CN1693329A - Process for preparing functional polyolefins resin mixed with rare earth compound - Google Patents
Process for preparing functional polyolefins resin mixed with rare earth compound Download PDFInfo
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- CN1693329A CN1693329A CN 200510016847 CN200510016847A CN1693329A CN 1693329 A CN1693329 A CN 1693329A CN 200510016847 CN200510016847 CN 200510016847 CN 200510016847 A CN200510016847 A CN 200510016847A CN 1693329 A CN1693329 A CN 1693329A
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Abstract
A process for preparing the functional polyolefin resin includes such steps as mixing polyolefin resin, RE compound including RE-naphthenic acid complex and RE oxide, peroxide as trigger and functional monomer, and reaction. Its advantages are high machinability and high strength of fused body.
Description
Technical field
The invention belongs to the preparing technical field of the functional polyolefin resin of rare earth compound participation.
Background technology
Polyolefin resin has that raw material is easy to get, cheap, comprehensive physical and mechanical properties is good, resistance to chemical attack, nontoxic, be easy to many advantages such as processing, have a wide range of applications in fields such as packing, household electrical appliances, automobile, decoration, buildings.Because polyolefin resin is a non-polar polymer, lack reactive group or polar group, its wetting ability, dyeability, with the cohesiveness of metal, pottery, glass polar materials and all relatively poor with the consistency of polymeric amide, polyester isopolarity polymkeric substance, this has limited its range of application to a great extent.Preparing functional polyolefin resin with reactivity or the unsaturated function monomer of polarity and polyolefin resin graft copolymerization, is the universal method that overcomes above shortcoming.Usually adopt the small molecules organo-peroxide as initiator, the free radical that utilizes its decomposition to produce causes the graft reaction between function monomer and polyolefin resin.Yet because the decomposition rate of organo-peroxide is subjected to the influence of its chemical structure and processing temperature, the concentration of the free radical that produces and life-span are difficult to control and skewness.Therefore, have following shortcoming with organo-peroxide as the functional polyolefin resin of initiator preparation: polyolefin resin easily degrades, crosslinked or degraded and crosslinked while and the side reaction of depositing, and causes the change of mechanical property or processing characteristics bad; The percentage of grafting of function monomer and grafting efficiency are low and homopolymerization easily takes place.Scandium, yttrium and the lanthanon that rare earth element is meant IIIB in the periodic table of elements by lanthanum to the lutetium general designation of totally 17 kinds of elements.Its principal character is from the cerium to the lutetium, and along with the increase of ordination number, the electronics of corresponding increase all is filled on the internal layer 4f degeneracy track, has characteristics such as unique light, electricity, magnetic because of the singularity of its 4f electron structure.Document and patent report are not seen in the monomeric research work of polyolefin melt grafting functional that rare earth compound participates in as yet.
Summary of the invention
" functional polyolefin resin that rare earth compound participates in " is designated hereinafter simply as " functional polyolefin resin " in present specification.
The purpose of this invention is to provide the preparation method of the functional polyolefin resin that the rare earth compound participation is arranged, thereby overcome the shortcoming that exists when adopting organo-peroxide to prepare functional polyolefin resin as initiator.Feature of the present invention is to introduce rare earth compound in the reaction system, and it comprises the naphthenate complex and the rare earth oxide of rare earth.Advantage of the present invention is that the grafting active site on the polyolefin resin is evenly distributed, stablizes in the reaction process; The percentage of grafting of function monomer and grafting efficiency height, homopolymerization trend are little; Suppressed degraded or the side reaction such as crosslinked of polyolefin resin in the functionalization process; The gained functional polyolefin resin has good machine-shaping property, the melt strength height, and its mechanical property remains unchanged substantially.
The needed starting material of the preparation method of functional polyolefin resin of the present invention, Step By Condition are as follows:
Starting material are:
A. polyolefin resin: polyethylene (comprising all kinds of ethylene-alpha-olefin copolymers); Polypropylene (comprising homo-polypropylene and Co-polypropylene); Ethylene-propylene copolymer comprises that weight ethylene content is 1%～80% the ethylene-propylene random copolymer and the Ethylene-Propylene Block Copolymer of weight ethylene content 5%～20%; Phenylethylene resin series comprises polystyrene, ethylene-styrene copolymer, high-impact polystyrene, acrylonitrile-butadiene-styrene copolymer;
B. rare earth compound comprises rare earth naphthenate complex and rare earth oxide.Its middle-weight rare earths naphthenate complex comprises cerium naphthenate, naphthenic acid praseodymium, neodymium naphthenate, naphthenic acid gadolinium and naphthenic acid holmium; Rare earth oxide comprises a kind of in lanthanide rare earth oxide (except the promethium oxide), Scium trioxide or the yttrium oxide or several;
C. peroxide initiator: dicumyl peroxide, dibenzoyl peroxide, 2,5-dimethyl-2, a kind of in two (tert-butyl peroxy base) hexanes of 5-;
D. function monomer: a kind of in MALEIC ANHYDRIDE, vinylformic acid, methacrylic acid, methyl methacrylate and the glytidyl methacrylate or several;
The preparation method's of functional polyolefin resin of the present invention step and condition are as follows:
(a) get 100 parts of polyolefin resin weight, and, get 0.0001～0.0090 mole of rare earth oxide again, 0.05～5 part of peroxide initiator weight, 1～15 part of function monomer weight its benchmark as other material weight umber proportioning; Or
100 parts of the gross weights of the polyolefin masterbatch of getting the rare earth naphthenate complex and corresponding polyolefin resin (polyolefin masterbatch is 10: 90～90: 10 with the parts by weight proportioning of corresponding polyolefin resin), and with its benchmark as other material weight umber proportioning, get 0.05～5 part of peroxide initiator weight again, 1～15 part of a kind of or several functionalities monomer weight.
