CN1298745C - Method for preparing hollow microspheres self film-formed in latex of low soap system - Google Patents
Method for preparing hollow microspheres self film-formed in latex of low soap system Download PDFInfo
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- CN1298745C CN1298745C CNB2005100135673A CN200510013567A CN1298745C CN 1298745 C CN1298745 C CN 1298745C CN B2005100135673 A CNB2005100135673 A CN B2005100135673A CN 200510013567 A CN200510013567 A CN 200510013567A CN 1298745 C CN1298745 C CN 1298745C
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Abstract
The present invention discloses a preparation method of a hollow microsphere by forming emulsion films by itself in a low soap system, which belongs to emulsion coating technology. The method comprises the steps that a polyacrylic ester seed emulsion and polyacrylic ester nuclear emulsion particles with carboxy groups are prepared in the low soap system; monomers of styrene/acrylonitrile, etc. are utilized to be polymerized on the core emulsion particles to prepare styrene/acrylonitrile polymer emulsion particles coated with middle layers; then acrylate and styrene copolymers having good film-formation properties are coated on the outermost layer; the styrene/acrylonitrile polymer microsphere having the advantages of good monodispersity of the particle diameter, regular hollow structure, certain strength and film self formation of the emulsion is prepared by alkali processing. The present invention has the advantages that the present invention adopts low soap emulsion polymerization technology and can effectively control the processes of core formation and growth of the emulsion particles by combining a hunger type feeding mode, and thereby, the hollow styrene/acrylonitrile polymer microsphere having the advantages of certain strength and film self formation of the emulsion is prepared. The particle diameter of the hollow styrene/acrylate polymer microsphere can reach more than 1000 nm.
Description
Technical field
But the present invention relates to the preparation method of the hollow microsphere of emulsion self film-formed in a kind of low soap system, belong to the emulsion coatings technology.
Background technology
People (Hollow latex particles:synthesis and applications) such as Charles J.McDonalds adopt alkali infiltration swelling legal system to get the hollow emulsion particle of submicron order, this method prepares the porous emulsion particle and has following defective: (a) emulsifying agent large usage quantity, and the aftertreatment of not only uneconomical but also emulsifying agent is difficulty; (b) each step be disposable reinforced, the less and skewness of prepared latex particle size; (c) emulsion particle is simple in structure, and range of application is narrower.But we propose a kind ofly to adopt low soap technology to prepare good, the big particle diameter of monodispersity, have the method for the hollow styrene-acrylic polymer microballoon of certain intensity and emulsion self film-formed thus.
Summary of the invention
But the object of the present invention is to provide the preparation method of the hollow microsphere of emulsion self film-formed in a kind of low soap system, the hollow emulsion particle hollow form that makes by this method is obvious, and the particle diameter monodispersity is good, middle layer intensity height, and skin is easy to film forming.Can be widely used in every field such as coating, papermaking, makeup.
The present invention is achieved by following technical proposals, the preparation method of monodispersed large grain-size hollow styrene-acrylic polymer microballoon in promptly a kind of low soap system.Its feature comprises following process:
(1) the solid content mass ratio is the preparation of 1.0～10% seed emulsion: the emulsifying agent Sodium dodecylbenzene sulfonate that will account for monomer total mass 0.2～1% joins in the reactor with deionized water, under agitation be warming up to 60～80 ℃, add one or both acrylic ester monomers and methacrylic acid or vinylformic acid again by (95～100): the mass ratio of (5～10) mixes the monomer mixed solution that obtains, adding accounts for the solution that monomer total mass 5～10% initiator ammonium persulfates are made into after continuing to stir 0～0.5h, at 60～80 ℃ of following insulation reaction 1～4h, make the solid content mass ratio and be 1.0～10% seed emulsion.
