CN1438255A - Method for preparing nano montmorillonite-phenylethylene in-situ intercalation polymer - Google Patents
Method for preparing nano montmorillonite-phenylethylene in-situ intercalation polymer Download PDFInfo
- Publication number
- CN1438255A CN1438255A CN 03115777 CN03115777A CN1438255A CN 1438255 A CN1438255 A CN 1438255A CN 03115777 CN03115777 CN 03115777 CN 03115777 A CN03115777 A CN 03115777A CN 1438255 A CN1438255 A CN 1438255A
- Authority
- CN
- China
- Prior art keywords
- vinylbenzene
- polynite
- polymkeric substance
- ammonium
- dimethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a method of making nano montmorillonite-styrene in-situ intercalation polymer, adopting positive-ion exchange to decorate layer-shaped inorganic nano montmorillonite material and organic intercalating agent, processing the decorated earth by dispersant to make the earth and the styrene form stable and even colloid solution, and then making in-situ polymerization to get it.
Description
Technical field:
The present invention relates to the preparation method of the in-situ inserted polymkeric substance of a kind of nano imvite-vinylbenzene, relate in particular to and a kind ofly polynite is modified and the polynite of modified is handled with dispersion agent with organic intercalation agent, make polynite and vinylbenzene form stabilized uniform colloidal solution, carry out in-situ polymerization then and obtain the novel method of polynite-vinylbenzene intercalation polymeric thing.The invention belongs to the polymkeric substance synthesis technical field.
Background technology:
Add mineral filler in the polymkeric substance and be for the intensity, modulus, barrier, thermotolerance, the dimensional stability that improve polymkeric substance and reduce cost etc., but tend to make that material becomes fragile, degradation under the transparency.And nano composite material can overcome the defective of common matrix material, when keeping former flexible of material and transparency, can also improve other performances of material such as tensile strength, modulus, barrier, thermotolerance, dimensional stability etc., so nano composite material more and more is subjected to paying attention to widely.Wherein nano imvite is a kind of typical natural layered silicate, and it is by the multiple stratum reticulare structure that two-layer silicon-oxy tetrahedron therebetween one alumina octahedral constitutes, and its interlamellar spacing is bigger, and polymer molecular chain easily is diffused into its interlayer and forms nano composite material.First polymkeric substance Nano composite material of montmorillonite that commercial value is arranged be 1987 by Japanese Toyota researchdevelopment center synthetic nylon 6/ clay nano hybrid materials, this material loses under the prerequisite of shock strength, toughness and transparency hardly, can improve the tensile strength and (the Usuki A.and Kojoma Y. such as tensile modulus, bending strength and composite bending modulus, heat-drawn wire, flame retardant resistance and barrier properties for gases of material significantly, Polym.Prepr., 28-447,1987).The quality of polynite and polymer phase capacitive directly has influence on performance of composites, and polystyrene is a non-polar polymer, and the consistency of it and polynite is relatively poor, is difficult to obtain the nano composite material of excellent performance.In order to obtain polystyrene/Nano composite material of montmorillonite, people (MasamiOkamoto such as Masami Okamoto, Satoshi Morita, Hideyuki Taguchi, Yong Hoon Kim, Tadao Kotaka andHiroshi Tateyama, Polymer, 41:3887-3890,2000) and people (XaoanFu and Syed Qutubuddin such as Syed Qutubuddin, Materials Letters, 42:12-15,2000) when modification is carried out in polynite with organic intercalation agent, it is compound and obtain nano composite material to adopt hyperacoustic method to make vinylbenzene and polynite carry out original position, they have adopted ultrasonic device polynite and vinylbenzene to be mixed and then the polymeric method, the equipment requirements height, and noise pollution is big, mixing time is long, efficient is low, only is suitable for laboratory scale, and is not suitable for producing in enormous quantities.
Summary of the invention:
The objective of the invention is at the deficiencies in the prior art, the preparation method of the in-situ inserted polymkeric substance of a kind of nano imvite-vinylbenzene is proposed, technology is simple, do not need specific installation, cost is low, be suitable for scale operation, and the performance of material keeps the impelling strength of original polystyrene substantially, can also improve its tensile strength simultaneously and increase molecular weight.
