CN104250508A - Preparation method for high-performance aqueous PP paint - Google Patents
Preparation method for high-performance aqueous PP paint Download PDFInfo
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- CN104250508A CN104250508A CN201410454021.0A CN201410454021A CN104250508A CN 104250508 A CN104250508 A CN 104250508A CN 201410454021 A CN201410454021 A CN 201410454021A CN 104250508 A CN104250508 A CN 104250508A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003973 paint Substances 0.000 title abstract description 9
- 239000004743 Polypropylene Substances 0.000 claims abstract description 58
- 239000000839 emulsion Substances 0.000 claims abstract description 26
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 poly(allyl chloride) Polymers 0.000 claims abstract description 24
- 229920001155 polypropylene Polymers 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 101000742062 Bos taurus Protein phosphatase 1G Proteins 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 5
- 229960002887 deanol Drugs 0.000 claims description 5
- 238000003811 acetone extraction Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 229920006243 acrylic copolymer Polymers 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 abstract description 4
- 229920000178 Acrylic resin Polymers 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 230000036571 hydration Effects 0.000 abstract 1
- 238000006703 hydration reaction Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000002318 adhesion promoter Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
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- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a preparation method for high-performance aqueous PP paint, and concretely relates to preparation of aqueous PP paint. The invention discloses synthesis of maleic anhydride modified poly(allyl chloride), preparation of an acrylic acid modified chlorinated polypropylene emulsion, and compounding of MCPP and an acrylic emulsion. The adhesive force of automobile paint to PP substrate is improved, the compatibility of CPP and acrylic resin is solved through hydration and the high-performance aqueous PP paint is prepared. The aqueous PP paint can be used in an original plant, and also can be used for repairing, the VOC content is reduced to 10% or less, environment protection is facilitated, usage and dependence on organic solvents are mitigated, and energy is effectively saved.
Description
Technical field
The present invention relates to a kind of preparation of water-based PP coating, particularly relate to a kind of by Acrylic modified chlorinated polypropylene and the preparation method carrying out the composite water-based PP coating of maleic anhydride graft.
Background technology
1) along with the high speed development of automotive industry, the consumption of car paint is also in continuous growth.Current domestic automobile coating is based on solvent system, and wherein a large amount of VOC discharges pollutes atmospheric environment, and in painting dressing automobiles process, wherein solvent-borne type PP coating environmental pollution is especially serious.Along with everybody is to the enhancing of environmental consciousness, relevant laws and regulations have been worked out in succession to limit VOC quantity discharged in countries in the world, so the Water-borne modification of PP coating is very urgent, the present invention is intended to the Water-borne modification realizing PP coating, adopts Acrylic modified chlorinated polypropylene and carries out that maleic anhydride graft is composite prepares high-performance water-based PP coating.This coating by water-based CPP and water-borne acrylic resin composite and obtain, greatly reduce more than the 75% VOC discharge of this coating, tool is nontoxic, nonflammable, very friendly to environment.
2) PP coating and application thereof are the problems that everybody extremely pays close attention to.PP plastics comprise alfon and propylene-ethylene copolymers, belong to non-polar plastic, because its surface energy is low, degree of crystallinity high, cause sticking power poor, and solvent resistance is strong, and film is difficult to attachment.
The poor adhesive force existed as adhesion promoter for CPP, problem with acrylic resin poor compatibility, the present invention adopts maleic anhydride modified CPP resin, thus strengthens its sticking power to PP ground.And the introducing of maleic anhydride also makes the Water-borne modification of CPP become possibility.Utilize phase inversion process to obtain MCPP emulsion, can be used as adhesion promoter and use.And MCPP emulsion and ACRYLIC EMULSION composite, there is not the problem of consistency, high-performance water-based PP coating can be obtained, greatly reduce operation sequence.
Summary of the invention:
In order to overcome the deficiencies in the prior art, the present invention relates to by Acrylic modified chlorinated polypropylene and the preparation method carrying out the composite water-based PP coating of maleic anhydride graft, adopt maleic anhydride modified CPP resin, thus strengthen its sticking power to PP ground, and the introducing of maleic anhydride also makes the Water-borne modification of CPP become possibility.Utilize phase inversion process to obtain MCPP emulsion, can be used as adhesion promoter and use.Utilize MCPP emulsion and ACRYLIC EMULSION to carry out composite, thus prepare the high-performance water-based PP coating had compared with strong adhesive force, better consistency and low VOC content.
