CN101143946A - Method for extruding and preparing maleation polypropylene by supercritical reaction - Google Patents
Method for extruding and preparing maleation polypropylene by supercritical reaction Download PDFInfo
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- CN101143946A CN101143946A CNA200710071080XA CN200710071080A CN101143946A CN 101143946 A CN101143946 A CN 101143946A CN A200710071080X A CNA200710071080X A CN A200710071080XA CN 200710071080 A CN200710071080 A CN 200710071080A CN 101143946 A CN101143946 A CN 101143946A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
- B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a method for preparing maleic polypropylene by supercritical reaction extrusion, wherein polypropylene, maleic series, additives and initiators are added into a screw extruder, and supercritical CO2 is injected into the system by a supercritical generation device, which makes up 0.1-20 percent of the total mass of reactant; the rotating speed of main screwed pole of the extruder is 50-600 rpm, and the extruder is divided into a plurality of heating areas, the temperature of the firs area is 180-220 DEG C, and the temperature of the other areas is 140-200 DEG C and the reaction time is 1-20 min. The grafting rate of maleic polypropylene prepared by the invention, with high grafting rate and grafting efficiency, can reach up to 1.2 percent, the grafting efficiency can reach up to 90 percent and the melt flow rate is adjustable within 5-50g/10min. The method of the invention is suitable for continuous production and has low energy consumption, and is environment-friendly. The product shows superiority in color, uniformity, processing property and mechanical property and so on, which is suitable for the fields of polymer compatilizer, adhesive and surface coating etc.
Description
Technical field
The present invention relates to prepare the method for maleation polypropylene, relate in particular to the method for extruding and preparing maleation polypropylene by supercritical reaction, belong to technical field of polymer materials.
Background technology
Polypropylene (PP) is the fastest resins for universal use of rate of growth in the polymer arts.Because its linear chain non-polar molecule structure, cause narrow molecular weight distribution, melt strength low, its wetting ability, cementability and radical reaction activity are unsatisfactory, are difficult to and polar polymer or filler blend, compound, have limited its range of application.
For improving this performance, often adopt the method for modifying of grafting polar group on main chain, make the graft product polar, wherein the research for grafted maleic anhydride is the most extensive.Traditional grafting method has solution graft copolymerization, the suspension grafting, solid phase grafting and fusion-grafting, in application, all there is certain shortcoming: solution graft copolymerization, suspension grafting and solid phase grafting have all been used organic solvent, environment is caused certain influence, and then both are subjected to organic solvent diffusion capabilities limits again, only carry out on the macromole surface.CN1605596 discloses in system and to have introduced supercritical CO 2 and carry out solid phase grafting, is reflected in the autoclave and carries out, and pressure is up to 10-30Mpa, and owing to be rhythmic reaction, long reaction time, production efficiency is low, is not suitable for large-scale industrialization production; Fusion-grafting is everlasting and is carried out in the forcing machine, and reaction is carried out continuously, and production efficiency is higher, keeps the fusion fluidised form for making raw material, chooses temperature of reaction more than the raw material fusing point.In industrial production, problem that is difficult to avoid of melting graft reaction is exactly that polyacrylic degraded is serious, has influenced polyacrylic crystallization melting behavior and broad perspectives thereof.Simultaneously, the percentage of grafting of product, particularly grafting efficiency are difficult to improve, and maleic anhydride has only the small portion reactive grafting in the raw material, has increased production cost, and influences the product purity quality.At present, in the research of the fusion-grafting reported, all can't overcome degraded and improve grafting efficiency simultaneously, thus effective control degradation, and the percentage of grafting and the grafting efficiency that further improve product become the key issue that needs to be resolved hurrily in the industrial production.
Summary of the invention
The objective of the invention is for overcoming main chain degraded and the low shortcoming of grafting efficiency under the existing industrial technology condition, a kind of method of extruding and preparing maleation polypropylene by supercritical reaction is provided, improves percentage of grafting and grafting efficiency when suppressing degraded in the polypropylene fusion graft maleinisation to be implemented in.