(2) the solid content mass ratio is the preparation of 7.0～15% carboxylated nuclear emulsions: add the deionized water dilution in the seed emulsion that makes toward step (1) in the time of 60～80 ℃, heating while stirring, drip one or both acrylic ester monomers and methacrylic acid or vinylformic acid and Vinylstyrene or methacrylate glycol ester again by (50～100): (5～50): the mixed solution of (2～5) mass ratio drips simultaneously and accounts for the emulsifying agent Sodium dodecylbenzene sulfonate of this step monomer total mass 0.2～1% and 0.3～3% the formulated aqueous solution of initiator ammonium persulfate.The dropping time is 2～10h, and all raw materials dropwise back insulation reaction 2～4h, makes the solid content mass ratio and be the nuclear emulsion of 7.0～15% band carboxyl.
(3) the solid content mass ratio is the preparation of the polyalcohol emulsion particle in 20～50% coated middle layers: in the time of 60～80 ℃, in the prepared carboxyl of step (2) the nuclear emulsion at the uniform velocity dropwise addition of acrylic acid esters monomer or vinylbenzene and Vinylstyrene or methacrylate glycol ester by (95～100): the mixed solution of (0～5) quality proportioning, dropping simultaneously accounts for the Sodium dodecylbenzene sulfonate of this step monomer total mass 0.2～1% and the aqueous solution of 0.3～3% ammonium persulphate.The dropping time is 2～10h, and all raw materials dropwise back insulation reaction 2～4h, makes the solid content mass ratio and be 20～50% the coated polyalcohol emulsion particle in middle layer.
(4) the solid content mass ratio is the preparation of 20～50% shell polymkeric substance: in the time of 60～80 ℃, in the prepared polymer emulsion of step (3) at the uniform velocity dropwise addition of acrylic acid esters monomer and vinylbenzene by (50～90): the mixed solution of (10～50) mass ratio drips simultaneously and accounts for the Sodium dodecylbenzene sulfonate of this step monomer total mass 0.2～1% and the aqueous solution that 0.3～3% ammonium persulphate is made into.The dropping time is 2～10h, and all raw materials dropwise back insulation reaction 2～4h, makes the solid content mass ratio and be 20～50% core-shell emulsion.
(5) alkaline purification: be initial pH value to 7～13 of 5～20% the resulting core-shell emulsion of sodium hydroxide solution regulating step (4) with concentration, under 90～120 ℃ of temperature, carrying out then and swelling 1～5h, obtain the hollow emulsion particle.
The invention has the advantages that: utilize low soap emulsion polymerization technology, under no micella state, carry out seeding polymerization, and by four polymerization stages, in polymerization process, adopt starved feed method, it is big to make particle diameter, the particle diameter monodispersity is good, and hollow structure is regular, has the hollow cinepazid polymer emulsion that certain intensity and emulsion can self film-formeds.Institute's synthetic hollow styrene-acrylic polymer microballoon can be widely used in Application Areass such as high-performance coating, papermaking, damping sound-deadening material.
Description of drawings
Fig. 1 is the electron micrograph of example 1 prepared hollow microsphere.Fig. 2 is the electron micrograph of example 2 prepared hollow microspheres.Fig. 3 is the electron micrograph of example 3 prepared hollow microspheres.Fig. 4 is the electron micrograph of example 4 prepared hollow microspheres.
Embodiment
Example 1
(1) preparation of seed emulsion is treated to continue to stir 0.5h after temperature rises to 80 ℃ with 0.063g emulsifying agent Sodium dodecylbenzene sulfonate with the 485g deionized water is disposable joins in the reactor that has thermometer, condenser, agitator and feeding device; Disposable then adding 5.5g methyl methacrylate, 6.5g butyl acrylate, 0.56g methacrylic acid stir 0.5h; The aqueous solution that disposable adding 1.0g ammonium persulphate and 15g deionized water are made into promptly gets seed emulsion behind the reaction 2.0h, reduces to room temperature and takes out standby.