The present invention is a kind of by Acrylic modified chlorinated polypropylene and the preparation method carrying out the composite water-based PP coating of maleic anhydride graft:
1) synthesis of maleic anhydride modified polychloroprene
In the reactor that agitator, thermometer and condensing works are housed, in a nitrogen environment, add the solution that 90-110 weight part Chlorinated Polypropylene III (CPP) and 8.5-10 parts by weight maleic anhydride and 150 parts by weight of toluene form, be heated with stirring to 100 DEG C-110 DEG C.Under temperature constant state, add 0.2-0.4 weight part BPO, add rear continuation reaction 1-2h after termination reaction.
After reaction terminates, with Rotary Evaporators except desolventizing, residuum is added in 100-120 pbw acetone, filter after abundant stirring, gained solid is dissolved in toluene, separate out in acetone, after repeating 3 times, gained solid is further purified with acetone extraction and obtains maleic anhydride modified polychloroprene in apparatus,Soxhlet's again.
2) preparation of Acrylic modified chlorinated polypropylene emulsion
A, 0.3g BPO is dissolved in (m (methyl methacrylate): m (β-dimethyl-aminoethylmethacrylate): m (butyl acrylate): m (methacrylic acid)=50: 14: 18:18) in acrylic monomer mixture.
B, under nitrogen protection, in 1000mL tetra-mouthfuls of round-bottomed flasks, adds 95-110g Chlorinated Polypropylene III (CPP) and 150mL toluene and is heated to 100 DEG C and make it to dissolve.Holding temperature, slowly instillation a liquid, about 1h drips off, and then holding temperature continues reaction 3-4h.After having reacted, be cooled to 60 DEG C, stirring is descended the dimethylamino-ethanol aqueous solution of dropping 10% to pH=7-8 and is stirred 30min and makes it abundant dispersion.Under high-speed stirring, in system, slowly drip distilled water make formation homogeneous latex emulsion, after continuing dispersion 50min, add surface active agent, be uniformly dispersed and obtain Acrylic modified chlorinated polypropylene emulsion.This emulsion is the Chlorinated Polypropylene III of modification and the mixture of acrylic copolymer.
3) MCPP and ACRYLIC EMULSION composite
Be equipped with whipping appts reactor in add the MCPP of 40-60 weight part, add the water of 100-140 weight part in whipping process slowly, the ACRYLIC EMULSION simultaneously adding 45-65 weight part is carried out composite, namely obtains high-performance water-based PP coating after about 1-2h.
Above-mentioned initiator is selected from organic amine or organic tin.
Above-mentioned neutralizing agent is ammoniacal liquor or triethylamine or dimethylethanolamine.Water-based PP coating of the present invention, has four advantages below:
(1) novelty by utilizing maleic anhydride modified CPP, improve its sticking power to PP ground;
(2) Water-borne modification that utilizes of novelty solves the compatibility problem of CPP and acrylic resin, can obtain high-performance water-based PP coating, save operation;
(3) the water-based PP coating of this project innovation exploitation both can be used for genuine, also can be used for repairing using.
(4) no matter this project water-based PP coating products is for genuine, or is all reduced to less than 10% for repairing its VOC content, very friendly to environment, dramatically reduces the use to organic solvent and dependence simultaneously, has effectively saved the energy.
Illustrate below by embodiment:
(1) material therefor in embodiment
In embodiment, material therefor is only citing, should not be considered as and limits scope of the present invention.
Chlorinated Polypropylene III chlorinity used is 25%-30%; Maleic anhydride purity is 98.2%.
(2) embodiment of the present invention
By the Chlorinated Polypropylene III (MCPP) of maleic anhydride graft, greatly strengthen its sticking power to PP ground.And the introducing of maleic anhydride also makes the Water-borne modification of CPP become possibility.Add ACRYLIC EMULSION carries out composite simultaneously, and its performance determines the performance of the high-performance water-based PP coating of the finished product.
Embodiment 1 of the present invention: the synthesis of maleic anhydride modified polychloroprene
In the reactor that agitator, thermometer and condensing works are housed, in a nitrogen environment, add the solution that 100 weight part Chlorinated Polypropylene IIIs (CPP) and 9 parts by weight maleic anhydride and 150 parts by weight of toluene form, be heated with stirring to 108 DEG C.Under temperature constant state, add 0.3 weight part BPO, add rear continuation reaction 1.5h after termination reaction.
