CN103030716B - Preparation method of modified dialkylene polymer - Google Patents
Preparation method of modified dialkylene polymer Download PDFInfo
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- CN103030716B CN103030716B CN201210585445.1A CN201210585445A CN103030716B CN 103030716 B CN103030716 B CN 103030716B CN 201210585445 A CN201210585445 A CN 201210585445A CN 103030716 B CN103030716 B CN 103030716B
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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 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 be 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 commercial field.But the processing characteristicies such as mobility, cohesiveness and winter hardiness are undesirable.Also limit 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 Industrial processes, though can meet ask for something, but mineral filler not easily disperses in the polymer, therefore relatively with the compatibility of other materials declines; The opposing party's rule introduces 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 retain the original advantageous property of polymkeric substance, thus meet 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 polymer chain.Though traditional chemical modification method can introduce functional group in polymer chain, but relatively bothers, and also unrealistic with traditional chemical process cut-out molecular chain.
The method that can realize diene-based polymer modification at present mainly comprises following several, at Can.J.Chem., before summary, cis-1,4-polybutadiene rubber is introduced functional group by cross metathesis reaction or is fallen low-molecular-weight work in 79,775-779 (2001).At " Olefin metathesis and metathesis polymerization ", 16th, p.379-380 before just having described the invention of Ge Labu catalyzer in (1997), 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, in 9675-9677 (2003), disclose, cis-1,4-polybutadiene rubber polymer chain is deposited be sheared successfully in case at ethene, vinyl alcohol small-numerator olefin; After Ge Labu catalyzer occurs, shaking pawl polyhutadiene such as acetoxyl, hydroxyl is the polyhutadiene of terminal functionality, obtained by olefin metathesis reactions, these contents also at Polymer, 42,4939-4945 (2001), Macromol., 33,1494-1496 (2000) and Polymer Degradation and Stability, open introduction in 96,1074-1080 (2011).In addition, Macromol., 25,5137-5144 (1992), Macromol., 26,872-874 (1993) and Macromol., 26, the alkene that 2137-2138 (1993) has set forth containing silicon substrate also carries out chain forging shearing and functional group's grafting as molecular weight regulator and functionality provider to polyhutadiene under the catalysis of W/Mo, and what obtain the bifunctional of f=2.0 shakes pawl oligopolymer.Pass through ROMP, 1,4-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, in 41,827-830 (2000).
In addition, at USP10,156,916B, US6,867,274, US7,022, in 789, carry out modified polymer by use containing suitably functionalized hydroxyl, ester group or acyclic olefin small molecules and comprise polyhutadiene, introduce the functional group wished, but the method introducing ester group is herein obtained by ring-opening metathesis polymerization method; In addition US Patent No. 3,692,872, US4,010,244 disclose the grafting and the segmented copolymer that utilize 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 to carry out grafted functional group to diene-based polymer especially cis-1,4-polybutadiene rubber or reduce molecular weight modifying, but also in diene-based polymer chain, do not introduce ester group isopolarity functional group by cross metathesis mode so far, autotelic adjustment diene-based polymer molecular weight simultaneously.At this, we wish to provide a kind of relatively easy method that can reach again modification object, make products obtained therefrom have 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 while adjustment polymericular weight on described polymer molecule the preparation method of the modified diene based polyalcohol of grafted polar functional group.
In order to solve above technical problem, the invention provides a kind of preparation method of modified diene polymer, comprising the following steps:
A) diene-based polymer is dissolved in organic solvent, obtain diene-based polymer solution;
B) molecular weight regulator is mixed with described diene-based polymer solution, obtain mixing solutions, and cross metathesis reaction occurs under the effect of catalyzer, obtain modified diene based polyalcohol;
Described molecular weight regulator has double bond and the first polar functional group; The second memory functional group is contained at described modified diene based polyalcohol two ends; Described first polar functional group and described second polar functional group 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, unsaturated double-bond is connected with alkene small molecules or its polymkeric substance of polar functional group.
Preferably, the functionality f of described molecular weight regulator meets following condition: 1≤f≤3.
Preferably, described molecular weight regulator accounts for the weight percent of diene-based polymer is 0.01% ~ 3%.
Preferably, described catalyzer has structure shown in formula I:
Wherein, M
afor 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 halide-ions part.
Preferably, described electron-neutral group is phosphorus-containing groups or assorted nitrogen Cabbeen.
Preferably, the temperature of reaction of described crossed ectopic reaction is 15 ~ 35 DEG C.
Preferably, the reaction times of described crossed ectopic reaction is 5 ~ 150min.
The invention provides a kind of preparation method of modified diene based polyalcohol, by diene-based polymer and molecular weight regulator and catalyst mix, wherein said molecular weight regulator has double bond and polar functional group, under the effect of catalyzer, molecular weight regulator can react with diene-based polymer generation crossed ectopic, the molecular chain of diene-based polymer is disconnected, form the diene-based polymer that segment is shorter, and by the polar functional group end-blocking in molecular weight regulator, finally obtain that there is polarity group can roll into a ball, and molecular weight distribution is wider, the modified diene based polyalcohol of molecular weight.Improve the low-temperature performance of diene-based polymer, mobility and cohesiveness.
