CN103030716A - Preparation method of modified dialkylene polymer - Google Patents
Preparation method of modified dialkylene polymer Download PDFInfo
- Publication number
- CN103030716A CN103030716A CN2012105854451A CN201210585445A CN103030716A CN 103030716 A CN103030716 A CN 103030716A CN 2012105854451 A CN2012105854451 A CN 2012105854451A CN 201210585445 A CN201210585445 A CN 201210585445A CN 103030716 A CN103030716 A CN 103030716A
- Authority
- CN
- China
- Prior art keywords
- preparation
- diene
- molecular weight
- polymer
- functional group
- 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
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a preparation method of a modified dialkylene polymer, which comprises the following steps that: a) the dialkylene polymer is dissolved in an organic solvent to form a dialkylene polymer solution; b) a molecular weight regulator is mixed with the dialkylene polymer solution to form a mixed solution which conducts crossed metathesis reaction under the action of a catalyst to form the modified dialkylene polymer; the molecular weight regulator has a double bond and a first polar functional group; the two ends of the modified dialkylene polymer contain second polar functional groups; and the first polar functional group is the same with or different from the second polar functional groups. With the adoption of the preparation method provided by the invention, the polar functional groups can be grafted on dialkylene polymer molecules while the molecular weight of the dialkylene polymer is reduced; the operation is simple; the reaction conditions are mild; and the preparation method is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the polymkeric substance preparation field, be specifically related to a kind of preparation method of modified diene based polyalcohol.
Background technology
Diene-based polymer is a kind of high molecular polymer that is polymerized by diene monomers.Because it has stable performance, higher molecular weight and narrower molecular weight distribution, diene-based polymer has been widely used in the middle of industrial production and the commercial field.But the processing characteristicies such as flowability, cohesiveness and winter hardiness are undesirable.Also limited the application of diene-based polymer in specific area.In order to overcome above-mentioned shortcoming, can in diene monomers, add some mineral fillers in the Industrial processes, though can satisfy ask for something, mineral filler is difficult for disperseing in polymkeric substance, therefore with the compatible relative decline of other materials; The opposing party's rule is to introduce corresponding functional group at polymer chain backbone end or side chain, and these functional groups can not only make polymkeric substance possess new character, and can keep the original advantageous property of polymkeric substance, thereby satisfies the requirement of production application.In order to reach above-mentioned requirements, polymericular weight should be lowered as requested, and functional group also should be grafted on the polymer chain.Though traditional chemical modification method can be introduced functional group in polymer chain, but relatively bother, and also unrealistic with traditional chemical process cut-out molecular chain.
Can realize that at present the diene-based polymer modification mainly comprises following several, at Can.J.Chem., among 79, the 775-779 (2001) summary before cis-1,4-polybutadiene rubber introduce functional group by the cross metathesis reaction or reduce the work of molecular weight.At " Olefin metathesis and metathesis polymerization ", 16th, p.379-380 in (1997) just by the agency of before the invention of Ge Labu catalyzer, the cross metathesis reaction that cis-1,4-polybutadiene rubber just occurs under the catalysis of mixed catalyst, and at Macromol.Chem., Rapid Commun., 12,419-425 (1991) and Macromol., 36, among the 9675-9677 (2003), disclose, the cis-1,4-polybutadiene rubber polymer chain is in the situation that ethene, vinyl alcohol small-numerator olefin exist is sheared successfully; After the Ge Labu catalyzer occurs, shake pawl polyhutadiene such as acetoxyl, hydroxyl is the polyhutadiene of terminal functionality, obtain by olefin metathesis reactions, these contents are also at Polymer, 42,4939-4945 (2001), Macromol., 33,1494-1496 (2000) and Polymer Degradation and Stability, the open introduction among 96, the 1074-1080 (2011).In addition, Macromol., 25,5137-5144 (1992), Macromol., 26,872-874 (1993) and Macromol., 26,2137-2138 (1993) has set forth the alkene that contains silicon substrate and also as molecular weight regulator and the supplier of functional group polyhutadiene has been carried out chain under the catalysis of W/Mo and forge and shear and functional group's grafting, obtained f=2.0 bifunctional shake the pawl oligopolymer.Pass through ROMP, 1, the 4-polyhutadiene can synthesize ring polyhutadiene, segmented copolymer and brush type polymkeric substance also have been published at Macromol., 42,6927-6931 (2009), Macromol., 28,2602-2606 (1995) and Polymer, among 41, the 827-830 (2000).
