CN103183771A - Nano-zinc-oxide-modified acrylate linear high-molecular polymer and preparation method thereof - Google Patents
Nano-zinc-oxide-modified acrylate linear high-molecular polymer and preparation method thereof Download PDFInfo
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- CN103183771A CN103183771A CN2011104539629A CN201110453962A CN103183771A CN 103183771 A CN103183771 A CN 103183771A CN 2011104539629 A CN2011104539629 A CN 2011104539629A CN 201110453962 A CN201110453962 A CN 201110453962A CN 103183771 A CN103183771 A CN 103183771A
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- titanium dioxide
- nanometer titanium
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- dioxide zinc
- polymkeric substance
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- 238000002360 preparation method Methods 0.000 title abstract description 18
- 229920000642 polymer Polymers 0.000 title abstract description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 title abstract 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 27
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- DCRSYTGOGMAXIA-UHFFFAOYSA-N zinc;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Zn+2] DCRSYTGOGMAXIA-UHFFFAOYSA-N 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 20
- 238000012986 modification Methods 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 17
- 235000019394 potassium persulphate Nutrition 0.000 claims description 17
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000004159 Potassium persulphate Substances 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 16
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 16
- 229920002521 macromolecule Polymers 0.000 claims description 13
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000000498 cooling water Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011787 zinc oxide Substances 0.000 abstract description 5
- 229920000058 polyacrylate Polymers 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 229960001296 zinc oxide Drugs 0.000 abstract 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 2
- 239000002245 particle Substances 0.000 abstract 1
- 239000003643 water by type Substances 0.000 description 15
- 229920000915 polyvinyl chloride Polymers 0.000 description 11
- 239000004800 polyvinyl chloride Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- -1 acrylic ester Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- AHVOFPQVUVXHNL-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.CCCCOC(=O)C=C AHVOFPQVUVXHNL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Abstract
The invention relates to a nano-zinc-oxide-modified acrylate linear high-molecular polymer and a preparation method thereof. The invention belongs to the technical field of PVC processing auxiliary material. According to the invention, during a methyl methacrylate and butyl acrylate copolymerization process or a methyl methacrylate homopolymerization process, nano-zinc-oxide is added, such that the acrylate polymer is prepared. A weight ratio of methyl methacrylate to butyl acrylate is 5-100:95-0. A nano-zinc-oxide dose is 0.1-20% of a polymerization monomer total weight. According to the invention, nano-zinc-oxide is used for modifying the acrylate high-molecular polymer which is a processing type acrylate linear high-molecular polymer. The acrylate polymer has the advantages of low cost and good particle state fluidity. With the polymer, prepared PVC profile has high surface smoothness. The preparation method is simple and feasible, and is easy to implement.
Description
Technical field
The present invention relates to a kind of nanometer titanium dioxide zinc modification esters of acrylic acid linear macromolecule polymkeric substance and method for making, belong to PVC processing aid technical field.
Background technology
PVC processing aid of the prior art, general normal employing esters of acrylic acid linear macromolecule polymkeric substance is the methyl methacrylate-butyl acrylate multipolymer, this copolymer pellet state is mobile generally, cost is high.General polyvinyl chloride resin is about 7000～9000 yuan/ton, methyl methacrylate-butyl acrylate multipolymer price is 21000～25000 yuan/ton, this price changes and constantly changes along with oil price, this auxiliary agent is on the high side for polyvinyl chloride resin, thereby the cost of the feasible PVC goods of producing rises, and the PVC section bar any surface finish degree that adopts this kind copolymer to go out is also general.
Summary of the invention
The purpose of this invention is to provide a kind of nanometer titanium dioxide zinc modification esters of acrylic acid linear macromolecule polymkeric substance and method for making, this acrylic polymer cost is low, and the graininess good fluidity, the PVC section bar any surface finish degree height of preparing thus.
Described nanometer titanium dioxide zinc modification esters of acrylic acid linear macromolecule polymkeric substance is in methyl methacrylate and butyl acrylate copolymerization or methyl methacrylate homopolymerization process, adds nanometer titanium dioxide zinc and makes; Wherein methyl methacrylate and butyl acrylate weight percent are 5～100: 95～0, and nanometer titanium dioxide zinc consumption is 0.1～20% of polymerization single polymerization monomer gross weight.