Accompanying drawing illustrates:
Fig. 1 is the infrared figure as the raw material cis-1,4-polybutadiene rubber in embodiment olefin cross metathesis method and polymethylmethacrylate and product;
Fig. 2 is the effect diagram of the different mass comparison molecular weight of product of diene-based polymer PB and MMA in the embodiment of the present invention 1 ~ 10;
In the selection diene-based polymer PB that Fig. 3 embodiment of the present invention 11 ~ 17 provides in C=C and MMA C=C mole for 1:1 time, the change in reaction times is to the effect diagram of molecular weight of product.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention instead of the restriction to patent requirements of the present invention.
The invention provides the preparation method of a kind of modification and olefin polymer, comprising: following steps:
Diene-based polymer is mixed with molecular weight regulator, cross metathesis reaction occurs under the effect of catalyzer, obtains modified diene based polyalcohol;
Described molecular weight regulator has double bond and the first polar functional group; The second memory functional group is contained at described modified diene based polyalcohol two ends; Described first polar functional group and described second polar functional group identical or different.
In above-mentioned steps, described diene-based polymer is can the diene-based polymer of direct or indirect modification, and described diene-based polymer has saturated or unsaturated diene polymerization to form.Be more preferably molecular weight 5000 ~ 100000 diene-based polymer, as cis-1,4-polybutadiene rubber, terpolymer EP rubber etc.Paracril, isoprene-isobutylene rubber etc., are more preferably.Because molecular weight is larger, molecular weight distribution is narrower, processing difficulties, especially the sulfidation of rubber, so can first use method provided by the invention to be reduced by molecular weight fractions before processing, make 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 to mix with molecular weight regulator, and the selection of catalyzer and adding.While can reacting with diene-based polymer generation crossed ectopic, diene-based polymer molecular chain is sheared, and by the polar functional group that described molecular weight regulator contains, end-blocking is carried out to the diene-based polymer molecular chain after shearing.According to the present invention, described molecular weight regulator elects acrylate and derivative, acrylamide and derivative thereof, vinyl cyanide and derivative thereof as, unsaturated double-bond is connected with alkene small molecules or its polymkeric substance of polar functional group.Be more preferably methyl methacrylate (MMA), 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, and diene-based polymer and molecular weight modifier generation crossed ectopic must be able to be impelled to react.According to the present invention, described catalyzer preferably has structure shown in formula I:
Wherein, M
afor ruthenium or osmium;
X
aand X
bit can be identical or different anion ligand; Prioritizing selection haloid element or the group containing haloid element.
L
aand L
bit can be identical or different neutral electron-donating group; Prioritizing selection phosphorus-containing groups or N-heterocyclic carbine;
R
aand R
bbe respectively hydrogen, aryl or aryloxy.
Above-mentioned catalyzer in reaction process can with molecular weight regulator molecule contacts, there is crossed ectopic reaction and form the metal carbene containing functional group, then metal carbene and diene polymer occur to shear and exchange, thus make the diene polymer molecular weight of macromolecule reduce, and by polar functional group end-blocking.Impel diene-based polymer and molecular weight regulator and functionality provider that cross metathesis occurs to react, carry out modification to diene-based polymer, and this catalyzer consumption in catalytic process is few, the reaction times is short, can greatly reduce the cost in industrial production.
The present invention provides a kind of method preparing the based polar functional group of both-end of functionality f=2.0, the diene-based polymer modification of adjustable molecular weight joint now.The step of described method specifically comprises: dissolved in organic solvent by diene-based polymer, obtain diene-based polymer solution, in described diene-based polymer solution, the mass concentration of diene-based polymer is 15 ~ 30%, is more preferably 20 ~ 25%, most preferably is 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 described diene-based polymer solution, heating mixing dissolution homogeneity processed, then described catalyzer is joined in the mixing solutions in described diene-based polymer and molecular weight regulator, carry out crossed ectopic reaction, the product obtained, through drying and distilling, drying, obtains modified diene based polyalcohol.
The weight ratio accounting for diene-based polymer according to molecular weight regulator of the present invention is preferably 0.01 ~ 3%, is more preferably 0.1% ~ 1%, most preferably is 0.2% ~ 0.8%;
Described Heating temperature is preferably 15 ~ 35 DEG C, is more preferably 20 ~ 30 DEG C, most preferably is 22 ~ 28 DEG C;
The time of described crossed ectopic reaction is preferably 5 ~ 150min, is more preferably 25 ~ 120min, most preferably is 45 ~ 90min;
According to the present invention, the distillation carried out described product preferably uses revolves steaming method, and described drying is preferably carried out at 35 DEG C.The preferred drying plant of described drying is vacuum drying oven.