(2) preparation of nuclear emulsion adds 25g seed emulsion and 100g deionized water, warming while stirring in above-mentioned identical reactor; Take by weighing 12g methyl methacrylate, 5g methacrylic acid, 0.08g Vinylstyrene simultaneously.Be made into monomer mixture, get the 0.14g ammonium persulphate, the 0.024g Sodium dodecylbenzene sulfonate is made into the aqueous solution with the 15g deionized water.After temperature rises to 80 ℃ in the question response device, drip the aqueous solution of monomer mixture and initiator, emulsifying agent simultaneously.Monomer mixture drips 6h, and the aqueous solution of initiator, emulsifying agent drips 6.5h, treat that all raw materials finish after, be incubated cooling discharge behind the 0.5h again.
(3) preparation of nucleocapsid emulsion particle takes by weighing the above-mentioned nuclear emulsion of 80g and packs in the identical reactor, add the 25g deionized water, warming while stirring, take by weighing 50g vinylbenzene, 18g vinyl cyanide, 0.7g Vinylstyrene simultaneously and be made into monomer mixed solution, get 0.54g ammonium persulphate, 0.13g Sodium dodecylbenzene sulfonate and 20g deionized water and be made into the aqueous solution.Treat that temperature rises to 75 ℃, drips monomer mixed solution and initiator, emulsifier aqueous solution simultaneously.The monomer mixed solution time 3h that feeds in raw material, the aqueous solution of initiator, the emulsifying agent time 3.5h that feeds in raw material, treat that all raw materials finish after, be incubated 0.5h again, cooling discharge.
(4) alkaline purification takes by weighing core-shell emulsion that 100g makes and packs into and have the reactor of whipping appts and reflux exchanger, regulate ph value of emulsion to 9 with 20% the sodium hydroxide solution for preparing in advance, be warming up to 100 ℃, under agitation be incubated 2.5h, cooling promptly obtains the aqueous hollow emulsion particle of inner bag.
(5) testing electronic microscope is diluted to solid content with above-mentioned emulsion and is about 15%, drips the polymer emulsion after 25 dilutions then in 10ml distilled water, with KQ-100DB type numerical control supersonic decollator ultra-sonic dispersion 10min.Get on the special-purpose little copper mesh of transmission electron microscope that emulsion sample drops in support membrane, to drip mass percent concentration on the little copper mesh of emulsion be 1～2 of 2% the ruthenium tetroxide aqueous solution scribbling then.Dry under light-illuminating, use Hitachi H-800 type transmission electron microscope then, under the condition of acceleration voltage 80kV, sample is taken pictures.Electron micrograph as shown in Figure 1.As can be seen from the figure, the latex particle size that makes by this method is approximately 1000nm, and the particle diameter monodispersity is good, and hollow structure is regular.
(6) the self film-formed property testing is positioned on the leveling board with circular (d=8cm) glass mold, pours into a mould a certain amount of above-mentioned latex, and its thickness is about 1mm, seasoning 24h under the room temperature.Finally obtain the powder of white, and can't form the successive smooth film
Example 2
(1) preparation of seed emulsion is identical with example 1 method.
(2) preparation of nuclear emulsion adds 20g seed emulsion and 80g deionized water, warming while stirring in above-mentioned identical reactor; Take by weighing 10g methyl methacrylate, 4g methacrylic acid, 0.064g Vinylstyrene simultaneously. be made into monomer mixed solution, get the 0.01g ammonium persulphate, the 0.018g Sodium dodecylbenzene sulfonate is made into the aqueous solution with the 10g deionized water.After temperature rises to 80 ℃ in the question response device, drip the aqueous solution of monomer mixed solution and initiator, emulsifying agent simultaneously.Monomer mixed solution drips 6h, and the aqueous solution of initiator, emulsifying agent drips 6.5h, treat that all raw materials finish after, be incubated cooling discharge behind the 0.5h again.
(3) preparation in emulsion particle middle layer takes by weighing the above-mentioned nuclear emulsion of 80g and packs in the identical reactor, add the 25g deionized water, warming while stirring, take by weighing 50g vinylbenzene, 18g vinyl cyanide, 0.7g Vinylstyrene simultaneously and be made into monomer mixed solution, get 0.54g ammonium persulphate, 0.13g Sodium dodecylbenzene sulfonate and 20g deionized water and be made into the aqueous solution.Treat that temperature rises to 75 ℃, drips monomer mixed solution and initiator, emulsifier aqueous solution simultaneously.The monomer mixed solution time 3h that feeds in raw material, the aqueous solution of initiator, the emulsifying agent time 3.5h that feeds in raw material, treat that all raw materials finish after, be incubated 0.5h again, cooling discharge.
(4) preparation of shell emulsion takes by weighing the above-mentioned middle layer of 60g emulsion and puts into reactor, add the 20g deionized water, warming while stirring, take by weighing butyl acrylate 30g simultaneously, vinylbenzene 14g is made into monomer mixed solution, take by weighing 0.64g ammonium persulphate, 0.16g Sodium dodecylbenzene sulfonate and 20g deionized water and be made into the aqueous solution, treat that temperature rises to 75 ℃, drips monomer mixed solution and initiator, emulsifier aqueous solution simultaneously.The monomer mixed solution time 3h that feeds in raw material, the aqueous solution of initiator, the emulsifying agent time 3.5h that feeds in raw material, treat that all raw materials finish after, be incubated 2h again, cooling discharge.
(5) alkaline purification takes by weighing core-shell emulsion that 100g makes and packs into and have the reactor of whipping appts and reflux exchanger, regulate ph value of emulsion to 9 with 20% the sodium hydroxide solution for preparing in advance, be warming up to 100 ℃, under agitation be incubated 4h, cooling promptly obtains the aqueous hollow emulsion particle of inner bag.
(6) testing electronic microscope is diluted to solid content with above-mentioned emulsion and is about 15%, drips the polymer emulsion after 25 dilutions then in 10ml distilled water, with KQ-100DB type numerical control supersonic decollator ultra-sonic dispersion 10min.Get on the special-purpose little copper mesh of transmission electron microscope that emulsion sample drops in support membrane, to drip mass percent concentration on the little copper mesh of emulsion be 1～2 of 2% the ruthenium tetroxide aqueous solution scribbling then.Dry under light-illuminating, use Hitachi H-800 type transmission electron microscope then, under the condition of acceleration voltage 80kV, sample is taken pictures.Electron micrograph as shown in Figure 1.As can be seen from the figure, the latex particle size that makes by this method is approximately 1000nm, and the particle diameter monodispersity is good, and hollow structure is regular.
(7) the self film-formed property testing is identical with example 1 method.Finally can obtain the film of skim white, smooth and flawless.
Example 3
(1) preparation of seed is identical with example 1 method.
(2) preparation of nuclear emulsion adds 25g seed emulsion and 100g deionized water, warming while stirring in above-mentioned identical reactor; Take by weighing 10g methyl methacrylate, 6.5g methacrylic acid, 0.082g Vinylstyrene simultaneously. be made into monomer mixed solution, get the 0.13g ammonium persulphate, the 0.03g Sodium dodecylbenzene sulfonate is made into the aqueous solution with the 15g deionized water.After temperature rises to 80 ℃ in the question response device, drip the aqueous solution of monomer mixed solution and initiator, emulsifying agent simultaneously.Monomer mixed solution drips 6.5h, and the aqueous solution of initiator, emulsifying agent drips 6h, treat that all raw materials finish after, be incubated cooling discharge behind the 0.5h again.
