CN102030960A - Preparation method of high-melt-strength polyolefine comprising hybrid long branch-chain structure - Google Patents
Preparation method of high-melt-strength polyolefine comprising hybrid long branch-chain structure Download PDFInfo
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- CN102030960A CN102030960A CN2010106180334A CN201010618033A CN102030960A CN 102030960 A CN102030960 A CN 102030960A CN 2010106180334 A CN2010106180334 A CN 2010106180334A CN 201010618033 A CN201010618033 A CN 201010618033A CN 102030960 A CN102030960 A CN 102030960A
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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
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
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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
- B29C48/03—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
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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Abstract
The invention discloses a preparation method of high-melt-strength polyolefine comprising a hybrid long branch-chain structure, comprising the following steps of: (1) weighting 100 parts by weight of polar monomer grafted polypropylene (a component A) with a grafting rate which is greater than or equal to 0.3 percent by weight, 5-30 parts by weight of polar monomer grafted polyethylene (a component B) with a grafting rate which is greater than or equal to 0.3 percent by weight, 1-10 parts by weight of amine or alcohol compound, 0-0.5 part by weight of antioxidant and 0-0.5 part by weight of light and heat stabilizing agent; (2) diluting the amine or alcohol compound into 20-80 percent by weight of solution by alcohol and/or ketone; (3) adding the component A, the component B, the antioxidant and the heat stabilizing agent into an extruder through a feeding hole, respectively adding the solution obtained in the step (2) and supercritical carbon dioxide from a first side line and a second side line, and melting and extruding to prepare the high-melt-strength polyolefine comprising the hybrid long branch-chain structure. The high-melt-strength polyolefine comprising the hybrid long branch-chain structure has good color, good mechanical property and good processing property and is suitable for the application fields of foaming, hot forming, film blowing and moulding, extruding, coating, and the like.
Description
Technical field
The present invention relates to a kind of high melt strength polyolefin that contains the hydridization long branched chain structure and preparation method thereof, relate in particular to supercritical reaction and extrude the method that preparation contains the high melt strength polyolefin of hydridization long branched chain structure, belong to technical field of polymer materials.
Background technology
Polypropylene (PP) industrial development is rapid, but the main at present high degree of isotacticity PP(iPP that adopts Ziegler-Natta and metallocene catalyst catalytic production), generally can not produce the secondary activity center, have only the linear chain structure, cause its narrow molecular weight distribution, shortcoming such as melt strength is low and refractory hangs down poor performance.And PP does not have strain hardening effect under molten state, has therefore limited the range of application of PP greatly.In addition, PP still is a kind of partially crystalline polymer, and softening temperature and fusing point are very approaching, melt strength descends rapidly after surpassing fusing point, cause when adopting thermoforming container wall thickness inhomogeneous, edge curl, contraction occur during extrusion coated calendering, abscess problem such as subside during extrusion foaming.Generally believe that the melt strength that increases PP is its important factor in the quicker growth in plastics market, acquisition broader applications.
The preparation high melt strength, propylene, can be by improving polyacrylic relative molecular mass, increasing methods such as relative molecular weight distribution, long-chain branchization, concrete implementation method has methods such as x ray irradiation x, blending and modifying, chemically crosslinked, solution graft copolymerization, fusion-grafting and in-situ polymerization.
Japanese Patent JP5531807 discloses a kind of PP, HDPE, LDPE and EPR blend, has improved melt strength, and makes foam material.U.S. Pat 4365004 improves melt strength by the LDPE blend of CPP and high fondant-strength.Chinese patent CN1775851A discloses polypropylene, graft polypropylene, polyethylene and aminated compounds blend and has extruded the preparation high melt strength, propylene.But owing to only adopt the extremely difficult homodisperse that reaches molecular level of the method for simple blend, the product mechanical property is undesirable.
The patent CN86100791 of Himont company adopts electronic cathode x ray irradiation x straight chain PP, make it to produce long chain branching, produce the HMSPP of higher weight average molecular mass and higher branch degree, but because PP is a semi-crystalline polymer, unformed part has produced grafting, and crystal region is then difficult, although can take some measures as reducing degree of crystallinity etc., but form a large amount of inhomogeneous gels easily, therefore exist the problem of product performance stability.Chinese patent CN1986589A and CN1432596A disclose and have adopted the method for esters of acrylic acid fusion-grafting polypropylene with the raising melt strength, but traditional frit reaction is extruded owing to high temperature causes the serious product over-all properties that influences of polypropylene backbone degraded.