In addition, at USP10,156,916B, US6,867,274, US7, in 022,789, by functionalized hydroxyl, ester group or acyclic olefin small molecules comes modified polymer to comprise polyhutadiene with containing suitably, introduce the functional group that wishes, but the method for introducing ester group herein is to obtain by the ring-opening metathesis polymerization method; US Patent No. 3,692 in addition, and 872, US4,010,244 discloses grafting and the segmented copolymer that utilizes the alkene ring opening metathesis polymerization to prepare polyhutadiene or polyisoprene.
Aforesaid method adopts free radical technology or other catalyzer and other olefin metathesis reactions types that diene-based polymer especially cis-1,4-polybutadiene rubber is carried out grafted functional group or reduces the molecular weight modification, yet also in the diene-based polymer chain, do not introduce ester group isopolarity functional group by the cross metathesis mode so far, simultaneously autotelic adjustment diene-based polymer molecular weight.At this, we wish to provide a kind of relatively easy method that can reach again the modification purpose, so that products obtained therefrom has the performance of expectation.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of can be when adjusting polymericular weight on described polymer molecule the preparation method of the modified diene based polyalcohol of grafting polar functional group.
In order to solve above technical problem, the invention provides a kind of preparation method of modified diene polymer, may further comprise the steps:
A) diene-based polymer is dissolved in the organic solvent, obtains diene-based polymer solution;
B) molecular weight regulator is mixed with described diene-based polymer solution, obtain mixing solutions, and the cross metathesis reaction occurs under the effect of catalyzer, obtain the modified diene based polyalcohol;
Described molecular weight regulator has two keys and the first polar functional group; The second memory functional group is contained at described modified diene based polyalcohol two ends; Described the first polar functional group and described the second polar functional group are identical or different.
Preferably, described diene-based polymer is cis-1,4-polybutadiene rubber, isoprene-isobutylene rubber, terpolymer EP rubber, paracril.
Preferably, described molecular weight regulator is acrylate and derivative, acrylamide and derivative thereof, vinyl cyanide and derivative thereof, is connected with alkene small molecules or its polymkeric substance of polar functional group on the unsaturated double-bond.
Preferably, the functionality f of described molecular weight regulator satisfies following condition: 1≤f≤3.
Preferably, to account for the weight percent of diene-based polymer be 0.01% ~ 3% to described molecular weight regulator.
Preferably, described catalyzer has structure shown in the formula I:
Wherein, M
ABe ruthenium or osmium;
X
AAnd X
BIt is identical or different anion ligand;
L
AAnd L
BIt is identical or different neutral electron-donating group;
R
AAnd R
BBe respectively hydrogen, aryl or aryloxy.
Preferably, described anion ligand is the halide-ions part.
Preferably, described neutral electron group is phosphorus-containing groups or assorted nitrogen Cabbeen.
Preferably, the temperature of reaction of described intersection dystopy reaction is 15 ~ 35 ℃.
Preferably, the reaction times of described intersection dystopy reaction is 5 ~ 150min.
The invention provides a kind of preparation method of modified diene based polyalcohol, with diene-based polymer and molecular weight regulator and catalyst mix, wherein said molecular weight regulator has two keys and polar functional group, under the effect of catalyzer, dystopy can occur to intersect with diene-based polymer and react in molecular weight regulator, the molecular chain of diene-based polymer is disconnected, form the shorter diene-based polymer of segment, and by the polar functional group end-blocking in the molecular weight regulator, finally obtaining having polarity group can roll into a ball, and molecular weight distribution is wider, the modified diene based polyalcohol of molecular weight.Improved the low-temperature performance of diene-based polymer, flowability and cohesiveness.
Description of drawings:
Fig. 1 is as the raw material cis-1,4-polybutadiene rubber in the embodiment alkene cross metathesis method and the infrared figure of polymethylmethacrylate and product;
Fig. 2 is the figure that affects that the different mass of diene-based polymer PB and MMA is compared molecular weight of product in the embodiment of the invention 1 ~ 10;
When the C=C mole was 1:1 among C=C and the MMA among the selection diene-based polymer PB that Fig. 3 embodiment of the invention 11 ~ 17 provides, the variation in reaction times was on the figure that affects of molecular weight of product.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that the just restriction for further specifying the features and advantages of the present invention rather than patent of the present invention being required of these descriptions.