(3) preparation in emulsion particle middle layer takes by weighing the above-mentioned nuclear emulsion of 100g and packs in the identical reactor, add the 30g deionized water, warming while stirring, take by weighing 60g vinylbenzene, 21g vinyl cyanide, 0.76g Vinylstyrene simultaneously and be made into monomer mixed solution, get 0.6g ammonium persulphate, 0.2g Sodium dodecylbenzene sulfonate and 25g water and be made into the aqueous solution.Treat that temperature rises to 75 ℃, drips monomer mixed solution and initiator, emulsifier aqueous solution simultaneously.The monomer mixed solution time 3.5h that feeds in raw material, the aqueous solution of initiator, the emulsifying agent time 4h that feeds in raw material, treat that all raw materials finish after, be incubated 0.5h again, cooling discharge.
(4) preparation of shell emulsion takes by weighing the above-mentioned middle layer of 60g emulsion and puts into reactor, add the 20g deionized water, warming while stirring, take by weighing butyl acrylate 24g simultaneously, vinylbenzene 22g is made into monomer mixed solution, take by weighing 0.64g ammonium persulphate, 0.16g Sodium dodecylbenzene sulfonate and 20g water and be made into the aqueous solution, treat that temperature rises to 75 ℃, drips monomer mixed solution and initiator, emulsifier aqueous solution simultaneously.The monomer mixed solution time 3h that feeds in raw material, the aqueous solution of initiator, the emulsifying agent time 3.5h that feeds in raw material, treat that all raw materials finish after, be incubated 2h again, cooling discharge.
(5) alkaline purification takes by weighing core-shell emulsion that 100g makes and packs into and have the reactor of whipping appts and reflux exchanger, regulate ph value of emulsion to 9 with 20% the sodium hydroxide solution for preparing in advance, be warming up to 100 ℃, under agitation be incubated 2.5h, cooling promptly obtains the aqueous hollow emulsion particle of inner bag.
(6) the testing electronic microscope method is identical with example 1, and electron micrograph as shown in Figure 2.As can be seen from the figure, latex particle size distributes comparatively even, and for about 800nm, but the hollow structure of part emulsion particle is not obvious and also have the minimum emulsion particle of a small amount of particle diameter to generate.Illustrated when in the end step is carried out alkaline purification that alkaline solution is not easy to penetrate into carboxylic stratum nucleare, causes alkaline purification incomplete because the time is short and thickness middle layer and shell is bigger.And the preparatory phase emulsifying agent consumption at shell is also bigger than normal, has generated the very little new emulsion particle of particle diameter.
(7) self film-formed property testing method is identical with example 1.Finally obtain the film of skim white, a small amount of crackle is arranged on the film.
Example 4
(1) preparation of seed is identical with example 1 method.
(2) preparation of nuclear emulsion grain adds 20g seed emulsion and 80g deionized water, warming while stirring in above-mentioned identical reactor; Take by weighing 8g methyl methacrylate, 6g methacrylic acid, 0.06g Vinylstyrene simultaneously. be made into monomer mixed solution, get the 0.1g ammonium persulphate, the 0.04g Sodium dodecylbenzene sulfonate is made into the aqueous solution with the 15g deionized water.After temperature rises to 80 ℃ in the question response device, drip the aqueous solution of monomer mixed solution and initiator, emulsifying agent simultaneously.Monomer mixed solution drips 3.0h, and the aqueous solution of initiator, emulsifying agent drips 3.5h, treat that all raw materials finish after, be incubated cooling discharge behind the 0.5h again.
(3) preparation of middle layer emulsion particle takes by weighing the above-mentioned nuclear emulsion of 80g and packs in the identical reactor, add the 25g deionized water, warming while stirring, take by weighing 45g vinylbenzene, 17g vinyl cyanide, 0.6g Vinylstyrene simultaneously and be made into monomer mixed solution, get 0.46g ammonium persulphate, 0.18g Sodium dodecylbenzene sulfonate and 20g water and be made into the aqueous solution.Treat that temperature rises to 75 ℃, drips monomer mixed solution and initiator, emulsifier aqueous solution simultaneously.The monomer mixed solution time 3h that feeds in raw material, the aqueous solution of initiator, the emulsifying agent time 3.5h that feeds in raw material, treat that all raw materials finish after, be incubated 0.5h again, cooling discharge.
