soft core duricrust that ethene-vinyl acetate copolymer emulsion is made core-shell emulsion, can more preferably reduce rubber powder and produce
During destruction to former emulsion structure, at utmost reduce the performance of former emulsion, obtain vitrification point preferably can
Redispersion latex powder.
2, use commercially available finished silicon oil product to be added directly in the core-shell emulsion prepared, utilize in core-shell emulsion from
The water that body exists carries out emulsifying is blended, and can to a certain degree reduce moisture, improves the solid content of pre-emulsion, more preferably improves spraying
When being dried, the rate of drying of spraying liquid material, reduces finished product redispersable latex powder moisture content.
3, the core-shell emulsion after silicone oil is blended emulsifying because silicone oil and the dispersed adsorption of modification of core-shell emulsion after emulsifying,
This emulsion is made to have good hydrophobicity, resistance to water and self water absorption rate of extremely low film, the Redispersable latex after spray drying
Powder again meet water-dispersible after at utmost reduce the performance of this emulsion, thus give the mortar using this redispersable latex powder
There is excellent hydrophobicity and resistance to water.
4, carry out mixed and modified by interpolation coupling agent in pre-emulsion, the redispersable latex powder glue of final products can be made
Powder film has good organic and inorganic parents' performance, has widely base material adaptability and adhesive force, and the bonding making mortar is strong
Degree has better lifting.
5, the emulsion preparation method of the present invention, compares emulsion polymerization way and structurally-modified side that other patents existing describe
For formula, this method is simpler, and operation possibility is higher, and raw material is easier to obtain.
Detailed description of the invention
One, embodiment
Embodiment 1
(1) preparation of core-shell emulsion: weigh 1000g ethene-vinyl acetate copolymer emulsion and insert in reaction unit, weigh
50g OPEO OP-10 emulsifying agent, adds in the middle of emulsion and low rate mixing, the emulsion in stirring is warming up to 40
DEG C, weigh 800g shell monomer (shell monomer consists of 75g methyl methacrylate, 725g vinylacetate), weigh 35g persulfuric acid
Potassium is dissolved in 700g water, shell monomer and potassium peroxydisulfate is slowly added dropwise respectively in reaction unit and (keeps both identical speed also
Drip off at about 30min), while dropping, start emulsification pretreatment, mulser rotating speed is 800r/min, and emulsifying 1h, emulsifying is complete
Continuing after one-tenth to keep reaction temperature at 40 DEG C, stirring 30min carries out ripening；
(2) silicone oil is blended emulsifying core-shell emulsion: weigh 240g amido silicon oil, is slowly added to step (1) gained core-shell emulsion
In and stir, keep 40 DEG C of reaction temperatures, (emulsifying agent is by isomery alcohol ether emulsifying agent E-1307:E-to weigh 150g emulsifying agent
1305=1:1 forms) disposably add in the middle of core-shell emulsion, after stirring, open after the pH value 6-6.5 by acetic acid regulation emulsion
Beginning emulsification pretreatment, mulser rotating speed 1000r/min, emulsifying 1-1.5h, constantly take a small amount of emulsion droplets after emulsifying 1h and be added to the water, see
Examine and whether have oil slick, layering to occur, if not occurring, taking 5ml emulsion 3000r/min high speed centrifugation in high speed centrifuge and separating
20min, if not occurring completing during the phenomenons such as layering, breakdown of emulsion emulsifying is blended；
(3) core-shell emulsion after the silicone oil of step (2) gained being blended emulsifying stands ripening, be cooled to room temperature after, add
Silicone oil is blended the core-shell emulsion amount 2% silane coupler KH570 after emulsifying, and low rate mixing i.e. obtains pre-to the ripening of rear standing
Emulsion；
(4) preparation of spray-dried emulsion: weigh 180g protecting colloid (polyvinyl alcohol 1788) and join in 720g hot water
Being dissolved into homogeneous solution, add in pre-emulsion, stir 10min after being down to room temperature, (commercial coating disappears to be simultaneously introduced a small amount of defoamer
Bubble auxiliary agent) carry out froth breaking, add before 450g anti-caking agent (800 mesh ground calcium carbonate) stirring 10-20min is spray-dried
Whole emulsion；
(5) preparation of redispersable latex powder: setting spray drying tower inlet temperature as 160 DEG C, feed rate is
11.5ml/min, outlet temperature is 70 DEG C, nebulizer rotating speed 250rpm；The pumping input of final emulsion is carried out to centrifugal atomizer
It is spray-dried, through redispersable latex powder prepared by cyclone collection, obtains final products.
