CN101805427A - Method for modifying butyl rubber by maleic anhydride - Google Patents
Method for modifying butyl rubber by maleic anhydride Download PDFInfo
- Publication number
- CN101805427A CN101805427A CN 201010155913 CN201010155913A CN101805427A CN 101805427 A CN101805427 A CN 101805427A CN 201010155913 CN201010155913 CN 201010155913 CN 201010155913 A CN201010155913 A CN 201010155913A CN 101805427 A CN101805427 A CN 101805427A
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- maleic anhydride
- isoprene
- reactor
- 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.)
- Pending
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for modifying butyl rubber by using maleic anhydride. The method comprises the following main steps of: filling the butyl rubber, the maleic anhydride and an organic solvent into a reactor; and performing the reaction of the maleic anhydride and the butyl rubber at a temperature which is higher than the boiling point of the solvent to obtain a target material. The method makes the butyl rubber react with a modifier completely, avoids using high-priced additives or/and raw materials, simplifies the preparation steps by which the maleic anhydride modifies the butyl rubber and is a butyl rubber modification method with a commercial value.
Description
Technical field
The present invention relates to the method for modifying of a kind of isoprene-isobutylene rubber (butyl rubber), specifically, relate to the method for a kind of employing maleic anhydride (maleic anhydride) modified butyl rubber.
Background technology
Isoprene-isobutylene rubber is the rubbery copolymer that formed by iso-butylene and a small amount of hydrocarbon olefin-copolymerization of conjugation (typical case as: the rubber copolymerized product of iso-butylene and isoprene, the content of isoprene is generally 1.5%～4.5%).Though isoprene-isobutylene rubber has good chemical stability, thermostability, resistance to air loss, watertightness and electrical insulating property etc. (the most outstanding is resistance to air loss and watertightness), but it is defectiveness also: since the polarity of isoprene-isobutylene rubber a little less than, cause the consistency of itself and other polymkeric substance relatively poor (for example poor, as can't to obtain the ideal toughening effect) with the consistency of nylon and the strong resin of vibrin isopolarity.For this reason, need carry out modification (main purpose is to increase its polarity), expand its range of application isoprene-isobutylene rubber.
US.Pat.No.2,845,403 and US 2004/0010089A1 (Pub.No.) preparation method of two kinds of modified butyl rubbers is disclosed respectively.By US.Pat.No.2,845,403 method of modifying that disclosed as can be known: when the reaction of maleic anhydride and isoprene-isobutylene rubber, need to add halogenated acid amides of N-and imide, and its temperature of reaction higher (135 ℃～200 ℃); And by US 2004/0010089A1 as can be known: it is when using modifying butyl rubber by maleic anhydride, used starting raw material is halogenated butyl rubber (promptly by the reaction of maleic anhydride and halogenated butyl rubber), and also need add (A) acid acceptor (as MgO) and (B) hindered amine and/or the hindered phenol of simple function group during reaction.
In sum, adopt in the modifying butyl rubber by maleic anhydride technology, exist the comparatively defective of complexity etc. of preparation cost higher [using additive and/or expensive raw material (halogenated butyl rubber)] and preparation process (reaction) as need existing.Given this, how to reduce the cost of modifying butyl rubber by maleic anhydride and simplify its preparation process (reaction) and just become the technical issues that need to address of the present invention.
Summary of the invention
The object of the invention is, a kind of method of modifying with isoprene-isobutylene rubber of commercial value is provided, and overcomes the defective that exists in the prior art.
The said isoprene-isobutylene rubber method of modifying of the present invention, its key step is: isoprene-isobutylene rubber, properties-correcting agent (as maleic anhydride etc.) and an amount of organic solvent are placed reactor, properties-correcting agent (as maleic anhydride etc.) is reacted under the temperature condition of the boiling point that is higher than used organic solvent with isoprene-isobutylene rubber, obtain target compound (modified butyl rubber).
The present invention has adopted the different and existing method that adopts solid phase method, scorification or solution method modified butyl rubber, and isoprene-isobutylene rubber and properties-correcting agent are reacted under the temperature condition of the boiling point that is higher than used organic solvent.So, isoprene-isobutylene rubber and properties-correcting agent were fully reacted, and can avoid again using expensive additive or/and raw material, and simplify preparation process.