(4) alkaline purification takes by weighing middle layer emulsion that 100g makes and packs into and have the reactor of whipping appts and reflux exchanger, regulate ph value of emulsion to 9 with 20% the sodium hydroxide solution for preparing in advance, be warming up to 100 ℃, under agitation be incubated 4h, cooling promptly obtains the aqueous hollow emulsion particle of inner bag.
(5) preparation of shell emulsion takes by weighing the above-mentioned middle layer emulsion through alkaline purification of 60g and puts into reactor, add the 20g deionized water, warming while stirring, take by weighing butyl acrylate 35g simultaneously, vinylbenzene 13g is made into monomer mixed solution, take by weighing 0.64g ammonium persulphate, 0.16g Sodium dodecylbenzene sulfonate and 20g water and be made into the aqueous solution, treat that temperature rises to 75 ℃, drips monomer mixed solution and initiator, emulsifier aqueous solution simultaneously.The monomer mixed solution time 3h that feeds in raw material, the aqueous solution of initiator, the emulsifying agent time 3.5h that feeds in raw material, treat that all raw materials finish after, be incubated 2h again, cooling discharge.
(6) the testing electronic microscope method is identical with example 1, and electron micrograph as shown in Figure 3.As can be seen from the figure, most of emulsion particle all has hollow structure, but size distribution is inhomogeneous, and the part latex particle is arranged is solid construction.When explanation prepares at the nuclear emulsion grain emulsifying agent consumption excessive and in the preparation process of middle layer emulsion particle feed rate too fast, caused the generation of new emulsion particle, do not contain carboxyl in these new emulsion particles, so by forming hollow structure after the alkaline purification yet.
(7) self film-formed property testing method is identical with example 1.Finally obtain the film of skim white, a small amount of crackle is arranged on the film.
Claims (1)
1. the preparation method of monodispersed large grain-size hollow styrene-acrylic polymer microballoon in the low soap system, its feature comprises following process:
(1) the solid content mass ratio is the preparation of 1.0～10% seed emulsion: the emulsifying agent Sodium dodecylbenzene sulfonate that will account for monomer total mass 0.2～1% joins in the reactor with deionized water, under agitation be warming up to 60～80 ℃, add one or both acrylic ester monomers and methacrylic acid or vinylformic acid again by (95～100): the mass ratio of (5～10) mixes the monomer mixed solution that obtains, adding accounts for the solution that monomer total mass 5～10% initiator ammonium persulfates are made into after continuing to stir 0～0.5h, at 60～80 ℃ of following insulation reaction 1～4h, make the solid content mass ratio and be 1.0～10% seed emulsion;
(2) the solid content mass ratio is the preparation of 7.0～15% carboxylated nuclear emulsions: add the deionized water dilution in the seed emulsion that makes toward step (1) in the time of 60～80 ℃, heating while stirring, drip one or both acrylic ester monomers and methacrylic acid or vinylformic acid and Vinylstyrene or methacrylate glycol ester again by (50～100): (5～50): the mixed solution of (2～5) mass ratio, drip the aqueous solution that the initiator ammonium persulfate of the emulsifying agent Sodium dodecylbenzene sulfonate account for this step monomer total mass 0.2～1% and 0.3～3% is mixed with simultaneously, the dropping time is 2～10h, all raw materials dropwise back insulation reaction 2～4h, make the solid content mass ratio and be the nuclear emulsion of 7.0～15% band carboxyl;
(3) the solid content mass ratio is the preparation of the polyalcohol emulsion particle in 20～50% coated middle layers: in the time of 60～80 ℃, at the uniform velocity dropwise addition of acrylic acid esters monomer or vinylbenzene are pressed (95～100) with Vinylstyrene or methacrylate glycol ester in the prepared carboxyl of step (2) the nuclear emulsion: the mixed solution of (0～5) mass ratio, drip simultaneously and account for the Sodium dodecylbenzene sulfonate of this step monomer total mass 0.2～1% and the aqueous solution of 0.3～3% ammonium persulphate, the dropping time is 2～10h, all raw materials dropwise back insulation reaction 2～4h, make the solid content mass ratio and be 20～50% the coated polyalcohol emulsion particle in middle layer;
(4) the solid content mass ratio is the preparation of 20～50% shell polymkeric substance: in the time of 60～80 ℃, in the prepared polymer emulsion of step (3) at the uniform velocity dropwise addition of acrylic acid esters monomer and vinylbenzene by (50～90): the mixed solution of (10～50) mass ratio, drip simultaneously and account for the Sodium dodecylbenzene sulfonate of this step monomer total mass 0.2～1% and the aqueous solution that 0.3～3% ammonium persulphate is made into, the dropping time is 2～10h, all raw materials dropwise back insulation reaction 2～4h, make the solid content mass ratio and be 20～50% core-shell emulsion;
(5) alkaline purification: be initial pH value to 7～13 of 5～20% the resulting core-shell emulsion of sodium hydroxide solution regulating step (4) with concentration, under 90～120 ℃ of temperature, carrying out then and swelling 1～5h, obtain the hollow emulsion particle.
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| CN100562358C (en) * | 2007-05-17 | 2009-11-25 | 浙江大学 | With the hydrogel microsphere is the method that template prepares hollow microsphere |
| CN101186661B (en) * | 2007-12-14 | 2012-09-19 | 深圳市纳微科技有限公司 | Method for preparing polymer particle |
| CN101982494B (en) * | 2010-09-07 | 2012-05-23 | 百利合化工（中山）有限公司 | Method for preparing hollow microsphere emulsion with covering power for printing paint |
| CN103524653B (en) * | 2012-07-02 | 2016-09-21 | 南亚塑胶工业股份有限公司 | The preparation of polymeric hollow microsphere |
| CN104725970A (en) * | 2013-12-18 | 2015-06-24 | 惠州湖工成松防水技术研发有限公司 | Coating |
| CN104004219A (en) * | 2014-04-28 | 2014-08-27 | 安徽红太阳新材料有限公司 | Method for preparing hollow microspheres by using waste rubber |
| CN105218750A (en) * | 2015-11-13 | 2016-01-06 | 华东理工大学 | A kind of preparation method of hollow plastic pigment |
| CN115197624B (en) * | 2022-07-14 | 2023-07-21 | 广东聚慧科技有限责任公司 | Phase-change microsphere dispersion liquid and preparation method thereof |
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| CN1063288A (en) * | 1991-01-09 | 1992-08-05 | 河北省建筑材料工业设计研究院 | Quaternary phenylpropyl water-soluble emulsion and synthetic method |
| CN1019821B (en) * | 1988-01-08 | 1992-12-30 | 亨尼希斯多夫尔钢铁工程有限公司 | The high-strength steel of material property improvement and good workability, especially reinforcing bar or drawing preformed material |
| CN1486996A (en) * | 2003-06-26 | 2004-04-07 | 江汉大学 | Prepn process of modified styrene-acrylic emulsion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1019821B (en) * | 1988-01-08 | 1992-12-30 | 亨尼希斯多夫尔钢铁工程有限公司 | The high-strength steel of material property improvement and good workability, especially reinforcing bar or drawing preformed material |
| CN1063288A (en) * | 1991-01-09 | 1992-08-05 | 河北省建筑材料工业设计研究院 | Quaternary phenylpropyl water-soluble emulsion and synthetic method |
| CN1486996A (en) * | 2003-06-26 | 2004-04-07 | 江汉大学 | Prepn process of modified styrene-acrylic emulsion |
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