The preparation method of the polyolefin masterbatch of its middle-weight rare earths naphthenate complex is as follows: at first with dimethylbenzene cerium naphthenate, naphthenic acid praseodymium, neodymium naphthenate, naphthenic acid gadolinium or naphthenic acid holmium are diluted respectively, spray equably on polyolefin resin again, after the polyolefin masterbatch of rare earth naphthenate complex is made in 50～60 ℃ of vacuum-drying, contain 0.004 mole of rare earth ion in the polyolefin masterbatch of wherein every 100g rare earth naphthenate complex.
Material by above-mentioned parts by weight proportioning is carried out mechanically mixing 2～10 minutes with Henschel mixing tank, drum tumbler or V-type mixing tank, obtain pre-mixed resin.
In addition, as required can also be in the blend material routinely consumption add the conventional auxiliary agent of plastics industry.
(b) will join by the pre-mixed resin that (a) obtains in the reactor, temperature of reaction is 130～230 ℃, reaction times is 1.5～10 minutes, and polyolefin resin prepares the functional polyolefin resin that rare earth compound participates at molten state and function monomer generation graft copolymerization.
Reactor of the present invention comprises mill, Banbury mixer, single screw extrusion machine or twin screw extruder.When adopting mill as reactor, temperature of reaction is 160～210 ℃, and the reaction times is 4～6 minutes; When adopting Banbury mixer as reactor, temperature of reaction is 170～230 ℃, and the reaction times is 5～10 minutes; When adopting single screw extrusion machine or twin screw extruder as reactor, temperature of reaction is 130～230 ℃, and the reaction times is 1.5～2.5 minutes.
The graft copolymer that obtains under refluxad is dissolved in its good solvent, again solution is poured in the precipitation agent of 2～3 times of its volumes and precipitated, thereby remove function monomer that has neither part nor lot in functionalization and the homopolymer thereof that contains in the graft product.With gained precipitation through vacuum-drying to constant weight, come the monomeric percentage of grafting of measurement function with methods such as acid base titration or infrared spectras.
Compare with independent organo-peroxide initiator system, the percentage of grafting of function monomer and grafting efficiency height, homopolymerization trend are little; The weight percentage of grafting of function monomer is 0.1%～10.0% in the functional polyolefin resin of preparation, can regulate on request; Degraded that polyolefin resin takes place in the functionalization process or side reaction such as crosslinked are inhibited to a certain extent; Functional polyolefin resin has good machine-shaping property, the melt strength height, and the low particularly extrusion swelling of melt elasticity obviously diminishes; Compare with matrix resin, the variation range of the tensile strength of functional polyolefin resin and modulus, flexural strength and modulus, shock strength, elongation at break etc. is within 10%.
The functional polyolefin resin of prepared in accordance with the method for the present invention is in following field extensive application: (1) prepares film forming with methods such as blowing, extrusion molding, calenderings, such film or use or compound with aluminium foil, polymeric amide, polyester, polyvinylidene chloride, ethylene-vinyl alcohol copolymer etc. separately are as the wrapping material of food, beverage, condiment, medicine and each based article; (2) directly be used as and mould-tack coat of steel, mould-matrix materials such as aluminium; (3) as the expanding material for preparing polyolefin/polyamide, polyolefine/polyester high molecule alloy material.
Embodiment
Below in conjunction with embodiment, the present invention is further set forth, but scope of the present invention is not limited to these embodiment.
Embodiment 1
Polypropylene, the weight content of therein ethylene are 5%, its melt flow rate (MFR) be 1.0g/10min (190 ℃, 2.16kg); The purity of rare earth oxide is 99.9%, and median size is 1.0～2.0 μ m; Dicumyl peroxide (DCP), analytical pure; Maleic anhydride (MAH) analytical pure.Get parts by weight and be 100 above-mentioned acrylic resin, and with its benchmark as other material weight umber proportioning, correspondingly get mole number respectively and be 0.0010 yttrium oxide, lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide, europium sesquioxide, gadolinium sesquioxide, terbium sesquioxide, dysprosium oxide, Holmium trioxide, Erbium trioxide, trioxide, ytterbium oxide or lutecium oxide, again respectively with 2.0 parts of 0.20 part of DCP weight and MAH weight premix 2 minutes in drum tumbler, obtain Preblend.
Above-mentioned Preblend is transported in the response type twin screw extruder, the screw diameter of forcing machine is 30mm, and length is 44, and setting forcing machine is 135～200 ℃ along charging opening to a mouthful mould direction temperature, die temperature is 190 ℃, and the residence time of material in forcing machine is about 1.5～2.0 minutes.Reactant per os mould is extruded, cooling, pelletizing, obtains finished product.The melt flow rate (MFR) of gained functional poly propylene, the monomeric percentage of grafting of MAH etc. are tested, and the results are shown in Table 1.
Embodiment 2
Polypropylene, its melt flow rate (MFR) are 0.7g/10min (190 ℃, 2.16kg)); The purity of rare earth oxide is 99.9%, and median size is 1.0～2.0 μ m; Dicumyl peroxide (DCP), analytical pure; Maleic anhydride (MAH), analytical pure.Get parts by weight and be 100 above-mentioned acrylic resin, and with its benchmark as other material weight umber proportioning, correspondingly get mole number respectively and be 0.0020 yttrium oxide, lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide, europium sesquioxide, gadolinium sesquioxide, terbium sesquioxide, dysprosium oxide, Holmium trioxide, Erbium trioxide, trioxide, ytterbium oxide or lutecium oxide, again respectively with 2.0 parts of 0.20 part of DCP weight and MAH weight premix 2 minutes in drum tumbler, obtain Preblend.Conversion unit and remaining reaction conditions are all identical with embodiment 1 with step, and test result is listed in the table 2.
Embodiment 3
Linear low density polyethylene (LLDPE), wherein the weight content of 1-butylene is 6 ± 0.5%, its melt flow rate (MFR) be 1.0g/10min (190 ℃, 2.16kg); The purity of rare earth oxide is 99.9%, and its median size is 1.0～2.0 μ m; 2,5-dimethyl-2, two (tert-butyl peroxy base) hexanes of 5-, analytical pure; Glytidyl methacrylate (GMA), analytical pure.Get parts by weight and be 100 above-mentioned LLDPE resin, and with its benchmark as other material weight umber proportioning, correspondingly get 0.0030 mole yttrium oxide, lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide, europium sesquioxide, gadolinium sesquioxide, terbium sesquioxide, dysprosium oxide, Holmium trioxide, Erbium trioxide, trioxide, ytterbium oxide or lutecium oxide respectively, again respectively with 2,5-dimethyl-2,6.0 parts of 0.25 part of two (tert-butyl peroxy base) hexane weight of 5-and GMA weight premix 5 minutes in drum tumbler obtains Preblend.
Above-mentioned Preblend is transported in the response type twin screw extruder, the screw diameter of forcing machine is 24mm, and length is 40, and setting forcing machine is 135～200 ℃ along charging opening to a mouthful mould direction temperature, die temperature is 190 ℃, and the residence time of material in forcing machine is 1.5～2.0 minutes.Reactant per os mould is extruded, cooling, pelletizing, obtains finished product.Test result is listed in the table 3.
Embodiment 4
Polypropylene, its melt flow rate (MFR) be 1.9g/10min (190 ℃, 2.16kg).The purity of rare earth oxide is 99.9%, and its median size is 1.0～2.0 μ m; Dicumyl peroxide (DCP), analytical pure; Maleic anhydride (MAH) analytical pure.Get parts by weight and be 100 above-mentioned acrylic resin, and with its benchmark as other material weight umber proportioning, correspondingly get 0.0045 mole yttrium oxide, lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide, europium sesquioxide, gadolinium sesquioxide, terbium sesquioxide, dysprosium oxide, Holmium trioxide, Erbium trioxide, trioxide, ytterbium oxide or lutecium oxide respectively, again respectively with 2.0 parts of 0.2 part of DCP weight and MAH weight premix 3 minutes in drum tumbler, obtain Preblend.Conversion unit and remaining reaction conditions are all identical with embodiment 3 with step.Test result is listed in the table 4.
Embodiment 5
High impact grade polystyrene (HIPS), its melt flow rate (MFR) be 3.1g/10min (230 ℃, 1.20Kg); The purity of rare earth oxide is 99.9%, and its median size is 1.0～2.0 μ m; Dicumyl peroxide (DCP), analytical pure; Glycidyl methacrylate (GMA), analytical pure.Get parts by weight and be 100 above-mentioned HIPS, and with its benchmark as other material weight umber proportioning, correspondingly get 0.0045 mole yttrium oxide, lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide, europium sesquioxide, gadolinium sesquioxide, terbium sesquioxide, dysprosium oxide, Holmium trioxide, Erbium trioxide, trioxide, ytterbium oxide or lutecium oxide respectively, in high speed agitator, mixed 5 minutes for 6.0 parts with 0.5 part of DCP weight and GMA weight respectively again, obtain Preblend.
The screw diameter of the twin screw extruder that adopts is 70mm, and length is 48, and setting forcing machine is 160～230 ℃ along charging opening to a mouthful mould direction temperature, and die temperature is 210 ℃, and the residence time of material in forcing machine is about 2.0～2.5 minutes.Reactant per os mould is extruded, cooling, pelletizing, obtains finished product.Test result is listed in the table 5.
Embodiment 6
Polypropylene, its melt flow rate (MFR) be 1.9g/10min (190 ℃, 2.16kg).The purity of rare earth oxide is 99.9%, and median size is 1.0～2.0 μ m; Dicumyl peroxide (DCP), analytical pure; Maleic anhydride (MAH) analytical pure.Get parts by weight and be 100 above-mentioned acrylic resin, and with its benchmark as other material weight umber proportioning, correspondingly get respectively 0.0080 mole yttrium oxide, lanthanum trioxide, cerium oxide, Praseodymium trioxide, Neodymium trioxide, Samarium trioxide, europium sesquioxide, gadolinium sesquioxide, terbium sesquioxide, dysprosium oxide, Holmium trioxide, Erbium trioxide, trioxide, ytterbium oxide or lutecium oxide, again respectively with 2.0 parts of 0.2 part of DCP weight and MAH weight premix 2～4 minutes in drum tumbler, obtain Preblend.Conversion unit and remaining reaction conditions are all identical with embodiment 3 with step.Test result is listed in the table 6.
Embodiment 7
Polypropylene, its melt flow rate (MFR) be 0.7g/10min (190 ℃, 2.16kg); Dicumyl peroxide (DCP), analytical pure; Maleic anhydride (MAH) analytical pure.Make the polypropylene masterbatch of cerium naphthenate according to the preparation method described in the summary of the invention (a), contain 0.004 mole of cerium ion in the polypropylene masterbatch of wherein every 100g cerium naphthenate.By the weight ratio of the polypropylene masterbatch of cerium naphthenate and virgin pp is that to be made into the gross weight umber in 10: 90,30: 70 or 50: 50 respectively be 100 resin, and with its benchmark as other material weight umber proportioning, again respectively with 2.0 parts of 0.20 part of DCP weight and MAH weight premix 3 minutes in drum tumbler, obtain Preblend.Conversion unit and remaining reaction conditions are all identical with embodiment 1 with step.The melt flow rate (MFR) of gained functional poly propylene is 13.1～17.6g/10min, and the monomeric percentage of grafting of MAH is 0.27%～0.31%.
Embodiment 8
Ethylene-styrene copolymer; Dicumyl peroxide (DCP), analytical pure; Methyl methacrylate, analytical pure.Make the ethylene-styrene copolymer masterbatch of naphthenic acid praseodymium according to the preparation method described in the summary of the invention (a), contain 0.004 mole of praseodymium ion in the ethylene-styrene copolymer masterbatch of wherein every 100g naphthenic acid praseodymium.By the weight ratio of the ethylene-styrene copolymer masterbatch of naphthenic acid praseodymium and pure ethylene-styrol copolymer is that to be made into the gross weight umber in 30: 70,40: 60 or 50: 50 be 100 resin, and with its benchmark as other material weight umber proportioning, in high speed agitator, mixed 5 minutes for 4.0 parts with 0.3 part of DCP weight and methyl methacrylate weight respectively again, obtain Preblend.
Above-mentioned Preblend is transported to single screw extrusion machine, the screw diameter of forcing machine is 30mm, and length is 44, and setting forcing machine is 150～190 ℃ along charging opening to a mouthful mould direction temperature, and die temperature is 180 ℃, and the residence time of material in forcing machine is about 1.5～2.0 minutes.Reactant per os mould is extruded, cooling, pelletizing, obtains finished product.The percentage of grafting of methyl methacrylate is 1.27%～1.45% in the gained graft copolymer.
Embodiment 9
Polypropylene, its melt flow rate (MFR) be 0.7g/10min (190 ℃, 2.16kg); Dicumyl peroxide (DCP), analytical pure; Maleic anhydride (MAH), analytical pure.Make the polypropylene masterbatch of neodymium naphthenate according to the preparation method described in the summary of the invention (a), contain 0.004 mole of neodymium ion in the polypropylene masterbatch of wherein every 100g neodymium naphthenate.By the weight ratio of the polypropylene masterbatch of neodymium naphthenate and virgin pp is that to be made into the gross weight umber in 50: 50,70: 30 or 90: 10 be 100 resin, and with its benchmark as other material weight umber proportioning, again respectively with 2.0 parts of 0.2 part of DCP weight and MAH weight premix 3 minutes in drum tumbler, obtain Preblend.Conversion unit and remaining reaction conditions are all identical with embodiment 1 with step.The melt flow rate (MFR) of gained functional poly propylene is 15.9～17.6g/10min, and the monomeric percentage of grafting of MAH is 0.29%～0.32%.
Embodiment 10
Acrylonitrile-butadiene-styrene terpolymer (ABS), its melt flow rate (MFR) be 2.0g/10min (200 ℃, 5.00Kg), bending elastic modulus 20.1MPa, tensile strength 34.2MPa, simply supported beam notched Izod impact strength 30.9KJ/m
2Dicumyl peroxide (DCP), analytical pure; Maleic anhydride (MAH) analytical pure.Make the ABS masterbatch of naphthenic acid gadolinium according to the preparation method described in the summary of the invention (a), contain 0.004 mole of gadolinium ion in the ABS masterbatch of wherein every 100g naphthenic acid gadolinium.By the weight ratio of the ABS masterbatch of naphthenic acid gadolinium and pure ABS resin is that to be made into the gross weight umber in 10: 90,20: 80 or 30: 70 be 100 resin, and with its benchmark as other material weight umber proportioning, in high speed agitator, mixed 5 minutes for 4.0 parts with 0.3 part of DCP weight and MAH weight respectively again, obtain Preblend.
Be set at 180 ℃ except that forcing machine is set at 150～200 ℃ and die temperature along charging opening to a mouthful mould direction temperature, conversion unit and remaining reaction conditions are all identical with embodiment 5 with step.The melt flow rate (MFR) of gained graft copolymer is 10.6～13.5g/10min, and the monomeric percentage of grafting of MAH is 1.02%～1.15%.Bending elastic modulus 20.9～the 23.9MPa of graft copolymer, tensile strength 28.4～33.5MPa, simply supported beam notched Izod impact strength 25.1～28.6KJ/m
2
Embodiment 11
Polypropylene, its melt flow rate (MFR) be 1.9g/10min (190 ℃, 2.16kg).Dicumyl peroxide (DCP), analytical pure; Maleic anhydride (MAH) analytical pure.Make the polypropylene masterbatch of naphthenic acid holmium according to the preparation method described in the summary of the invention (a), contain 0.004 mole of holmium ion in the polypropylene masterbatch of wherein every 100g naphthenic acid holmium.By the weight ratio of the polypropylene masterbatch of naphthenic acid holmium and virgin pp is that to be made into the gross weight umber in 70: 30,80: 20 or 90: 10 be 100 resin, and with its benchmark as other material weight umber proportioning, again respectively with 2.0 parts of 0.20 part of DCP weight and MAH weight premix 3 minutes in drum tumbler, obtain Preblend.
Above-mentioned Preblend is joined in two rollers of mill, setting two roll temperatures is 180 ℃, and roll spacing is 1～2mm, and mixing 5min also beats triangle bag several back sheet down.The melt flow rate (MFR) of gained functional poly propylene is 17.6～22.8g/10min, and the monomeric percentage of grafting of MAH is 0.28%～0.31%, and mechanical property remains unchanged.
Embodiment 12
Propylene-ethylene block copolymer, the weight content of therein ethylene are 10%, its melt flow rate (MFR) be 2.0g/10min (190 ℃, 2.16kg), tensile strength is 26.6MPa, elongation at break is 220%, simple beam impact strength is 25.1KJ/m
2The purity of Praseodymium trioxide, terbium sesquioxide and Erbium trioxide is 99.9%, and its median size is 1.0～2.0 μ m; Benzoyl peroxide (BPO), analytical pure; Vinylformic acid (AA), analytical pure.Get parts by weight and be aforesaid propylene-ethylene block copolymer of 100, and with its benchmark as other material weight umber proportioning, correspondingly get 0.0045 mole Praseodymium trioxide, terbium sesquioxide or Erbium trioxide respectively, again respectively with 10.0 parts of 0.5 part of BPO weight and AA weight premix 10 minutes in homogenizer, obtain Preblend.
Conversion unit and remaining reaction conditions are all identical with embodiment 5 with step.The melt flow rate (MFR) of gained graft copolymer is 2.6～5.5g/10min, and the monomeric percentage of grafting of AA is 4.3%～5.6%, and grafting efficiency is 55.4%～68.4%.Tensile strength is 26.0～28.5MPa, and elongation at break is 200%～220%, and simple beam impact strength is 23.2～25.8KJ/m
2
Embodiment 13
High-impact polystyrene (HIPS), its melt flow rate (MFR) be 3.1g/10min (230 ℃, 1.20Kg), tensile strength 31.0MPa, elongation at break 35%, cantilever beam impact strength 125.3J/m.The purity of Scium trioxide, cerium oxide and lutecium oxide is 99.9%, and its median size is 1.0～2.0 μ m; Dicumyl peroxide (DCP), analytical pure; Maleic anhydride (MAH) analytical pure.Get parts by weight and be 100 above-mentioned HIPS, and with its benchmark as other material weight umber proportioning, correspondingly get 0.0045 mole Scium trioxide, cerium oxide and lutecium oxide respectively, in high speed agitator, mixed 5 minutes for 10.0 parts with 0.5 part of DCP weight and MAH weight respectively again, obtain Preblend.
Above-mentioned Preblend is joined in the Haake Banbury mixer, is 180 ℃ in temperature, and rotating speed is to react 6min under 50 rev/mins the condition.The melt flow rate (MFR) of gained functionalization high-impact polystyrene is 19.6～25.5g/10min, the monomeric percentage of grafting of MAH is 2.8%～3.2%, tensile strength is 27.5～30.8MPa, and elongation at break is 20%～32%, cantilever beam impact strength 106.1～125.4J/m.Compare with the grafting system that does not add rare earth oxide, the monomeric percentage of grafting of MAH improves 6%～14%, and mechanical property slightly descends.With graft copolymer and polybutylene terephthalate (PBT) blend, by SEM it is distributed mutually and to observe, the interface of PBT/HIPS-g-MAH system is obviously different with the interface of PBT/HIPS, the dispersed phase particles size obviously diminishes, be evenly distributed, difficulty is distinguished interface structure, and interfacial phase is to coarse, alternate bonding enhancing.
Table 1
| Rare earth compound | Consumption (mol/100g PP) | Melt flow rate (MFR) (g/10min) | The percentage of grafting of MAH (%) |
| ??/ | ??/ | ??5.50 | ??0.35 |
| Yttrium oxide | ??0.0010 | ??5.41 | ??0.35 |
| Lanthanum trioxide | ??0.0010 | ??5.50 | ??0.35 |
| Cerium oxide | ??0.0010 | ??5.24 | ??0.36 |
| Praseodymium trioxide | ??0.0010 | ??5.24 | ??0.35 |
| Neodymium trioxide | ??0.0010 | ??6.00 | ??0.36 |
| Samarium trioxide | ??0.0010 | ??5.70 | ??0.35 |
| Europium sesquioxide | ??0.0010 | ??5.31 | ??0.35 |
| Gadolinium sesquioxide | ??0.0010 | ??6.76 | ??0.36 |
| Terbium sesquioxide | ??0.0010 | ??5.20 | ??0.35 |
| Dysprosium oxide | ??0.0010 | ??4.77 | ??0.34 |
| Holmium trioxide | ??0.0010 | ??6.01 | ??0.36 |
| Erbium trioxide | ??0.0010 | ??5.87 | ??0.35 |
| Trioxide | ??0.0010 | ??5.38 | ??0.35 |
| Ytterbium oxide | ??0.0010 | ??5.03 | ??0.34 |
| Lutecium oxide | ??0.0010 | ??4.90 | ??0.35 |
*Example 1,2,3,4,6 test condition is: 190 ℃, 2.16Kg.The test condition of example 5 is: 230 ℃, and 1.2Kg.
Table 2
| Rare earth compound | Consumption (mol/100gPP) | Melt flow rate (MFR) (g/10min) | The percentage of grafting of MAH (%) |
| ??/ | ??/ | ??17.60 | ??0.29 |
| Yttrium oxide | ??0.0020 | ??17.88 | ??0.29 |
| Lanthanum trioxide | ??0.0020 | ??18.29 | ??0.29 |
| Cerium oxide | ??0.0020 | ??20.49 | ??0.30 |
| Praseodymium trioxide | ??0.0020 | ??19.36 | ??0.29 |
| Neodymium trioxide | ??0.0020 | ??20.61 | ??0.31 |
| Samarium trioxide | ??0.0020 | ??19.81 | ??0.29 |
| Europium sesquioxide | ??0.0020 | ??19.60 | ??0.29 |
| Gadolinium sesquioxide | ??0.0020 | ??21.98 | ??0.31 |
| Terbium sesquioxide | ??0.0020 | ??17.13 | ??0.29 |
| Dysprosium oxide | ??0.0020 | ??17.80 | ??0.28 |
| Holmium trioxide | ??0.0020 | ??18.67 | ??0.30 |
| Erbium trioxide | ??0.0020 | ??18.21 | ??0.30 |
| Trioxide | ??0.0020 | ??17.71 | ??0.29 |
| Ytterbium oxide | ??0.0020 | ??16.73 | ??0.29 |
| Lutecium oxide | ??0.0020 | ??18.20 | ??0.29 |
Table 3
| Rare earth compound | Consumption (mol/100g LLDPE) | Melt flow rate (MFR) (g/10min) | The percentage of grafting of GMA (%) | Gel content (%) |
| ??/ | ??/ | ??2.50 | ??1.05 | ??17.2 |
| Yttrium oxide | ??0.0030 | ??2.45 | ??1.07 | ??16.7 |
| Lanthanum trioxide | ??0.0030 | ??2.30 | ??1.13 | ??18.4 |
| Cerium oxide | ??0.0030 | ??2.20 | ??1.17 | ??15.3 |
| Praseodymium trioxide | ??0.0030 | ??2.60 | ??1.11 | ??16.4 |
| Neodymium trioxide | ??0.0030 | ??3.02 | ??1.11 | ??14.7 |
| Samarium trioxide | ??0.0030 | ??2.44 | ??1.16 | ??17.6 |
| Europium sesquioxide | ??0.0030 | ??2.80 | ??1.13 | ??17.4 |
| Gadolinium sesquioxide | ??0.0030 | ??4.34 | ??1.25 | ??22.4 |
| Terbium sesquioxide | ??0.0030 | ??2.70 | ??1.05 | ??17.0 |
| Dysprosium oxide | ??0.0030 | ??2.55 | ??1.06 | ??17.5 |
| Holmium trioxide | ??0.0030 | ??3.20 | ??1.20 | ??19.3 |
| Erbium trioxide | ??0.0030 | ??3.45 | ??1.12 | ??18.9 |
| Trioxide | ??0.0030 | ??2.63 | ??1.02 | ??17.4 |
| Ytterbium oxide | ??0.0030 | ??2.50 | ??1.14 | ??18.0 |
| Lutecium oxide | ??0.0030 | ??2.87 | ??1.05 | ??17.7 |
Table 4
| Rare earth compound | Consumption (mol/100g PP) | Melt flow rate (MFR) (g/10min) | The percentage of grafting of MAH (%) |
| ??/ | ??/ | ??17.60 | ??0.27 |
| Yttrium oxide | ??0.0045 | ??34.40 | ??0.27 |
| Lanthanum trioxide | ??0.0045 | ??40.30 | ??0.29 |
| Cerium oxide | ??0.0045 | ??38.90 | ??0.30 |
| Praseodymium trioxide | ??0.0045 | ??33.50 | ??0.29 |
| Neodymium trioxide | ??0.0045 | ??32.20 | ??0.29 |
| Samarium trioxide | ??0.0045 | ??36.00 | ??0.30 |
| Europium sesquioxide | ??0.0045 | ??33.90 | ??0.29 |
| Gadolinium sesquioxide | ??0.0045 | ??36.30 | ??0.32 |
| Terbium sesquioxide | ??0.0045 | ??27.90 | ??0.27 |
| Dysprosium oxide | ??0.0045 | ??25.60 | ??0.25 |
| Holmium trioxide | ??0.0045 | ??32.30 | ??0.31 |
| Erbium trioxide | ??0.0045 | ??31.50 | ??0.29 |
| Trioxide | ??0.0045 | ??28.90 | ??0.26 |
| Ytterbium oxide | ??0.0045 | ??32.40 | ??0.29 |
| Lutecium oxide | ??0.0045 | ??26.30 | ??0.27 |
Table 5
| Rare earth compound | Consumption (mol/100g HIPS) | Melt flow rate (MFR) (g/10min) | The percentage of grafting of GMA (%) |
| ??/ | ??/ | ??5.60 | ??0.89 |
| Yttrium oxide | ??0.0060 | ??5.45 | ??0.89 |
| Lanthanum trioxide | ??0.0060 | ??5.31 | ??0.92 |
| Cerium oxide | ??0.0060 | ??6.20 | ??1.10 |
| Praseodymium trioxide | ??0.0060 | ??5.63 | ??0.91 |
| Neodymium trioxide | ??0.0060 | ??7.34 | ??1.08 |
| Samarium trioxide | ??0.0060 | ??5.47 | ??0.96 |
| Europium sesquioxide | ??0.0060 | ??5.81 | ??1.03 |
| Gadolinium sesquioxide | ??0.0060 | ??9.34 | ??1.14 |
| Terbium sesquioxide | ??0.0060 | ??6.70 | ??0.89 |
| Dysprosium oxide | ??0.0060 | ??6.55 | ??0.91 |
| Holmium trioxide | ??0.0060 | ??7.27 | ??1.02 |
| Erbium trioxide | ??0.0060 | ??7.45 | ??1.07 |
| Trioxide | ??0.0060 | ??5.67 | ??0.92 |
| Ytterbium oxide | ??0.0060 | ??5.50 | ??0.90 |
| Lutecium oxide | ??0.0060 | ??5.87 | ??0.95 |
Table 6
| Rare earth compound | Consumption (mol/100g PP) | Melt flow rate (MFR) (g/10min) | The percentage of grafting of MAH (%) |
| ??/ | ??/ | ??17.60 | ??0.27 |
| Yttrium oxide | ??0.0080 | ??27.52 | ??0.26 |
| Lanthanum trioxide | ??0.0080 | ??32.24 | ??0.27 |
| Cerium oxide | ??0.0080 | ??31.12 | ??0.29 |
| Praseodymium trioxide | ??0.0080 | ??26.80 | ??0.27 |
| Neodymium trioxide | ??0.0080 | ??25.76 | ??0.29 |
| Samarium trioxide | ??0.0080 | ??28.80 | ??0.28 |
| Europium sesquioxide | ??0.0080 | ??27.12 | ??0.28 |
| Gadolinium sesquioxide | ??0.0080 | ??29.04 | ??0.30 |
| Terbium sesquioxide | ??0.0080 | ??22.32 | ??0.26 |
| Dysprosium oxide | ??0.0080 | ??20.48 | ??0.24 |
| Holmium trioxide | ??0.0080 | ??25.84 | ??0.29 |
| Erbium trioxide | ??0.0080 | ??25.20 | ??0.28 |
| Trioxide | ??0.0080 | ??23.12 | ??0.25 |
| Ytterbium oxide | ??0.0080 | ??25.92 | ??0.28 |
| Lutecium oxide | ??0.0080 | ??21.04 | ??0.26 |
Claims (11)
1, the preparation method of the functional polyolefin resin of rare earth compound participation, its step and condition are as follows:
(a) get 100 parts of polyolefin resin weight, and with its benchmark as other material weight umber proportioning, correspondingly get 0.0001～0.0090 mole of rare earth compound again, 0.05～5 part of peroxide initiator weight, 1～15 part of function monomer weight, they are joined in Henschel mixing tank, drum tumbler or the V-type mixing tank mechanically mixing 2～10 minutes, obtain pre-mixed resin;
(b) pre-mixed resin that step (a) is obtained joins in the reactor, and temperature of reaction is 130～230 ℃, and the reaction times is 1.5～10 minutes, and polyolefin resin prepares functional polyolefin resin at molten state and function monomer generation graft copolymerization;
2, the preparation method of the functional polyolefin resin of rare earth compound participation according to claim 1, it is characterized in that in described (a) that the parts by weight proportioning by the polyolefin masterbatch of rare earth naphthenate complex and corresponding polyolefin resin is 10: 90～90: 10, the polyolefin masterbatch of getting the rare earth naphthenate complex is with 100 parts of the gross weights of corresponding polyolefin resin and with its benchmark as other material weight umber proportioning; Remaining raw material and proportioning, step and condition are with claim 1;
3, the preparation method of the functional polyolefin resin that participates in of rare earth compound according to claim 1 and 2 is characterized in that polyolefin resin in described (a) is that the weight content of polyethylene, polypropylene, ethene is that the weight content of 1%～80% ethylene-propylene random copolymer, ethene is a kind of in 5%～20% Ethylene-Propylene Block Copolymer, ethylene-styrene copolymer, polystyrene, high-impact polystyrene and the acrylonitrile-butadiene-styrene copolymer resin;
4, the preparation method of the functional polyolefin resin that participates in according to claim 1,2 or 3 described rare earth compounds, it is characterized in that described (a) middle-weight rare earths compound is the rare earth naphthenate complex, comprise a kind of in cerium naphthenate, naphthenic acid praseodymium, neodymium naphthenate, naphthenic acid gadolinium and the naphthenic acid holmium;
5, the preparation method of the functional polyolefin resin that participates in according to claim 1 or 3 described rare earth compounds, it is characterized in that described (a) middle-weight rare earths compound is a rare earth oxide, comprise a kind of in lanthanide rare earth oxide (except the promethium oxide), Scium trioxide and the yttrium oxide or several;
6, the preparation method of the functional polyolefin resin that participates in according to claim 1,2,3,4 or 5 described rare earth compounds, it is characterized in that described peroxide initiator is dicumyl peroxide, dibenzoyl peroxide and 2,5-dimethyl-2, a kind of in two (tert-butyl peroxy base) hexanes of 5-;
7, the preparation method of the functional polyolefin resin that participates in according to claim 1,2,3,4,5 or 6 described rare earth compounds is characterized in that described function monomer is a kind of in MALEIC ANHYDRIDE, vinylformic acid, methacrylic acid, methyl methacrylate and the glytidyl methacrylate or several;
8, the preparation method of the functional polyolefin resin that participates in according to the described rare earth compound of claim 1 to 7, when it is characterized in that reactor in described (b) is mill, temperature of reaction is 160～210 ℃, the reaction times is 4～6 minutes;
9, the preparation method of the functional polyolefin resin that participates in according to the described rare earth compound of any one claim of claim 1 to 7, when it is characterized in that reactor is Banbury mixer in described (b), temperature of reaction is 170～230 ℃, and the reaction times is 5～10 minutes;
10, the preparation method of the functional polyolefin resin that participates in according to the described rare earth compound of any one claim of claim 1 to 7, when it is characterized in that reactor is single screw extrusion machine in described (b), temperature of reaction is 130～230 ℃, and the reaction times is 1.5～2.5 minutes;
11, the preparation method of the functional polyolefin resin that participates in according to the described rare earth compound of any one claim of claim 1 to 7, when it is characterized in that reactor is twin screw extruder in described (b), temperature of reaction is 130～230 ℃, and the reaction times is 1.5～2.5 minutes.
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| CN113956605A (en) * | 2021-12-03 | 2022-01-21 | 四川大学 | Application of oxide in preparation of resin composition capable of being selectively metallized through laser activation |
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