The invention provides a kind of modification and the preparation method of olefin polymer comprises: following steps:
Diene-based polymer is mixed with molecular weight regulator, the cross metathesis reaction occurs under the effect of catalyzer, obtain the modified diene based polyalcohol;
Described molecular weight regulator has two keys and the first polar functional group; The second memory functional group is contained at described modified diene based polyalcohol two ends; Described the first polar functional group and described the second polar functional group are identical or different.
In the above-mentioned steps, described diene-based polymer is the direct or indirect diene-based polymer of modification, and described diene-based polymer is to have saturated or unsaturated diene polymerization to form.More preferably molecular weight is at 5000 ~ 100000 diene-based polymer, such as cis-1,4-polybutadiene rubber, and terpolymer EP rubber etc.Paracril, isoprene-isobutylene rubber etc., more preferably.Because molecular weight is larger, molecular weight distribution is narrower, processing difficulties, especially the sulfidation of rubber, so can use first method provided by the invention that molecular weight is partly reduced in first being processed, so that diene-based polymer can have preferred molecular weight and molecualr weight distribution, reduce difficulty of processing.
The step of most critical of the present invention is diene-based polymer is mixed with molecular weight regulator, and the selection of catalyzer and adding.When can the dystopy reaction occur to intersect with diene-based polymer, the diene-based polymer molecular chain is sheared, and carried out end-blocking by the polar functional group that contains on the described molecular weight regulator diene-based polymer molecular chain after to shearing.According to the present invention, described molecular weight regulator is elected acrylate and derivative, acrylamide and derivative thereof, vinyl cyanide and derivative thereof as, is connected with alkene small molecules or its polymkeric substance of polar functional group on the unsaturated double-bond.Methyl methacrylate (MMA) more preferably, β-dimethyl-aminoethylmethacrylate.Hydroxyethyl methylacrylate most preferably is MMA.
According to the present invention, the selection of catalyzer is also most important to method provided by the invention, must be able to impel diene-based polymer and molecular weight to adjust the dystopy reaction occurs to intersect.According to the present invention, described catalyzer is preferably has structure shown in the formula I:
Wherein, M
ABe ruthenium or osmium;
X
AAnd X
BIt can be identical or different anion ligand; The preferential group of selecting haloid element or containing haloid element.
L
AAnd L
BIt can be identical or different neutral electron-donating group; Preferential phosphorus-containing groups or the N-heterocyclic carbine selected;
R
AAnd R
BBe respectively hydrogen, aryl or aryloxy.
Above-mentioned catalyzer can contact with the molecular-weight adjusting agent molecule in reaction process, the dystopy reaction that occurs to intersect forms the metal carbene that contains functional group, then exchange occurs to shear in metal carbene and diene polymer, thereby the diene polymer molecular weight of macromolecule is reduced, and by the polar functional group end-blocking.Impel diene-based polymer and molecular weight regulator and the supplier of functional group that the cross metathesis reaction occurs, diene-based polymer is carried out modification, and this catalyzer consumption in catalytic process is few, the reaction times is short, can greatly reduce the cost in the industrial production.
The present invention provides a kind of adjustable diene-based polymer modification of both-end base stage functional group, molecular weight for preparing functionality f=2.0 now.The step of described method specifically comprises: diene-based polymer is dissolved in the organic solvent, obtain diene-based polymer solution, the mass concentration of diene-based polymer is 15 ~ 30% in the described diene-based polymer solution, more preferably 20 ~ 25%, most preferably be 22 ~ 24%.According to the present invention, described organic solvent is preferably 1,2 ethylene dichloride, glycol dibromide, chloroform or methylene dichloride.
After obtaining diene-based polymer solution, described molecular weight regulator is added in the described diene-based polymer solution, it is even that heating mixes solution processed, then described catalyzer is joined in the mixing solutions in described diene-based polymer and the molecular weight regulator, the dystopy of intersecting reaction, the product that obtains obtains the modified diene based polyalcohol through drying and distilling, drying.