Embodiment 2
(1) preparation of core-shell emulsion: weigh 1000g ethene-vinyl acetate copolymer emulsion and insert in reaction unit, weigh
50g OPEO OP-10 emulsifying agent adds in the middle of emulsion and low rate mixing, and the emulsion in stirring is warming up to 40
DEG C, weigh 800g shell monomer (shell monomer consists of 75g methyl methacrylate, 725g vinylacetate), weigh 35g persulfuric acid
Potassium is dissolved in 700g water, shell monomer and potassium peroxydisulfate is slowly added dropwise respectively in the middle of reaction unit and (keeps both identical speed
And drip off at about 30min), while dropping, starting emulsification pretreatment, mulser rotating speed 800r/min, emulsifying 1h, emulsifying is complete
Continuing after one-tenth to keep reaction temperature at 40 DEG C, stirring 30min carries out ripening；
(2) silicone oil is blended emulsifying core-shell emulsion: weigh 240g amido silicon oil, is slowly added to step (1) gained core-shell emulsion
In the middle of stir, keep 40 DEG C of reaction temperatures, (emulsifying agent is by fatty alcohol-polyoxyethylene ether AEO-9: pungent to weigh 240g emulsifying agent
Base phenol polyethenoxy ether OP-4=1:1 forms) disposably add in the middle of core-shell emulsion, after stirring, regulate emulsion pH with acetic acid
Start emulsification pretreatment, mulser rotating speed 1000r/min, emulsifying 1.5h after=6, constantly take a small amount of emulsion droplets after emulsifying 1h and add water
In, seeing whether that oil slick, layering occur, if not occurring, having taken 5ml emulsion 3000r/min high speed centrifugation in high speed centrifuge
Separate 20min, if not occurring completing during the phenomenons such as layering, breakdown of emulsion emulsifying is blended；
(3) core-shell emulsion after the silicone oil of step (2) gained being blended emulsifying stands ripening, be cooled to room temperature after, add
Silicone oil is blended the core-shell emulsion amount 4% titanate coupling agent NDZ-201 after emulsifying, and low rate mixing stands ripening to rear and get final product
To pre-emulsion；
(4) preparation of spray-dried emulsion: weigh 180g protecting colloid (polyvinyl alcohol 1788) and join in 720g hot water
It is dissolved into homogeneous solution, adds after being down to room temperature in pre-emulsion, stir 10min, be simultaneously introduced a small amount of defoamer (commercial coating
Antifoam additives) carry out froth breaking, before addition 450g anti-caking agent (800 mesh ground calcium carbonate) stirring 10-20min is spray-dried
Final emulsion；
(5) preparation of redispersable latex powder: setting spray drying tower inlet temperature as 165 DEG C, feed rate is 12ml/
Min, outlet temperature is 75 DEG C, nebulizer rotating speed 250rpm；The pumping input of final emulsion is carried out spray dried to centrifugal atomizer
Dry, through redispersable latex powder prepared by cyclone collection, obtain final products.
In above-described embodiment, the mixing speed of each step controls, at 300-400r/min, to be slowly stirred with mix homogeneously as mesh
, general control is at about 300 r/min.
Two, properties of product test
1, the physical property of redispersable latex powder of the present invention
2, the performance that redispersable latex powder of the present invention is applied in the middle of putty
The redispersable latex powder that the embodiment of the present invention 1 is prepared and commercially available ethene-vinyl acetate Redispersable latex
Powder product (abbreviation commercially available prod) adds with 1%, 2%, 3% volume in the middle of putty, tests putty combination property, and result is as follows:
The putty performance comparison of table 1 1% volume redispersable latex powder
The putty performance comparison of table 2 2% volume redispersable latex powder
Table 3 3% volume redispersable latex powder putty performance comparison
By table 1,2,3 it can be seen that the redispersable latex powder of the present invention application in the middle of putty is compared with commercially available prod
Having good adhesion strength to show, water absorption performance is the most prominent, and this is owing to redispersable latex powder of the present invention has well
Hydrophobicity and resistance to water, therefore can effectively reduce putty water absorption, also be such under the conditions of low-dosage, and along with volume
Raising effect be especially apparent.
