CN104211860B - Preparation method of modified natural skim rubber - Google Patents
Preparation method of modified natural skim rubber Download PDFInfo
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- CN104211860B CN104211860B CN201410488274.XA CN201410488274A CN104211860B CN 104211860 B CN104211860 B CN 104211860B CN 201410488274 A CN201410488274 A CN 201410488274A CN 104211860 B CN104211860 B CN 104211860B
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Abstract
The invention belongs to the field of rubber processing and relates to a preparation method of modified natural skim rubber. The preparation method comprises the steps of pre-processing natural skim rubber and dissolving the natural skim rubber in methylbenzene, dropwise adding a mixed solution prepared by an oil soluble initiating agent and fluorinated acrylate monomer after temperature rise to obtain a natural skim rubber grafted copolymer coarse product solution; pouring methyl alcohol into the natural skim rubber grafted copolymer coarse product solution and performing precipitation and filtering to obtain a coarse product; using petroleum ether to perform extraction on the coarse product, and then using acetone to perform extraction and drying to obtain a fluorinated acrylate grafted natural skim rubber copolymer. The preparation method is simple and convenient, the process is easy to control, reaction conditions are gentle, original advantages of the natural skim rubber can be kept and the natural skim rubber can also have specific weather resistance and organic solvent resistance of a fluorine-containing polymer, thermo-oxidative aging resistance, ozone resistance, ultraviolet ray resistance and the like through fluorine-containing functionalized chemical modification on natural skim rubber molecular chains.
Description
Technical field
The invention belongs to rubber processing, relate to a kind of method of modifying of natural skim rubber, particularly relate to the preparation method of the clear grafting rubbers fluoro-acrylate copolymer of a kind of solid natural gum.
Background technology
Latex on natural rubber tree, in the process of the dense newborn natural rubber latex of preparative centrifugation, the molecular weight produced is low, it is clear that the by product of drc low (rubber hydrocarbon concentration) is glue, glue is obtained natural skim rubber (NR-s) clearly after solidifying drying, the drc clear due to glue is lower, about about 5%, containing a large amount of non-rubber component, therefore, skim rubber second-rate, variability is large, easy incipient scorch, mechanical property is relatively low, generally be only applicable to the rubber item that specification of quality is not high, range of application is limited, therefore Rubber processing industry needs to carry out modification to natural skim rubber, to its performance can be improved.
At present, the domestic and international study on the modification for natural skim rubber mainly adopts Nano-meter CaCO3
3, polyorganosilicate, imvite modified and hydrogenation modification is carried out to natural rubber molecular chain.As, Alex, R. [Alex is waited, R.and C.Nah (2006) .Journal of Applied Polymer Science 102 (4): 3277-3285] adopt alkali and tensio-active agent pre-treatment natural gum clear, eliminate the aqueous phase of clarification, become cream, add polyorganosilicate and prepare polyorganosilicate/rubber nano composite material by the method that formic acid condenses, find tensile strength, modulus and heat aging performance improve.Fang Haixiong etc. [Fang Haixiong, symbol new (2007). Guangdong chemical industry (08): 26-28] adopt emulsion coagulation method, have studied Nano-meter CaCO3
3the preparation of/skim rubber matrix material and mechanical property.Result shows: emulsion coagulation method prepares Nano-meter CaCO3
3mixing velocity, mixing time during/skim rubber matrix material, Nano-meter CaCO3
3adding Way and Nano-meter CaCO3
3the mechanical property of consumption on matrix material has larger impact, and the composite material combination property prepared of the emulsion coagulation method composite material combination property standby compared with mechanical blending legal system is good.[the Chen Guixiong such as Chen Guixiong, Qin Jianzhong, et al. (2008). " performance study of modification skim rubber and matrix material thereof. " rubber industry (08): 476-479] adopt organically-modified sodium-based montmorillonite to carry out composite modified to skim rubber, preparation modification skim rubber, and with assorted glue, loudspeaker chewing-gum, latex foam and waste water glue compound, research modification skim rubber and the properties of matrix material thereof.Result shows, modified adhesive clear rubber plasticity initial value (P
0) increase substantially compared with skim rubber with plasticity retention(percentage) (PRI value), physicals and thermal characteristics are also obviously improved; Significantly improve compared with the physicals of the matrix materials such as modification skim rubber/assorted glue and assorted glue etc., P
0also increase is in various degree had with PRI value.Simma, K. [Simma is waited, K., G.L.Rempel, et al. (2009) .Polymer Degradation and Stability 94 (11): 1914-1923] adopt and modification is carried out to the method for natural skim rubber unsaturated double-bond hydrogenation, ozone resistance gets a promotion.