The weight ratio that accounts for diene-based polymer according to molecular weight regulator of the present invention is preferably 0.01 ~ 3%, and more preferably 0.1% ~ 1%, most preferably be 0.2% ~ 0.8%;
Described Heating temperature is preferably 15 ~ 35 ℃, more preferably 20 ~ 30 ℃, most preferably is 22 ~ 28 ℃;
The time of described intersection dystopy reaction is preferably 5 ~ 150min, and more preferably 25 ~ 120min most preferably is 45 ~ 90min;
According to the present invention, the steaming method of revolving is preferably used in the distillation that described product carries out, described drying is preferably carried out under 35 ℃.The preferred drying plant of described drying is vacuum drying oven.
Resulting product can be analyzed by any suitable technology, FT-IR for example,
1H NMR analyzes to characterize the structure of product; Gpc analysis is used for characterizing the molecular weight of product, proved response carry out degree; The Ubbelohde viscometer analysis then is used for secondary proof GPC the reliability of the data.
In the present invention, take cis-1,4-polybutadiene rubber as embodiment.In the presence of catalyzer, react, generate target product.
Embodiment
Below all experiments all under nitrogen atmosphere, finish.
Embodiment 1 ~ 11
The dissolving of 22wt% cis-1,4-polybutadiene rubber: the cis-1,4-polybutadiene rubber of 700mg is placed 25mL1,2-CH
2ClCH
2Among the Cl, be stirred to fully dissolving under the room temperature, configure the solution of 10 groups of same concentrations.
Proportionally in each group cis-1,4-polybutadiene rubber solution, add methyl methacrylate (MMA), stir, then be heated to 25 ℃, after homo(io)thermism, add alkene cross metathesis catalyzer, after reaction finishes, take out rapidly reactant, revolve steaming, the product that obtains is as for being dried to weight in 35 ℃ of vacuum drying ovens.Then by FT-IR, 1H NMR product is carried out structural analysis, GPC carries out the molecular weight test to it.Detected result as shown in Figure 2, molecular weight reduces along with the increase of the add-on of MMA, when the MMA add-on was 0.1 ~ 1wt%, molecular weight can be kept an average level, this moment molecular weight distribution also more consistent.
Reaction conditions such as following table:
Table 1MMA/PB changes arrangement
Embodiment 12 ~ 19
The dissolving of 22wt% cis-1,4-polybutadiene rubber: the cis-1,4-polybutadiene rubber of 4900mg is placed 175mL1,2-CH
2ClCH
2Among the Cl, be stirred to fully dissolving under the room temperature.Be configured to the solution of 7 groups of same concentrations.
According to PB
=/ MMA
=Mol ratio is that the ratio of 1:1 adds methyl methacrylate (MMA), stir, then be heated to respectively 15 ℃, 25 ℃ and 25 ℃, after homo(io)thermism, add alkene cross metathesis catalyzer, after reaction finishes, take out rapidly reactant, revolve steaming, the product that obtains is as for being dried to weight in 35 ℃ of vacuum drying ovens.Then by FT-IR, 1H NMR product is carried out structural analysis, GPC carries out the molecular weight test to it.Detected result as shown in Figure 3.Heating temperature is higher, and the molecular-weight average of modified diene based polyalcohol is larger, illustrates that the present invention can draw by the control temperature of reaction modified diene based polyalcohol of different literals amount.Can also reach a conclusion by Fig. 3, after reaction proceeded to 25min, it is steady that reaction begins to become, and the variation of product literal amount is less, and the size of molecular weight is homogeneous comparatively.
Reaction conditions such as following table:
Table 2 reaction times changes arrangement
Above preparation method to a kind of modified diene based polyalcohol provided by the invention is described in detail; having used specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention; can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the preparation method of a modified diene polymer is characterized in that, may further comprise the steps:
A) diene-based polymer is dissolved in the organic solvent, obtains diene-based polymer solution;
B) molecular weight regulator is mixed with described diene-based polymer solution, obtain mixing solutions, and the cross metathesis reaction occurs under the effect of catalyzer, obtain the modified diene based polyalcohol;
Described molecular weight regulator has two keys and the first polar functional group; The second memory functional group is contained at described modified diene based polyalcohol two ends; Described the first polar functional group and described the second polar functional group are identical or different.
