CN100427510C - Hollow polymer colloid grain and its production - Google Patents
Hollow polymer colloid grain and its production Download PDFInfo
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- CN100427510C CN100427510C CNB2006100281994A CN200610028199A CN100427510C CN 100427510 C CN100427510 C CN 100427510C CN B2006100281994 A CNB2006100281994 A CN B2006100281994A CN 200610028199 A CN200610028199 A CN 200610028199A CN 100427510 C CN100427510 C CN 100427510C
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- mono
- unsaturated monomer
- vinyl unsaturated
- hydrophobicity
- polymkeric substance
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- 229920000642 polymer Polymers 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000000084 colloidal system Substances 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 58
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 55
- 239000000839 emulsion Substances 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000003973 paint Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 27
- 238000009736 wetting Methods 0.000 claims description 24
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- 239000004816 latex Substances 0.000 abstract description 11
- 229920000126 latex Polymers 0.000 abstract description 11
- 239000000049 pigment Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract 3
- 230000000379 polymerizing effect Effects 0.000 abstract 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 239000000123 paper Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004908 Emulsion polymer Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
A hollow polymer emulsoid particle, its production and use are disclosed. The emulsoid particle consists of nuclear-layer polymer and at least two shell polymers, the nuclear-layer polymer is prepared by emulsion polymerizing 2-80wt% hydrophilic mono-vinyl unsaturated monomer with 20-98wt% hydrophobic mono-vinyl unsaturated monomer; The first shell polymer is prepared by emulsion polymerizing 60-99wt% hydrophobic mono-vinyl unsaturated monomer; The second shell polymer is prepared by emulsion polymerizing 80-100wt% hydrophobic mono-vinyl unsaturated monomer. It can be used for plastic pigment, paper coating and latex paint. It has better covering rate, glossiness, ink absorption and wet strength.
Description
Technical field
The present invention relates to a kind of polyalcohol emulsion particle and preparation method thereof, relate in particular to a kind of hollow polymer emulsion particle and preparation method thereof.
Technical background
In recent years, there were some Chinese patents to announce the preparation and the application of relevant hollow latex successively.Disclose a kind of preparation method of multilayer emulsion polymkeric substance as Chinese patent CN1220273, the low emulsion polymer of dried tap density that this method is prepared can be used as plastic pigments and is used for paper coating and emulsion paint, improves the hiding rare of filming.This patent is claimed and can be accomplished to do the minimum macropore latex that reaches 0.46 grams per milliliter of tap density.
Chinese patent CN1237598 then discloses a kind of spherosome pigment dyestuff that is used for paper or board coating, and this pigment dyestuff is that one deck is examined two-layer shell structure, and second layer shell is the polymkeric substance of second-order transition temperature-50～-15 ℃ of scopes.The inventor claims the polymer particle of this kind structure, can also improve the intensity of paper or cardboard when using as plastic pigments.
Above-mentioned patent all adopts the conventional emulsion polymerization technique to synthesize the emulsion polymer of hydrophilic core, hydrophobicity shell.Yet the ratio that accounts for the emulsion particle volume when nuclear adopts traditional technology to be difficult to examine coating fully greater than 20% the time, and the destruction that can cause the alkali swelling to cause nucleocapsid structure is difficult to obtain the bigger hollow latex of hollow volume.
Summary of the invention
The object of the present invention is to provide a kind of hollow polymer emulsion particle and preparation method thereof, to overcome deficiency of the prior art.
Hollow polymer emulsion particle of the present invention is a kind of hud typed emulsion polymer, comprising: a stratum nucleare polymkeric substance and at least two shell polymkeric substance, the stratum nucleare polymkeric substance is close to stratum nucleare and is followed successively by the first shell polymkeric substance, the second shell polymkeric substance outward in the inside.