Fluoropolymer has extremely strong oleophobic, hydrophobicity; preferably optical property; high heat-resisting, excellent weather resistance, chemical-resistant reagent and weathering resistance and ultralow frictional coefficient and good biocompatibility; the very big concern of material supply section scholar has been obtained as a kind of polymeric constituent; now, become at antifouling and automatic cleaning coating, history relic is protected; bio-sensing, one of field preparation important source material with excellent performance such as solar energy equipment.Up to now, the report of the chemically modified study on the modification molecular chain of skim rubber being carried out to functional fluoropolymer is not yet had.
Summary of the invention
The object of the invention is the preparation method that a kind of modified natural skim rubber is provided for the deficiencies in the prior art, by carrying out the chemically modified modification of functional fluoropolymer at the clear rubber molecular chain of natural gum, at side chain graft fluoropolymer, the original advantage of natural skim rubber can be kept, natural skim rubber can be given again and possess the distinctive weathering resistance of fluoropolymer, organic solvent-resistant, heat oxygen aging resistance, ozone resistance and uviolresistance, excellent dielectric properties, wear resistance, surface property etc., this method simple process, process easily controls, reaction conditions is gentle.
The present invention with the natural skim rubber of solid for raw material, pass through solution grafting, adopt grafted monomer and the continuous constant current dripping method of initiator, fluorinated acrylate monomer grafted fluoropolymer acrylate monomer on the clear rubbery polyisoprene molecular chain of natural gum is caused with oil-soluble initiator, introduce fluoropolymer segment, functional fluoropolymer modification is carried out to the clear rubber molecule main chain of natural gum.
Object of the present invention is achieved through the following technical solutions:
A preparation method for modified natural skim rubber, comprises the following steps:
1, with the natural skim rubber 24h of acetone extraction, dry, obtain the natural skim rubber of pre-treatment.
2, according to the mass fraction, 2 ~ 6 parts of natural skim rubbers of pre-treatment are carried out Mechanical Crushing, is placed in reaction vessel, then add 70 ~ 75 parts of toluene, reaction vessel is warming up to 50 DEG C simultaneously, is stirred to dissolving, obtain the clear rubber solutions of natural gum.
3, be dissolved in toluene by oil-soluble initiator, fluorinated acrylate monomer, stand-by, wherein, oil-soluble initiator is the quality in fluorinated acrylate monomer, and its consumption is 0.7 ~ 1.5wt%.Fluorinated acrylate monomer is that its consumption is 20 ~ 60wt% with the clear rubber mass gauge of natural gum.In this step, toluene is in fluorinated acrylate monomer mass fraction, and every part of fluorinated acrylate monomer uses 2 ~ 4 parts of toluene.
4, clear for natural gum rubber solutions is warming up to 75 ~ 90 DEG C, then by step 3) in the mixing solutions of the initiator that obtains and fluorinated acrylate monomer, with the speed of 0.15mL/min, drip in reactor, react 4 ~ 8h again after dripping, after question response terminates, add Resorcinol termination reaction, cooling, obtains the clear rubber graft copolymer crude product in solution of natural gum.
5, pour clear for natural gum rubber graft crude product in solution into methyl alcohol to precipitate, filter, wash 3 times, put into the dry 24h of 50 DEG C of vacuum drying ovens, obtain the clear rubber graft copolymer crude product of natural gum.