After reaction terminates, with Rotary Evaporators except desolventizing, residuum is added in 100 pbw acetone, filter after abundant stirring, gained solid is dissolved in toluene, separate out in acetone, after repeating 3 times, gained solid is further purified with acetone extraction and obtains maleic anhydride modified polychloroprene in apparatus,Soxhlet's again.
Embodiment 2 of the present invention:
The preparation method that a kind of high-performance water-based PP coating is provided in the present invention, it comprises:
1) synthesis of maleic anhydride modified polychloroprene
In the reactor that agitator, thermometer and condensing works are housed, in a nitrogen environment, add the solution that 105 weight part Chlorinated Polypropylene IIIs (CPP) and 9.5 parts by weight maleic anhydride and 150 parts by weight of toluene form, be heated with stirring to 105 DEG C.Under temperature constant state, add 0.3 weight part BPO, add rear continuation reaction 1.5h after termination reaction.
After reaction terminates, with Rotary Evaporators except desolventizing, residuum is added in 110 pbw acetone, filter after abundant stirring, gained solid is dissolved in toluene, separate out in acetone, after repeating 3 times, gained solid is further purified with acetone extraction and obtains maleic anhydride modified polychloroprene in apparatus,Soxhlet's again.
2) preparation of Acrylic modified chlorinated polypropylene emulsion
A, 0.3 weight part BPO are dissolved in (m (methyl methacrylate): m (β-dimethyl-aminoethylmethacrylate): m (butyl acrylate): m (methacrylic acid)=50: 14: 18:18) in acrylic monomer mixture.
B, under nitrogen protection, in 1000mL tetra-mouthfuls of round-bottomed flasks, adds 100g Chlorinated Polypropylene III (CPP) and 150mL toluene and is heated to 100 DEG C and make it to dissolve.Holding temperature, slowly instillation a liquid, about 1h drips off, and then holding temperature continues reaction 3.5h.After having reacted, be cooled to 60 DEG C, stirring is descended the dimethylamino-ethanol aqueous solution of dropping 10% to pH=7-8 and is stirred 30min and makes it abundant dispersion.Under high-speed stirring, in system, slowly drip distilled water make the dispersed emulsion of formation, continue dispersion 50min, add surface active agent, be uniformly dispersed and obtain Acrylic modified chlorinated polypropylene emulsion.This emulsion is the Chlorinated Polypropylene III of modification and the mixture of acrylic copolymer.
3, composite
Be equipped with whipping appts reactor in add the MCPP of 45 weight parts, add the water of 110 weight parts in whipping process slowly, the ACRYLIC EMULSION simultaneously adding 60 weight parts is carried out composite, namely obtains high-performance water-based PP coating after about 1-2h.
Use common testing methods in paint field, the correlated performance obtaining water-based PP coating is as shown in the table:
| Project | Test result |
| Paint film appearance | Smooth, without shrinkage cavity |
| VOC(g/L) | ≤100 |
| Construction solid part/wt% | ≥20 |
| Pencil hardness | ≥H |
| Sticking power (cross-hatching) | ≤1 |
Claims (3)
1. a preparation method for high-performance water-based PP coating, its feature:
1) synthesis of maleic anhydride modified polychloroprene
Agitator is being housed, in the reactor of thermometer and condensing works, in a nitrogen environment, add the solution that 90-110 weight part Chlorinated Polypropylene III and 8.5-10 parts by weight maleic anhydride and 150 parts by weight of toluene form, be heated with stirring to 100 DEG C-110 DEG C, under temperature constant state, add 0.2-0.4 weight part BPO, add rear continuation reaction 1-2h after termination reaction, after reaction terminates, with Rotary Evaporators except desolventizing, residuum is added in 100-120 pbw acetone, filter after abundant stirring, gained solid is dissolved in toluene, separate out in acetone again, after repeating 3 times, gained solid is further purified with acetone extraction and obtains maleic anhydride modified polychloroprene in apparatus,Soxhlet's,
2) preparation of Acrylic modified chlorinated polypropylene emulsion
A, 0.3g BPO is dissolved in acrylic monomer mixture, and composition is: (m (methyl methacrylate): m (β-dimethyl-aminoethylmethacrylate): m (butyl acrylate): m (methacrylic acid)=50: 14: 18:18);
B, under nitrogen protection, in 1000mL tetra-mouthfuls of round-bottomed flasks, add 95-110g Chlorinated Polypropylene III and 150mL toluene and be heated to 100 DEG C and make it to dissolve, holding temperature, slow instillation a liquid, about 1h drips off, then holding temperature continues reaction 3-4h, after having reacted, be cooled to 60 DEG C, stir the dimethylamino-ethanol aqueous solution of dropping 10% to pH=7-8 and stir 30min and make it abundant dispersion, under high-speed stirring, in system, slowly drip distilled water make formation homogeneous latex emulsion, after continuing dispersion 50min, add surface active agent, be uniformly dispersed and obtain Acrylic modified chlorinated polypropylene emulsion, this emulsion is the Chlorinated Polypropylene III of modification and the mixture of acrylic copolymer,
3) MCPP and ACRYLIC EMULSION composite
Be equipped with whipping appts reactor in add the MCPP of 40-60 weight part, add the water of 100-140 weight part in whipping process slowly, the ACRYLIC EMULSION simultaneously adding 45-65 weight part is carried out composite, namely obtains high-performance water-based PP coating after about 1-2h.
2. the preparation method of a kind of high-performance water-based PP coating according to claim 1, is characterized in that printing and distributing agent is selected from organic amine or organic tin.
3. the preparation method of a kind of high-performance water-based PP coating according to claim 1, is characterized in that neutralizing agent is ammoniacal liquor or triethylamine or dimethylethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410454021.0A CN104250508A (en) | 2014-09-06 | 2014-09-06 | Preparation method for high-performance aqueous PP paint |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410454021.0A CN104250508A (en) | 2014-09-06 | 2014-09-06 | Preparation method for high-performance aqueous PP paint |
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| CN104250508A true CN104250508A (en) | 2014-12-31 |
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| CN201410454021.0A Pending CN104250508A (en) | 2014-09-06 | 2014-09-06 | Preparation method for high-performance aqueous PP paint |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118297A (en) * | 2017-06-16 | 2017-09-01 | 江苏三木化工股份有限公司 | A kind of synthetic method of the modified thermoplastic acrylic resin of chlorinated polypropylene acid |
| CN109456657A (en) * | 2018-10-22 | 2019-03-12 | Ppg涂料(天津)有限公司 | Conductive primer composition and preparation method |
| CN111234084A (en) * | 2020-01-10 | 2020-06-05 | 江苏利思德新材料有限公司 | Vinyl chloride copolymer emulsion for water-based anticorrosive paint and preparation method and application thereof |
| CN114316857A (en) * | 2022-01-07 | 2022-04-12 | 瑞红锂电池材料(苏州)有限公司 | Water-based modified acrylate emulsion and preparation method and application thereof |
| CN114854253A (en) * | 2022-06-02 | 2022-08-05 | 江苏利信新型建筑模板有限公司 | Film-coated building aluminum alloy template and preparation method thereof |
| CN115820049A (en) * | 2023-01-01 | 2023-03-21 | 浙江佑谦特种材料有限公司 | Water-based PP (polypropylene) treating agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111234084A (en) * | 2020-01-10 | 2020-06-05 | 江苏利思德新材料有限公司 | Vinyl chloride copolymer emulsion for water-based anticorrosive paint and preparation method and application thereof |
| CN111234084B (en) * | 2020-01-10 | 2022-02-18 | 江苏利思德新材料有限公司 | Vinyl chloride copolymer emulsion for water-based anticorrosive paint and preparation method and application thereof |
| CN114316857A (en) * | 2022-01-07 | 2022-04-12 | 瑞红锂电池材料(苏州)有限公司 | Water-based modified acrylate emulsion and preparation method and application thereof |
| CN114854253A (en) * | 2022-06-02 | 2022-08-05 | 江苏利信新型建筑模板有限公司 | Film-coated building aluminum alloy template and preparation method thereof |
| CN115820049A (en) * | 2023-01-01 | 2023-03-21 | 浙江佑谦特种材料有限公司 | Water-based PP (polypropylene) treating agent and preparation method thereof |
| CN115820049B (en) * | 2023-01-01 | 2024-01-12 | 浙江佑谦特种材料有限公司 | Water-based PP (Polypropylene) treating agent and preparation method thereof |
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Application publication date: 20141231 |