The product obtained can be analyzed by any suitable technology, such as FT-IR,
1h NMR analyzes the structure characterizing product; Gpc analysis is used for characterizing the molecular weight of product, proved response carry out degree; Ubbelohde viscometer analysis is then used for the reliability of secondary proof GPC data.
In the present invention, take cis-1,4-polybutadiene rubber as embodiment.React in the presence of a catalyst, generate target product.
Embodiment
Experiments all below completes all under nitrogen atmosphere.
Embodiment 1 ~ 11
The dissolving of 22wt% cis-1,4-polybutadiene rubber: the cis-1,4-polybutadiene rubber of 700mg is placed in 25mL1,2-CH
2clCH
2in Cl, stirred at ambient temperature, to dissolving completely, configures the solution of 10 groups of same concentrations.
Proportionally in each group cis-1,4-polybutadiene rubber solution, add methyl methacrylate (MMA), stir, then 25 DEG C are heated to, olefin cross metathesis catalyzer is added after homo(io)thermism, after reaction terminates, rapid taking-up reactant, revolves steaming, and the product obtained is dried to weight as in 35 DEG C of vacuum drying ovens.Then carry out structural analysis by FT-IR, 1H NMR to product, GPC carries out molecular weight test to it.As shown in Figure 2, molecular weight reduces along with the increase of the add-on of MMA detected result, and when MMA add-on is 0.1 ~ 1wt%, molecular weight can maintain an average level, and molecular weight distribution is now also more consistent.
Reaction conditions is as following table:
Table 1MMA/PB change arranges
Embodiment 12 ~ 19
The dissolving of 22wt% cis-1,4-polybutadiene rubber: the cis-1,4-polybutadiene rubber of 4900mg is placed in 175mL1,2-CH
2clCH
2in Cl, stirred at ambient temperature is to dissolving completely.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 15 DEG C, 25 DEG C and 25 DEG C are heated to respectively, olefin cross metathesis catalyzer is added after homo(io)thermism, after reaction terminates, rapid taking-up reactant, revolves steaming, and the product obtained is dried to weight as in 35 DEG C of vacuum drying ovens.Then carry out structural analysis by FT-IR, 1H NMR to product, GPC carries out 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 the modified diene based polyalcohol of different literals amount by controlling temperature of reaction.Can also be reached a conclusion by Fig. 3, after reaction proceeds to 25min, reaction starts the steady of change, and the change of product word amount is less, and the size of molecular weight is comparatively homogeneous.
Reaction conditions is as following table:
The change of table 2 reaction times arranges
Above the preparation method of a kind of modified diene based polyalcohol provided by the invention is described in detail; apply specific case herein to set forth principle of the present invention and embodiment; the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention; can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (9)
1. a preparation method for modified diene polymer, is characterized in that, comprises the following steps:
A) diene-based polymer is dissolved in organic solvent, obtain diene-based polymer solution;
B) molecular weight regulator is mixed with described diene-based polymer solution, obtain mixing solutions, and cross metathesis reaction occurs under the effect of catalyzer, obtain modified diene based polyalcohol;
Described molecular weight regulator has double bond and the first polar functional group; The second polar functional group is contained at described modified diene based polyalcohol two ends; Described first polar functional group and described second polar functional group identical or different;
Described molecular weight regulator is acrylate and derivative, acrylamide and derivative thereof, vinyl cyanide and derivative thereof.
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, is characterized in that, the functionality f of described molecular weight regulator meets following condition: 1≤f≤3.
4. preparation method according to claim 1, is characterized in that, the weight percent that described molecular weight regulator accounts for diene-based polymer is 0.01% ~ 3%.
5. preparation method according to claim 1, is characterized in that, described catalyzer has structure shown in formula I:
Wherein, M
afor 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.
6. preparation method according to claim 5, is characterized in that, described anion ligand is halide-ions part.
7. want the preparation method described in 5 according to right, it is characterized in that, described electron-neutral group is phosphorus-containing groups or assorted nitrogen Cabbeen.
8. preparation method according to claim 1, is characterized in that, the temperature of reaction of described crossed ectopic reaction is 15 ~ 35 DEG C.
9. preparation method according to claim 1, is characterized in that, the reaction times of described crossed ectopic reaction is 5 ~ 150min.
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| 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 |
| 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 |
| 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 |
Citations (3)
| 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 |
| CN102321247A (en) * | 2011-05-18 | 2012-01-18 | 华东师范大学 | Olefin translocation and modification method for rubber and elastomer |
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| EP2027920B1 (en) * | 2007-08-21 | 2014-10-08 | LANXESS Deutschland GmbH | Catalysts for metathesis reactions |
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| 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 |
| CN102321247A (en) * | 2011-05-18 | 2012-01-18 | 华东师范大学 | Olefin translocation and modification method for rubber and elastomer |
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