For realizing such purpose, in technical scheme of the present invention, adopted elder generation that polynite is modified with organic intercalation agent, the polynite of modified is handled with dispersion agent again, last and vinylbenzene carries out original position compound preparation method, thereby prepares the in-situ inserted polymkeric substance of nano imvite-vinylbenzene.
Inventive method is carried out as follows:
1, adopt base exchange method that organic intercalation agent is carried out in the inorganic nano polynite and modify, with 1 part in nano imvite powder, solvent 5-50 part high-speed stirring, rotating speed is 500-4000 rev/min, forms the suspension of stable polynite; The organic intercalation agent that adds 0.003-3 part in 10 parts of solvents stirs and makes it abundant dissolving, then this solution 0.5-3 part is joined in the suspension of polynite under 20-300 ℃ of temperature vigorous stirring 0.5-100 hour.After the filtration throw out is washed with hot solvent, stirred 0.5-10 hour, filter.Washing process repeats 2-5 time, to remove wherein remaining organism, with final product in 60 ℃ of following vacuum-dryings.
2, be to mix 5-60 minute on 500-6000 rev/min the high-speed mixer with the dispersion agent of organo montmorillonite 80-99.9 part of obtaining in the step 1 and 0.1-20 part, thereby make the polynite that can form stable and uniform colloidal solution with vinylbenzene at 30-120 ℃, rotating speed.
3, in polymerization equipment, be that nano imvite material in the step 2 of 0.05%-40% and the weight percent styrene monomer that is 60%-99.95% is at room temperature even with magnetic stirrer with weight percent, add 0.5 ‰-5% the initiator be equivalent to vinylbenzene weight again, 40-150 ℃ of following isothermal polymerization 4-50 hour, make the in-situ inserted polymkeric substance of nano imvite-vinylbenzene.
Inorganic nano polynite of the present invention is for to be of a size of nano level at least on the one dimension direction, the disperse phase yardstick is the 1-100 nanometer.
Solvent of the present invention is toluene, dimethylbenzene, perhydronaphthalene, whiteruss, kerosene, water, ethanol, methyl alcohol, acetone.
Organic intercalation agent of the present invention is the hexadecyl brometo de amonio, the n-cetyltrimethyl ammonium, dimethyl benzene ethyl dodecyl chlorination ammonium, two dodecyl chlorination ammoniums, octadecyl bromination ammonium, cetyl trimethylammonium bromide, methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride, two octadecyl bromination ammoniums, hexadecyl-phenyl-azo pyridine ammonium chloride, vinyl benzyl-dimethyl dodecyl chlorination ammonium, vinyl benzyl-dimethyl cetyl chloride ammonium, methylacryoyloxyethyl-benzyl-dimethyl brometo de amonio, two octadecyl bromination ammoniums, the 3,5-dimethylphenyl octadecyl ammonium chloride, dimethyl stearyl ammonium chloride, vinyl benzyl-dimethyl dodecyl bromination ammonium.
Dispersion agent of the present invention is whiteruss, Resins, epoxy, silane coupling agent, metatitanic acid coupling agent, silicone oil, vulcabond, glycerine, ethylene glycol.
Initiator of the present invention is azo-bis-isobutyl cyanide (AIBN), dicumyl peroxide (DCP), benzamide (BPO), t-butyl peroxide (TBP).
The present invention has overcome vinylbenzene and polynite is difficult to the blended weakness, technology is simple, do not need specific installation, cost is low, be suitable for scale operation, and improved its tensile strength and increased molecular weight when the performance of material has kept the impelling strength of original polystyrene substantially, and heat decomposition temperature also obviously improves 20-80 ℃, and the wide industrial application prospect is arranged.