And solution graft copolymerization is not only wasted resource owing to need a large amount of solvents in the process of producing, and the more important thing is that solvent produces harm to surrounding environment and individual.Fusion-grafting is then because there are problems such as the easy oxidative degradation of polypropylene in operation at high temperature.
Summary of the invention
The purpose of this invention is to provide high melt strength polyolefin that contains the hydridization long branched chain structure of a kind of melt flow rate (MFR) wide ranges, gel-free and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is: this preparation method who contains the high melt strength polyolefin of hydridization long branched chain structure comprises the steps:
(1) take by weighing each raw material by following prescription:
A component 100 weight parts
B component 5 ~ 30 weight parts
C component 1 ~ 10 weight part
Antioxidant 0～0.5 weight part
Light and thermally stable agent 0～0.5 weight part
Described A component is percentage of grafting 〉=0.3%(weight) the polar monomer graft polypropylene, the B component is the polar monomer fusion-grafting polyethylene of percentage of grafting 〉=0.3%, described polar monomer be in acid anhydrides, acid, the ester any or appoint several combinations; The C component is amine or alcohol compound;
(2) the C component being diluted to mass percent concentration with alcohol and/or ketone is 20%～80% solution;
(3) solution that step (2) is obtained from first side line to join the screw extrusion press supercritical CO
2Fluid from second side line adds screw extrusion press, and with A component and B component and antioxidant and thermo-stabilizer from spout adding screw extrusion press, melt extrude the high melt strength polyolefin that obtains containing the hydridization long branched chain structure; Described supercritical CO
2The fluidic mass rate is 0.1 ~ 20% of A component and a B constituent mass flow total amount; Screw speed is 100 ~ 300 rev/mins, and extrusion temperature is 140 ~ 220 ℃.
Further, the percentage of grafting of A component of the present invention is 0.5%～5%.
Further, A component of the present invention be in maleic anhydride inoculated polypropylene, acrylic acid-grafted polypropylene, methacrylic acid graft polypropylene, the glycidyl methacrylate graft polypropylene any or appoint several mixtures.
Further, B component of the present invention be in maleic anhydride grafted polyethylene, acrylic acid-grafted polyethylene, methacrylic acid grafted polyethylene and the glycidyl methacrylate graft polyethylene any or appoint several compounds or compound grafts.
Further, the component of B described in the present invention be in polar monomer grafted high density polyethylene, polar monomer grafted linear low-density polyethylene, the polar monomer grafting new LDPE (film grade) any or appoint several mixtures.
Further, the percentage of grafting of B component of the present invention is 0.5%～5%(weight).
Among the present invention, described aminated compounds is thanomin, triethyl diamines, quadrol, Ursol D, 1,4-butanediamine, 1, any in the diamine of 6-hexanediamine, Amino Terminated polyether(ATPE) and the Amino Terminated polyether(ATPE) tertiary amine compound or several mixture; Alcohol compound be ethylene glycol, polyoxyethylene glycol any or appoint several mixtures.
In the present invention, mainly utilize the specific functional groups on amino in amine, the alcohol compound or hydroxyl and polypropylene grafted thing, the polycthylene grafted thing to react, thereby produce long branched chain structure, reach the final purpose that improves melt strength.
Antioxidant described in the present invention can adopt 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, in amino p-cresol, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester of the 6-tertiary butyl-alpha, alpha-dimethyl and the Tyox B any or several mixture.
Light and thermally stable agent described in the present invention is two (2,2,6, the 6-tetramethyl-piperidyl) certain herbaceous plants with big flowers two acid esters, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-in 5-chlorinated benzotriazole and the calcium stearate any or appoint several mixtures.
Compared with prior art, beneficial effect of the present invention is:
The present invention prepares hydridization high melt strength polyolefin resin by the continuous extrusion molding of response type twin screw extruder fusion, and uses supercritical CO
2Auxiliary extruding strengthened the diffusion of molecule greatly when having suppressed degradation of polypropylene effectively, further promote the generation of reaction.In the reaction process, amine, alcohol compound (C component) react as specific function group in chainextender and the polyolefine grafts, linear polypropylene molecule, sub polyethylene subchain are coupled together, thereby can generate the adjustable novel hybride polyolefine of melt flow rate (MFR) that each grafting site contains two long branched chain structures, have gel-free, temperature sensitive property is good and the strain hardening characteristic.This product has all embodied its superiority in all many-sides such as color and luster, mechanical property and processing characteristicies, and preparation technology is simple, and product is transparent, is applicable to foaming, thermoforming, film blowing and extrudes Application Areass such as coating.