The method of extruding and preparing maleation polypropylene by supercritical reaction of the present invention, its step is as follows:
(1) reactant is by weight:
100 parts of polypropylene
1～15 part of maleation series matter
0～3 part of auxiliary agent
0.1～6 part of initiator
(2) above-mentioned reactant is introduced in the screw extrusion press, and utilized supercritical CO
2Generating unit injects supercritical CO in reaction system
2Fluid, supercritical CO
2The fluidic quality accounts for the 0.1%-20% of reactant total mass, 50 rev/mins-600 rev/mins of forcing machine driving screw rotating speeds, screw extrusion press divides a plurality of heating zone, wherein first Heating Zone Temperature is 180 ℃-220 ℃, 140 ℃-200 ℃ of all the other Heating Zone Temperature, reacted 1-20 minute, extruded product is through devolatilization, cooling, granulation, dry getting final product.
Above-mentioned polypropylene is that molecular weight ranges is the commercial isotactic homopolymerization of 10000g/mol-1000000g/mol or copolymerized type propene polymer particle, powder or its mixture.
Among the present invention, said maleation series matter can be any or several compound in toxilic acid, maleic anhydride, dibutyl maleinate, vinylformic acid, glycidyl acrylate and the glycidyl methacrylate.
Said initiator can be dicumyl peroxide, Diisopropyl azodicarboxylate, 2,5-dimethyl-2, any in 5-di-tert-butyl peroxide normal hexane and the dibenzoyl peroxide or several mixture.
Among the present invention, said auxiliary agent can adopt vinylbenzene, antioxidant, the light and thermally stable agent, hydrotalcite, polynite, diatomite, clay, vinyl silanes, in lime carbonate and the polyphosphoric acid amine any or several compound, wherein antioxidant is 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester, four (4-hydroxyls-3,5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester, 2, the 6-tertiary butyl-4-methylphenol, 2, the amino p-cresol of the 6-tertiary butyl-alpha, alpha-dimethyl, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) one or more compounds in ester and the Tyox B, the light and thermally stable agent is two (2,2,6, the 6-tetramethyl-piperidyl) certain herbaceous plants with big flowers two acid esters, one or more compounds in 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole and the calcium stearate.
Add antioxidant, light and thermally stable agent commonly used, can avoid the oxidative degradation of polypropylene in melt extruding process, add hydrotalcite, polynite, diatomite, clay, vinyl silanes, lime carbonate, polyphosphoric acid amine etc., can reduce cost and improve the low-smoke and flame retardant performance.
Among the preparation method of the present invention, the temperature that the supercritical CO 2 generating unit is set is 50 ℃-200 ℃, and pressure is 8.0Mpa-30Mpa, 80 ℃-180 ℃ of preferred temperature, and pressure 8.0Mpa-15Mpa generates supercritical CO
2Fluid is introduced by the screw extrusion press side line.
Used forcing machine is single screw rod or double-screw type, and length-to-diameter ratio L/D is 24: 1-48: 1.
Among the preparation method of the present invention, the mode that reactant is introduced in the screw extrusion press has following several:
1) the direct premix charging of maleation series matter and auxiliary agent and initiator and polypropylene;
2) maleation series matter and auxiliary agent and the charging of polypropylene premix, and initiator becomes the side entry feed of the solution of 20%-80% from screw extrusion press with ethanol, acetone or both mixture diluted;
3) polypropylene and the charging of auxiliary agent premix, and the maleation series matter becomes the side entry feed of the solution of 20%-80% from screw extrusion press with initiator with ethanol, acetone or both mixture diluted;
4) maleation series matter and the charging of polypropylene premix, auxiliary agent becomes the side entry feed of the solution of 20%-80% from screw extrusion press with initiator with ethanol, acetone or both mixture diluted.
Beneficial effect of the present invention is:
More traditional fusion-grafting prepares the method for maleation polypropylene, and innovation of the present invention is to introduce supercritical technology, utilizes supercritical CO
2Lower critical temperature and emergent pressure and in polymer melt good swelling behavior, reduce temperature of reaction reinforcing mass transfer simultaneously, thereby reach the purpose that suppresses degraded, improves grafting efficiency.Compared with prior art, the invention has the advantages that the maleation graft product, percentage of grafting can reach 0.3-1.2%, and grafting efficiency can reach 50-90%, and the melt flow rate (MFR) scope is 5-50g/10min.Can make that maleation series matter and auxiliary agent and initiator addition reduce greatly in the raw material, reduce cost, and the product purity height, degraded simultaneously obviously weakens, and performance improves.
Embodiment
Further specify the present invention below in conjunction with embodiment.Following example only is in order to illustrate, rather than limitation of the present invention.
Embodiment 1
Get 100 parts of polypropylene, 1 part of toxilic acid, 1 part of vinylbenzene and 2, the composite assistant of the 6-tertiary butyl-4-methylphenol, 6 parts of Diisopropyl azodicarboxylate initiators, mix fully from the barrel charging, adopting L/D is 24: 1 twin screw extruder, and implantation quality accounts for 0.5% supercritical CO of reactant total mass in reaction system
2Fluid, 600 rev/mins of forcing machine driving screw rotating speeds divide 2 heating zone, 220 ℃ of first Heating Zone Temperature, 190 ℃ of second Heating Zone Temperature were reacted 1 minute, carried out performance test after the granulation of gained extruded product, and its performance inventory is in table 1.
Embodiment 2
Get 100 parts of polypropylene, 2 parts of maleic anhydrides, 0.5 part 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester, calcium stearate and lime carbonate composite assistant, mix fully from the barrel charging, 0.6 part of dicumyl peroxide initiator becomes 20% solution with alcohol dilution, from the sidepiece adding reaction system of screw extrusion press, adopting L/D is 36: 1 twin screw extruder, and implantation quality accounts for 5% supercritical CO of reactant total mass in reaction system
2Fluid, 150 rev/mins of forcing machine driving screw rotating speeds divide 2 heating zone, 180 ℃ of first Heating Zone Temperature, 160 ℃ of second Heating Zone Temperature were reacted 4 minutes, and the gained extruded product carries out performance test after granulation, and its performance inventory is in table 1.
Embodiment 3
Get 100 parts of polypropylene, from the barrel charging, with 15 parts of glycidyl methacrylate, the composite assistant of 3 parts of diatomite and lime carbonate and 1 part 2,5-dimethyl-2,5-di-tert-butyl peroxide normal hexane initiator is diluted to 80% solution with the ethanol acetone mixed solvent, from the sidepiece adding reaction system of screw extrusion press, adopting L/D is 48: 1 single screw extrusion machine, and implantation quality accounts for 2% supercritical CO of reactant total mass in reaction system
2Fluid, 50 rev/mins of forcing machine driving screw rotating speeds divide 3 heating zone, 200 ℃ of first Heating Zone Temperature, 180 ℃ of second Heating Zone Temperature, 170 ℃ of the 3rd Heating Zone Temperature, reacted 20 minutes, the gained extruded product carries out performance test after granulation, and its performance inventory is in table 1.
Embodiment 4
Get 100 parts of polypropylene, 10 parts of toxilic acid fourth diester, mix fully from the barrel charging, with 2.5 parts of vinyl silanes and four (4-hydroxyls-3,5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester composite assistant, 0.1 part of dibenzoyl peroxide initiator becomes 65% solution with alcohol dilution, from the sidepiece adding reaction system of screw extrusion press, adopting L/D is 36: 1 single screw extrusion machine, and implantation quality accounts for 20% supercritical CO of reactant total mass in reaction system
2Fluid, 200 rev/mins of forcing machine driving screw rotating speeds, divide 5 heating zone, 180 ℃ of first Heating Zone Temperature, 170 ℃ of second Heating Zone Temperature, 160 ℃ of the 3rd Heating Zone Temperature, 150 ℃ of the 4th Heating Zone Temperature, 140 ℃ of slender acanthopanax hot-zone temperature were reacted 2 minutes, the gained extruded product carries out performance test after granulation, its performance inventory is in table 1.
Embodiment 5
Get 100 parts of polypropylene, the compound monomer altogether of 1 part of methacrylic acid and maleic anhydride, mix fully from the barrel charging, 0.5 part of dicumyl peroxide initiator become 30% solution with acetone diluted, add the reaction system from the sidepiece of screw extrusion press, adopting L/D is 36: 1 twin screw extruder, and implantation quality accounts for 15% supercritical CO of reactant total mass in reaction system
2Fluid, 100 rev/mins of forcing machine driving screw rotating speeds, divide 4 heating zone, 180 ℃ of first Heating Zone Temperature, 170 ℃ of second Heating Zone Temperature, 160 ℃ of the 3rd Heating Zone Temperature, 150 ℃ of the 4th Heating Zone Temperature, reacted 3 minutes, the gained extruded product carries out performance test after granulation, and its performance inventory is in table 1.
Embodiment 6
Get 100 parts of polypropylene, from the barrel charging, with 5 parts of vinylformic acid and the compound monomer altogether of methacrylic anhydride glycidyl ester, 1.5 part polynite and 4 part 2,5-dimethyl-2,5-di-tert-butyl peroxide normal hexane and dibenzoyl peroxide composite initiator are diluted to 50% solution with ethanol acetone double solvents, from the sidepiece adding reaction system of screw extrusion press, adopting L/D is 36: 1 twin screw extruder, and implantation quality accounts for 10% supercritical CO of reactant total mass in reaction system
2Fluid, 150 rev/mins of forcing machine driving screw rotating speeds divide 2 heating zone, 190 ℃ of first Heating Zone Temperature, 170 ℃ of second Heating Zone Temperature were reacted 4 minutes, and the gained extruded product carries out performance test after granulation, and its performance inventory is in table 1.
Embodiment 7
Get 100 parts of polypropylene, the compound monomer altogether of 5 parts of maleic anhydrides and toxilic acid fourth diester, 2 parts of Diisopropyl azodicarboxylates and dibenzoyl peroxide (1: 1) composite initiator, mix fully from the barrel charging, adopting L/D is 3: 1 single screw extrusion machine, and implantation quality accounts for 0.1% supercritical CO of reactant total mass in reaction system
2Fluid, 300 rev/mins of forcing machine driving screw rotating speeds divide 2 heating zone, 220 ℃ of first Heating Zone Temperature, 200 ℃ of second Heating Zone Temperature were reacted 10 minutes, and the gained extruded product carries out performance test after granulation, and its performance inventory is in table 1.
The The performance test results of table 1 embodiment 1-7
| Sample | Percentage of grafting (%) | Grafting efficiency (%) | Melt flow rate (g/10min) |
| Embodiment 1 | 0.3 | 30 | 5 |
| Embodiment 2 | 1.2 | 60 | 10 |
| Embodiment 3 | 1.2 | 8 | 41 |
| Embodiment 4 | 1.0 | 10 | 26 |
| Embodiment 5 | 0.9 | 90 | 19 |
| Embodiment 6 | 1.0 | 20 | 39 |
| Embodiment 7 | 1.1 | 22 | 50 |
Claims (9)
1. the method for extruding and preparing maleation polypropylene by supercritical reaction, its step is as follows:
(1) reactant is by weight:
100 parts of polypropylene
1～15 part of maleation series matter
0～3 part of auxiliary agent
0.1～6 part of initiator
(2) above-mentioned reactant is introduced in the screw extrusion press, and utilized supercritical CO
2Generating unit injects supercritical CO in reaction system
2Fluid, supercritical CO
2The fluidic quality accounts for the 0.1%-20% of reactant total mass, 50 rev/mins-600 rev/mins of forcing machine driving screw rotating speeds, screw extrusion press divides a plurality of heating zone, wherein first Heating Zone Temperature is 180 ℃-220 ℃, 140 ℃-200 ℃ of all the other Heating Zone Temperature, reacted 1-20 minute, extruded product is through devolatilization, cooling, granulation, dry getting final product.
2. the method for extruding and preparing maleation polypropylene by supercritical reaction according to claim 1 is characterized in that polypropylene is that molecular weight ranges is isotactic homopolymerization type or copolymerized type propene polymer particle, powder or its mixture of 10000g/mol-1000000g/mol.
3. the method for extruding and preparing maleation polypropylene by supercritical reaction according to claim 1 is characterized in that the maleation series matter is any or several compound in toxilic acid, maleic anhydride, dibutyl maleinate, vinylformic acid, glycidyl acrylate and the glycidyl methacrylate.
4. the method for extruding and preparing maleation polypropylene by supercritical reaction according to claim 1, it is characterized in that initiator is dicumyl peroxide, Diisopropyl azodicarboxylate, 2,5-dimethyl-2, any in 5-di-tert-butyl peroxide normal hexane and the dibenzoyl peroxide or several mixture.
5. the method for extruding and preparing maleation polypropylene by supercritical reaction according to claim 1, it is characterized in that auxiliary agent is a vinylbenzene, antioxidant, the light and thermally stable agent, hydrotalcite, polynite, diatomite, clay, vinyl silanes, in lime carbonate and the polyphosphoric acid amine any or several compound, wherein antioxidant is 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester, four (4-hydroxyls-3,5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester, 2, the 6-tertiary butyl-4-methylphenol, 2, the amino p-cresol of the 6-tertiary butyl-alpha, alpha-dimethyl, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) one or more compounds in ester and the Tyox B, the light and thermally stable agent is two (2,2,6, the 6-tetramethyl-piperidyl) certain herbaceous plants with big flowers two acid esters, one or more compounds in 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole and the calcium stearate.
6. the method for extruding and preparing maleation polypropylene by supercritical reaction according to claim 1 is characterized in that said supercritical CO
2Generating unit, it is 50 ℃-200 ℃ that its temperature is set, pressure is 8.0Mpa-30Mpa, generates supercritical CO
2Fluid is introduced by the screw extrusion press side line.
7. the method for extruding and preparing maleation polypropylene by supercritical reaction according to claim 6 is characterized in that said supercritical CO
2Generating unit, it is 80 ℃-180 ℃ that temperature is set, pressure is 8.0Mpa-15Mpa.
8. the method for extruding and preparing maleation polypropylene by supercritical reaction according to claim 1 is characterized in that used forcing machine is single screw rod or double-screw type, and length-to-diameter ratio L/D is 24: 1-48: 1.
9. the method for extruding and preparing maleation polypropylene by supercritical reaction according to claim 1 is characterized in that the mode that reactant is introduced in the screw extrusion press has following several:
1) the direct premix charging of maleation series matter and auxiliary agent and initiator and polypropylene;
2) maleation series matter and auxiliary agent and the charging of polypropylene premix, and initiator becomes the side entry feed of the solution of 20%-80% from screw extrusion press with ethanol, acetone or both mixture diluted;
3) polypropylene and the charging of auxiliary agent premix, and the maleation series matter becomes the side entry feed of the solution of 20%-80% from screw extrusion press with initiator with ethanol, acetone or both mixture diluted;
4) maleation series matter and the charging of polypropylene premix, auxiliary agent becomes the side entry feed of the solution of 20%-80% from screw extrusion press with initiator with ethanol, acetone or both mixture diluted.
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| CNA200710071080XA CN101143946A (en) | 2007-09-04 | 2007-09-04 | Method for extruding and preparing maleation polypropylene by supercritical reaction |
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| CN101445612B (en) * | 2008-12-22 | 2011-04-27 | 华南理工大学 | Method for preparing thermoplastic elastomer by supercritical fluid assisted dynamic vulcanization |
| CN102127281A (en) * | 2010-12-31 | 2011-07-20 | 浙江大学 | Method for extruding and preparing high melt strength polypropylene with long branched chain structure through supercritical reaction |
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| WO2013007095A1 (en) | 2011-07-08 | 2013-01-17 | 中国石油天然气股份有限公司 | Supercritical carbon dioxide-assisted solid-phase grafting modification method for polypropylene |
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| CN103772612A (en) * | 2012-10-25 | 2014-05-07 | 合肥杰事杰新材料股份有限公司 | Preparation method for maleic anhydride-grafted polypropylene |
| CN105622850A (en) * | 2016-03-30 | 2016-06-01 | 北京海科华昌新材料技术有限公司 | Efficient and environment-friendly preparation method of double-monomer solid-phase grafted PP (polypropylene) |
| CN106032398A (en) * | 2015-03-12 | 2016-10-19 | 中国科学院宁波材料技术与工程研究所 | A preparing method of long-chain branched polypropylene |
| CN110317399A (en) * | 2019-06-29 | 2019-10-11 | 浙江大学 | Expanded flame-retardant polypropylene lightweighting materials and its continuous extrusion foaming preparation method |
| CN112608413A (en) * | 2020-11-25 | 2021-04-06 | 成都金发科技新材料有限公司 | Maleic anhydride grafted polypropylene with low free maleic anhydride content and low-emission glass fiber reinforced polypropylene composite material prepared from maleic anhydride grafted polypropylene |
| CN114591508A (en) * | 2021-12-07 | 2022-06-07 | 宁波能之光新材料科技股份有限公司 | Preparation method of high-purity graft modified polypropylene |
| CN114605651A (en) * | 2021-12-07 | 2022-06-10 | 宁波能之光新材料科技股份有限公司 | Preparation method of modified polyethylene based on supercritical grafting reaction |
| CN116903982A (en) * | 2023-07-28 | 2023-10-20 | 广东丙辛新材料有限公司 | High-strength corrosion-resistant polypropylene composite material and preparation method thereof |
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2007
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