Said stratum nucleare polymkeric substance by based on the hydrophobicity mono-vinyl unsaturated monomer of the wetting ability mono-vinyl unsaturated monomer of stratum nucleare total polymer 2-80% and 20-98% by emulsion polymerization prepared;
The said first shell polymkeric substance by based on the hydrophobicity mono-vinyl unsaturated monomer of the 60-99% of the first shell total polymer by emulsion polymerization prepared;
The second shell polymkeric substance by based on the hydrophobicity mono-vinyl unsaturated monomer of the 80-100% of the second shell total polymer by emulsion polymerization prepared;
The said stratum nucleare polymkeric substance and the first shell polymer weight ratio are 2: 1～1: 30, and the second-order transition temperature of the first shell polymkeric substance is 55-150 ℃;
The weight of said second layer shell polymkeric substance is the 10-60% of the first layer shell polymer weight, and the second-order transition temperature of second layer shell polymkeric substance is 80-150 ℃;
Said hollow polymer emulsion particle both can use volatile alkali also can use non-volatile alkali swelling under 90-100 ℃ condition.
Said wetting ability mono-vinyl unsaturated monomer is selected from vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate or vinyl acetate;
Hydrophobicity mono-vinyl unsaturated monomer is selected from vinylbenzene, vinyl toluene, the C9 above acrylate of above tertiary ethylene carbonate C4 or methacrylic ester.
The preparation method of hollow polymer emulsion particle of the present invention comprises the steps:
(1) be that the wetting ability mono-vinyl unsaturated monomer of 2-80% and the hydrophobicity mono-vinyl unsaturated monomer of 20-98% pass through emulsion polymerization prepared stratum nucleare polymer emulsion with weight percent, method of emulsion polymerization is a kind of method of routine, and its processing condition Cao is with in beautiful " polymer emulsion " book detailed description being arranged;
(2) with the stratum nucleare polymer emulsion of hydrophobicity mono-vinyl unsaturated monomer and wetting ability mono-vinyl unsaturated monomer adding step (1), prepare product by emulsion polymerization: polymer emulsion with the first layer shell of being close to stratum nucleare;
In the gross weight of hydrophobicity mono-vinyl unsaturated monomer and wetting ability mono-vinyl unsaturated monomer, the insatiable hunger of hydrophobicity mono-vinyl accounts for 60-99%, and wetting ability mono-vinyl unsaturated monomer accounts for 1-40%;
The stratum nucleare polymer emulsion of step (1): hydrophobicity mono-vinyl unsaturated monomer and wetting ability mono-vinyl unsaturated monomer=1: 0.01～10, weight ratio;
(3) hydrophobicity mono-vinyl unsaturated monomer and wetting ability mono-vinyl unsaturated monomer are added step (2) product, prepare product by emulsion polymerization: have the polymer emulsion of being close to the first layer shell;
In the gross weight of hydrophobicity mono-vinyl unsaturated monomer and wetting ability mono-vinyl unsaturated monomer, hydrophobicity mono-vinyl unsaturated monomer accounts for 80-100%, and wetting ability mono-vinyl unsaturated monomer accounts for 0-20%;
The product of step (2): hydrophobicity mono-vinyl unsaturated monomer and wetting ability mono-vinyl unsaturated monomer=1: 0.1～10, weight ratio;
Said hydrophobicity mono-vinyl unsaturated monomer is selected from a kind of in vinylbenzene, vinyl toluene, the C9 above acrylate of above tertiary ethylene carbonate C4 or the methacrylic ester;
Said wetting ability mono-vinyl unsaturated monomer is selected from a kind of in vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate or the vinyl acetate;
According to preferable methods of the present invention, the reinforced time of the first layer mix monomer is not less than 2.5 hours, and preferred 2.5～5 hours, the reinforced time of second layer mix monomer was not less than 1.5 hours, preferred 1.5～3.5 hours.
The hollow polymer emulsion particle that adopts aforesaid method to obtain, be the bigger hollow latex of a kind of hollow volume, the ratio that nuclear accounts for the emulsion particle volume is 60-80%, the hollow polymer emulsion particle that is much higher than the traditional technology preparation, and the shell polymkeric substance will be examined coating fully, the destruction that can cause the alkali swelling to cause nucleocapsid structure not can be used as the preparation that plastic pigments is used for paper coating and emulsion paint, improves the hiding rare of filming.During the face that prepared hollow latex is added paper to was coated with, paper of whiteness, glossiness, print gloss, ink absorption and wet picking strength all had obvious improvement.