Embodiment:
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1:
Add 0.387mol dimethyl stearyl ammonia chloride in the beaker of 500ml, 0.047mol concentrated hydrochloric acid and 100ml deionized water are heated to 80 ℃ with this solution, make dimethyl stearyl ammonium chloride intercalator.In addition, 50 gram polynites are dispersed in 400ml80 ℃ the solvent deionized water, stir.Dispersion liquid with this polynite joins in the solution that contains dimethyl stearyl ammonium chloride intercalator then, and vigorous stirring 1 hour.After the filtration white precipitate is placed the beaker of 500ml, add 400ml hot water, stirred 1 hour, and filter.This process repeats more than three times, to remove wherein residual ammonium salt.Final product filtration and cooling drying is standby.Be to mix 20 minutes on 800 rev/mins the high-speed mixer then with the organo montmorillonite that makes 45 grams and the 0.6 dispersion agent vulcabond that restrains, thereby make the polynite that can form stable and uniform colloidal solution with vinylbenzene at 80 ℃, rotating speed.The above-mentioned polynite that obtains 5 grams are made it to mix with magnetic stirrer in large beaker with 100ml vinylbenzene, add 0.5g initiator azo-bis-isobutyl cyanide, restir is even, 80 ℃ of pre-polymerizations of constant temperature 30 minutes, then 60 ℃ of following constant temperature polymerizations 24 hours, obtain the in-situ inserted polymkeric substance of nano imvite-vinylbenzene, this mixture is than using the pure stretched polystyrene intensity with the method preparation to improve 20%, molecular weight improves 2 times, heat decomposition temperature has improved 35 ℃, and impact property remains unchanged substantially.
Embodiment 2:
Add 0.483mol methylacryoyloxyethyl-benzyl-dimethyl chlorination amine in the beaker of 500ml, 0.058mol concentrated hydrochloric acid and 100ml deionized water are heated to 90 ℃ with this solution, make methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride intercalator.In addition, 45 gram polynites are dispersed in 500ml90 ℃ the solvent deionized water, stir.Dispersion liquid with this polynite joins in the solution that contains methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride intercalator then, and vigorous stirring 1 hour.After the filtration white precipitate is placed the beaker of 1000ml, add 700ml hot water, stirred 1 hour, and filter.This process repeats more than three times, to remove wherein residual ammonium salt.Final product filtration and cooling drying is standby.Be to mix 15 minutes on 600 rev/mins the high-speed mixer then with the organo montmorillonite that makes 30 grams and the 0.4 dispersant liq paraffin that restrains, thereby make the polynite that can form stable and uniform colloidal solution with vinylbenzene at 70 ℃, rotating speed.The above-mentioned polynite that obtains 3 grams are made it to mix with magnetic stirrer in large beaker with 100ml vinylbenzene, add 0.5g initiator benzamide, restir is even, 100 ℃ of pre-polymerizations of constant temperature 30 minutes, then 80 ℃ of following constant temperature polyase 13s 0 hour, obtain the in-situ inserted polymkeric substance of nano imvite-vinylbenzene, this mixture is than using the pure stretched polystyrene intensity with the method preparation to improve 30%, molecular weight improves 1.6 times, heat decomposition temperature has improved 48 ℃, and impact property remains unchanged substantially.
Embodiment 3:
Add 0.437mol octadecyl bromination amine in the beaker of 500ml, 0.053mol concentrated hydrochloric acid and 250ml deionized water are heated to 70 ℃ with this solution, make octadecyl bromination ammonium intercalator.In addition, 45 gram polynites are dispersed in 500ml90 ℃ the etoh solvent, stir.Dispersion liquid with this polynite joins in the solution that contains the agent of octadecyl bromination ammonium layer then, and vigorous stirring 2 hours.After the filtration white precipitate is placed the beaker of 1000ml, add 750ml hot water, stirred 1.5 hours, and filter.This process repeats more than three times, to remove wherein residual ammonium salt.Final product filtration and cooling drying is standby.Be to mix 30 minutes on 700 rev/mins the high-speed mixer then with the organo montmorillonite that makes 45 grams and the 0.6 dispersion agent silane coupling agent that restrains, thereby make the polynite that can form stable and uniform colloidal solution with vinylbenzene at 75 ℃, rotating speed.The above-mentioned polynite that obtains 4 grams are made it to mix with magnetic stirrer in large beaker with 100ml vinylbenzene, add 0.5g initiator dicumyl peroxide (DCP), restir is even, constant temperature 110 pre-polymerizations 50 minutes, then 90 ℃ of following constant temperature polymerizations 48 hours, obtain the in-situ inserted polymkeric substance of nano imvite-vinylbenzene, this mixture is than using the pure stretched polystyrene intensity with the method preparation to improve 24%, molecular weight improves 1.4 times, heat decomposition temperature has improved 70 ℃, and impact property remains unchanged substantially.