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.
Comparative Examples 1:
Taking by weighing the 100kg percentage of grafting is 0.3%(weight) maleic anhydride inoculated polypropylene, 20kg percentage of grafting be 0.3%(weight) maleic anhydride graft new LDPE (film grade) polyethylene, 0.3kg oxidation inhibitor four (4-hydroxyl-3,5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester, 0.2kg three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester and 0.5kg stablizer calcium stearate, after stirring thorough mixing, from length-to-diameter ratio L/D is the spout adding of the twin screw extruder of 48:1, and rate of feeding is 200g/min; Other takes by weighing the 5kg quadrol, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of 20 g/min, first side line from forcing machine behind 50% the solution; Do not add supercritical CO
2Fluid, the control screw speed is 100 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of first heating zone is 220 ℃, and the extrusion temperature of other heating zone is 200 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 1:
Taking by weighing the 100kg percentage of grafting is 0.3%(weight) maleic anhydride inoculated polypropylene, 20kg percentage of grafting be 0.3%(weight) maleic anhydride graft new LDPE (film grade), 0.3kg oxidation inhibitor four (4-hydroxyl-3,5-di-tert-butyl-phenyl propionic acid) pentaerythritol ester, 0.2kg three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester and 0.5kg stablizer calcium stearate, after stirring thorough mixing, from length-to-diameter ratio L/D is the spout adding of the twin screw extruder of 48:1, and rate of feeding is 200g/min; Other takes by weighing the 5kg quadrol, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of 20 g/min, first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 4 g/min, at this moment supercritical CO
2The fluidic mass rate be about maleic anhydride inoculated polypropylene and maleic anhydride graft new LDPE (film grade) the mass rate total amount 2%.The control screw speed is 100 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 160 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 2:
Taking by weighing the 100kg percentage of grafting is 0.5%(weight) methacrylic acid graft polypropylene, 5kg percentage of grafting be 0.5%(weight) methacrylic acid grafted high density polyethylene polyethylene, 0.5kg oxidation inhibitor 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester and 0.5kg stablizer two (2,2,6, the 6-tetramethyl-piperidyl) certain herbaceous plants with big flowers two acid esters, after stirring thorough mixing, be the spout adding of the twin screw extruder of 36:1 from length-to-diameter ratio L/D, rate of feeding is 60g/min; Other takes by weighing the 10kg thanomin, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of 7.5 g/min, first side line from forcing machine behind 80% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 12g/min, at this moment supercritical CO
2The fluidic mass rate is about 20% of methacrylic acid graft polypropylene and the poly mass rate total amount of methacrylic acid grafted high density polyethylene.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 140 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 3:
Taking by weighing the 100kg percentage of grafting is 2%(weight) acrylic acid-grafted polypropylene, 30kg percentage of grafting be 0.5%(weight) acrylic acid-grafted new LDPE (film grade), 0.3kg 2, the 6-tertiary butyl-4-methylphenol and 0.3kg stablizer 2-(2 '-hydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl)-the 5-chlorinated benzotriazole, after stirring thorough mixing, from length-to-diameter ratio L/D is the spout adding of the twin screw extruder of 24:1, and rate of feeding is 100g/min; Other takes by weighing 1kg triethyl diamines, and becoming mass concentration with alcohol dilution is to be injected into the forcing machine with the speed of 20 g/min, first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 0.5g/min, at this moment supercritical CO
2The fluidic mass rate be about acrylic acid-grafted polypropylene and acrylic acid-grafted new LDPE (film grade) the mass rate total amount 0.5%.The control screw speed is: 100 rev/mins, it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 160 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 4:
Taking by weighing the 100kg percentage of grafting is 0.5%(weight) glycidyl methacrylate graft polypropylene and 20kg percentage of grafting be 0.5%(weight) the glycidyl methacrylate graft new LDPE (film grade), 0.3kg 2, amino p-cresol of the 6-tertiary butyl-alpha, alpha-dimethyl and 0.3kg stablizer two (2,2,6, the 6-tetramethyl-piperidyl) certain herbaceous plants with big flowers diacid is the spout adding of the twin screw extruder of 36:1 from length-to-diameter ratio L/D, and rate of feeding is 100g/min; Other takes by weighing the 8kg Ursol D, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 10 g/min, first side line from forcing machine behind 80% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 5g/min, at this moment supercritical CO
2The fluidic mass rate be about vest base glycidyl acrylate graft polypropylene and glycidyl methacrylate graft new LDPE (film grade) the mass rate total amount 5%.The control screw speed is 200 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 150 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 5:
Taking by weighing the 100kg percentage of grafting is 2%(weight) maleic anhydride inoculated polypropylene and 20kg percentage of grafting be 0.5%(weight) the maleic anhydride graft linear low density polyethylene, do not add oxidation inhibitor and stablizer, from length-to-diameter ratio L/D is the spout adding of the twin screw extruder of 48:1, and rate of feeding is 100g/min; Other takes by weighing 10kg 1, the 4-butanediamine, and being diluted to mass concentration with ethanol (50%) and acetone (50%) mixing solutions is to be injected into the forcing machine with the speed of 20g/min first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 1g/min, at this moment supercritical CO
2The fluidic mass rate be about maleic anhydride inoculated polypropylene and maleic anhydride graft linear low density polyethylene the mass rate total amount 1%.The control screw speed is 100 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein first heating zone is 180 ℃, and other heating zone are 150 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 6:
Taking by weighing the 100kg percentage of grafting is 0.5%(weight) maleic anhydride inoculated polypropylene and 20kg percentage of grafting be 0.5%(weight) acrylic acid-grafted linear low density polyethylene, 0.2kg 2, amino p-cresol of the 6-tertiary butyl-alpha, alpha-dimethyl and 0.2kg 3,5-di-t-butyl-4-hydroxy phenylpropionic acid octadecyl ester and stablizer 0.1kg two (2,2,6, the 6-tetramethyl-piperidyl) certain herbaceous plants with big flowers diacid and 0.2kg 2-(2 '-hydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl)-the 5-chlorinated benzotriazole, from length-to-diameter ratio L/D is the spout adding of the twin screw extruder of 36:1, and rate of feeding is 100g/min; Other takes by weighing the diamine of 8kg Amino Terminated polyether(ATPE), and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 10 g/min, first side line from forcing machine behind 80% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 5g/min, at this moment supercritical CO
2The fluidic mass rate be about the acrylic acid-grafted linear low density polyethylene of maleic anhydride inoculated polypropylene the mass rate total amount 5%.The control screw speed is 200 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: first heating zone is 180 ℃ a extrusion temperature, and other heating zone are 150 ℃ extrusion temperature; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 7:
Taking by weighing the 100kg percentage of grafting is 2%(weight) maleic anhydride inoculated polypropylene and 20kg percentage of grafting be 0.5%(weight) the methacrylic acid grafted linear low-density polyethylene, do not add oxidation inhibitor and stablizer, from length-to-diameter ratio L/D is the spout adding of the twin screw extruder of 48:1, and rate of feeding is 100g/min; Other takes by weighing 10kg Amino Terminated polyether(ATPE) tertiary amine, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 1g/min, at this moment supercritical CO
2The fluidic mass rate be about maleic anhydride inoculated polypropylene and methacrylic acid grafted linear low-density polyethylene the mass rate total amount 1%.The control screw speed is 100 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 150 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 8:
Taking by weighing the 80kg percentage of grafting is 5%(weight) maleic anhydride inoculated polypropylene, 20kg percentage of grafting be 3%(weight) acrylic acid-grafted polypropylene, 20kg percentage of grafting be 0.5%(weight) glycidyl methacrylate grafted linear low-density polyethylene, do not add oxidation inhibitor and stablizer, after stirring thorough mixing, from length-to-diameter ratio L/D is the spout adding of the twin screw extruder of 36:1, and rate of feeding is 100g/min; Other takes by weighing 10 parts of ethylene glycol, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 20g/min, at this moment supercritical CO
2The fluidic mass rate be about maleic anhydride inoculated polypropylene, acrylic acid-grafted polypropylene, glycidyl methacrylate grafted linear low-density polyethylene the mass rate total amount 20%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 140 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 9:
Taking by weighing the 100kg percentage of grafting is 2%(weight) maleic anhydride inoculated polypropylene, 20kg percentage of grafting be 0.5%(weight) the maleic anhydride graft high density polyethylene(HDPE), do not add oxidation inhibitor and stablizer, after stirring thorough mixing, from length-to-diameter ratio L/D is the spout adding of the twin screw extruder of 36:1, and rate of feeding is 100g/min; Other takes by weighing the 10kg polyoxyethylene glycol, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 10g/min, at this moment supercritical CO
2The fluidic mass rate be about maleic anhydride inoculated polypropylene, maleic anhydride graft high density polyethylene(HDPE) the mass rate total amount 10%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 150 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 10:
Taking by weighing the 100kg percentage of grafting is 2%(weight) maleic anhydride inoculated polypropylene, 20kg percentage of grafting be 0.5%(weight) acrylic acid-grafted high density polyethylene(HDPE), do not add oxidation inhibitor and stablizer, after stirring thorough mixing, from length-to-diameter ratio L/D is the spout adding of the twin screw extruder of 36:1, and rate of feeding is 100g/min; Other takes by weighing the 10kg polyoxyethylene glycol, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 0.2g/min, at this moment supercritical CO
2The fluidic mass rate be about maleic anhydride inoculated polypropylene, acrylic acid-grafted high density polyethylene(HDPE) the mass rate total amount 0.2%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 160 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.
Embodiment 11:
Taking by weighing the 100kg percentage of grafting is 2%(weight) maleic anhydride inoculated polypropylene, 20kg percentage of grafting be 0.5%(weight) the methacrylic acid grafted high density polyethylene, do not add oxidation inhibitor and stablizer, after stirring thorough mixing, from length-to-diameter ratio L/D is the spout adding of the twin screw extruder of 36:1, and rate of feeding is 100g/min; Other takes by weighing the 10kg polyoxyethylene glycol, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 0.1g/min, at this moment supercritical CO
2The fluidic mass rate be about maleic anhydride inoculated polypropylene, methacrylic acid grafted high density polyethylene the mass rate total amount 0.1%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 170 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 12:
Taking by weighing the 100kg percentage of grafting is 2%(weight) maleic anhydride inoculated polypropylene, 20kg percentage of grafting be 0.5%(weight) the glycidyl methacrylate graft high density polyethylene(HDPE), do not add oxidation inhibitor and stablizer, after stirring thorough mixing, from length-to-diameter ratio L/D is the spout adding of the twin screw extruder of 36:1, and rate of feeding is 100g/min; Other takes by weighing the 10kg polyoxyethylene glycol, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 10g/min, at this moment supercritical CO
2The fluidic mass rate be about maleic anhydride grafted polypropylene, glycidyl methacrylate graft high density polyethylene(HDPE) the mass rate total amount 10%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 150 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Embodiment 13:
Taking by weighing the 100kg percentage of grafting is 2%(weight) maleic anhydride inoculated polypropylene, 10kg percentage of grafting be 0.5%(weight) glycidyl methacrylate graft high density polyethylene(HDPE), 10kg percentage of grafting be 0.5%(weight) the methacrylic acid grafted high density polyethylene, do not add oxidation inhibitor and stablizer, after stirring thorough mixing, from length-to-diameter ratio L/D is the spout adding of the twin screw extruder of 36:1, and rate of feeding is 100g/min; Other takes by weighing 10 parts of polyoxyethylene glycol, and becoming mass concentration with acetone diluted is to be injected into the forcing machine with the speed of 20g/min first side line from forcing machine behind 50% the solution; Supercritical CO
2Fluid joins forcing machine, supercritical CO from second side line of twin screw extruder
2The fluidic rate of feeding is 10g/min, at this moment supercritical CO
2The fluidic mass rate be about maleic anhydride grafted polypropylene, glycidyl methacrylate graft high density polyethylene(HDPE), methacrylic acid grafted high density polyethylene the mass rate total amount 10%.The control screw speed is 300 rev/mins, and it is 8 heating zone that twin screw extruder is divided into, and wherein: the extrusion temperature of first heating zone is 180 ℃, and the extrusion temperature of other heating zone is 150 ℃; Extruding pelletization obtains high fondant-strength hydridization polyolefin resin.Get sample segment and carry out mechanical property, tests such as melt flow rate (MFR) the results are shown in Table 1.
Table 1
By table 1 as seen, compare with Comparative Examples 1, embodiment 1-13 adds supercritical CO in extrusion
2After, extrusion temperature descends significantly, and the product mechanical property all improves a lot, and melting index descends.Proof the present invention uses supercritical CO
2Suppress the generation of degraded effectively, and helped the diffusion of molecule, promoted the carrying out of graft reaction.Adopt present technique invention scheme, according to reaction mechanism, it is big to make the melting index scope by the variation component ratio, and regulatable hydridization long-chain branch polyolefine.Above-mentioned each scheme products obtained therefrom is carried out gel content determining, and gel content is zero.
Claims (9)
1. a preparation method who contains the high melt strength polyolefin of hydridization long branched chain structure is characterized in that comprising the steps:
1) take by weighing each raw material by following prescription:
A component 100 weight parts
B component 5 ~ 30 weight parts
C component 1 ~ 10 weight part
Antioxidant 0～0.5 weight part
Light and thermally stable agent 0～0.5 weight part
Described A component is percentage of grafting 〉=0.3%(weight) the polar monomer graft polypropylene, the B component is percentage of grafting 〉=0.3%(weight) polar monomer fusion-grafting polyethylene, described polar monomer be in acid anhydrides, acid, the ester any or appoint several combinations; The C component is amine or alcohol compound;
(2) the C component being diluted to mass percent concentration with alcohol and/or ketone is 20%～80% solution;
(3) solution that step (2) is obtained from first side line to join the screw extrusion press supercritical CO
2Fluid from second side line adds screw extrusion press, and with A component and B component and antioxidant and thermo-stabilizer from spout adding screw extrusion press, melt extrude the high melt strength polyolefin that obtains containing the hydridization long branched chain structure; Described supercritical CO
2The fluidic mass rate be A component and B component the mass rate summation 0.1 ~ 20%; Screw speed is 100 ~ 300 rev/mins, and extrusion temperature is 140 ~ 220 ℃.
2. the preparation method who contains the high melt strength polyolefin of long branched chain structure according to claim 1, the percentage of grafting that it is characterized in that described A component is 0.5%～5%(weight).
3. the preparation method who contains the high melt strength polyolefin of long branched chain structure according to claim 1 and 2 is characterized in that: described A component be in maleic anhydride inoculated polypropylene, acrylic acid-grafted polypropylene, methacrylic acid graft polypropylene, the glycidyl methacrylate graft polypropylene any or appoint several mixtures.
4. the preparation method who contains the high melt strength polyolefin of long branched chain structure according to claim 1 is characterized in that: described B component be in maleic anhydride grafted polyethylene, acrylic acid-grafted polyethylene, methacrylic acid grafted polyethylene, the glycidyl methacrylate graft polyethylene any or appoint several mixtures.
5. the preparation method who contains the high melt strength polyolefin of long branched chain structure according to claim 1 is characterized in that: described B component be in polar monomer grafted high density polyethylene, polar monomer grafted linear low-density polyethylene, the polar monomer grafting new LDPE (film grade) any or appoint several mixtures.
6. according to claim 1, the 4 or 5 described preparation methods that contain the high melt strength polyolefin of long branched chain structure, it is characterized in that: the percentage of grafting of described B component is 0.5%～5%(weight).
7. the preparation method who contains the high melt strength polyolefin of long branched chain structure according to claim 1, it is characterized in that: described C component or thanomin, triethyl diamines, quadrol, Ursol D, 1,4-butanediamine, 1, any in the diamine of 6-hexanediamine, Amino Terminated polyether(ATPE), the Amino Terminated polyether(ATPE) tertiary amine compound or several mixture; Or in the ethylene glycol, polyoxyethylene glycol any or appoint several mixtures.
8. the preparation method who contains the high melt strength polyolefin of long branched chain structure according to claim 1, it is characterized in that: described 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, in amino p-cresol, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester of the 6-tertiary butyl-alpha, alpha-dimethyl, the Tyox B any or several mixture.
9. the preparation method who contains the high melt strength polyolefin of long branched chain structure according to claim 1, it is characterized in that: described light and thermally stable agent is two (2,2,6,6-tetramethyl-piperidyl) certain herbaceous plants with big flowers two acid esters, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-in the 5-chlorinated benzotriazole, calcium stearate any or appoint several mixtures.
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