CN1814658A - Functionalized polyolefin long-acting trickle film and preparing method - Google Patents
Functionalized polyolefin long-acting trickle film and preparing method Download PDFInfo
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- CN1814658A CN1814658A CN 200610016615 CN200610016615A CN1814658A CN 1814658 A CN1814658 A CN 1814658A CN 200610016615 CN200610016615 CN 200610016615 CN 200610016615 A CN200610016615 A CN 200610016615A CN 1814658 A CN1814658 A CN 1814658A
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Abstract
This invention relates to a functional polyolefin long time effective flow film and its preparation method, which applies the polyether tetra-basic alcohol to be reacted with maleic anhydride or crylic acid to get functional monomers, pre-radiates the polyolefin resin with beta or gamma rays, then carries out smelt graft reaction to the processed polyolefin resin, the functional monomers and electron donating reagent then to blow-molding the graft product to a functional polyolefin long time effective flow film and the valid time is 25-45 days and 13-16 months.
Description
Technical field
The present invention relates to a kind of functionalized polyolefin long-acting trickle film and preparation method thereof.
Background technology
Polyethylene, ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethene-1-octene copolymer, ethylene-vinyl acetate copolymer, polypropylene, poly-1-butylene is the good and cheap universal macromolecular material of over-all properties, but limited the expansion of its range of application to a certain extent because of its nonpolar characteristic, the monomer molecule that the method that adopts reaction to extrude will contain polar group is grafted on the polymer molecular chain, utilize the polarity and the reactivity of polar group, can give macromolecular material many new performances, as cohesiveness, wetting ability, dyeability, ageing resistance, static resistance etc.
Nonpolar Shed Film of Polyolefin wetting ability is bad, is in use condensing one deck white water droplet on the canopy film internal surface, and a large amount of water droplets are attached to film surface, be difficult to flow down, influence seeing through of light, cause canopy temperature, ground temperature low along the canopy film, high humidity, crop growth environment are not good, and the ripening stage postpones.Because following of water droplet can cause seedling rot, mashed seedling, cause the various diseases of fruit and vegetable, thereby influence fruit and vegetable output simultaneously.Solve Shed Film of Polyolefin wetting ability problem, two kinds of methods of general employing, a kind of is interior additive process, to have exactly surface-active drip agent make master batch mix with polyolefin resin the back blown film, drip agent with hydrophilic radical is little by little moved to film surface, make water-wet, the fine liquid particles that condenses in film surface can spread expansion formation moisture film rapidly and flow down along film, thereby plays the effect of anti-water droplet.Interior additive process adopts the simple drip agent (major ingredient is polyvalent alcohol and ester organic micromolecule compound thereof) that adds to realize traditionally, because the consistency of this type of drip agent and matrix resin is not good, very easily move, break away from the film surface because of volatilizing, dissolve, wash or rubbing easily after moving to the surface, so the drip life-span is shorter.Another kind is the outer method that is coated with, exactly water-dropping proof agent solution is coated in the plastics film surface, make its possess hydrophilic property, it is easy to use to be coated with method outward, wettability is good, but relatively poor, the problems such as cost is higher, persistence is poor, processing inconvenience of sticking power that have the drip agent and the plastics film of coating are so its application is restricted.Additive process is produced anti-dropping film in the domestic main employing at present, and the drip lasting period of this film is short, generally has only about three, four months.People's such as Zhou Xie " polymaleic anhydride high fatty alcohol ester synthetic and to poly Research on Surface Modification ", the functional polymer journal, 2003,6 (3): 347, and Chinese invention patent " a kind of agricultural long-acting fog-free film " (application number 02131397.6, publication number CN1485359A), all be that the method that adopts copolymerization to increase the drip agent molecular weight delays its loss in anti-dropping film, the synthetic drip agent does not have two key reaction active groups, the same inner additive type that belongs to the conventional flow drops, the anti-dropping film drip lasting period of adding this class drip agent is also shorter.Be grafted on the polymer molecular chain if function monomer promptly can be had the drip agent molecule of reactive behavior, drip agent just can not run off along with the water droplet on canopy film surface, and this will improve the drip life-span of polyolefine anti-dropping film greatly.The contriver authorized on a patent " preparation method of functional polyolefin resin " (publication number CN1482151A, patent No. ZL03142815.0), by adopt pre-irradiation, add to electronics reagent, reaction extrudes the sour or derivatives thereof that will contain unsaturated group and is grafted on the molecular polyolefin chain, prepared the polyolefine binding resin.