The method for making of described nanometer titanium dioxide zinc modification esters of acrylic acid linear macromolecule polymkeric substance: in glassed steel reaction vessels, add water, open and stir, 60～75 rev/mins of mixing speed add emulsifying agent, methyl methacrylate and butyl acrylate, the capping still; Open heating, when reactor temperature reaches 65～68 ℃, add initiator, when reactor temperature began to rise, polyreaction began in the reactor, opened the cooling water for cooling this moment, when temperature rises to the summit, no longer rise and when beginning to descend, in still, add nanometer titanium dioxide zinc; When temperature continues to drop to 60～65 ℃, close cooling water, when treating that temperature in the kettle drops to 45～48 ℃ naturally, blowing, drying obtains Powdered nanometer titanium dioxide zinc modification esters of acrylic acid linear polymeric polymkeric substance.
Described emulsifying agent is sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or OP-10.
Described emulsifying agent consumption is 0.1～3% of polymerization single polymerization monomer gross weight.
Described initiator is Potassium Persulphate or Sodium Persulfate.
Described initiator amount is 0.05～0.5% of polymerization single polymerization monomer gross weight.
The consumption of described water is 1.3～1.6 times of polymerization single polymerization monomer gross weight.
Beneficial effect of the present invention is as follows:
The present invention adopts nanometer titanium dioxide zinc modification acrylic ester high molecular type polymkeric substance, it is processed-type esters of acrylic acid linear polymeric polymkeric substance, this acrylic polymer cost is low, and graininess good fluidity, the PVC section bar any surface finish degree height of preparing thus, and the preparation method is simple, and is easy to implement.
Embodiment
Be described further below in conjunction with the present invention of embodiment.
Embodiment 1
1500 kilograms of softening waters, 900 kilograms of methyl methacrylates, 100 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 2 kilograms on nanometer titanium dioxide zinc.
Described copolymer method is as follows:
Add the softening water of set amount in the glassed steel reaction vessels, open and stir, 75 rev/mins of mixing speed add emulsifying agent, methyl methacrylate and butyl acrylate, and the capping still is opened heating, when reactor temperature reaches 65 ℃, add initiator.When reactor temperature began to rise, polyreaction began in the reactor, opened the cooling water for cooling this moment.When temperature rises to the summit, no longer rise, and when beginning to descend, in still, add nanometer titanium dioxide zinc, when temperature continues to drop to 65 ℃, close cooling water, when treating that temperature in the kettle drops to 45 ℃ naturally, blowing, drying become pulverous nanometer titanium dioxide zinc modification acrylic ester high molecular type polymkeric substance.
Embodiment 2
1500 kilograms of softening waters, 900 kilograms of methyl methacrylates, 100 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 10 kilograms on nanometer titanium dioxide zinc.Embodiment 2 preparation methods such as embodiment 1.
Embodiment 3
1500 kilograms of softening waters, 900 kilograms of methyl methacrylates, 100 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 50 kilograms on nanometer titanium dioxide zinc.Embodiment 3 preparation methods such as embodiment 1.
Embodiment 4
1500 kilograms of softening waters, 900 kilograms of methyl methacrylates, 100 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 100 kilograms on nanometer titanium dioxide zinc.Embodiment 4 preparation methods such as embodiment 1.
Embodiment 5
1500 kilograms of softening waters, 900 kilograms of methyl methacrylates, 100 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 150 kilograms on nanometer titanium dioxide zinc.Embodiment 5 preparation methods such as embodiment 1.
Embodiment 6
1500 kilograms of softening waters, 900 kilograms of methyl methacrylates, 100 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 200 kilograms on nanometer titanium dioxide zinc.Embodiment 6 preparation methods such as embodiment 1.
Embodiment 7
1500 kilograms of softening waters, 800 kilograms of methyl methacrylates, 200 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 2 kilograms on nanometer titanium dioxide zinc.Embodiment 7 preparation methods such as embodiment 1.
Embodiment 8
1500 kilograms of softening waters, 800 kilograms of methyl methacrylates, 200 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 10 kilograms on nanometer titanium dioxide zinc.Embodiment 8 preparation methods such as embodiment 1.