3, the performance that redispersable latex powder of the present invention is applied in gap filler
The redispersable latex powder embodiment of the present invention 1 obtained adds pottery wall ground with commercially available prod with 1%, 2% volume
In brick gap filler, contrasting gap filler water absorption, result is as follows:
Table 4 1% volume redispersable latex powder gap filler water absorption contrasts
Table 5 2% volume redispersable latex powder gap filler water absorption contrasts
By table 4,5 it can be seen that redispersable latex powder of the present invention has the hydrophobicity of excellence, can reduce with high degree
The water absorption of gap filler, individually adds this rubber powder and can meet standard-required performance, and commercially available common redispersable latex powder list
Solely adding and be extremely difficult to standard water absorption requirement, existing usual way is additionally to add hydrophober in gap filler formula to reduce and fill out
Seam agent water absorption, redispersable latex powder the most of the present invention has great advantage.
4, the performance that redispersable latex powder of the present invention is applied in EPS heat insulation system decorative mortar
Redispersable latex powder of the present invention is added in EPS heat insulation system decorative mortar with commercially available prod with 1%, 2% volume,
Testing the performance of decorative mortar, result is as follows:
Table 6 1% volume redispersable latex powder EPS sheet decorative mortar contrast test
Table 7 2% volume redispersable latex powder EPS sheet decorative mortar contrast test
From table 6,7 it can be seen that the redispersable latex powder of the present invention changes owing to adding coupling agent emulsion building-up process
Property, this rubber powder can more preferably and organic interface parents' binding ability of the inorganic interface of cement mortar and EPS sheet, therefore at EPS sheet material
This kind of organic interface cohesive force is more prominent, and presents the broken plate effect of preferably bonding.
Redispersable latex powder of the present invention the water-fast adhesion strength of EPS sheet decorative mortar under the conditions of different addition quantity the most excellent
In commercially available prod, and water-fast adhesion strength data are almost close to former strong adhesion strength data, it can be seen that adding the present invention can
After the mortar immersion of redispersion latex powder, there is more excellent resistance to water.
The EPS sheet heat insulation system water absorption of redispersable latex powder of the present invention is far below adding commercially available prod mortar, individually
Add 2% volume and i.e. meet standard performance criteria requirement, it is seen that the redispersable latex powder of the present invention is warp in emulsion building-up process
It is modified that silicone oil is blended emulsifying, makes final products have good hydrophobicity, and high degree reduces the water absorption of mortar.
Claims (7)
1. a preparation method for silicone oil blending and modifying core-shell emulsion, in turn includes the following steps:
(1) preparation of core-shell emulsion: weigh core emulsion based on a certain amount of ethene-vinyl acetate copolymer emulsion, by core breast
Liquid is entirely within reaction unit, adds the emulsifying agent of shell monomer amount 2%-8%, stirs and be warming up to 35-45 DEG C, weighing
The shell monomer of core emulsion amount 50%-70%, weighs the initiator of shell monomer amount 2%-6% simultaneously, is slowly added dropwise respectively into reaction unit
In, and make both be added dropwise to complete with the identical time, keep reaction temperature at 35-45 DEG C and to start emulsification pretreatment while dropping
1-1.5 hour, obtain the core-shell emulsion of stable and uniform；
Above-mentioned shell monomer is one or more in vinylacetate, acrylate or methyl methacrylate；Emulsifying agent is nonyl
One or more in base phenol polyethenoxy ether NP series, OPEO OP series or alkylbenzenesulfonate；Cause
Agent is Ammonium persulfate. or potassium peroxydisulfate；
(2) silicone oil is blended emulsifying core-shell emulsion: weigh the silicone oil of core-shell emulsion amount 8-10%, is slowly added dropwise and obtains into step (1)