2. preparation method according to claim 1 is characterized in that, described diene-based polymer is cis-1,4-polybutadiene rubber, isoprene-isobutylene rubber, terpolymer EP rubber, paracril.
3. preparation method according to claim 1, it is characterized in that, described molecular weight regulator is acrylate and derivative, acrylamide and derivative thereof, vinyl cyanide and derivative thereof, is connected with alkene small molecules or its polymkeric substance of polar functional group on the unsaturated double-bond.
4. preparation method according to claim 3 is characterized in that, the functionality f of described molecular weight regulator satisfies following condition: 1≤f≤3.
5. preparation method according to claim 4 is characterized in that, the weight percent that described molecular weight regulator accounts for diene-based polymer is 0.01% ~ 3%.
6. preparation method according to claim 1 is characterized in that, described catalyzer has structure shown in the formula I:
Wherein, M
ABe ruthenium or osmium;
X
AAnd X
BIt is identical or different anion ligand;
L
AAnd L
BIt is identical or different neutral electron-donating group;
R
AAnd R
BBe respectively hydrogen, aryl or aryloxy.
7. preparation method according to claim 6 is characterized in that, described anion ligand is the halide-ions part.
8. preparation method according to claim 6 is characterized in that, described neutral electron group is phosphorus-containing groups or assorted nitrogen Cabbeen.
9. preparation method according to claim 1 is characterized in that, the temperature of reaction of described intersection dystopy reaction is 15 ~ 35 ℃.
10. preparation method according to claim 1 is characterized in that, the reaction times of described intersection dystopy reaction is 5 ~ 150min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210585445.1A CN103030716B (en) | 2012-12-28 | 2012-12-28 | Preparation method of modified dialkylene polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210585445.1A CN103030716B (en) | 2012-12-28 | 2012-12-28 | Preparation method of modified dialkylene polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103030716A true CN103030716A (en) | 2013-04-10 |
| CN103030716B CN103030716B (en) | 2015-06-17 |
Family
ID=48018152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210585445.1A Expired - Fee Related CN103030716B (en) | 2012-12-28 | 2012-12-28 | Preparation method of modified dialkylene polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103030716B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078848A (en) * | 2019-04-08 | 2019-08-02 | 江苏龙蟠科技股份有限公司 | A kind of preparation method of Liquid Ethylene Propylene Methylene |
| CN113896959A (en) * | 2020-06-22 | 2022-01-07 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer and preparation method thereof |
| CN115181197A (en) * | 2022-06-30 | 2022-10-14 | 海南天然橡胶产业集团股份有限公司 | End group functionalized liquid natural rubber and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1922225A (en) * | 2004-02-23 | 2007-02-28 | 兰塞克斯公司 | Process for the preparation of low molecular weight nitrile rubber |
| EP2028194A1 (en) * | 2007-08-21 | 2009-02-25 | Lanxess Deutschland GmbH | Metathesis of nitrile rubbers in the presence of transition metal complex catalysts |
| US20090076226A1 (en) * | 2007-08-21 | 2009-03-19 | Lanxess Deutschland Gmbh | Catalysts for metathesis reactions |
| CN102321247A (en) * | 2011-05-18 | 2012-01-18 | 华东师范大学 | Olefin translocation and modification method for rubber and elastomer |
-
2012
- 2012-12-28 CN CN201210585445.1A patent/CN103030716B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1922225A (en) * | 2004-02-23 | 2007-02-28 | 兰塞克斯公司 | Process for the preparation of low molecular weight nitrile rubber |
| EP2028194A1 (en) * | 2007-08-21 | 2009-02-25 | Lanxess Deutschland GmbH | Metathesis of nitrile rubbers in the presence of transition metal complex catalysts |
| US20090076226A1 (en) * | 2007-08-21 | 2009-03-19 | Lanxess Deutschland Gmbh | Catalysts for metathesis reactions |
| CN102321247A (en) * | 2011-05-18 | 2012-01-18 | 华东师范大学 | Olefin translocation and modification method for rubber and elastomer |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078848A (en) * | 2019-04-08 | 2019-08-02 | 江苏龙蟠科技股份有限公司 | A kind of preparation method of Liquid Ethylene Propylene Methylene |