Embodiment
Embodiment 1
The preparation of stratum nucleare polymer emulsion:
In 1000 milliliters reactor, add 341.4 gram water, and under nitrogen atmosphere, be warming up to 85 ℃, add 6.67 gram weight concentration and be 30% seed emulsion (median size is the phenylpropyl alcohol water dispersion of 30 nanometers) and 5.4 gram weight concentration and be 7.5% ammonium persulfate solution, Dropwise 50 gram weight concentration is 2% ammonium persulfate solution and by emulsion mixture that following component constituted simultaneously then:
80 gram water, the sodium lauryl sulphate of 0.87 gram weight concentration 23%, 120 gram vinylbenzene, 80 gram vinylformic acid.The reinforced time is 2 hours, the reinforced insulation 1 hour that finishes.Be cooled to room temperature and filter discharging.Obtain 30% solid content, median size is the emulsion of 142 nanometers.
Embodiment 2
The preparation of multi-functional hollow latex
In one 1000 milliliters reactor, add 263.0 gram water, and under nitrogen atmosphere, be warming up to 85 ℃, adding 66.67 gram embodiment 1 prepared stratum nucleare polymer emulsion, 5.4 gram weight concentration are 7.5% ammonium persulfate solution;
Simultaneously Dropwise 56 gram weight concentration are 2.2% ammonium persulfate solution and by emulsion mixture that following component constituted then:
80 gram water, the CO436 (alkylphenol ether sodium sulfate) of 1.38 grams, 32 gram butyl acrylates, 44.2 gram methyl methacrylates, 90.5 gram vinylbenzene, 3.5 gram vinylformic acid;
The reinforced time of above-mentioned emulsion mixture is 2 hours; Finish, drip immediately by 20 gram butyl acrylates and the 10 gram mixtures that vinylbenzene constituted, reinforced 1 hour time;
Add ammonium persulfate solution, the reinforced time is 3 hours.After reinforced being all over, 85 ℃ are incubated 20 minutes down.Then add 0.2 gram CO436, be warming up to 95 ℃, dripping 67 gram weight concentration in 30 minutes gradually is 28% ammoniacal liquor; 95 ℃ are incubated 1 hour down.
Be cooled to room temperature and filter discharging.
Obtaining solid content is that 30% (weight), particulate median size are the emulsion of 350 nanometers.
Embodiment 3
The application performance of multi-functional hollow latex:
Be used for the coating that face is coated with by following formulation: (weight)
85 parts of kaolin, 15 parts of embodiment 2 gained latex (over dry), 4 portions of modified starches, 12 parts of styrene-butadiene latexes, 0.01 part of defoamer Bevaloid681F (the inferior product in French sieve ground), solid content 60.2%, pH=9.0.
The employing ivory board is a body paper, and test result such as table 1 are tested in the coating back according to GB.
The comparative example 1
100 parts kaolin, 4 parts modified starch, 12 parts styrene-butadiene latex, 0.01 part of defoamer Bevaloid681F (the inferior product in French sieve ground), solid content 60.2%, pH=9.1;
The employing ivory board is a body paper, and test result such as table 1 are tested in the coating back according to GB.
| Project | The comparative example 1 | Embodiment 4 |
| Whiteness, % | 92.9 | 93.6 |
| The paper glossiness, % | 57 | 62 |
| Print gloss, % | 93 | 97 |
| Ink absorption, % | 19 | 22 |
| Wet picking strength, % | 40.0 | 17.1 |
By table 1 as seen, during the face that uses embodiment 2 prepared hollow latex to add paper to was coated with, paper of whiteness, glossiness, print gloss, ink absorption and wet picking strength all had obvious improvement.
Claims (6)
1. a hollow polymer emulsion particle comprises a stratum nucleare polymkeric substance and at least two shell polymkeric substance, and the stratum nucleare polymkeric substance is close to stratum nucleare and is followed successively by the first shell polymkeric substance, the second shell polymkeric substance outward in the inside, it is characterized in that:
Said stratum nucleare polymkeric substance by based on the hydrophobicity mono-vinyl unsaturated monomer of the wetting ability mono-vinyl unsaturated monomer of the 2-80% of stratum nucleare total polymer and 20-98% by emulsion polymerization prepared;
The said first shell polymkeric substance by based on the hydrophobicity mono-vinyl unsaturated monomer of the 60-99% of the first shell total polymer by emulsion polymerization prepared;
The second shell polymkeric substance by the hydrophobicity mono-vinyl unsaturated monomer of the 80-100% of the second shell total polymer by emulsion polymerization prepared;
The second-order transition temperature of the first shell polymkeric substance is 55-150 ℃;
The second-order transition temperature of second layer shell polymkeric substance is 80-150 ℃.
2. hollow polymer emulsion particle according to claim 1 is characterized in that, the said stratum nucleare polymkeric substance and the first shell polymer weight ratio are 2: 1～1: 30.
3. hollow polymer emulsion particle according to claim 1 is characterized in that, the weight of said second layer shell polymkeric substance is the 10-60% of the first layer shell polymer weight.
4. according to each described hollow polymer emulsion particle of claim 1～3, it is characterized in that said wetting ability mono-vinyl unsaturated monomer is selected from acrylic or methacrylic acid.
5. according to the preparation method of each described hollow polymer emulsion particle of claim 1～4, it is characterized in that, comprise the steps:
(1) be that the wetting ability mono-vinyl unsaturated monomer of 2-80% and the hydrophobicity mono-vinyl unsaturated monomer of 20-98% pass through emulsion polymerization prepared stratum nucleare polymer emulsion with weight percent;
(2) with the stratum nucleare polymer emulsion of hydrophobicity mono-vinyl unsaturated monomer and wetting ability mono-vinyl unsaturated monomer adding step (1), prepare product by emulsion polymerization: polymer emulsion with the first layer shell of being close to stratum nucleare;
In the gross weight of hydrophobicity mono-vinyl unsaturated monomer and wetting ability mono-vinyl unsaturated monomer, hydrophobicity mono-vinyl unsaturated monomer accounts for 60-99%, and wetting ability mono-vinyl unsaturated monomer accounts for 1-40%;
The stratum nucleare polymer emulsion of step (1): hydrophobicity mono-vinyl unsaturated monomer and wetting ability mono-vinyl unsaturated monomer=1: 0.01～10, weight ratio;
(3) hydrophobicity mono-vinyl unsaturated monomer and wetting ability mono-vinyl unsaturated monomer are added step (2) product, prepare product by emulsion polymerization: have the polymer emulsion of being close to the first layer shell;
In the gross weight of hydrophobicity mono-vinyl unsaturated monomer and wetting ability mono-vinyl unsaturated monomer, hydrophobicity mono-vinyl unsaturated monomer accounts for 80-100%, and wetting ability mono-vinyl unsaturated monomer accounts for 0-20%;
The product of step (2): hydrophobicity mono-vinyl unsaturated monomer and wetting ability mono-vinyl unsaturated monomer=1: 0.1～10, weight ratio;
Said hydrophobicity mono-vinyl unsaturated monomer is selected from a kind of in vinylbenzene, vinyl toluene, the above tertiary ethylene carbonate of C9, the above acrylate of C4 or the methacrylic ester;
Said wetting ability mono-vinyl unsaturated monomer is selected from a kind of in the acrylic or methacrylic acid;
The reinforced time of the first layer mix monomer is 2.5～5 hours, and the reinforced time of second layer mix monomer is 1.5～3.5 hours.
6. according to the application of each described hollow polymer emulsion particle of claim 1～4, it is characterized in that, be used for the preparation of paper coating and emulsion paint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100281994A CN100427510C (en) | 2006-06-27 | 2006-06-27 | Hollow polymer colloid grain and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100281994A CN100427510C (en) | 2006-06-27 | 2006-06-27 | Hollow polymer colloid grain and its production |
Publications (2)
| Publication Number | Publication Date |
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| CN1896110A CN1896110A (en) | 2007-01-17 |
| CN100427510C true CN100427510C (en) | 2008-10-22 |
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| CNB2006100281994A Active CN100427510C (en) | 2006-06-27 | 2006-06-27 | Hollow polymer colloid grain and its production |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012533667A (en) * | 2009-07-22 | 2012-12-27 | ビーエーエスエフ ソシエタス・ヨーロピア | Use of film-forming polymers and coatings for organic hollow particles |
| CN102898577A (en) * | 2012-08-29 | 2013-01-30 | 华南理工大学 | Polymeric hollow latex particles and preparation method thereof |
| CN104086689B (en) * | 2014-07-03 | 2016-11-16 | 南京工业大学 | Large-particle-size high-crosslinking-degree hollow polymer microparticle and preparation method thereof |
| MY177219A (en) * | 2014-08-22 | 2020-09-09 | Arkema Inc | Voided latex particles |
| WO2016028511A1 (en) | 2014-08-22 | 2016-02-25 | Arkema Inc. | Voided latex particles |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040039A (en) * | 1988-05-20 | 1990-02-28 | 罗姆和哈斯公司 | Absorbed the light tight polymer beads of multilayer of non-polymeric acid |
| US5639805A (en) * | 1991-12-13 | 1997-06-17 | Korea Chemical Co., Ltd. | Process for preparing core-shell emulsion polymer particles and resulting product containing such particles |
| CN1220273A (en) * | 1997-11-05 | 1999-06-23 | 罗姆和哈斯公司 | Process for preparing polymer emulsions and polymers formed therefrom |
| CN1237598A (en) * | 1998-05-18 | 1999-12-08 | 罗姆和哈斯公司 | Hollow sphere organic pigment for paper or paper coatings |
| CN1346833A (en) * | 2000-09-29 | 2002-05-01 | 罗姆和哈斯公司 | Process for chemical modifying surface of emulsion polymer particles |
| CN1432582A (en) * | 2002-01-07 | 2003-07-30 | 罗姆和哈斯公司 | Emulsion polymer and its prepn process |
| US20050085560A1 (en) * | 1997-11-05 | 2005-04-21 | Blankenship Robert M. | Swollen multi-stage emulsion polymers with low bulk densities |
| US20060009587A1 (en) * | 2004-07-06 | 2006-01-12 | Kim Hae Y | Method of preparing emulsion polymer with hollow structure and emulsion polymer prepared by the method |
-
2006
- 2006-06-27 CN CNB2006100281994A patent/CN100427510C/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040039A (en) * | 1988-05-20 | 1990-02-28 | 罗姆和哈斯公司 | Absorbed the light tight polymer beads of multilayer of non-polymeric acid |
| US5639805A (en) * | 1991-12-13 | 1997-06-17 | Korea Chemical Co., Ltd. | Process for preparing core-shell emulsion polymer particles and resulting product containing such particles |
| CN1220273A (en) * | 1997-11-05 | 1999-06-23 | 罗姆和哈斯公司 | Process for preparing polymer emulsions and polymers formed therefrom |
| US20050085560A1 (en) * | 1997-11-05 | 2005-04-21 | Blankenship Robert M. | Swollen multi-stage emulsion polymers with low bulk densities |
| CN1237598A (en) * | 1998-05-18 | 1999-12-08 | 罗姆和哈斯公司 | Hollow sphere organic pigment for paper or paper coatings |
| CN1346833A (en) * | 2000-09-29 | 2002-05-01 | 罗姆和哈斯公司 | Process for chemical modifying surface of emulsion polymer particles |
| CN1432582A (en) * | 2002-01-07 | 2003-07-30 | 罗姆和哈斯公司 | Emulsion polymer and its prepn process |
| US20060009587A1 (en) * | 2004-07-06 | 2006-01-12 | Kim Hae Y | Method of preparing emulsion polymer with hollow structure and emulsion polymer prepared by the method |
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|---|---|
| CN1896110A (en) | 2007-01-17 |
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