Summary of the invention
One of purpose of the present invention provides a kind of functionalized polyolefin long-acting trickle film; Another object of the present invention provides a kind of preparation method of functionalized polyolefin long-acting trickle film.
A kind of functionalized polyolefin long-acting trickle film of the present invention, grafted has the function monomer structural formula of reactive behavior and is on the molecular polyolefin chain:
Another object of the present invention provides a kind of preparation method of functionalized polyolefin long-acting trickle film, and its step and condition are:
(1) has the function monomer preparation of the functionalized polyolefin long-acting trickle film of reactive behavior
MALEIC ANHYDRIDE or vinylformic acid, polyethers tetravalent alcohol, solvent, catalyzer, stopper are joined in the reactor, feed nitrogen, heated and stirred, MALEIC ANHYDRIDE wherein or vinylformic acid: polyethers tetravalent alcohol: catalyzer: stopper: the ratio of solvent, count 0.95-1.25 with mole: 0.95-1.25: 10
-3-10
-2: 10
-3-10
-2: 3-6.05, reaction times 2-10 hour, temperature of reaction 60-100 ℃, reaction product through 50-65 ℃ be decompressed to-0.08--0.12MPa removes solvent, obtains having the function monomer of the functionalized polyolefin long-acting trickle film of reactive behavior.
(2) pre-irradiation of polyolefin resin
Adopt
60Co carries out pre-irradiation with gamma-rays to polyolefin resin as irradiation source, and the pre-irradiation dosage range is 5KGy-80KGy; Or adopt rumbatron as irradiation source, and with the β ray polyolefin resin being carried out pre-irradiation, the pre-irradiation dosage range is 5KGy-80KGy.
(3) polyolefine and function monomer fusion-grafting polymerization with functionalized polyolefin long-acting trickle film of reactive behavior
Fusion-grafting is aggregated in response type single screw extrusion machine or the twin screw extruder and carries out.The pre-irradiation polyolefin resin that step (2) is obtained joins in the main hopper of response type single screw extrusion machine or twin screw extruder, the function monomer that step (1) is obtained and inject for electronics reagent through the liquid charging opening of response type single screw extrusion machine or twin screw extruder with reactive behavior, the polyolefin resin quality is in 100 parts, the monomeric consumption of above-mentioned functions is 2.0-10 part, and above-mentioned consumption to electronics reagent is 0.05-2 part; Temperature of reaction is controlled at 130-250 ℃, extrudes, and granulation obtains fusion-grafting polymerization pellet;
(4) preparation of functionalized polyolefin long-acting trickle film
Step (3) is obtained polyolefine to join in the inflation film manufacturing machine after the function monomer fusion-grafting polymerization pellet with reactive behavior mixes with the masterbatch that contains photostabilizer, pigment and heat preserving agent, 130-240 ℃ of blown film temperature, blowing obtains functionalized polyolefin long-acting trickle film.
The present invention relates to polyolefin resin is polyethylene, ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethene-1-octene copolymer, ethylene-vinyl acetate copolymer, polypropylene or poly-1-butylene.
Solvent of the present invention be toluene, dimethylbenzene, ethyl acetate, acetone wherein one or more; Catalyzer is wherein one or more of sulfuric acid, tosic acid, Witco 1298 Soft Acid, trifluoroacetic acid, trichoroacetic acid(TCA); Stopper is MEHQ or Resorcinol.
What the present invention relates to is triphenyl phosphite or para benzoquinone to electronics reagent.
The photostabilizer that contains in the masterbatch of the present invention is Chimassorb944, and the pigment that contains is phthalocyanine blue, and the heat preserving agent that contains is a talcum powder.