Embodiment 9
1500 kilograms of softening waters, 800 kilograms of methyl methacrylates, 200 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 50 kilograms on nanometer titanium dioxide zinc.Embodiment 9 preparation methods such as embodiment 1.
Embodiment 10
1500 kilograms of softening waters, 800 kilograms of methyl methacrylates, 200 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 100 kilograms on nanometer titanium dioxide zinc.Embodiment 10 preparation methods such as embodiment 1.
Embodiment 11
1500 kilograms of softening waters, 800 kilograms of methyl methacrylates, 200 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 150 kilograms on nanometer titanium dioxide zinc.Embodiment 11 preparation methods such as embodiment 1.
Embodiment 12
1500 kilograms of softening waters, 800 kilograms of methyl methacrylates, 200 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 200 kilograms on nanometer titanium dioxide zinc.Embodiment 12 preparation methods such as embodiment 1.
Embodiment 13
1500 kilograms of softening waters, 1000 kilograms of methyl methacrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, 200 kilograms on nanometer titanium dioxide zinc.Embodiment 13 preparation methods such as embodiment 1.
Comparative Examples 1
1500 kilograms of softening waters, 900 kilograms of methyl methacrylates, 100 kilograms of butyl acrylates, 1 kilogram of Potassium Persulphate, 15 kilograms of sodium laurylsulfonates, among Comparative Examples 1 preparation method, all the other are as embodiment 1 except not adding the nanometer zinc oxide.
Comparative Examples 2
1500 kilograms of softening waters, 800 kilograms of methyl methacrylates, 200 kilograms of butyl acrylates, 1.1 kilograms of Potassium Persulphates, 12 kilograms of sodium laurylsulfonates, among Comparative Examples 2 preparation methods, all the other are as embodiment 1 except not adding the nanometer zinc oxide.
Experimental result is as follows:
1, embodiment 1～13 and Comparative Examples 1～2 are carried out that performance index detect and cost is estimated as shown in table 1 belowly, wherein cost keeping is according to the market value of in late December, 2011.
Table 1 polymer performance index and cost table
Annotate: asterisk more multilist shows that the graininess flowability is more good.
2, the mensuration of PVC product surface smooth finish:
Each 1.5 weight part of multipolymer with preparing in embodiment 1～13 and the Comparative Examples 1～2 join in the following prescription, make 15 parts in test material, test its smooth finish respectively:
It is as follows to fill a prescription, and each component is in parts by weight:
Above-mentioned each component is joined in the high-speed mixer, open and stir, when temperature is elevated to 110 degrees centigrade, the cooling blowing when temperature is reduced to room temperature, uses twin screw section bar forcing machine to produce section bar, the section bar any surface finish degree that observation makes, the result is as shown in table 2 below:
The bright and clean kilsyth basalt of the PVC section bar that table 2 is prepared
| Embodiment | Smooth finish (visual inspection) |
| Embodiment 1 | 3 stars |
| Embodiment 2 | 4 stars |
| Embodiment 3 | 5 stars |
| Embodiment 4 | 4 stars |
| Embodiment 5 | 5 stars |
| Embodiment 6 | 5 stars |
| Embodiment 7 | 4 stars |
| Embodiment 8 | 3 stars |
| Embodiment 9 | 4 stars |
| Embodiment 10 | 4 stars |
| Embodiment 11 | 5 stars |
| Embodiment 12 | 5 stars |
| Embodiment 13 | 5 stars |
| Comparative Examples 1 | 3 stars |
| Comparative Examples 2 | 3 stars |
Annotate: asterisk more multilist shows that bright and clean degree is more high.
By above experimental result as can be known, embodiment 1～13 is owing to adopt nanometer titanium dioxide zinc modification acrylic ester high molecular type polymkeric substance, the polymkeric substance cost that makes reduces, and the graininess good fluidity, best is 5 stars, the PVC section bar any surface finish degree height of preparing thus, the highest 5 stars that also reach, and Comparative Examples 1～2 graininess flowability generally has only 2 stars, and any surface finish degree is also general, has only 3 stars.
Claims (7)
1. a nanometer titanium dioxide zinc modification esters of acrylic acid linear macromolecule polymkeric substance is characterized in that: in methyl methacrylate and butyl acrylate copolymerization or methyl methacrylate homopolymerization process, add nanometer titanium dioxide zinc and make; Wherein methyl methacrylate and butyl acrylate weight percent are 5～100: 95～0, and nanometer titanium dioxide zinc consumption is 0.1～20% of polymerization single polymerization monomer gross weight.