In core-shell emulsion, keep reaction temperature at 35-45 DEG C, weigh the emulsifying agent of silicone oil amount 60-65%, disposably join nucleocapsid breast
In liquid, stirring, be to start emulsification pretreatment after 6-6.5 with the pH value of pH adjusting agent regulation system, emulsification times is 1-1.5h,
Take a small amount of emulsion droplets to be added to the water, observe and occur without oil slick, lamination, i.e. obtain the core-shell emulsion after silicone oil is blended emulsifying；
Above-mentioned silicone oil is containing hydrogen silicone oil, hydroxy silicon oil, amido silicon oil, methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, methyl chlorobenzene
One or more in base silicone oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil or methyl vinyl silicon oil；PH adjusting agent
For phosphoric acid, acetic acid or citric acid；Emulsifying agent is NPE NP series, OPEO OP series, alkane
One or more in base benzene sulfonate, isomery alcohol ether E-1300 series or fatty alcohol-polyoxyethylene ether AEO series；
(3) silicone oil of step (2) gained is blended emulsifying core-shell emulsion stand ripening, be cooled to room temperature after, add silicone oil be blended
The coupling agent of core-shell emulsion amount 1%-6% after emulsifying, low rate mixing, to after uniformly, stands ripening and i.e. obtains silicone oil blending and modifying core
Shell emulsion；Coupling agent is one or both in silane coupler KH series or titanate coupling agent NDZ series；Above-mentioned steps
(2) after emulsion reaction carries out 1h, constantly taking a small amount of emulsion droplets and be added to the water, having seen whether that oil slick, layering occur, if not having
Oil slick, layering occur, take 5ml blending emulsion and separate 20min with 3000r/min high speed centrifugation in high speed centrifuge, if not going out
Now judge during the phenomenon such as layering, breakdown of emulsion emulsifying is blended.
The preparation method of silicone oil blending and modifying core-shell emulsion the most according to claim 1: it is characterized in that: described preparation side
In method, step (1) shell monomer and initiator drip off in 25-35min.
The preparation method of silicone oil blending and modifying core-shell emulsion the most according to claim 2: it is characterized in that: described preparation side
In method, the mulser rotating speed of step (1) emulsification pretreatment is 800r/min, and the mulser rotating speed of step (2) emulsification pretreatment is
1000r/min。
4. the silicone oil blending and modifying core-shell emulsion that the arbitrary described preparation method of claim 1-3 obtains.
5. a preparation method for redispersable latex powder, in turn includes the following steps:
(1) spray-dried emulsion prepares: weigh the silicone oil blending and modifying nucleocapsid breast that the arbitrary preparation method of claim 1-3 obtains
Liquid, as pre-emulsion, joins pre-after the protecting colloid of pre-emulsion amount 5%-10% is dissolved in water into the solution that solid content is 20%
In emulsion, it is simultaneously introduced proper quantity of defoaming agent, stirs 10-15min, add the anti-caking agent of pre-emulsion amount 5%-20%, stir 10-
20min, the final emulsion before being spray-dried；
(2) preparation of redispersable latex powder: setting spray drying tower inlet temperature as 160 ± 5 DEG C, feed rate is 10-
12ml/min, outlet temperature is 70 ± 5 DEG C, nebulizer rotating speed 250rpm；The pumping input of final emulsion is entered to centrifugal atomizer
Row is spray-dried, and through redispersable latex powder prepared by cyclone collection, obtains final products.
The preparation method of redispersable latex powder the most according to claim 5, it is characterised in that: in described preparation method,
The protecting colloid of step (1) is polyvinyl alcohol；Anti-caking agent is one or both in ground calcium carbonate, silicon dioxide.
7. the redispersable latex powder that preparation method described in a claim 5 or 6 obtains.
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| DE4402409A1 (en) * | 1994-01-27 | 1995-08-03 | Wacker Chemie Gmbh | Redispersible dispersion powder composition, process for its preparation and its use |
| JP3901385B2 (en) * | 1999-04-19 | 2007-04-04 | 電気化学工業株式会社 | Ethylene-vinyl acetate copolymer emulsion and method for producing the same |
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