The preparation method of a kind of functionalized polyolefin long-acting trickle film provided by the invention.The functionalized polyolefin long-acting trickle film function monomer that has reactive behavior by preparation, the superoxide that adopts energetic ray pre-irradiation polyolefin resin to produce causes, the functionalized polyolefin long-acting trickle film function monomer that will have reactive behavior in the method for utilizing reaction to extrude on the response type forcing machine is grafted on the molecular polyolefin chain, functionalized polyolefin long-acting trickle film function monomer with reactive behavior is bonded together with covalent linkage and molecular polyolefin chain, in the polyolefine crystallisation process, be subjected to the repulsion of molecular chain, functionalized polyolefin long-acting trickle film function monomer with reactive behavior will be positioned at plane of crystal, have in the functionalized polyolefin long-acting trickle film function monomer of reactive behavior and contain ehter bond, hydroxyl, carboxyl, hydrophilic radicals such as ester group, very easily by water infiltration, increased polyolefin film polarity and with the affinity of water, thereby make polyolefin film very easily form water membrane, realize the drip function by water infiltration and on the surface.Because having the functionalized polyolefin long-acting trickle film function monomer of reactive behavior is grafted on the molecular polyolefin chain, therefore segregation and loss no longer appear, realize the long-acting anti-dropping performance, this preparation method is the desirable approach that solves polyolefine anti-dropping film long-acting anti-dropping.
A kind of functionalized polyolefin long-acting trickle film advantage of the present invention is: the function monomer that (1) will have the functionalized polyolefin long-acting trickle film of reactive behavior is grafted on the molecular polyolefin chain, overcome the normal flow drops migration, the shortcoming of invalid loss such as separate out, admittedly have the long-acting anti-dropping phase; (2) the pre-irradiation polyolefin resin is 1.2-5.7% (mass ratio) with the percentage of grafting with functionalized polyolefin long-acting trickle film function monomer of reactive behavior, grafting efficiency is 40-80% (mass ratio), reduced the homopolymerization trend of functionalized polyolefin long-acting trickle film function monomer, restrained degraded or the crosslinking reaction of polyolefin resin in the functionalization process with reactive behavior; (3) Zhi Bei functional polyolefin anti-dropping film has the long drip lasting period, quickens under the drip test conditions at 60 ℃, and the drip lasting period of functionalized polyolefin long-acting trickle film is 25-45 days (membrane area dewfall 30% was for losing efficacy); The drip lasting period of commercial anti-dropping film is 6-8 days under the equal conditions, the commodity anti-dropping film of functionalized polyolefin long-acting trickle film and stack pile is carried out the outdoor canopy of buckleing, the drip lasting period of functionalized polyolefin long-acting trickle film is 13-16 month, and the lasting period of commodity anti-dropping film is 3-4 month.
Embodiment
Embodiment 1
With molecular weight 840 polyethers tetravalent alcohol 0.19mol, dimethylbenzene 0.11mol, Resorcinol 2 * 10
-4Mol, tosic acid 2 * 10
-4Agitator is equipped with in the mol adding, thermometer, reflux condensing tube, liquid drips pipe, in the reactor of nitrogen ingress pipe and heating unit, the 0.19mol MALEIC ANHYDRIDE is dissolved in the liquid that fills 0.49mol acetone to drip in the pipe, feed nitrogen, heated and stirred, the temperature of liquid in the reactor is raised to 50 ℃, open liquid and drip the pipe switch, begin to drip liquid, 30 minutes dropping time, dropwise and be warming up to 100 ℃, reacted 2 hours, finish reaction, reduce the temperature to 65 ℃, be decompressed to-0.08MPa, remove and to desolvate, obtain having the function monomer of the functionalized polyolefin long-acting trickle film of reactive behavior.
With 100 parts of (quality) new LDPE (film grade)s (LDPE), on the rumbatron device, carry out pre-irradiation with the β ray, pre-irradiation dosage is 5KGy.
Will be through the LDPE of pre-irradiation, join in the response type twin screw extruder main hopper, the functionalized polyolefin long-acting trickle film function monomer 2.0 parts (quality) that will have reactive behavior injects through the liquid charging opening with giving electronics reagent para benzoquinone 0.05 part (quality), carries out the extruding graft polymerization.The screw diameter of forcing machine is 30mm, and length-to-diameter ratio is 44,11 sections heating, is followed successively by 130,150 from spout to each section of mouth mould temperature when reaction is extruded, 170,190,210,210,250,250,220,200, and 200 ℃, reactant per os mould is extruded, granulation.
With the graft polymerization pellet with contain Chimassorb944, phthalocyanine blue and talcous masterbatch and mix, carry out blown film with Haake Φ 30 inflation film manufacturing machines, inflation film manufacturing machine each section temperature from the spout to the die head is followed successively by 130,150,170,190,220,240,220 ℃, obtain functionalized polyolefin long-acting trickle film, thickness 0.10mm.Functionalized polyolefin long-acting trickle film is covered on the acceleration drip instrument, commercial goods anti-dropping film with stack pile under 60 ℃ of water temperatures quickens the drip test jointly, the drip lasting period of functionalized polyolefin long-acting trickle film is 25-42 days, and the lasting period of commodity anti-dropping film is 6-8 days.