6, by clear for natural gum rubber graft copolymer crude product, first use sherwood oil extracting 24h, after vacuum-drying, then use acetone extraction 24h, dry, obtain the clear rubbery copolymer of fluorinated acrylate grafting natural gum.
Described oil-soluble initiator is the one in benzoyl peroxide, isopropyl benzene hydroperoxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl.
Described fluorinated acrylate monomer is one or more in trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester, vinylformic acid hexafluoro butyl ester, vinylformic acid ten trifluoro monooctyl ester.
Compared with prior art, tool of the present invention has the following advantages:
1, the present invention adopts solution graft polymerization method and permanent dropping technology, and reacting balance, technique is simple.
The hydrogenation modification technique of 2, relatively traditional natural skim rubber, reaction conditions of the present invention is gentle, and technique is simple and easy to control, need not high pressure, catalysis.
3, chemically modified modification is carried out, with Nano-meter CaCO3 from the clear rubber molecule backbone structure of natural gum
3, polyorganosilicate, the clear rubber phase ratio of natural gum of class montmorillonite filled modification, can not cause and cause rheological property to be deteriorated because of mineral filler, more easily carry out following process.
Accompanying drawing explanation
The principle schematic of Fig. 1 natural gum clear grafting rubbers fluorinated acrylate copolymerization.
The infrared spectrogram of the natural skim rubber of Fig. 2 pre-treatment.
Fig. 3 is the infrared spectrogram of the clear rubbery copolymer of embodiment one gained fluorinated acrylate grafting natural gum.
Fig. 4 is the infrared spectrogram of the clear rubbery copolymer of embodiment two gained fluorinated acrylate grafting natural gum.
Fig. 5 is the infrared spectrogram of the clear rubbery copolymer of embodiment three gained fluorinated acrylate grafting natural gum.
Fig. 6 is the infrared spectrogram of the clear rubbery copolymer of embodiment four gained fluorinated acrylate grafting natural gum.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.
Embodiment one
0.015g benzoyl peroxide and 1.00g Hexafluorobutyl mathacrylate are dissolved in 5.00g toluene stand-by.
With the natural skim rubber 24h of acetone extraction, dry, obtain the natural skim rubber of pre-treatment.Pretreated for 2.5g natural skim rubber is carried out Mechanical Crushing, is placed in reaction vessel, then add 70g toluene, reaction vessel is warming up to 50 DEG C, is stirred to dissolving with employing mechanical stirrer simultaneously, obtains the clear rubber solutions of natural gum, and temperature is risen to 85 DEG C.Then adopt HL-2B digital display constant flow pump (Industrial Co., Ltd. of upper Nereid section) by the mixing solutions of the initiator for preparing and fluorinated acrylate monomer above, with the speed of 0.15mL/min, drip in reactor, 7h is reacted again after dripping, after question response terminates, cooling, adds 0.05g Resorcinol termination reaction, obtains natural gum clear rubber graft copolymer thing crude product in solution.
Pour clear for natural gum rubber graft crude product in solution into methyl alcohol to precipitate, filter, wash 3 times, put into the dry 24h of 50 DEG C of vacuum drying ovens, then use sherwood oil extracting 24h respectively, after vacuum-drying, then use acetone extraction 24h, drying, obtains the clear rubbery copolymer of fluorinated acrylate grafting natural gum.
Fig. 2 is the infrared spectrogram of the natural skim rubber of pre-treatment, and as can be seen from Fig., pretreated natural skim rubber is at 2962cm
-1, 2927cm
-1, 2855cm
-1there is the C-H stretching vibration peak of obvious methyl, methylene radical and methyne, at 1450cm
-1, 1376cm
-1, 836cm
-1there is the unsymmetrically formation vibration of methylene radical, formation vibration outside the formation vibration of methyl and the two face replacing c h bond on carbon-to-carbon double bond of cis.Fig. 3 is the infrared spectrogram of the clear rubbery copolymer of fluorinated acrylate grafting natural gum of the gained of the present embodiment, in figure except the major absorbance peak of above-mentioned natural skim rubber, at 1734cm
-1obvious C=O stretching vibration, this belongs to the carbonyl absorption of fluorinated acrylate, in addition at 1266cm
-1~ 1314cm
-1small peak also belong to the stretching vibration absorption peak of C-F, this shows the natural skim rubber of the successful grafting of fluorinated acrylate, obtains the clear rubbery copolymer of fluorinated acrylate grafting natural gum.
Embodiment two
0.016g isopropyl benzene hydroperoxide and 2.019g trifluoroethyl methacrylate are dissolved in 5.006g toluene stand-by.
With the natural skim rubber 24h of acetone extraction, dry, obtain the natural skim rubber of pre-treatment.Pretreated for 5.044g natural skim rubber is carried out Mechanical Crushing, is placed in reaction vessel, then add 70.200g toluene, simultaneous reactions container is warming up to 50 DEG C, be stirred to dissolving with employing mechanical stirrer simultaneously, obtain the clear rubber solutions of natural gum, and temperature is risen to 85 DEG C.Then adopt HL-2B digital display constant flow pump (Industrial Co., Ltd. of upper Nereid section) by the mixing solutions of the initiator for preparing and fluorinated acrylate monomer above, with the speed of 0.15mL/min, drip in reactor, 5h is reacted again after dripping, after question response terminates, cooling, adds 0.05g Resorcinol termination reaction, obtains natural gum clear rubber graft copolymer thing crude product in solution.
Pour clear for natural gum rubber graft crude product in solution into methyl alcohol to precipitate, filter, wash 3 times, put into the dry 24h of 50 DEG C of vacuum drying ovens, then use sherwood oil extracting 24h respectively, after vacuum-drying, then use acetone extraction 24h, drying, obtains the clear rubbery copolymer of fluorinated acrylate grafting natural gum.
Fig. 4 is the infrared spectrogram of the present embodiment products therefrom.
Embodiment three
0.018g 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2.050g methacrylic acid ten trifluoro monooctyl ester are dissolved in 5.006g toluene stand-by.
With the natural skim rubber 24h of acetone extraction, dry, obtain the natural skim rubber of pre-treatment.Pretreated for 5.000g natural skim rubber is carried out Mechanical Crushing, is placed in reaction vessel, then add 70.000g toluene, simultaneous reactions container is warming up to 50 DEG C, be stirred to dissolving with employing mechanical stirrer simultaneously, obtain the clear rubber solutions of natural gum, and temperature is risen to 80 DEG C.Then adopt HL-2B digital display constant flow pump (Industrial Co., Ltd. of upper Nereid section) by the mixing solutions of the initiator for preparing and fluorinated acrylate monomer above, with the speed of 0.15mL/min, drip in reactor, 5h is reacted again after dripping, after question response terminates, cooling, adds 0.05g Resorcinol termination reaction, obtains natural gum clear rubber graft copolymer thing crude product in solution.
Pour clear for natural gum rubber graft crude product in solution into methyl alcohol to precipitate, filter, wash 3 times, put into the dry 24h of 50 DEG C of vacuum drying ovens, then use sherwood oil extracting 24h respectively, after vacuum-drying, then use acetone extraction 24h, drying, obtains the clear rubbery copolymer of fluorinated acrylate grafting natural gum.
Fig. 5 is the infrared spectrogram of the present embodiment products therefrom.
Embodiment four
0.018g azo-bis-iso-dimethyl and 2.001g vinylformic acid hexafluoro butyl ester are dissolved in 7.008g toluene stand-by.
With the natural skim rubber 24h of acetone extraction, dry, obtain the natural skim rubber of pre-treatment.Pretreated for 5.000g natural skim rubber is carried out Mechanical Crushing, is placed in reaction vessel, then add 70.091g toluene, simultaneous reactions container is warming up to 50 DEG C, be stirred to dissolving with employing mechanical stirrer simultaneously, obtain the clear rubber solutions of natural gum, and temperature is risen to 80 DEG C.Then adopt HL-2B digital display constant flow pump (Industrial Co., Ltd. of upper Nereid section) by the mixing solutions of the initiator for preparing and fluorinated acrylate monomer above, with the speed of 0.15mL/min, drip in reactor, 6h is reacted again after dripping, after question response terminates, cooling, adds 0.05g Resorcinol termination reaction, obtains natural gum clear rubber graft copolymer thing crude product in solution.
Pour clear for natural gum rubber graft crude product in solution into methyl alcohol to precipitate, filter, wash 3 times, put into the dry 24h of 50 DEG C of vacuum drying ovens, then use sherwood oil extracting 24h respectively, after vacuum-drying, then use acetone extraction 24h, drying, obtains the clear rubbery copolymer of fluorinated acrylate grafting natural gum.
Fig. 6 is the infrared spectrogram of the present embodiment products therefrom.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (2)
1. a preparation method for modified natural skim rubber, is characterized in that, comprises the following steps:
1), with the natural skim rubber 24h of acetone extraction, dry, obtain the natural skim rubber of pre-treatment;
2), according to the mass fraction, 2 ~ 6 parts of natural skim rubbers of pre-treatment are carried out Mechanical Crushing, is placed in reaction vessel, then add 70 ~ 75 parts of toluene, reaction vessel is warming up to 50 DEG C simultaneously, is stirred to dissolving, obtain the clear rubber solutions of natural gum;
3), be dissolved in toluene by oil-soluble initiator, fluorinated acrylate monomer, stand-by, wherein, oil-soluble initiator is the quality in fluorinated acrylate monomer, and its consumption is 0.7 ~ 1.5wt%; Fluorinated acrylate monomer is that its consumption is 20 ~ 60wt% with the clear rubber mass gauge of natural gum; Toluene is in fluorinated acrylate monomer mass fraction, and every part of fluorinated acrylate monomer uses 2 ~ 4 parts of toluene; Described fluorinated acrylate monomer is one or more in trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester, vinylformic acid hexafluoro butyl ester, vinylformic acid ten trifluoro monooctyl ester;
4), clear for natural gum rubber solutions is warming up to 75 ~ 90 DEG C, then by step 3) in the mixing solutions of the initiator that obtains and fluorinated acrylate monomer, with the speed of 0.15mL/min, drip in reactor, react 4 ~ 8h again after dripping, after question response terminates, add Resorcinol termination reaction, cooling, obtains the clear rubber graft copolymer crude product in solution of natural gum;
5), pour clear for natural gum rubber graft crude product in solution into methyl alcohol and precipitate, filter, wash 3 times, put into 50 DEG C of vacuum drying ovens drying 24h, obtain the clear rubber graft copolymer crude product of natural gum;
6), by clear for natural gum rubber graft copolymer crude product, first use sherwood oil extracting 24h, after vacuum-drying, then use acetone extraction 24h, dry, obtain the clear rubbery copolymer of fluorinated acrylate grafting natural gum.
2. preparation method according to claim 1, is characterized in that: described oil-soluble initiator is the one in benzoyl peroxide, isopropyl benzene hydroperoxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803872A (en) * | 2005-12-05 | 2006-07-19 | 南开大学 | Styrene, divinylbenzene and natural rubber copolymer and preparation method thereof |
| CN102504049A (en) * | 2011-11-17 | 2012-06-20 | 海南大学 | Method for recovering skim rubber |
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| DE602004017914D1 (en) * | 2004-08-04 | 2009-01-02 | Pirelli & C Spa | THERMOPLASTIC ELASTOMER MATERIAL AND MANUFACTURING METHOD THEREFOR |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803872A (en) * | 2005-12-05 | 2006-07-19 | 南开大学 | Styrene, divinylbenzene and natural rubber copolymer and preparation method thereof |
| CN102504049A (en) * | 2011-11-17 | 2012-06-20 | 海南大学 | Method for recovering skim rubber |
Non-Patent Citations (2)
| Title |
|---|
| 改性胶清橡胶及其复合材料的性能研究;陈贵雄等;《橡胶工业》;20080825;第55卷(第08期);全文 * |
| 纳米CaCO_3/胶清橡胶复合材料的研究;方海雄等;《广东化工》;20070825;第34卷(第08期);全文 * |
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