Embodiment 4:
Add the two dodecyl chlorination amine of 0.461mol in the beaker of 500ml, 0.057mol concentrated hydrochloric acid and 300ml deionized water are heated to 70 ℃ with this solution, make two dodecyl chlorination amine intercalators.In addition, 50 gram polynites are dispersed in 400ml85 ℃ the solvent glycerin, stir.Then the dispersion liquid of this polynite is joined in the solution that contains two dodecyl chlorination amine intercalators, and vigorous stirring 0.5 hour.After the filtration white precipitate is placed the beaker of 1000ml, add 650ml hot water, stirred 1 hour, and filter.This process repeats more than three times, to remove wherein residual ammonium salt.Final product filtration and cooling drying is standby.Be to mix 40 minutes on 800 rev/mins the high-speed mixer then with the organo montmorillonite that makes 35 grams and the 0.4 dispersion agent Resins, epoxy that restrains, thereby make the polynite that can form stable and uniform colloidal solution with vinylbenzene at 70 ℃, rotating speed.The above-mentioned polynite that obtains 3.5 grams are made it to mix with magnetic stirrer in large beaker with 100ml vinylbenzene, add 0.3g initiator azo-bis-isobutyl cyanide, restir is even, 90 ℃ of pre-polymerizations of constant temperature 20 minutes, then 70 ℃ of following constant temperature polymerase 17s 2 hours, obtain the in-situ inserted polymkeric substance of nano imvite-vinylbenzene, this mixture is than using the pure stretched polystyrene intensity with the method preparation to improve 20%, molecular weight improves 1.6 times, heat decomposition temperature has improved 72 ℃, and impact property remains unchanged substantially.
Claims (6)
1, the preparation method of the in-situ inserted polymkeric substance of a kind of nano imvite-vinylbenzene is characterized in that carrying out as follows:
1) adopt base exchange method that organic intercalation agent is carried out in the inorganic nano polynite and modify, with 1 part in nano imvite powder, solvent 5-50 part high-speed stirring, rotating speed is 500-4000 rev/min, forms the suspension of stable polynite; The organic intercalation agent that in 10 parts of solvents, adds 0.003-3 part, stirring makes it abundant dissolving, then this solution 0.5-3 part is joined in the suspension of polynite, under 20-300 ℃ of temperature vigorous stirring 0.5-100 hour, after the filtration throw out is washed with hot solvent, stirred 0.5-10 hour, filter, washing process repeats 2-5 time, to remove wherein remaining organism, with final product in 60 ℃ of following vacuum-dryings;
2) be to mix 5-60 minute on 500-6000 rev/min the high-speed mixer with the dispersion agent of organo montmorillonite 80-99.9 part of obtaining in the step 1 and 0.1-20 part, thereby make the polynite that can form stable and uniform colloidal solution with vinylbenzene at 30-120 ℃, rotating speed;
3) in polymerization equipment, be that nano imvite material in the step 2 of 0.05%-40% and the weight percent styrene monomer that is 60%-99.95% is at room temperature even with magnetic stirrer with weight percent, add 0.5 ‰-5% the initiator be equivalent to vinylbenzene weight again, 40-150 ℃ of following isothermal polymerization 4-50 hour, make the in-situ inserted polymkeric substance of nano imvite-vinylbenzene.
2, the preparation method of the in-situ inserted polymkeric substance of nano imvite-vinylbenzene as claimed in claim 1 is characterized in that described inorganic nano polynite for to be of a size of nano level at least on the one dimension direction, and the disperse phase yardstick is the 1-100 nanometer.
3, the preparation method of the in-situ inserted polymkeric substance of nano imvite-vinylbenzene as claimed in claim 1 is characterized in that described solvent is toluene, dimethylbenzene, perhydronaphthalene, whiteruss, kerosene, water, ethanol, methyl alcohol, acetone.