Embodiment 2
With molecular weight is that 1016 polyethers tetravalent alcohol 1.875mol, toluene 9.075mol are to Witco 1298 Soft Acid 1.5 * 10
-2Mol, Resorcinol 1.5 * 10
-2Agitator is equipped with in the mol adding, thermometer, reflux condensing tube, liquid drips pipe, nitrogen is poured in the reactor of pipe and heating unit, place liquid to drip pipe the acrylic acid solution of 1.875mol, feed nitrogen, heated and stirred, fluid temperature in the reactor is raised to 50 ℃, open liquid and drip the pipe switch, begin to drip liquid, 40 minutes dropping time, dropwise and be warming up to 60 ℃, reacted 10 hours, finish reaction, reduce the temperature to 50 ℃, be decompressed to-0.12MPa, remove mixed solvent, obtain having the function monomer of the functionalized polyolefin long-acting trickle film of reactive behavior.
With 100 parts of (quality) ethene-butene-1 copolymers, butene content 5% (quality),
60Carry out pre-irradiation with gamma-rays on the Co device, pre-irradiation dosage is 80KGy.
Will be through the ethene-butene-1 copolymer of pre-irradiation, join in the response type twin screw extruder main hopper, the functionalized polyolefin long-acting trickle film function monomer 10 parts (quality) that will have reactive behavior injects through the liquid charging opening with giving electronics reagent para benzoquinone 2 parts (quality), carries out the extruding graft polymerization.The screw diameter of forcing machine is 72mm, and length-to-diameter ratio is 48,12 sections heating, is followed successively by 130,150 from spout to each section of mouth mould temperature when reaction is extruded, 170,190,210,220,230,250,250,245, and 230,210 ℃.Reactant per os mould is extruded, granulation.
With the GH200 high-speed mixer with extruding graft polymeric particle with contain Chimassorb944, phthalocyanine blue and talcous masterbatch and mix, carry out blown film with SL65 blown film unit, inflation film manufacturing machine each section temperature from the spout to the die head is followed successively by 130,150,170,190,210,240,210 ℃, obtain functionalized polyolefin long-acting trickle film, thickness 0.10mm.The tensile strength of functionalized polyolefin long-acting trickle film is 27.8MPa (vertically), 24.3MPa (laterally); Elongation at break was 584% (vertically), 715% (laterally); Angle tear strength 79KN/m (vertically), 98KN/m (laterally); Transmittance 87%.Functionalized polyolefin long-acting trickle film is covered on the acceleration drip instrument, commercial goods anti-dropping film with stack pile under 60 ℃ of water temperatures quickens the drip test, the drip lasting period of functionalized polyolefin long-acting trickle is 30-43 days, and the lasting period of commercial goods anti-dropping film is 6-8 days.The commodity anti-dropping film of functionalized polyolefin long-acting trickle film and stack pile is carried out the outdoor canopy of buckleing, and the drip lasting period of functionalized polyolefin long-acting trickle film is 13-16 month, and the lasting period of commodity anti-dropping film is 3-4 month.
Embodiment 3
With molecular weight is 488 polyethers tetravalent alcohol 2mol, dimethylbenzene 3mol, to Witco 1298 Soft Acid 2 * 10
-3Mol, Resorcinol 2 * 10
-3Agitator is equipped with in the mol adding, thermometer, reflux condensing tube, liquid drips pipe, nitrogen is poured in the reactor of pipe and heating unit, the 2mol MALEIC ANHYDRIDE is dissolved in the liquid that fills 6.075mol acetone to drip in the pipe, feed nitrogen, heated and stirred, fluid temperature in the reactor is raised to 50 ℃, open liquid and drip the pipe switch, begin to drip liquid, 55 minutes dropping time, dropwise and be warming up to 85 ℃, reacted 8 hours, finish reaction, reduce the temperature to 60 ℃, be decompressed to-0.1MPa, remove and to desolvate, obtain having the function monomer of the functionalized polyolefin long-acting trickle film of reactive behavior.
With 100 parts of (quality) ethene-1-octene copolymers, octene content 9% (quality) is carried out pre-irradiation with the β ray on the rumbatron device, and pre-irradiation dosage is 50KGy.