2. the method for making of the described nanometer titanium dioxide zinc modification of claim 1 an esters of acrylic acid linear macromolecule polymkeric substance, it is characterized in that: in reactor, add water, open and stir, 60～75 rev/mins of mixing speed, add emulsifying agent, methyl methacrylate and butyl acrylate, the capping still; Open heating, when reactor temperature reaches 65～68 ℃, add initiator, when reactor temperature began to rise, polyreaction began in the reactor, opened the cooling water for cooling this moment, when temperature rises to the summit, no longer rise and when beginning to descend, in still, add nanometer titanium dioxide zinc; When temperature continues to drop to 60～65 ℃, close cooling water, when treating that temperature in the kettle drops to 45～48 ℃ naturally, blowing, drying obtains Powdered nanometer titanium dioxide zinc modification esters of acrylic acid linear polymeric polymkeric substance.
3. the method for making of nanometer titanium dioxide zinc modification esters of acrylic acid linear macromolecule polymkeric substance according to claim 2 is characterized in that described emulsifying agent is sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or OP-10.
4. according to the method for making of claim 2 or 3 described nanometer titanium dioxide zinc modification esters of acrylic acid linear macromolecule polymkeric substance, it is characterized in that described emulsifying agent consumption is 0.1～3% of polymerization single polymerization monomer gross weight.
5. the method for making of nanometer titanium dioxide zinc modification esters of acrylic acid linear macromolecule polymkeric substance according to claim 2 is characterized in that described initiator is Potassium Persulphate or Sodium Persulfate.
6. according to the method for making of claim 2 or 5 described nanometer titanium dioxide zinc modification esters of acrylic acid linear macromolecule polymkeric substance, it is characterized in that described initiator amount is 0.05～0.5% of polymerization single polymerization monomer gross weight.
7. the method for making of nanometer titanium dioxide zinc modification esters of acrylic acid linear macromolecule polymkeric substance according to claim 2, the consumption that it is characterized in that described water is 1.3～1.6 times of polymerization single polymerization monomer gross weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110453962.9A CN103183771B (en) | 2011-12-30 | 2011-12-30 | Nano zinc dioxide impact-resistant modification acrylate class linear macromolecule polymkeric substance and method for making |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110453962.9A CN103183771B (en) | 2011-12-30 | 2011-12-30 | Nano zinc dioxide impact-resistant modification acrylate class linear macromolecule polymkeric substance and method for making |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103183771A true CN103183771A (en) | 2013-07-03 |
| CN103183771B CN103183771B (en) | 2016-01-20 |
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| CN201110453962.9A Expired - Fee Related CN103183771B (en) | 2011-12-30 | 2011-12-30 | Nano zinc dioxide impact-resistant modification acrylate class linear macromolecule polymkeric substance and method for making |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1554681A (en) * | 2003-12-26 | 2004-12-15 | 中国科学院山西煤炭化学研究所 | Acrylic ester modifier and preparation and use in bisphenol A poly carbonate |
| WO2007112503A1 (en) * | 2006-04-03 | 2007-10-11 | The University Of Sydney | Polymer product and interfacial polymerisation process using raft agent |
| CN101372527A (en) * | 2008-10-21 | 2009-02-25 | 河北科技大学 | Nano-zinc oxide/acrylic ester grafting composite emulsion and preparation thereof |
-
2011
- 2011-12-30 CN CN201110453962.9A patent/CN103183771B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1554681A (en) * | 2003-12-26 | 2004-12-15 | 中国科学院山西煤炭化学研究所 | Acrylic ester modifier and preparation and use in bisphenol A poly carbonate |
| WO2007112503A1 (en) * | 2006-04-03 | 2007-10-11 | The University Of Sydney | Polymer product and interfacial polymerisation process using raft agent |
| CN101372527A (en) * | 2008-10-21 | 2009-02-25 | 河北科技大学 | Nano-zinc oxide/acrylic ester grafting composite emulsion and preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨凡等: "聚丙烯酸酯接枝纳米ZnO 弹性体的制备及其对POM光稳定性的研究", 《塑料工业》 * |
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