4, the preparation method of the in-situ inserted polymkeric substance of nano imvite-vinylbenzene as claimed in claim 1 is characterized in that described organic intercalation agent is the hexadecyl brometo de amonio, the n-cetyltrimethyl ammonium, dimethyl benzene ethyl dodecyl chlorination ammonium, two dodecyl chlorination ammoniums, octadecyl bromination ammonium, cetyl trimethylammonium bromide, methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride, two octadecyl bromination ammoniums, hexadecyl-phenyl-azo pyridine ammonium chloride, vinyl benzyl-dimethyl dodecyl chlorination ammonium, vinyl benzyl-dimethyl cetyl chloride ammonium, methylacryoyloxyethyl-benzyl-dimethyl brometo de amonio, two octadecyl bromination ammoniums, the 3,5-dimethylphenyl octadecyl ammonium chloride, dimethyl stearyl ammonium chloride, vinyl benzyl-dimethyl dodecyl bromination ammonium.
5, the preparation method of the in-situ inserted polymkeric substance of nano imvite-vinylbenzene as claimed in claim 1 is characterized in that described dispersion agent is whiteruss, Resins, epoxy, silane coupling agent, metatitanic acid coupling agent, silicone oil, vulcabond, glycerine, ethylene glycol.
6, the preparation method of the in-situ inserted polymkeric substance of nano imvite-vinylbenzene as claimed in claim 1 is characterized in that described initiator is azo-bis-isobutyl cyanide (AIBN), dicumyl peroxide (DCP), benzamide (BPO), t-butyl peroxide (TBP).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03115777 CN1216085C (en) | 2003-03-13 | 2003-03-13 | Method for preparing nano montmorillonite-phenylethylene in-situ intercalation polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03115777 CN1216085C (en) | 2003-03-13 | 2003-03-13 | Method for preparing nano montmorillonite-phenylethylene in-situ intercalation polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1438255A true CN1438255A (en) | 2003-08-27 |
| CN1216085C CN1216085C (en) | 2005-08-24 |
Family
ID=27674130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03115777 Expired - Fee Related CN1216085C (en) | 2003-03-13 | 2003-03-13 | Method for preparing nano montmorillonite-phenylethylene in-situ intercalation polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1216085C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400607C (en) * | 2004-09-20 | 2008-07-09 | 中国科学院化学研究所 | Preparation method of heat stability reinforced nano-montmorillonite |
| CN101705079A (en) * | 2009-10-28 | 2010-05-12 | 无锡润鹏复合新材料有限公司 | Method for preparing novel solid lubricant microspheres for drilling fluid |
| CN101010367B (en) * | 2004-07-14 | 2010-12-15 | 新加坡科技研究局 | Nanometer composite material and its preparing method |
| CN104744842A (en) * | 2015-03-24 | 2015-07-01 | 合肥会通新材料有限公司 | Polystyrene composite material reinforced by in situ-polymerization of montmorillonite intercalation and preparation method of polystyrene composite material |
| CN107057118A (en) * | 2017-04-19 | 2017-08-18 | 江苏海明斯新材料科技有限公司 | A kind of preparation method of enhancing by polymer copolymer resins intercalation modifying nanoscale organic silicic acid magnesium lithium |
| CN109745962A (en) * | 2019-03-15 | 2019-05-14 | 南京大学 | A kind of mixed and modified organo montmorillonite and its synthetic method and application |
| CN112812370A (en) * | 2021-01-05 | 2021-05-18 | 深圳市锦昊辉实业发展有限公司 | Inorganic flame retardant, preparation method thereof and application thereof in preparing sealant |
-
2003
- 2003-03-13 CN CN 03115777 patent/CN1216085C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101010367B (en) * | 2004-07-14 | 2010-12-15 | 新加坡科技研究局 | Nanometer composite material and its preparing method |
| CN100400607C (en) * | 2004-09-20 | 2008-07-09 | 中国科学院化学研究所 | Preparation method of heat stability reinforced nano-montmorillonite |
| CN101705079A (en) * | 2009-10-28 | 2010-05-12 | 无锡润鹏复合新材料有限公司 | Method for preparing novel solid lubricant microspheres for drilling fluid |
| CN101705079B (en) * | 2009-10-28 | 2013-04-17 | 无锡润鹏复合新材料有限公司 | Method for preparing novel solid lubricant microspheres for drilling fluid |