Will be through the ethene-1-octene copolymer of pre-irradiation, join in the response type twin screw extruder main hopper, the functionalized polyolefin long-acting trickle film function monomer 5 parts (quality) that will have reactive behavior injects through the liquid charging opening with giving electronics reagent para benzoquinone 0.1 part (quality), carries out the extruding graft polymerization.The screw diameter 70mm of forcing machine, length-to-diameter ratio is 48,11 sections heating, and each section temperature was followed successively by 130,150,170 from spout to the mouth mould when reaction was extruded, and 190,210,230,240,240,250,230,200 ℃, reactant per os mould is extruded, granulation.
With extruding graft polymeric particle with contain Chimassorb944, phthalocyanine blue and talcous masterbatch and mix, carry out blown film with Φ 90 blown film units, inflation film manufacturing machine each section temperature from the spout to the die head is 130,150,170,190,240,220,200,200 ℃, obtain functionalized polyolefin long-acting trickle film, thickness 0.10mm.Functionalized polyolefin long-acting trickle film is covered on the acceleration drip instrument, commercial goods anti-dropping film with stack pile under 60 ℃ of water temperatures quickens the drip test, the drip lasting period of functionalized polyolefin long-acting trickle is 25-35 days, and the lasting period of the commercial goods anti-dropping film of stack pile is 6-8 days.The commodity anti-dropping film of functionalized polyolefin long-acting trickle film and stack pile is carried out the outdoor canopy of buckleing, and the drip lasting period of functionalized polyolefin long-acting trickle film is 13-15 month, and the lasting period of commodity anti-dropping film is 3-4 month.
Embodiment 4
With molecular weight is 664 polyethers tetravalent alcohol 1.875mol, dimethylbenzene 9.075mol, to Witco 1298 Soft Acid 1.5 * 10
-3Mol, Resorcinol 1.5 * 10
-3Agitator is equipped with in the mol adding, thermometer, reflux condensing tube, liquid drips pipe, nitrogen is poured in the reactor of pipe and heating unit, place liquid to drip pipe the acrylic acid solution of 1.875mol, feed nitrogen, heated and stirred, fluid temperature in the reactor is raised to 50 ℃, open liquid and drip the pipe switch, begin to drip liquid, 40 minutes dropping time dropwised and is warming up to 100 ℃ of reactions 10 hours, finished reaction, reduce the temperature to 50 ℃, be decompressed to-0.08MPa, remove mixed solvent, obtain having the function monomer of the functionalized polyolefin long-acting trickle film of reactive behavior.
With ethene-vinyl acetate copolymer (EVA), VA content 5% (quality) carries out pre-irradiation with gamma-rays on the 80Co device with 100 parts (quality), and pre-irradiation dosage is 5KGy.
Will be through the EVA of pre-irradiation, join in the response type single screw extrusion machine main hopper, the functionalized polyolefin long-acting trickle film function monomer 2 parts (quality) that will have reactive behavior injects through the liquid charging opening with giving electronics reagent para benzoquinone 0.05 part (quality), carries out the extruding graft polymerization.The screw diameter of forcing machine is 90mm, and compression ratio is 2.5, and length-to-diameter ratio is 48,12 sections heating, is followed successively by 130,150 from spout to each section of mouth mould temperature when reaction is extruded, 170,190,210,220,230,240,250,240,230,215 ℃, reactant per os mould is extruded, granulation.
With extruding graft polymeric particle with contain Chimassorb944, phthalocyanine blue and talcous masterbatch and mix, carry out blown film with Φ 120 blown film units, inflation film manufacturing machine each section temperature from the charging opening to the die head is 130,150,170,190,210,230,240,210,190,190 ℃, obtain functionalized polyolefin long-acting trickle film, thickness 0.10mm.Functionalized polyolefin long-acting trickle film is covered on the acceleration drip instrument, commercial goods anti-dropping film with stack pile under 60 ℃ of water temperatures quickens the drip test, the drip lasting period of functionalized polyolefin long-acting trickle is 30-45 days, and the lasting period of the commercial goods anti-dropping film of stack pile is 10-12 days.The commodity anti-dropping film of functionalized polyolefin long-acting trickle film and stack pile is carried out the outdoor canopy of buckleing, and the drip lasting period of functionalized polyolefin long-acting trickle film is 13-17 month, and the lasting period of commodity anti-dropping film is 5-6 month.
Embodiment 5
With molecular weight 840 polyethers tetravalent alcohol 0.19mol, vinylformic acid 0.19mol, dimethylbenzene 0.6mol, Resorcinol 2 * 10
-4Mol, tosic acid 2 * 10
-4The mol adding is equipped with in the reactor of agitator, thermometer, reflux condensing tube, nitrogen ingress pipe and heating unit, feed nitrogen, heated and stirred, be warming up to 100 ℃ of reactions 10 hours, finish reaction, reduce the temperature to 65 ℃, be decompressed to-0.12MPa, remove and to desolvate, obtain having the function monomer of the functionalized polyolefin long-acting trickle film of reactive behavior.
With 100 parts of (quality) ethene-1-hexene copolymers, hexene content 8% (quality) carries out pre-irradiation with the β ray on the rumbatron device, and pre-irradiation dosage is 80KGy.
Will be through the ethene-1-hexene copolymer of pre-irradiation, join in the response type twin screw extruder main hopper, the functionalized polyolefin long-acting trickle film function monomer 10 parts (quality) that will have reactive behavior injects through the liquid charging opening with giving electronics reagent para benzoquinone 2 parts (quality), carries out the extruding graft polymerization.The screw diameter of forcing machine is 30mm, and length-to-diameter ratio is 44,11 sections heating, is followed successively by 130,150 from spout to each section of mouth mould temperature when reaction is extruded, 170,190,210,210,250,250,220,200, and 190 ℃, reactant per os mould is extruded, granulation.
With extruding graft polymeric particle with contain Chimassorb944, phthalocyanine blue and talcous masterbatch and mix, carry out blown film with Haake Φ 30 inflation film manufacturing machines, inflation film manufacturing machine each section temperature from the spout to the die head is 130,160,190,220,240,210,200,190 ℃, obtain functionalized polyolefin long-acting trickle film, thickness 0.10mm.Functionalized polyolefin long-acting trickle film is covered on the acceleration drip instrument, commercial goods anti-dropping film with stack pile under 60 ℃ of water temperatures quickens the drip test jointly, the drip lasting period of functionalized polyolefin long-acting trickle film is 25-41 days, and the lasting period of commodity anti-dropping film is 6-8 days.
Embodiment 6
With molecular weight 664 polyethers tetravalent alcohol 0.19mol, MALEIC ANHYDRIDE 0.19mol, dimethylbenzene 0.6mol, Resorcinol 2 * 10
-3Mol, tosic acid 2 * 10
-3The mol adding is equipped with in the reactor of agitator, thermometer, reflux condensing tube, nitrogen ingress pipe and heating unit, feed nitrogen, heated and stirred, the temperature of liquid in the reactor is raised to 100 ℃, reacted 8 hours, finish reaction, reduce the temperature to 60 ℃, be decompressed to-0.1MPa, remove and to desolvate, obtain having the function monomer of the functionalized polyolefin long-acting trickle film of reactive behavior.
With 100 parts of (quality) polypropylene, on the rumbatron device, carry out pre-irradiation with the β ray, pre-irradiation dosage is 40KGy.
Will be through the polypropylene of pre-irradiation, join in the response type twin screw extruder main hopper, the functionalized polyolefin long-acting trickle film function monomer 6 parts (quality) that will have reactive behavior injects through the liquid charging opening with giving electronics reagent para benzoquinone 0.2 part (quality), carries out the extruding graft polymerization.The screw diameter of forcing machine is 30mm, and length-to-diameter ratio is 44,11 sections heating, is followed successively by 130,150 from spout to each section of mouth mould temperature when reaction is extruded, 170,190,210,210,250,250,220,200, and 195 ℃, reactant per os mould is extruded, granulation.
With extruding graft polymeric particle with contain Chimassorb944, phthalocyanine blue and talcous masterbatch and mix, carry out blown film with Haake Φ 30 inflation film manufacturing machines, inflation film manufacturing machine each section temperature from the spout to the die head is 130,160,190,220,240,210,200,195 ℃, obtain functionalized polyolefin long-acting trickle film, thickness 0.10mm.Functionalized polyolefin long-acting trickle film is covered on the acceleration drip instrument, commercial goods anti-dropping film with stack pile under 60 ℃ of water temperatures quickens the drip test jointly, the drip lasting period of functionalized polyolefin long-acting trickle film is 25-40 days, and the lasting period of commodity anti-dropping film is 6-8 days.
Embodiment 7
With molecular weight 1016 polyethers tetravalent alcohol 0.19mol, dimethylbenzene 0.1mol, Resorcinol 2 * 10
-4Mol, tosic acid 2 * 10
-4Agitator is equipped with in the mol adding, thermometer, reflux condensing tube, liquid drips pipe, in the reactor of nitrogen ingress pipe and heating unit, the 0.19mol MALEIC ANHYDRIDE is dissolved in the liquid that fills 0.5mol acetone to drip in the pipe, feed nitrogen, heated and stirred, the temperature of liquid in the reactor is raised to 50 ℃, open liquid and drip the pipe switch, begin to drip liquid, 30 minutes dropping time, dropwise and be warming up to 60 ℃, reacted 10 hours, finish reaction, reduce the temperature to 50 ℃, be decompressed to-0.12MPa, remove and to desolvate, obtain having the function monomer of the functionalized polyolefin long-acting trickle film of reactive behavior.
With 100 parts (quality) poly-1-butylene, on the 60Co device, carry out pre-irradiation with gamma-rays, pre-irradiation dosage is 40KGy.
Will be through the poly-1-butylene of pre-irradiation, join in the response type single screw extrusion machine main hopper, the functionalized polyolefin long-acting trickle film function monomer 5 parts (quality) that will have reactive behavior injects through the liquid charging opening with giving electronics reagent para benzoquinone 0.05 part (quality), carries out the extruding graft polymerization.The screw diameter of forcing machine is 35mm, and length-to-diameter ratio is 40,11 sections heating, is followed successively by 130,150 from spout to each section of mouth mould temperature when reaction is extruded, 170,190,210,210,250,230,220,205, and 195 ℃, reactant per os mould is extruded, granulation.
With extruding graft polymeric particle with contain Chimassorb944, phthalocyanine blue and talcous masterbatch and mix, carry out blown film with Haake Φ 30 inflation film manufacturing machines, inflation film manufacturing machine each section temperature from the spout to the die head is 130,160,190,220,240,220,205,195 ℃, obtain functionalized polyolefin long-acting trickle film, thickness 0.10mm.Functionalized polyolefin long-acting trickle film is covered on the acceleration drip instrument, commercial goods anti-dropping film with stack pile under 60 ℃ of water temperatures quickens the drip test jointly, the drip lasting period of functionalized polyolefin long-acting trickle film is 25-40 days, and the lasting period of commodity anti-dropping film is 6-8 days.
Claims (3)
1. a functionalized polyolefin long-acting trickle film is characterized in that, grafted has the function monomer structural formula of reactive behavior and is on the molecular polyolefin chain:
2. the preparation method of a kind of functionalized polyolefin long-acting trickle film as claimed in claim 1 is characterized in that, its step and condition are as follows:
(1) has the function monomer preparation of the functionalized polyolefin long-acting trickle film of reactive behavior
MALEIC ANHYDRIDE or vinylformic acid, polyethers tetravalent alcohol, solvent, catalyzer, stopper are joined in the reactor, feed nitrogen, heated and stirred, MALEIC ANHYDRIDE wherein or vinylformic acid: polyethers tetravalent alcohol: catalyzer: stopper: the ratio of solvent, count 0.95-1.25 with mole: 0.95-1.25: 10
-3-10
-2: 10
-3-10
-2: 3-6.05, reaction times 2-10 hour, temperature of reaction 60-100 ℃, reaction product through 50-65 ℃ be decompressed to-0.08--0.12MPa removes solvent, obtains having the function monomer of the functionalized polyolefin long-acting trickle film of reactive behavior;
(2) pre-irradiation of polyolefin resin
Adopt
60Co carries out pre-irradiation with gamma-rays to polyolefin resin as irradiation source, and the pre-irradiation dosage range is 5KGy-80KGy;
(3) polyolefine and function monomer fusion-grafting polymerization with functionalized polyolefin long-acting trickle film of reactive behavior
Fusion-grafting is aggregated in response type single screw extrusion machine or the twin screw extruder and carries out, the pre-irradiation polyolefin resin that step (2) is obtained joins in the main hopper of response type single screw extrusion machine or twin screw extruder, the function monomer that step (1) is obtained and inject for electronics reagent through the liquid charging opening of response type single screw extrusion machine or twin screw extruder with reactive behavior, the polyolefin resin quality is in 100 parts, the monomeric consumption of above-mentioned functions is 2.0-10 part, and above-mentioned consumption to electronics reagent is 0.05-2 part; Temperature of reaction is controlled at 130-250 ℃, extrudes, and granulation obtains fusion-grafting polymerization pellet;
(4) preparation of functionalized polyolefin long-acting trickle film
Step (3) is obtained polyolefine to join in the inflation film manufacturing machine after the function monomer fusion-grafting polymerization pellet with reactive behavior mixes with the masterbatch that contains photostabilizer, pigment and heat preserving agent, 130-240 ℃ of blown film temperature, blowing obtains functionalized polyolefin long-acting trickle film;
Said polyolefin resin is polyethylene, ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethene-1-octene copolymer, ethylene-vinyl acetate copolymer, polypropylene or poly-1-butylene;
Said solvent be toluene, dimethylbenzene, ethyl acetate, acetone wherein one or more;
Said is triphenyl phosphite or para benzoquinone to electronics reagent;
Said catalyzer is: sulfuric acid, tosic acid, to a kind of of Witco 1298 Soft Acid, trifluoroacetic acid, trichoroacetic acid(TCA) or several;
Said stopper is MEHQ or Resorcinol;
The said photostabilizer masterbatch that contains is to contain the masterbatch that photostabilizer is Chimassorb944;
The said pigment masterbatch that contains is the masterbatch that contains phthalocyanine blue;
The said heat preserving agent masterbatch that contains is for containing promising talcous masterbatch.
3. the preparation method of a kind of functionalized polyolefin long-acting trickle film according to claim 2 is characterized in that adopting rumbatron as irradiation source, with the β ray polyolefine is carried out pre-irradiation, and the pre-irradiation dosage range is 5KGy-80KGy.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002133A (en) * | 2010-10-08 | 2011-04-06 | 中国科学院长春应用化学研究所 | Polyolefin resin for long-lasting drip film and preparation method thereof |
| CN107226891A (en) * | 2017-06-09 | 2017-10-03 | 中国科学院长春应用化学研究所 | A kind of anti-dropping film resin and preparation method and application |
| CN109627489A (en) * | 2018-12-05 | 2019-04-16 | 浙江比例聚合科技股份有限公司 | A kind of agricultural film long-acting anti-dropping agent |
| CN112210202A (en) * | 2020-10-15 | 2021-01-12 | 临安市助剂化工有限公司 | Agricultural film dripping agent and preparation process thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA924249B (en) * | 1991-06-21 | 1993-03-31 | Himont Inc | Process for grafting vinyl monomers on particulate olefin polymers |
| MY133783A (en) * | 1999-07-28 | 2007-11-30 | Dow Global Technologies Inc | Hydrogenated block polymers having elasticity and articles made therefrom |
| US6444722B1 (en) * | 2000-11-02 | 2002-09-03 | Basell Poliolefine Italia S.P.A. | Making polyolefin graft copolymers with low molecular weight side chains using a polymeric peroxide as an initiator |
| US6518327B1 (en) * | 2000-11-02 | 2003-02-11 | Basell Poliolefine Italia S.P.A. | Irradiation process for making olefin graft copolymers with low weight side chains |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002133A (en) * | 2010-10-08 | 2011-04-06 | 中国科学院长春应用化学研究所 | Polyolefin resin for long-lasting drip film and preparation method thereof |
| CN102002133B (en) * | 2010-10-08 | 2012-07-25 | 中国科学院长春应用化学研究所 | Polyolefin resin for long-lasting drip film and preparation method thereof |
| CN107226891A (en) * | 2017-06-09 | 2017-10-03 | 中国科学院长春应用化学研究所 | A kind of anti-dropping film resin and preparation method and application |
| CN109627489A (en) * | 2018-12-05 | 2019-04-16 | 浙江比例聚合科技股份有限公司 | A kind of agricultural film long-acting anti-dropping agent |
| CN112210202A (en) * | 2020-10-15 | 2021-01-12 | 临安市助剂化工有限公司 | Agricultural film dripping agent and preparation process thereof |
| CN112210202B (en) * | 2020-10-15 | 2022-05-20 | 临安市助剂化工有限公司 | Agricultural film dripping agent and preparation process thereof |
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| CN100455620C (en) | 2009-01-28 |
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