Description of drawings
Fig. 1 is the infrared spectrum by the modifying butyl rubber by maleic anhydride of embodiment one preparation.
Embodiment
Said isoprene-isobutylene rubber is meant among the present invention: by the rubbery copolymer that iso-butylene and a small amount of hydrocarbon olefin-copolymerization of conjugation form, wherein the hydrocarbon olefin ratios of iso-butylene and conjugation is 75: 25～98: 2.
Rubber copolymerized product with iso-butylene and isoprene is example (wherein the ratio of iso-butylene and isoprene is 75: 25～98: 2) below, concrete method of modifying of setting forth the said isoprene-isobutylene rubber of the present invention, the key step of described method of modifying is: with the isoprene-isobutylene rubber of 100 parts by weight, the organic solvent of 100 parts by weight～300 parts by weight place can be airtight and withstand voltage reactor, having under rare gas element (as nitrogen or the argon gas etc.) existence condition, in this reactor, add the maleic anhydride of 1 parts by weight～20 parts by weight and the initiator of 0.05 parts by weight～10 parts by weight, reinforced finishing, airtight this reactor, and with its under 80 ℃～140 ℃ conditions (as reactor being placed the heating unit that is provided with temperature regulating device), placed 1 hour～30 hours, material in the reactor is poured in the precipitation agent, stirred 1 hour～5 hours, successively after filtration, extracting and dried target compound (maleic anhydride modified isoprene-isobutylene rubber);
Wherein: the consumption of organic solvent, maleic anhydride and initiator calculates and gets based on the consumption of isoprene-isobutylene rubber;
Said organic solvent is selected from: alkylbenzene, C
1～C
4Haloalkane, C
1～C
6Alkane, 5-6 unit's naphthenic hydrocarbon or tetrahydrofuran (THF) in a kind of, two or more mixture; Preferred solvent is: by C
1～C
3Alkyl substituted benzene, C
3～C
6Alkane, C
1～C
4Alkyl chloride, hexanaphthene or/and tetrahydrofuran (THF); Best solvent is: normal hexane, hexanaphthene, toluene, dimethylbenzene, tetrahydrofuran (THF), methylene dichloride, trichloromethane, vinyl trichloride are or/and sym.-tetrachloroethane;
Said initiator is selected from: a kind of in Diisopropyl azodicarboxylate, dibenzoyl peroxide, di-isopropyl peroxydicarbonate, tert-butyl peroxy acetate, peroxidized t-butyl perbenzoate or the dicumyl peroxide, two or more mixture;
Said precipitation agent is acetone and/or ethanol, and its consumption is 1～10 times of a volume of material (preferred 5～10 times) in the reactor;
In said extraction steps, used extract (solvent) is acetone and/or ethanol;
In said drying step, its drying temperature should be controlled at 40 ℃～80 ℃, and be 5～40 hours time of drying.
The present invention adopts maleic anhydride to pass through " solvent-thermal method " (promptly carrying out modified-reaction under the temperature condition of the boiling point that is higher than used organic solvent) modified butyl rubber.Advantages such as it is simple that the present invention has preparation process (reaction), and the isoprene-isobutylene rubber modified effect is preferable are a kind of isoprene-isobutylene rubber method of modifying that possesses commercial value.
The present invention is further elaborated below by embodiment, and its purpose only is better to understand content of the present invention.Therefore the cited case does not limit protection scope of the present invention.
Embodiment one
With 10g isoprene-isobutylene rubber (1751, Beijing yanshan petrochemical company limited, down together), 30ml toluene adds in the autoclave, carried out bubbling 30 minutes with argon gas, add the 1g maleic anhydride again, 0.6g dibenzoyl peroxide, put into 120 ℃ of baking ovens after the autoclave lid tightened, placed 3 hours, use water cooling then, open autoclave, pour solution into 10 times and in the acetone of its volume, precipitate, on magnetic stirring apparatus, stirred (100 rev/mins of rotating speeds) 2 hours, to remove unreacted matters, suction filtration then, and the solid that suction filtration is obtained with the acetone extracting after 24 hours in 65 ℃ of vacuum drying ovens after dry 48 hours target compound (modifying butyl rubber by maleic anhydride).