| CN104744842A (en) * | 2015-03-24 | 2015-07-01 | 合肥会通新材料有限公司 | Polystyrene composite material reinforced by in situ-polymerization of montmorillonite intercalation and preparation method of polystyrene composite material |
| CN107057118A (en) * | 2017-04-19 | 2017-08-18 | 江苏海明斯新材料科技有限公司 | A kind of preparation method of enhancing by polymer copolymer resins intercalation modifying nanoscale organic silicic acid magnesium lithium |
| CN107057118B (en) * | 2017-04-19 | 2018-10-16 | 江苏海明斯新材料科技有限公司 | A kind of preparation method of enhancing by polymer copolymer resins intercalation modifying nanoscale organic silicic acid magnesium lithium |
| CN109745962A (en) * | 2019-03-15 | 2019-05-14 | 南京大学 | A kind of mixed and modified organo montmorillonite and its synthetic method and application |
| WO2020186795A1 (en) * | 2019-03-15 | 2020-09-24 | 南京大学 | Mixed modified organic montmorillonite, synthesis method thereof, and application thereof |
| CN112812370A (en) * | 2021-01-05 | 2021-05-18 | 深圳市锦昊辉实业发展有限公司 | Inorganic flame retardant, preparation method thereof and application thereof in preparing sealant |
| CN112812370B (en) * | 2021-01-05 | 2022-12-27 | 深圳市锦昊辉实业发展有限公司 | Inorganic flame retardant, preparation method thereof and application thereof in preparing sealant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1216085C (en) | 2005-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103275355B (en) | Organic modified molybdenum disulfide nanosheet layer and preparation method thereof | |
| CN107325268B (en) | graphene/PET (polyethylene terephthalate) nano composite material and preparation method thereof | |
| CN100347201C (en) | Method of preparing polymer/montmorillonid nano-composite material by montmorillonoid in-situ organization | |
| CN1865319A (en) | Process for preparing nano grade amino silicon oil emulsion | |
| CN107722352A (en) | A kind of chain alkyl amino-functionalization graphene and preparation method thereof | |
| CN1792961A (en) | Engineering material synthesized by mica | |
| CN103910997A (en) | Permanent antistatic antibacterial polyamide 6/polypropylene composite material | |
| CN1951979A (en) | Conductive polyanion/starch shell-core type composite microsphere and its preparation method | |
| CN1216085C (en) | Method for preparing nano montmorillonite-phenylethylene in-situ intercalation polymer | |
| Yang et al. | Preparation of uniform silica/polypyrrole core/shell microspheres and polypyrrole hollow microspheres by the template of modified silica particles using different modified agents | |
| CN102875973A (en) | Modified carbon nanotube/thermosetting resin composite and preparation method thereof | |
| CN102372811A (en) | Preparation method of macroporous organic/inorganic nanometer composite resin | |
| CN1884393A (en) | Transparent ferric oxide easily disperse in organic medium and its production method | |
| CN100427511C (en) | Dispersion and directional arraying method of carbon nanotube based magnetic material in polymer | |
| CN100358943C (en) | Process for preparing carbon nano pipe/polyhenylethylene nano conducting composite | |
| CN111574984A (en) | Method for modifying polymer, compound polymer prepared by method and application of compound polymer | |
| CN108676164B (en) | Preparation method of polymer hybrid hollow microspheres through click chemical interface reaction | |
| CN107629297B (en) | Polyethylene/polystyrene/organic modified montmorillonite composite material and preparation method thereof | |
| CN1775850A (en) | Montmorillonite/rare-earth particle/polymer ternary nano composite material and its preparing method | |
| CN1256378C (en) | Method for preparing nano composite material of polyethylene/montmorillonite | |
| CN1291991C (en) | Preparation method of multihydroxy sesqui siloxane | |
| CN105693959B (en) | The preparation method of magnetic molecularly imprinted polymer with hydrogen bond array | |
| CN1431255A (en) | Luminous nano composite material and its preparing method | |
| CN1209408C (en) | Polypropylene composite material capable of sending blue green light under the condition of UV tigght irradiation | |
| CN1966586A (en) | Reactive, monodispersed surface modified silver nanoparticle and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |