CN104292392A - Preparation method of high-purity grafted functionalized copolymer - Google Patents
Preparation method of high-purity grafted functionalized copolymer Download PDFInfo
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- CN104292392A CN104292392A CN201410502367.3A CN201410502367A CN104292392A CN 104292392 A CN104292392 A CN 104292392A CN 201410502367 A CN201410502367 A CN 201410502367A CN 104292392 A CN104292392 A CN 104292392A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention relates to a preparation method of a high-purity grafted functionalized copolymer. The preparation method comprises the following steps: mixing and adding matrix resin, an antioxidant, an ultraviolet absorbent, other auxiliaries, an initiator and a grafted monomer into a double-screw extruder, grafting and copolymerizing at the melting temperature of the matrix resin, to obtain a crude grafted copolymer; adding the crude grafted copolymer into an autoclave, heating, keeping constant temperature, injecting carbon dioxide until the carbon dioxide is at supercritical state, maintaining for 5-120min, performing pressure relief to obtain the high-purity grafted functionalized copolymer. The high-purity grafted copolymer is prepared by firstly performing melt-grafting reaction through the double-screw extruder and purifying supercritical carbon dioxide, so that the preparation method is unique and novel and simple in preparation technology.
Description
Technical field
The invention belongs to the preparation field of high pure block copolymer, particularly a kind of preparation method of high-purity graft-functionalized multipolymer.
Background technology
Graft copolymerization, as the important means of polymer modification, is industrially widely used.The graft copolymer prepared by graft copolymerization, as the compatilizer in polymer alloy, can make two or more inconsistent materials originally effectively merge, thus obtains the high molecule alloy material of high-performance multifunction effectively.In addition, graft copolymer also has and applies widely in binder resin.Such as food packaging material is exactly that the material coextrusion of multiple opposed polarity forms, effectively bonding in order to effectively realize between opposed polarity macromolecular material, then must use graft copolymer.
But in graft copolymerization process, grafted monomer cannot transform completely, remains in copolymer product, not only can bring the disadvantageous effect such as peculiar smell, xanthochromia, also affects the performance of end article.Therefore, carry out follow-up purifying process to grafting copolymerization product, the non-graft reaction monomer that removing is wherein residual, reducing the volatile organic content in product, is the key of improving the quality of products.But graftomer traditional is at present all generally carry out the extraction of simple low molecular weight volatile thing by installing vacuum extractor on reactor, short owing to extracting the time, equipment vacuum degree is not high, low molecular weight volatile thing in product can not be removed completely, so some enterprise is in order to obtain pure graftomer, also need to carry out aftertreatment to product, be mainly: 1, graftomer is placed in loft drier, the low molecular weight volatile thing moving to particles of graft polymer surface is constantly taken away by hot air circulation, due to low molecular weight volatile thing, travelling speed is very slow in the polymer, this method needs chronic, energy consumption is very large, and can not ensure to remove low molecular weight volatile thing completely, 2, use all kinds of SOLVENTS to soak graft copolymerization product, go out wherein unreacted monomer with solvent extraction.Such treatment process cost is high, environmental pollution large, and efficiency is very low.And there is the graft copolymerization product that this kind of Methods For Purification obtains, also cannot use in the goods of food product pack, the contour hygienic requirements of medical packaging.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of high-purity graft-functionalized multipolymer, the present invention adopts and first carries out melting graft reaction through twin screw extruder, then purifies with supercritical co, preparation high-purity graft copolymer, very unique novelty, preparation technology is simple.
The preparation method of a kind of high-purity graft-functionalized multipolymer of the present invention, comprising:
(1) by matrix resin 100 parts, 0.3 part, oxidation inhibitor, UV light absorber 0.5 part, other auxiliary agents 0.5 part, initiator 0.0002-0.0005 part, grafted monomer 0.5-5 part, mixing adds in twin screw extruder, more than matrix resin melt temperature, carry out graft copolymerization, obtain thick graft copolymer;
(2) above-mentioned thick graft copolymer is added in autoclave, be heated to 32-160 DEG C, constant temperature, injecting carbon dioxide gas enters supercritical state to carbonic acid gas, the pressure of carbonic acid gas and supercritical state, make the state that graft copolymer reaches swelling wherein, keep 5-120min, release, carbon dioxide in release autoclave, graft copolymer recovers non-solvent swelling state, and volatile organic matter wherein removes with carbonic acid gas, obtain the graft copolymer product that high-purity, volatile organic matter are residual, obtain high-purity graft-functionalized multipolymer.
In described step (1), matrix resin is polyethylene, polypropylene, ethylene-octene copolymer, polystyrene, styrene-butadiene copolymer, SBS, the SBS of hydrogenation, styrene-isoprene copolymer, SIS, the SIS of hydrogenation, ethylene-propylene-non-conjugated diene hydrocarbon copolymer (terpolymer EP rubber), ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic acid copolymer, one or more in polyphenylene oxide.
In described step (1), oxidation inhibitor is antioxidant 1010, antioxidant 1076 or oxidation inhibitor 225 (commercially available); UV light absorber is ultraviolet absorbent UV-531, UV light absorber UV-329 or UV light absorber 7003 (commercially available).
In described step (1), other auxiliary agents are the mixture of EBS lubricant (ethylene bis stearic acid amide), grafting auxiliary agent.Wherein grafting auxiliary agent is a kind of in vinylbenzene, acetone and butanone or their mixture.
In described step (1), initiator is benzoyl peroxide and derivative, Diisopropyl azodicarboxylate and derivative thereof, 2, one or more in 5-dimethyl-2,5-bis(t-butylperoxy) hexane and derivative, dicumyl peroxide and derivative thereof, cyclohexanone peroxide and derivative thereof.
In described step (1), grafted monomer is one or more in MALEIC ANHYDRIDE (maleic anhydride), maleic acid (toxilic acid), FUMARIC ACID TECH GRADE (fumaric acid), vinylformic acid, methyl methacrylate, glycidyl methacrylate, vinylbenzene.
In described step (1), melt temperature is 160-300 DEG C.
In described step (2), injecting carbon dioxide is to pressure 7.5-45MPa, and carbonic acid gas enters supercritical state.
In described step (2), the release time is 1-5s.
In the graft-functionalized multipolymer of the middle gained of described step (2), volatile organic content is less than 0.1%.
As preferably, in step (2), be the graft copolymer of polyethylene, polypropylene, polystyrene, ethylene-octene copolymer for matrix resin, temperature is 32 to 60 DEG C.
As preferably, in step (2), be the graft copolymer of ethylene-propylene-non-conjugated diene hydrocarbon copolymer (terpolymer EP rubber), ethylene-vinyl alcohol copolymer for matrix resin, temperature is 60 to 80 DEG C.
As preferably, in step (2), be the graft copolymer of ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer for matrix resin, temperature is 80 to 100 DEG C.
As preferably, in step (2), for the graft copolymer that matrix resin is styrene-butadiene copolymer, SBS, styrene-isoprene copolymer, SIS, temperature is 100 to 120 DEG C.
As preferably, in step (2), be the graft copolymer of the SBS of hydrogenation, the SIS of hydrogenation for matrix resin, temperature is 120 to 140 DEG C.
As preferably, in step (2), be the graft copolymer of polyphenylene oxide for matrix resin, temperature is 140 to 160 DEG C.
As preferably, in step (2), be the graft copolymer of glycidyl methacrylate for grafted monomer, supercritical co pressure is 7.5-15MPa.
As preferably, in step (2), be the graft copolymer of methyl methacrylate for grafted monomer, supercritical co pressure is 12-20MPa.
As preferably, in step (2), be cinnamic graft copolymer for grafted monomer, supercritical co pressure is 18-25MPa.
As preferably, in step (2), be acrylic acid graft copolymer for grafted monomer, supercritical co pressure is 24-28MPa.
As preferably, in step (2), be the graft copolymer of MALEIC ANHYDRIDE (maleic anhydride) for grafted monomer, supercritical co pressure is 27-35MPa.
As preferably, in step (2), be the graft copolymer of maleic acid (toxilic acid) for grafted monomer, supercritical co pressure is 33-40MPa.
As preferably, in step (2), be the graft copolymer of FUMARIC ACID TECH GRADE (fumaric acid) for grafted monomer, supercritical co pressure is 40-45MPa.
As preferably, in step (2), graft copolymer prepared by the matrix resin for oxygen-free atom, supercritical co swelling time is 5-80min.
The present invention adopts and first carries out melting graft reaction through twin screw extruder, then purifies with supercritical co, and preparation high-purity graft copolymer, preparation technology is simple.Take twin screw as reaction vessel, the production of continuous high-efficient can be realized, and raw material mixes.Supercritical co has the good characteristic of gas and liquid simultaneously, has both had the high diffusibility of gas, has again the dissolving power of liquid, has the characteristic of low viscosity, low surface tension concurrently simultaneously.Based on the characteristic that these are outstanding, in the supercritical state, carbonic acid gas can penetrate in graft copolymer effectively, makes graft copolymer swelling.After swelling, volatile organic matter residual in graft copolymer is diffused in carbonic acid gas, and after keeping certain hour release, volatile organic matter is together discharged with carbonic acid gas, obtains the graft copolymer of high-purity.CO 2 supercritical state easily reaches, and cheap, nontoxic, does not have the problem of solvent residual of conventional solvent method of purification, also without the need to the operation such as recovery of solvent again.Therefore through the high-purity graft copolymer that this patent Methods For Purification obtains, not only cost for purification reduces, and can be applied to food and medicine and pack in the field of contour hygienic standard.
beneficial effect
The present invention adopts and first carries out melting graft reaction through twin screw extruder, then purifies with supercritical co, preparation high-purity graft copolymer, very unique novelty, and preparation technology is simple; CO 2 supercritical state easily reaches, and cheap, nontoxic, does not have the problem of solvent residual of conventional solvent method of purification, also without the need to the operation such as recovery of solvent again.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
The preparation of high-purity polypropylene grafted maleic anhydride graft copolymer:
According to the following formulation, thick polypropylene grafted maleic anhydride multipolymer is prepared with twin screw extruder fusion-grafting:
(1) polypropylene 100 parts of (2) antioxidant 1010s 0.3 part
(3) ultraviolet absorbent UV-531 0.5 part of (4) butanone 0.5 part
(5) Diisopropyl azodicarboxylate 0.0003 part of (6) maleic anhydride 2.0 parts
The thick polypropylene grafted maleic anhydride multipolymer obtained by twin screw extruder is placed in the autoclave of in advance constant temperature to 50 DEG C.Use topping-up pump to inject carbon dioxide to 30MPa pressure, make carbonic acid gas enter supercritical state.Keep pressure 60 minutes.Release rapidly afterwards, the release time is 3 seconds.Accurately take the polypropylene grafted maleic anhydride multipolymer of purifying through supercritical co, through soxhlet type in acetone 12 hours, the volatile organic matter of the trace that removing is wherein residual.Again the polypropylene grafted maleic anhydride polymkeric substance after process is placed in 100 DEG C of vacuum drying ovens to dry to constant weight.Compared by mass loss before and after acetone treatment, show that graft copolymer is after supercritical co is purified, volatile organic content is wherein 0.06%.
Embodiment 2
The preparation of high-purity ethylene-vinyl alcohol copolymer graft glycidyl methacrylate multipolymer.
According to the following formulation, crude ethylene-vinyl alcohol copolymer graft glycidyl methacrylate multipolymer is prepared with twin screw extruder fusion-grafting:
(1) ethylene-vinyl alcohol copolymer 100 parts of (2) antioxidant 1076s 0.3 part
(3) 0.5 part, UV light absorber UV-3290.5 part (4) acetone
(5) benzoyl peroxide 0.0002 part of (6) glycidyl methacrylate 1.8 parts
The crude ethylene prepared by twin screw extruder-vinyl alcohol copolymer graft glycidyl methacrylate multipolymer is placed in the autoclave of in advance constant temperature to 75 DEG C.Use topping-up pump to inject carbon dioxide to 15MPa pressure, make carbonic acid gas enter supercritical state.Keep pressure 90 minutes.Release rapidly afterwards, the release time is 3 seconds.Accurately take the ethylene-vinyl alcohol copolymer graft glycidyl methacrylate multipolymer of purifying through supercritical co, through soxhlet type in acetone 12 hours, the volatile organic matter of the trace that removing is wherein residual.Again the ethylene-vinyl alcohol copolymer graft glycidyl methacrylate multipolymer after process is placed in 100 DEG C of vacuum drying ovens to dry to constant weight.Compared by mass loss before and after acetone treatment, show that graft copolymer is after supercritical co is purified, volatile organic content is wherein 0.09%.
Embodiment 3
The preparation of high-purity ethylene-acrylic copolymer graft phenylethene multipolymer:
According to the following formulation, crude ethylene-acrylic copolymer graft phenylethene multipolymer is prepared with twin screw extruder fusion-grafting:
(1) 2250.3 parts, ethylene-acrylic acid copolymer 100 parts of (2) oxidation inhibitor
(3) UV light absorber 70030.5 parts of (4) EBS lubricants 0.5 part
(5) 2,5-dimethyl-2,5-bis(t-butylperoxy) hexanes 0.0004 part of (6) vinylbenzene 4.0 parts
The ethylene-acrylic acid copolymer graft phenylethene multipolymer obtained by twin screw extruder is placed in the autoclave of in advance constant temperature to 100 DEG C.Use topping-up pump to inject carbon dioxide to 21MPa pressure, make carbonic acid gas enter supercritical state.Keep pressure 90 minutes.Release rapidly afterwards, the release time is 4 seconds.Accurately take the ethylene-acrylic acid copolymer graft phenylethene multipolymer of purifying through supercritical co, through soxhlet type in acetone 12 hours, the volatile organic matter of the trace that removing is wherein residual.Again the ethylene-acrylic acid copolymer graft phenylethene multipolymer after process is placed in 100 DEG C of vacuum drying ovens to dry to constant weight.Compared by mass loss before and after acetone treatment, show that graft copolymer is after supercritical co is purified, volatile organic content is wherein 0.10%.
Embodiment 4
The preparation of high pure benzene ethylene-butadiene copolymer grafted methacrylic acid methyl terpolymer.
According to the following formulation, crude styrene-butadienecopolymer grafted methacrylic acid methyl terpolymer is prepared with twin screw extruder fusion-grafting:
(1) 2250.3 parts, styrene-butadiene copolymer 100 parts of (2) oxidation inhibitor
(3) UV light absorber V-5310.5 part (4) vinylbenzene 0.5 part
(5) dicumyl peroxide 0.0002 part of (6) methyl methacrylate 2.0 parts
The crude styrene prepared by twin screw extruder-butadienecopolymer grafted methacrylic acid methyl terpolymer is placed in the autoclave of in advance constant temperature to 110 DEG C.Use topping-up pump to inject carbon dioxide to 15MPa pressure, make carbonic acid gas enter supercritical state.Keep pressure 45 minutes.Release rapidly afterwards, the release time is 3 seconds.Accurately take the styrene-butadiene copolymer grafted methacrylic acid methyl terpolymer of purifying through supercritical co, through soxhlet type in acetone 12 hours, the volatile organic matter of the trace that removing is wherein residual.Again the styrene-butadiene copolymer grafted methacrylic acid methyl terpolymer after process is placed in 100 DEG C of vacuum drying ovens to dry to constant weight.Compared by mass loss before and after acetone treatment, show that graft copolymer is after supercritical co is purified, volatile organic content is wherein 0.07%.
Embodiment 5
The purification of polyphenylene oxide graft acrylic acid graft copolymer.
According to the following formulation, thick polyphenylene oxide grafted propylene acid copolymer is prepared with twin screw extruder fusion-grafting:
The thick polyphenylene oxide graft acrylic acid graft copolymer prepared by twin screw extruder is placed in the autoclave of in advance constant temperature to 150 DEG C.Use topping-up pump to inject carbon dioxide to 28MPa pressure, make carbonic acid gas enter supercritical state.Keep pressure 100 minutes.Release rapidly afterwards, the release time is 2 seconds.Accurately take the polyphenylene oxide graft acrylic acid graft copolymer of purifying through supercritical co, through soxhlet type in acetone 12 hours, the volatile organic matter of the trace that removing is wherein residual.Again the polyphenylene oxide graft acrylic acid graft copolymer after process is placed in 100 DEG C of vacuum drying ovens to dry to constant weight.Compared by mass loss before and after acetone treatment, show that graft copolymer is after supercritical co is purified, volatile organic content is wherein 0.03%.
Claims (10)
1. a preparation method for high-purity graft-functionalized multipolymer, comprising:
(1) by matrix resin 100 parts, 0.3 part, oxidation inhibitor, UV light absorber 0.5 part, other auxiliary agents 0.5 part, initiator 0.0002-0.0005 part, grafted monomer 0.5-5 part, mixing adds in twin screw extruder, carries out graft copolymerization, obtains thick graft copolymer;
(2) add in autoclave by above-mentioned thick graft copolymer, be heated to 32-160 DEG C, constant temperature, injecting carbon dioxide gas enters supercritical state to carbonic acid gas, and keep 5-120min, release, obtains graft-functionalized multipolymer.
2. the preparation method of a kind of high-purity graft-functionalized multipolymer according to claim 1, it is characterized in that: in described step (1), matrix resin is polyethylene, polypropylene, ethylene-octene copolymer, polystyrene, styrene-butadiene copolymer, SBS, the SBS of hydrogenation, styrene-isoprene copolymer, SIS, the SIS of hydrogenation, ethylene-propylene-non-conjugated diene hydrocarbon copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic acid copolymer, one or more in polyphenylene oxide.
3. the preparation method of a kind of high-purity graft-functionalized multipolymer according to claim 1, is characterized in that: in described step (1), oxidation inhibitor is antioxidant 1010, antioxidant 1076 or oxidation inhibitor 225; UV light absorber is ultraviolet absorbent UV-531, UV light absorber UV-329 or UV light absorber 7003.
4. the preparation method of a kind of high-purity graft-functionalized multipolymer according to claim 1, is characterized in that: in described step (1), other auxiliary agents are the mixture of EBS lubricant, grafting auxiliary agent; Wherein grafting auxiliary agent is one or more in vinylbenzene, acetone and butanone.
5. the preparation method of a kind of high-purity graft-functionalized multipolymer according to claim 1, it is characterized in that: in described step (1), initiator is benzoyl peroxide and derivative, Diisopropyl azodicarboxylate and derivative thereof, 2, one or more in 5-dimethyl-2,5-bis(t-butylperoxy) hexane and derivative, dicumyl peroxide and derivative thereof, cyclohexanone peroxide and derivative thereof.
6. the preparation method of a kind of high-purity graft-functionalized multipolymer according to claim 1, is characterized in that: in described step (1), grafted monomer is one or more in MALEIC ANHYDRIDE, maleic acid, FUMARIC ACID TECH GRADE, vinylformic acid, methyl methacrylate, glycidyl methacrylate, vinylbenzene.
7. the preparation method of a kind of high-purity graft-functionalized multipolymer according to claim 1, it is characterized in that: described step carries out graft copolymerization in (1) more than matrix resin melt temperature, matrix resin melt temperature is 160-300 DEG C.
8. the preparation method of a kind of high-purity graft-functionalized multipolymer according to claim 1, is characterized in that: in described step (2), injecting carbon dioxide is to pressure 7.5-45MPa, and carbonic acid gas enters supercritical state.
9. the preparation method of a kind of high-purity graft-functionalized multipolymer according to claim 1, is characterized in that: in described step (2), the release time is 1-5s.
10. the preparation method of a kind of high-purity graft-functionalized multipolymer according to claim 1, is characterized in that: in the graft-functionalized multipolymer of the middle gained of described step (2), volatile organic matter amount percentage composition is less than 0.1%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108546531A (en) * | 2018-03-15 | 2018-09-18 | 宁波能之光新材料科技股份有限公司 | A kind of preparation method of the binder resin of low VOC content |
| CN108822467A (en) * | 2018-04-25 | 2018-11-16 | 宁波能之光新材料科技股份有限公司 | A method of high-purity grafted olefin polymers are prepared using supercritical technology |
| CN113968940A (en) * | 2021-11-29 | 2022-01-25 | 山东京博石油化工有限公司 | Method for preparing low-odor polypropylene grafted maleic anhydride beads under assistance of supercritical carbon dioxide |
-
2014
- 2014-09-26 CN CN201410502367.3A patent/CN104292392A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108546531A (en) * | 2018-03-15 | 2018-09-18 | 宁波能之光新材料科技股份有限公司 | A kind of preparation method of the binder resin of low VOC content |
| CN108822467A (en) * | 2018-04-25 | 2018-11-16 | 宁波能之光新材料科技股份有限公司 | A method of high-purity grafted olefin polymers are prepared using supercritical technology |
| CN113968940A (en) * | 2021-11-29 | 2022-01-25 | 山东京博石油化工有限公司 | Method for preparing low-odor polypropylene grafted maleic anhydride beads under assistance of supercritical carbon dioxide |
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Application publication date: 20150121 |