The gained target compound is carried out infrared analysis, and the gained collection of illustrative plates is seen Fig. 1.As shown in Figure 1: at 2950cm
-1There are the stretching vibration absorption peak of methyl methylene radical, 1470cm in the place
-1The place is the scissoring vibration absorption peak of methylene radical, 1388cm
-1With 1365cm
-1The place is the flexural vibration absorption peak of methyl, 1227cm
-1Be C-C stretching vibration absorption peak, 1639cm
-1The place is the C=C charateristic avsorption band of isoprene-isobutylene rubber, more than all be the charateristic avsorption band of isoprene-isobutylene rubber.The infrared spectrum of graft product is at 1855cm
-1, 1714cm
-1New peak has appearred, wherein 1855cm
-1The place is the more weak asymmetric stretching vibration absorption peak of acid anhydrides C=O, 1714cm
-1The place is the C=O stretching vibration absorption peak [1] of acid anhydrides, and the Infrared spectroscopy of reaction product shows has maleic anhydride monomer successfully to insert on the isoprene-isobutylene rubber macromolecular chain really.
With chemical titration the percentage of grafting of maleic anhydride, concrete grammar is as follows: accurately take by weighing sample (being accurate to 0.001g) behind the 1.0g purifying, be dissolved in an amount of toluene, heating for dissolving, the NaOH-methanol solution that the cooling back adds 0.05mol/L carries out saponification backflow 1h, drips 1～2 phenolphthalein indicator then.With the HCl-Virahol standard solution titration of 0.05mol/L to terminal.
The percentage of grafting G of product
YImplication: the percentage ratio that contains maleic anhydride monomer in the graft product.Its calculation formula is as follows:
In the formula, N1, N2 are respectively the concentration (mol/L) of the used HCl-aqueous isopropanol of the used NaOH-methanol solution of titration and back titration; V1, V2 are respectively the volume (mL) of the used HCl-aqueous isopropanol of the used NaOH-methanol solution of titration and back titration; W is the quality (g) that takes by weighing sample behind the purifying; After maleic anhydride open loop of 2 expressions two carboxyls are arranged.Promptly obtaining percentage of grafting according to analytical results is 1.14wt% maleic anhydride graft isoprene-isobutylene rubber multipolymer.
Embodiment two
With the 10g isoprene-isobutylene rubber, 30ml toluene and 1ml chloroform add in the autoclave, carried out bubbling 10 minutes with argon gas, add the 2g maleic anhydride again, the 1g di-isopropyl peroxydicarbonate, put into 120 ℃ of baking ovens after the autoclave lid tightened, placed 1.5 hours, use water cooling then, open autoclave, pouring solution into 10 times of volume ratios to its volume is to precipitate in ethanol-acetone of 1: 1, on magnetic stirring apparatus, stirred (500 rev/mins of rotating speeds) 1 hour, to remove unreacted matters, suction filtration then, and the solid that suction filtration is obtained is with acetone extracting after 24 hours in 80 ℃ of vacuum drying ovens dry 5 hours, adopting the analytical procedure identical with embodiment one promptly to obtain percentage of grafting is 0.59%wt maleic anhydride graft isoprene-isobutylene rubber multipolymer.
Embodiment three
With the 10g isoprene-isobutylene rubber, 100ml dimethylbenzene adds in the autoclave, carried out bubbling 20 minutes with argon gas, add the 1.2g maleic anhydride again, 0.8g dicumyl peroxide, put into 140 ℃ of baking ovens after the autoclave lid tightened, placed 3 hours, use water cooling then, open autoclave, pouring solution into 10 times precipitates in the acetone of its volume, on magnetic stirring apparatus, stirred (100 rev/mins of rotating speeds) 1 hour, to remove unreacted matters, suction filtration then, and the solid that suction filtration is obtained is with acetone extracting after 24 hours in 65 ℃ of vacuum drying ovens dry 48 hours, adopting the analytical procedure identical with embodiment one promptly to obtain percentage of grafting is 1.23wt% maleic anhydride graft isoprene-isobutylene rubber multipolymer.
Embodiment four
With the 10g isoprene-isobutylene rubber, the 10ml hexanaphthene adds in the autoclave, carried out bubbling 20 minutes with argon gas, add the 0.1g maleic anhydride again, 0.05g tert-butyl peroxy acetate, put into 100 ℃ of baking ovens after the autoclave lid tightened, placed 10 hours, use water cooling then, open autoclave, pouring solution into 10 times precipitates in the acetone of its volume, on magnetic stirring apparatus, stirred (50 rev/mins of rotating speeds) 10 hours, to remove unreacted matters, suction filtration then, and the solid that suction filtration is obtained is with acetone extracting after 24 hours in 65 ℃ of vacuum drying ovens dry 48 hours, adopting the analytical procedure identical with embodiment one promptly to obtain percentage of grafting is 0.11%wt maleic anhydride graft isoprene-isobutylene rubber multipolymer.
Embodiment five
With the 10g isoprene-isobutylene rubber, 20ml methylene dichloride and 20ml1,1, the 2-trichloroethane adds in the autoclave, carried out bubbling 20 minutes with argon gas, add the 0.6g maleic anhydride again, 0.1g peroxidized t-butyl perbenzoate and 0.1g peroxidized t-butyl perbenzoate, put into 80 ℃ of baking ovens after the autoclave lid tightened, placed 30 hours, use water cooling then, open autoclave, pour solution into 10 times and in the acetone of its volume, precipitate, on magnetic stirring apparatus, stirred (200 rev/mins of rotating speeds) 1 hour, to remove unreacted matters, suction filtration then, and the solid that suction filtration is obtained is with acetone extracting after 24 hours in 65 ℃ of vacuum drying ovens dry 48 hours, adopting the analytical procedure identical with embodiment one promptly to obtain percentage of grafting is 0.45%wt maleic anhydride graft isoprene-isobutylene rubber multipolymer.
Embodiment six
With the 10g isoprene-isobutylene rubber, 10ml tetrahydrofuran (THF) and 20ml tetrachloroethane add in the autoclave, carried out bubbling 20 minutes with nitrogen, add the 0.2g maleic anhydride again, 0.08g Diisopropyl azodicarboxylate, put into 80 ℃ of baking ovens after the autoclave lid tightened, placed 30 hours, use water cooling then, open autoclave, pouring solution into 10 times precipitates in the acetone of its volume, on magnetic stirring apparatus, stirred (200 rev/mins of rotating speeds) 5 hours, to remove unreacted matters, suction filtration then, and the solid that suction filtration is obtained is with acetone extracting after 24 hours in 65 ℃ of vacuum drying ovens dry 48 hours, adopting the analytical procedure identical with embodiment one promptly to obtain percentage of grafting is 0.14%wt maleic anhydride graft isoprene-isobutylene rubber multipolymer.
Claims (8)
1. the method for a modified butyl rubber, it is characterized in that, the key step of said method is: isoprene-isobutylene rubber, maleic anhydride and organic solvent are placed reactor, maleic anhydride and isoprene-isobutylene rubber are reacted under the temperature condition that is higher than used organic solvent boiling point, obtain target compound;
Wherein: said organic solvent is selected from: alkylbenzene, C
1～C
4Haloalkane, C
1～C
6Alkane, 5-6 unit's naphthenic hydrocarbon or tetrahydrofuran (THF) in a kind of, two or more mixture.
2. the method for claim 1 is characterized in that, wherein said isoprene-isobutylene rubber is meant: the rubber copolymerized product of iso-butylene and isoprene.
3. method as claimed in claim 1 or 2 is characterized in that, the isoprene-isobutylene rubber of wherein per 100 parts by weight, the consumption of maleic anhydride are 1 parts by weight～20 parts by weight, and the consumption of organic solvent is 100 parts by weight～300 parts by weight.
4. method as claimed in claim 3, it is characterized in that, the key step of said method is: with the isoprene-isobutylene rubber of 100 parts by weight, the organic solvent of 100 parts by weight～300 parts by weight place can be airtight and withstand voltage reactor, having under the rare gas element existence condition, in this reactor, add the maleic anhydride of 1 parts by weight～20 parts by weight and the initiator of 0.05 parts by weight～10 parts by weight, reinforced finishing, airtight this reactor, and with it under 80 ℃～140 ℃ conditions, placed 1 hour～30 hours, material in the reactor is poured in the precipitation agent, stirred 1 hour～5 hours, successively after filtration, extracting and dried target compound;
Wherein: said organic solvent is: by C
1～C
3Alkyl substituted benzene, C
3～C
6Alkane, C
1～C
4Alkyl chloride, hexanaphthene or/and tetrahydrofuran (THF);
Said initiator is: Diisopropyl azodicarboxylate, dibenzoyl peroxide, di-isopropyl peroxydicarbonate, tert-butyl peroxy acetate, peroxidized t-butyl perbenzoate and/or dicumyl peroxide;
Said precipitation agent is acetone and/or ethanol, and its consumption is 1 times～10 times of volume of material in the reactor;
In said extraction steps, used extract is acetone and/or ethanol.
5. method as claimed in claim 4 is characterized in that, wherein said organic solvent is: normal hexane, hexanaphthene, toluene, dimethylbenzene, tetrahydrofuran (THF), methylene dichloride, trichloromethane, vinyl trichloride are or/and sym.-tetrachloroethane.
6. method as claimed in claim 4 is characterized in that, wherein said rare gas element is nitrogen or argon gas.
7. method as claimed in claim 4 is characterized in that, wherein the drying temperature of said drying step is 40 ℃～80 ℃, and be 5 hours～40 hours time of drying.
8. method as claimed in claim 4 is characterized in that, wherein the precipitation agent consumption is 5 times～10 times of volume of material in the reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010155913 CN101805427A (en) | 2010-04-23 | 2010-04-23 | Method for modifying butyl rubber by maleic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010155913 CN101805427A (en) | 2010-04-23 | 2010-04-23 | Method for modifying butyl rubber by maleic anhydride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101805427A true CN101805427A (en) | 2010-08-18 |
Family
ID=42607390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010155913 Pending CN101805427A (en) | 2010-04-23 | 2010-04-23 | Method for modifying butyl rubber by maleic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101805427A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432724A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Carboxylate butyl rubber and preparation method thereof |
| CN105753415A (en) * | 2016-05-21 | 2016-07-13 | 夏百庆 | Method for preparing cement mortar from waste rubber and bone meal |
| CN105778000A (en) * | 2014-12-16 | 2016-07-20 | 中国石油天然气股份有限公司 | Isoprene rubber grafted maleic anhydride and preparation method thereof |
| CN107223142A (en) * | 2015-02-17 | 2017-09-29 | 株式会社Lg化学 | Modified isobutene isoprene rubber, its preparation method and cured product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974621A (en) * | 2006-12-07 | 2007-06-06 | 武汉工程大学 | Modified rubber powder and its prepn and use |
| CN101223201A (en) * | 2005-07-11 | 2008-07-16 | 朗盛公司 | Liquid maleated butyl rubber |
| US20080227876A1 (en) * | 2007-03-12 | 2008-09-18 | Klaus Thiele | Method for the modification of rubber and thermoplastic waste by means of grafting during a grinding process, and use of the rubber and thermoplastic waste modified in this way |
-
2010
- 2010-04-23 CN CN 201010155913 patent/CN101805427A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101223201A (en) * | 2005-07-11 | 2008-07-16 | 朗盛公司 | Liquid maleated butyl rubber |
| CN1974621A (en) * | 2006-12-07 | 2007-06-06 | 武汉工程大学 | Modified rubber powder and its prepn and use |
| US20080227876A1 (en) * | 2007-03-12 | 2008-09-18 | Klaus Thiele | Method for the modification of rubber and thermoplastic waste by means of grafting during a grinding process, and use of the rubber and thermoplastic waste modified in this way |
Non-Patent Citations (1)
| Title |
|---|
| 《Journal of Polymer Science Part A: Polymer Chemistry》 20051213 Makoto Kato et al Preparation and properties of isobutylene-isoprene rubber-clay nanocomposites 1182-1188 1-8 , 2 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432724A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Carboxylate butyl rubber and preparation method thereof |
| CN105778000A (en) * | 2014-12-16 | 2016-07-20 | 中国石油天然气股份有限公司 | Isoprene rubber grafted maleic anhydride and preparation method thereof |
| CN107223142A (en) * | 2015-02-17 | 2017-09-29 | 株式会社Lg化学 | Modified isobutene isoprene rubber, its preparation method and cured product |
| CN107223142B (en) * | 2015-02-17 | 2019-08-06 | 株式会社Lg化学 | Modified butyl rubber, preparation method and cured product |
| CN105753415A (en) * | 2016-05-21 | 2016-07-13 | 夏百庆 | Method for preparing cement mortar from waste rubber and bone meal |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ahmad et al. | Chain Transfer to Polymer and Branching in Controlled Radical Polymerizations of n‐Butyl Acrylate | |
| US9487614B2 (en) | Process for radical grafting of a diene elastomer | |
| CN101805427A (en) | Method for modifying butyl rubber by maleic anhydride | |
| WO2013039152A1 (en) | Polyolefin having terminal double bond, and method for producing same | |
| JP6859220B2 (en) | Method for Producing Functionalized Elastomer by Allyl Borylation | |
| US20130144013A1 (en) | Process for Preparing High Impact Monovinylaromatic Polymers in the Presence of a Borane Complex | |
| CN101805426B (en) | Modified butyl rubber | |
| Enayati et al. | Ultrafast SET-LRP in biphasic mixtures of the non-disproportionating solvent acetonitrile with water | |
| Valente et al. | Catalytic Chain Transfer (co‐) Polymerization: Unprecedented Polyisoprene CCG and a New Concept to Tune the Composition of a Statistical Copolymer | |
| Li et al. | Visible light induced controlled cationic polymerization by in situ generated catalyst from manganese carbonyl | |
| Naruse et al. | Direct Observation of a Cyclic Vinyl Polymer Prepared by Anionic Polymerization using N‐Heterocyclic Carbene and Subsequent Ring‐Closure without Highly Diluted Conditions | |
| Yang et al. | Direct synthesis of highly reactive polyisobutylenes via cationic polymerization of isobutylene co‐initiated with TiCl4 in nonpolar hydrocarbon media | |
| Wang et al. | Synthesis of Block Copolymers Containing Polybutadiene Segments by Combination of Coordinative Chain Transfer Polymerization, Ring‐Opening Polymerization, and Atom Transfer Radical Polymerization | |
| CA2561908A1 (en) | A process for the preparation of vinylaromatic (co)polymers grafted on an elastomer in a controlled way | |
| CN109251263B (en) | Low cis-polybutadiene rubber and preparation method thereof, and HIPS resin and preparation method thereof | |
| CN102766303B (en) | Crystalline high cis copolymer elastomer/styryl polymer composite material and its preparation method | |
| LU504304B1 (en) | Modified styrene-butadiene rubber and the process for preparing the same and bitumen waterproofing membrane | |
| CN115353586B (en) | Preparation method of linear copolymer | |
| Ma et al. | Regulation of cis and trans microstructures of isoprene units in alternating copolymers via “space-limited” living species in anionic polymerization | |
| Wang et al. | Sulfonated polystyrene brushes grafted onto magnetic nanoparticles as recoverable catalysts for efficient synthesis of ethyl N‐phenylformimidate | |
| CN105330773B (en) | Rare earth catalyst composition and a kind of rare earth catalyst and its preparation method and application | |
| Martínez | Synthesis of PVC‐g‐PS through stereoselective nucleophilic substitution on PVC | |
| Kaneko et al. | Synthesis and characterization of polypropylene‐based block copolymers possessing polar segments via controlled radical polymerization | |
| US10315463B2 (en) | Method for synthesising a polymer having a hydroxyaryl group, product obtained using said method and composition containing same | |
| Huang et al. | Synthesis of azide end‐functionalized isotactic polypropylene building block and renewed modular synthesis of diblock copolymers of isotactic polypropylene and poly (ε‐caprolactone) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100818 |