| CN110078848B (en) * | 2019-04-08 | 2022-04-29 | 江苏龙蟠科技股份有限公司 | Preparation method of liquid ethylene propylene rubber |
| CN113896959A (en) * | 2020-06-22 | 2022-01-07 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer and preparation method thereof |
| CN113896959B (en) * | 2020-06-22 | 2023-05-30 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer and preparation method thereof |
| CN115181197A (en) * | 2022-06-30 | 2022-10-14 | 海南天然橡胶产业集团股份有限公司 | End group functionalized liquid natural rubber and preparation method and application thereof |
| CN115181197B (en) * | 2022-06-30 | 2024-04-02 | 海南天然橡胶产业集团股份有限公司 | End group functionalized liquid natural rubber and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103030716B (en) | 2015-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10570238B2 (en) | Thermoplastic elastomers via atom transfer radical polymerization of plant oil | |
| Schmidt et al. | Lignin-based polymeric surfactants for emulsion polymerization | |
| Chung et al. | Synthesis and characterization of Pluronic® grafted chitosan copolymer as a novel injectable biomaterial | |
| Imaz et al. | N‐vinylcaprolactam‐based microgels: Synthesis and characterization | |
| Tao et al. | Cross-linked nanospheres of poly (2-cinnamoylethyl methacrylate) with immediately attached surface functional groups | |
| Pispas | Double hydrophilic block copolymers of sodium (2‐sulfamate‐3‐carboxylate) isoprene and ethylene oxide | |
| KR20170012234A (en) | Poly(acrylated polyol) and method for making and using thereof as asphalt rubber modifiers, adhesives, fracking additives, or fracking fluids | |
| Audouin et al. | Star polymers by cross‐linking of linear poly (benzyl‐l‐glutamate) macromonomers via free‐radical and RAFT polymerization. A simple route toward peptide‐stabilized nanoparticles | |
| Pfaff et al. | Glycopolymer‐Grafted Polystyrene Nanospheres | |
| Goikoetxea et al. | Polymerization kinetics and microstructure of waterborne acrylic/alkyd nanocomposites synthesized by miniemulsion | |
| CN103030716B (en) | Preparation method of modified dialkylene polymer | |
| Jamaluddin et al. | Synthesis, characterization, and properties of hydrogenated liquid natural rubber | |
| Kim et al. | Effect of PVA in dispersion polymerization of MMA | |
| CN110227419A (en) | A kind of humic acid/beta cyclo dextrin polymer, complex microsphere and preparation method thereof | |
| Wang et al. | Preparation of poly (methyl methacrylate)–poly (acrylonitrile‐co‐butadiene) core–shell nanoparticles | |
| CN108148188B (en) | Comb type polyester compound and preparation method thereof | |
| Fan et al. | Synthesis of biocompatible tadpole-shaped copolymer with one poly (ethylene oxide)(PEO) ring and two poly (ɛ-caprolactone)(PCL) tails by combination of glaser coupling with ring-opening polymerization | |
| Beezer et al. | Post‐polymerization modification of branched polyglycidol with N‐Hydroxy phthalimide to give ratio‐controlled amino‐oxy functionalized species | |
| Wang et al. | Organic solvent‐free catalytic hydrogenation of diene‐based polymer nanoparticles in latex form: Part I. Preparation of nano‐substrate | |
| Carro et al. | Rheological properties in aqueous solution for hydrophobically modified polyacrylamides prepared in inverse emulsion polymerization | |
| CN106832111A (en) | A kind of multi-functional smooth hydraulic pressure splits the preparation method of liquid drag reducer | |
| Zhang et al. | Preparation of starch-g-PMMA, starch-g-P (MMA/BMA) and starch-g-P (MMA/MA) nanoparticles and their reinforcing effect on natural rubber by latex blending: a comparative study | |
| Ronco et al. | Toughened polystyrene nanoparticles through high-solids miniemulsion polymerization | |
| CN113999354B (en) | Amphiphilic block polymer nanoparticles with different morphologies and preparation method and application thereof | |
| Tan et al. | Catalyst‐Free One‐Step Preparation of Self‐Crosslinked pH‐Responsive Vesicles |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150617 Termination date: 20201228 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |