CN101376683A - Preparation of high melt strength polypropylene - Google Patents
Preparation of high melt strength polypropylene Download PDFInfo
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- CN101376683A CN101376683A CNA2008100512432A CN200810051243A CN101376683A CN 101376683 A CN101376683 A CN 101376683A CN A2008100512432 A CNA2008100512432 A CN A2008100512432A CN 200810051243 A CN200810051243 A CN 200810051243A CN 101376683 A CN101376683 A CN 101376683A
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Abstract
The invention discloses a method for preparing polypropylene with high melt strength, which comprises melt-blending polypropylene, monomer containing double bond, peroxide, dithiocarbamate series substance and antioxidant. The dithiocarbamate is added as adjuvant to inhibit the propylene degradation of the peroxide, improve the graft ratio, reduce monomer amount containing double bond, and save the cost. The obtained polypropylene with high melt strength has melt strength more than 2-15 times of that of raw material, and gel content smaller than 10%.
Description
Technical field
The present invention relates to a kind of preparation method of high melt strength, propylene.
Background technology
Polypropylene (PP) is as a kind of thermoplastic macromolecule material of excellent property, have density little, nontoxic, be easy to characteristics such as machine-shaping, product high comprehensive performance, application is very extensive at aspects such as automobile, household electrical appliance, electronics, packing and building materials, has become kind with fastest developing speed in the resins for universal use.Although PP has many good qualities, but because the inherent characteristics of propylene polycoordination reaction, carry out the PP that propylene polymerization mostly obtains linear structure with Ziegler-Natta catalyst and metallocene catalyst, and line style PP melt strength under molten state is low, when stretching, melt can not show strain hardening effect, directly cause PP some defectives when melt-processed, comprise edge curl and contraction when high speed is extrusion coated, occur molten hanging down and local attenuation when thermoforming, abscess subsides etc. when fluid flow instability and extrusion foaming when the co-extrusion of multilayered structure.Therefore, have the polypropylene of strain hardening effect under the exploitation molten state, promptly high melt strength, propylene is imperative.Improving at present melt strength of polypropylene mainly realizes by following approach: (1) in the polymerization process of resin or the polymerization later stage carry out graft reaction, on main polymer chain, introduce the side chain of length; (2) carry out non-reacted blending and modifying, in matrix polymer, introduce other components of high relative molecular weight; (3) directly polymkeric substance is carried out reaction modifyings such as controlled grafting, crosslinked and degraded.Mainly contain by specific implementation method: x ray irradiation x method, reaction extrusion molding, polymeric kettle method, solution grafting, dynamic crosslinking method, melt blending modification method etc.
Wen etc. are at its paper (Macromolecules that delivers, 2002,35, adopt metallocene catalyst in semicontinuous reactor, at first to generate the terminal polypropylene chains that has two keys 3838-3843), then with this macromolecular chain as monomer, in propylene polymerization processes, insert, and then generate the polypropylene of long chain branching.Langston etc. also adopt metallocene catalyst, add butenyl vinylbenzene in propylene polymerization processes, obtain long branched chain structure polypropylene (Macromolecules, 2005,38,5849-5853).Improve polyacrylic melt strength by polymerization and also only be in the research exploratory stage at present.
Early 1990s, Himont company (CN86100791A, CN1105033A, EP190889) adopts radiation polypropylene generation free radical in cryogenic vacuum or the nitrogen, grafting then heats up, the technology of final high temperature deactivation, successfully obtain long-chain branching polypropylene, and obtained commercial applications, but this method and technology conditional request height, facility investment is big.Akzo Nobel (the WO9749759 of company; WO9927007) under nitrogen protection;, extrude by reaction and to obtain long-chain branching polypropylene as initiator with the peroxy dicarbonates compound, form more gel structure but when obtaining high branching content, follow.
Patent CN1045107A, CN1055372A have set forth and have adopted superoxide initiation grafting modified polypropene powder in polymeric kettle to obtain having the acrylic resin of strain hardening behavior.Another patent (CN1432596A) adopts 2,5-dimethyl-2, two (tert-butyl hydroperoxide) hexanes of 5-and diacrylate-1, the acetone soln of 6-butanediol ester mixes, join in the polypropylene powder melt in the twin screw extruder by injection, carry out grafting, obtain high bath strength acrylic resin.One piece of open report (Journal of Applied Polymer Science, vol.61,1395～1404,1996) adopts polypropylene and polyfunctional monomer pentaerythritol triacrylate to react in the presence of superoxide can make high melt strength, propylene.Another piece of writing report (Journal of Applied Polymer Science, vol.66,809～819,1997) adopt polypropylene and polyethylene, trimethylammonium triacrylate under the effect of superoxide, extrude the high melt strength, propylene of preparation branching by twin screw.Yet the introducing of superoxide can make polypropylene that degraded significantly takes place, and reduces polyacrylic mechanical property greatly.In order to suppress polyacrylic excessive degradation, promote the grafting branching reaction, D.Graebling introduces thiuram compound in its patent US5569717.China applies for a patent CN200510117710 and also discloses similar method.The structure of thiuram compound is as follows:
Wherein X is 1 or 2, R
1, R
2, R
3And R
4Alkyl or aryl for C atomicity 1-10.When patent US5569717 pointed out X=2, effect was better.But thiurams auxiliary agent smell is bigger, and polyacrylic grafting efficiency is still waiting further raising simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing high melt strength, propylene.Can improve polyacrylic melt strength significantly and can suppress the polyacrylic degraded that causes by superoxide again to a great extent, can also control the content of gel simultaneously, polyacrylic processing characteristics is greatly improved.
A kind of preparation method of high melt strength, propylene, its starting material comprise: polypropylene, contain monomer, superoxide, dithiocarbamate(s) auxiliary agent and the oxidation inhibitor of two keys;
Described polypropylene comprises: the polypropylene powder of ecosystem, polypropylene granules, homo-polypropylene or Co-polypropylene; The polypropylene powder that not pass through any processing of the polypropylene powder of described ecosystem for from preparation facilities, obtaining;
Described polypropylene weight-average molecular weight 50000～1500000g/mol, preferable weight-average molecular weight 100000～600000g/mol.
The monomer that contains two keys can promote the combination between the polypropylene macromolecular radical as linking agent, forms long branched chain structure.Change the polypropylene that its consumption and kind can make different degrees of branching and different crosslinking degrees.
The described monomer that contains two keys: the monomer that contains two keys preferably contains the monomer of two two keys, contain the monomer of three two keys and contain in the monomer of four two keys one or more;
The described monomer that contains two two keys is selected from one or more in diacrylate and binary unsaturated olefin and the derivative thereof; In preferred methacrylate triglycol ester, methacrylate TEG ester, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, Vinylstyrene and the two toxilic acid two propylene esters one or more;
The described monomer that contains three two keys is selected from one or more in triacrylate and the triallyl, one or more in preferred Viscoat 295, ethoxylated trimethylolpropane triacrylate, propoxylation Viscoat 295 and the triallyl cyanurate;
The described monomer that contains four two keys is selected from one or more in the tetraacrylate, one or more in preferred tetramethylol methane tetraacrylate, tetramethylolmethane tetramethyl-acrylate and the ethoxylation tetramethylol methane tetraacrylate;
The described monomer consumption that contains two keys is 5～120mmol/kg polypropylene, and preferable amount is 10～60mmol/kg polypropylene.
Superoxide can make polypropylene chains produce macromolecular radical as initiator.
Described superoxide is: cumyl hydroperoxide, diisopropylbenzenehydroperoxide, firpene base hydrogen peroxide, dicumyl peroxide, two (tert-butyl peroxide) diisopropylbenzene(DIPB), tertiary butyl cumyl peroxide, 4, two (tert-butyl peroxy base) n-butyl pentanoates, 2 of 4-, two (tert-butyl peroxy base) butane, 2 of 2-, 5-dimethyl-2,5-two (tert-butyl peroxy base) hexane, ditertiary butyl peroxide, two t-amyl peroxy things, t-butyl peroxy isobutyl carbonate propyl ester or 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexin;
Described amount of peroxide is 0.5～9mmol/kg polypropylene, and preferable amount is 2～4mmol/kg polypropylene;
Described superoxide is 0.2～3 minute 160～260 ℃ of half-life, is 0.5～1.2 minute 160～260 ℃ of half-life preferably;
It is the activity and the concentration of regulation and control free radical that the dithiocarbamate(s) auxiliary agent mainly acts on, and prevents polyacrylic excessive degradation, improves polyacrylic grafting efficiency.
The present invention adopts the dithiocarbamate(s) material to regulate and control polyacrylic graft reaction, and its structure is as follows:
Wherein, R
1, R
2Identical or different, be alkyl, cycloalkyl heterocycle or the aryl of C atomicity 1-10; M is metallic element, metallicity strong non-metallic element or non-metal cations; Described metallic element is Ni, Fe, Zn, Cu, Pb, Bi, Cd, and the non-metallic element that described metallicity is strong is Te, Se, and described non-metal cations is NH
4 +, [H
2NC
4H
10]
+
The preferred cupric dimethyldithiocarbamate of described dithiocarbamate(s) auxiliary agent, zinc-ethylphenyl dithiocarbamate, zinc diethyldithiocarbamate, ziram, zinc dibutyl dithiocarbamate or ferric dimethyl dithiocarbamate; Cupric dimethyldithiocarbamate more preferably;
Described dithiocarbamate(s) consumption is 0.2～6mmol/kg polypropylene, and preferable amount is 0.5～3mmol/kg polypropylene.
Described oxidation inhibitor is various types of plastics oxidation inhibitor: phenolic antioxidant, amine antioxidants or composite antioxidant; Described phenolic antioxidant is BHT, Irganox 1010, Irganox565, Irganox 1076, Irganox 245, Antioxidant BB10, Antioxidant2246, Nocrac 300, goodrite 3114 or goodrite3125;
Described amine antioxidants is KY401, oxidation inhibitor 4010NA, oxidation inhibitor 4020, oxidation inhibitor 4030 or phenothiazine-type oxidation inhibitor;
Described composite antioxidant is oxidation inhibitor B215, oxidation inhibitor B225 or oxidation inhibitor B900;
The consumption of described oxidation inhibitor is 0～6g/kg polypropylene, and preferable amount is 0.6～4g/kg polypropylene.
A kind of processing method of preparation of high melt strength, propylene has 2 kinds, and its step and condition are as follows respectively:
1) join in 160～260 ℃ of Banbury mixeies after according to proportioning raw material being mixed, rotating speed is 20～120 rev/mins, and the reaction times is 1～15 minute, is mixed to moment of torsion discharging when constant; Perhaps, earlier polypropylene and oxidation inhibitor are joined in 160～260 ℃ of Banbury mixeies, after treating polypropylene fusion, add monomer, the dithiocarbamate(s) auxiliary agent that contains two keys according to proportioning, add superoxide after mixing again and carry out reactive blending, be mixed to moment of torsion discharging when constant, obtain a kind of high melt strength, propylene.
2) according to proportioning raw material being mixed the back adds in single screw extrusion machine or the twin screw extruder, 20～120 rev/mins of single screw extrusion machine rotating speeds, 40～400 rev/mins of twin screw extruder rotating speeds, single screw extrusion machine or twin screw extruder feeding section temperature are 160～190 ℃, single screw extrusion machine or the twin screw extruder temperature from melt zone to the mouth mould is 180～260 ℃, extruding pelletization obtains a kind of high melt strength, propylene.
Beneficial effect: the melt strength of the high melt strength, propylene that preparation method of the present invention is prepared has improved twice than raw material, reaches as high as 15 times, and its gel content is less than 10%.
Dithiocarbamate(s) auxiliary agent use temperature wide ranges, action effect is good, can further reduce the consumption that contains double bond monomer, thereby reduces the manufacturing cost of high melt strength, propylene.
The used major equipment of the present invention is Banbury mixer, single screw extrusion machine or twin screw extruder, and facility investment is few, and technology is simple, implements easily, and is with low cost.The products obtained therefrom melt strength obviously improves, and can be used for extrusion coated, thermoforming, foaming, blow-molded article.
The testing apparatus that the present invention adopts in an embodiment is as follows:
Melt strength is measured: adopt RH-7D type capillary rheometer and gottfert " rheotens " melt strength tester;
Melt flow rate (MFR): adopt SRZ-400D type melt flow rate (MFR) determinator;
Gel content (gel%): take by weighing the polypropylene specimen about 0.2g, wrap, weigh, boiled eight hours, weigh after the drying with little dimethylbenzene that boils with 200 purpose nickel screens.
Gel content (gel%)=(the original weight of dry back polypropylene weight/polypropylene) * 100
Embodiment
Embodiment 1 gets 50g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min) and 0.1g oxidation inhibitor B215 pre-mixing.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is dissolved in the acetone according to the polyacrylic consumption of 3.8mmol/kg, Viscoat 295 is dissolved in the acetone according to the polyacrylic consumption of 44mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa joins in the material chamber of Banbury mixer then, and temperature is set at: 175 ℃ in a district, 180 ℃ in ℃ 180, three districts, two districts, rotating speed: 60 rev/mins, react the stable back discharging of moment of torsion in 7 minutes.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 2 is with 50g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min), 0.1g oxidation inhibitor B215 and cupric dimethyldithiocarbamate pre-mixing, and the consumption of cupric dimethyldithiocarbamate is the 1.84mmol/kg polypropylene.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is dissolved in the acetone according to the polyacrylic consumption of 3.8mmol/kg, Viscoat 295 is dissolved in the acetone according to the polyacrylic consumption of 44mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa joins in the material chamber of Banbury mixer then, and temperature is set at: 175 ℃ in a district, 180 ℃ in ℃ 180, three districts, two districts, rotating speed: 60 rev/mins, react the stable back discharging of moment of torsion in 7 minutes.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 3 is with 500g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min) and 1g oxidation inhibitor B215 pre-mixing.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is dissolved in the acetone according to the polyacrylic consumption of 3.4mmol/kg, Viscoat 295 is dissolved in the acetone according to the polyacrylic consumption of 20mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa joins L/D=40 then, and Φ is in the twin screw extruder of 24mm, the speed setting of forcing machine is 100 rev/mins, forcing machine is divided into eight heating zone, is respectively: 185 ℃, 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 230 ℃, and extruding pelletization.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 4 is with 500g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min), 1g oxidation inhibitor B215 and cupric dimethyldithiocarbamate pre-mixing, and the consumption of cupric dimethyldithiocarbamate is the 1.64mmol/kg polypropylene.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is dissolved in the acetone according to the polyacrylic consumption of 3.4mmol/kg, Viscoat 295 is dissolved in the acetone according to the polyacrylic consumption of 20mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa, join L/D=40 then, Φ is in the twin screw extruder of 24mm, the speed setting of forcing machine is 100 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 230 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 5 is with polypropylene (homo-polypropylene powder, melting index are 7.2g/10min), 0.1g oxidation inhibitor B215 and the cupric dimethyldithiocarbamate pre-mixing of 50g, and the consumption of cupric dimethyldithiocarbamate is the 1.84mmol/kg polypropylene.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is dissolved in the acetone according to the polyacrylic consumption of 3.8mmol/kg, Viscoat 295 is dissolved in the acetone according to the polyacrylic consumption of 88mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa joins in the material chamber of Banbury mixer then, and temperature is set at: 175 ℃ in a district, 180 ℃ in ℃ 180, three districts, two districts, rotating speed: 60 rev/mins, react the stable back discharging of moment of torsion in 7 minutes.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 6 is with 50g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min), 0.1g oxidation inhibitor B215 and cupric dimethyldithiocarbamate pre-mixing, and the consumption of cupric dimethyldithiocarbamate is the 1.84mmol/kg polypropylene.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is dissolved in the acetone according to the polyacrylic consumption of 3.8mmol/kg, Viscoat 295 is dissolved in the acetone according to the polyacrylic consumption of 110mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa joins in the material chamber of Banbury mixer then, and temperature is set at: 175 ℃ in a district, 180 ℃ in two districts, 180 ℃ in three districts, rotating speed: 60 rev/mins, react the stable back discharging of moment of torsion in 7 minutes.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 7 is with 500g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min) and cupric dimethyldithiocarbamate pre-mixing, and the consumption of cupric dimethyldithiocarbamate is the 0.2mmol/kg polypropylene.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is dissolved in the acetone according to the polyacrylic consumption of 0.5mmol/kg, Viscoat 295 is dissolved in the acetone according to the polyacrylic consumption of 5mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa, join L/D=40 then, Φ is in the twin screw extruder of 24mm, the speed setting of forcing machine is 100 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 230 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 8 is with 500g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min), 1g oxidation inhibitor B215 and cupric dimethyldithiocarbamate pre-mixing, and the consumption of cupric dimethyldithiocarbamate is the 1.64mmol/kg polypropylene.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is dissolved in the acetone according to the polyacrylic consumption of 3.4mmol/kg, Viscoat 295 is dissolved in the acetone according to the polyacrylic consumption Viscoat 295 of 30mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa, join L/D=40 then, Φ is in the twin screw extruder of 24mm, the speed setting of forcing machine is 100 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 230 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 9 is with 500g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min), 1g oxidation inhibitor B215 and cupric dimethyldithiocarbamate pre-mixing, and the consumption of cupric dimethyldithiocarbamate is the 1.64mmol/kg polypropylene.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is according to the polyacrylic consumption of 3.4mmol/kg, Viscoat 295 is dissolved in the acetone according to the polyacrylic consumption of 40mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa, join L/D=40 then, Φ is in the twin screw extruder of 24mm, the speed setting of forcing machine is 100 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 230 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 10 is with 500g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min), 3g oxidation inhibitor B215 and cupric dimethyldithiocarbamate pre-mixing, and the consumption of cupric dimethyldithiocarbamate is the 6mmol/kg polypropylene.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is dissolved in the acetone according to the polyacrylic consumption of 9mmol/kg, Viscoat 295 is dissolved in the acetone according to the polyacrylic consumption of 120mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa, join L/D=40 then, Φ is in the twin screw extruder of 24mm, the speed setting of forcing machine is 100 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 230 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 11 is with 500g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min), 1g oxidation inhibitor B215 and cupric dimethyldithiocarbamate pre-mixing, and the consumption of cupric dimethyldithiocarbamate is the 1.64mmol/kg polypropylene.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is dissolved in the acetone according to the polyacrylic consumption of 3.4mmol/kg, 1, the 6-hexanediyl ester is dissolved in the acetone according to the polyacrylic consumption of 40mmol/kg, dissolving fully back is sprayed acetone soln in premixed polypropylene powder uniformly, puts into 40 ℃ vacuum drying oven drying 12 hours, vacuum tightness 10
-6MPa, join L/D=40 then, Φ is in the twin screw extruder of 24mm, the speed setting of forcing machine is 100 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 230 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 12 is with 500g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min), 1g oxidation inhibitor B215 and cupric dimethyldithiocarbamate pre-mixing, and the cupric dimethyldithiocarbamate consumption is the 1.64mmol/kg polypropylene.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is dissolved in the acetone according to the polyacrylic consumption of 3.4mmol/kg, tetramethylol methane tetraacrylate is dissolved in the acetone according to the polyacrylic consumption of 40mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa, join L/D=40 then, Φ is in the twin screw extruder of 24mm, the speed setting of forcing machine is 100 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 230 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 13 is with 500g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min), 1g oxidation inhibitor B215 and cupric dimethyldithiocarbamate pre-mixing, and the consumption of cupric dimethyldithiocarbamate is the 1.64mmol/kg polypropylene.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is according to the polyacrylic consumption of 3.4mmol/kg, Viscoat 295 is dissolved in the acetone according to the polyacrylic consumption of 40mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa, join L/D=40 then, Φ is in the twin screw extruder of 24mm, the speed setting of forcing machine is 40 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 230 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Embodiment 14 is with 500g polypropylene (homo-polypropylene powder, melting index are 7.2g/10min), 1g oxidation inhibitor B215 and cupric dimethyldithiocarbamate pre-mixing, and the consumption of cupric dimethyldithiocarbamate is the 1.64mmol/kg polypropylene.With 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane is according to the polyacrylic consumption of 3.4mmol/kg, Viscoat 295 is dissolved in the acetone according to the polyacrylic consumption of 40mmol/kg, dissolving back is fully sprayed acetone soln in premixed polypropylene powder uniformly, put into 40 ℃ dry 12 hours of vacuum drying oven, vacuum tightness 10
-6MPa, join L/D=40 then, Φ is in the twin screw extruder of 24mm, the speed setting of forcing machine is 400 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 230 ℃, extruding pelletization obtains high bath strength acrylic resin.Get sample segment and carry out performance test and melt strength mensuration.The results are shown in Table one.
Table one. by the test result of embodiment sample that 1-12 obtains
| Sequence number | Melting index (g/10min) | Melt strength (cN) | Compound viscosity (Pa.s) | Tensile strength (MPa) | Elongation at break (%) | Gel content (%) |
| Virgin pp | 7.2 | 2.0 | 16000 | 37 | 300 | 0 |
| Embodiment 1 | 31.1 | 1.6 | 2000 | 39 | 16 | 0 |
| Embodiment 2 | 5.6 | 8.7 | 14900 | 40 | 15 | 0.8 |
| Embodiment 3 | 20.4 | 2.1 | 3400 | 38 | 30 | 0 |
| Embodiment 4 | 4.8 | 10 | 21000 | 39 | 62 | 0 |
| Embodiment 5 | 2.4 | 17 | 25000 | 38 | 57 | 1.0 |
| Embodiment 6 | 2.2 | 18 | 26000 | 40 | 57 | 1.0 |
| Embodiment 7 | 4.3 | 12 | 23000 | 39 | 83 | 0 |
| Embodiment 8 | 0.7 | 26 | 30000 | 39 | 80 | 0.4 |
| Embodiment 9 | 0.4 | 30 | 40000 | 38 | 76 | 0.5 |
| Embodiment 10 | 0.2 | 36 | 48000 | 39 | 60 | 3.6 |
| Embodiment 11 | 2.5 | 16 | 24000 | 38 | 86 | 0 |
| Embodiment 12 | 0.3 | 34 | 35000 | 39 | 55 | 1.6 |
| Embodiment 13 | 0.8 | 27 | 31000 | 39 | 70 | 0.1 |
| Embodiment 14 | 0.5 | 35 | 39000 | 40 | 60 | 0.8 |
Compound viscosity is the value when radian frequency is 0.01 (rad/s).
Claims (10)
1. the preparation method of a high melt strength, propylene, it is characterized in that: (1) its starting material comprise: polypropylene, contain monomer, superoxide, dithiocarbamate(s) auxiliary agent and the oxidation inhibitor of two keys;
Described polypropylene comprises: the polypropylene powder of ecosystem, polypropylene granules, homo-polypropylene or Co-polypropylene;
Described polypropylene weight-average molecular weight 50000～1500000g/mol;
The described monomer that contains two keys is the monomer that the contains two keys monomer that preferably contains two two keys, contain the monomer of three two keys and contain in the monomer of four two keys one or more;
The described monomer that contains two two keys is selected from one or more in diacrylate and binary unsaturated olefin and the derivative thereof; In preferred methacrylate triglycol ester, methacrylate TEG ester, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, Vinylstyrene and the two toxilic acid two propylene esters one or more;
The described monomer that contains three two keys is selected from one or more in triacrylate and the triallyl, one or more in preferred Viscoat 295, ethoxylated trimethylolpropane triacrylate, propoxylation Viscoat 295 and the triallyl cyanurate;
The described monomer that contains four two keys is selected from one or more in the tetraacrylate, one or more in preferred tetramethylol methane tetraacrylate, tetramethylolmethane tetramethyl-acrylate and the ethoxylation tetramethylol methane tetraacrylate;
The described monomer consumption that contains two keys is 5～120mmol/kg polypropylene;
Described superoxide is cumyl hydroperoxide, diisopropylbenzenehydroperoxide, firpene base hydrogen peroxide, dicumyl peroxide, two (tert-butyl peroxide) diisopropylbenzene(DIPB), tertiary butyl cumyl peroxide, 4, two (tert-butyl peroxy base) n-butyl pentanoates, 2 of 4-, two (tert-butyl peroxy base) butane, 2 of 2-, 5-dimethyl-2,5-two (tert-butyl peroxy base) hexane, ditertiary butyl peroxide, two t-amyl peroxy things, t-butyl peroxy isobutyl carbonate propyl ester or 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexin;
Described amount of peroxide is 0.5～9mmol/kg polypropylene; Described superoxide is 0.2～3 minute 160～260 ℃ of half-life;
Described dithiocarbamate(s) auxiliary agent, its structure is as follows:
Wherein, R
1, R
2Identical or different, be alkyl, cycloalkyl heterocycle or the aryl of C atomicity 1-10; M is metallic element, metallicity strong non-metallic element or non-metal cations; Described metallic element is Ni, Fe, Zn, Cu, Pb, Bi, Cd, and the non-metallic element that described metallicity is strong is Te, Se, and described non-metal cations is NH
4 +, [H
2NC
4H
10]
+
Described dithiocarbamate(s) consumption is 0.2～6mmol/kg polypropylene;
Described oxidation inhibitor is various types of plastics oxidation inhibitor: phenolic antioxidant, amine antioxidants or composite antioxidant; Described phenolic antioxidant is BHT, Irganox 1010, Irganox565, Irganox 1076, Irganox 245, Antioxidant BB10, Antioxidant2246, Nocrac 300, goodrite 3114 or goodrite 3125;
Described amine antioxidants is KY401, oxidation inhibitor 4010NA, oxidation inhibitor 4020, oxidation inhibitor 4030 or phenothiazine-type oxidation inhibitor;
Described composite antioxidant is oxidation inhibitor B215, oxidation inhibitor B225 or oxidation inhibitor B900;
The consumption of described oxidation inhibitor is 0～6g/kg polypropylene;
(2) step of preparation technology's method and condition are as follows:
Join in 160～260 ℃ of Banbury mixeies after according to proportioning raw material being mixed, rotating speed is 20～120 rev/mins, and the reaction times is 1～15 minute, is mixed to moment of torsion discharging when constant; Perhaps, earlier polypropylene and oxidation inhibitor are joined in 160～260 ℃ of Banbury mixeies, after treating polypropylene fusion, add monomer, the dithiocarbamate(s) auxiliary agent that contains two keys according to proportioning, add superoxide after mixing again and carry out reactive blending, be mixed to moment of torsion discharging when constant, obtain a kind of high melt strength, propylene.
2. the preparation method of a kind of high melt strength, propylene as claimed in claim 1 is characterized in that, the step and the condition of described (2) preparation technology's method are as follows:
According to proportioning raw material being mixed the back adds in single screw extrusion machine or the twin screw extruder, 20～120 rev/mins of single screw extrusion machine rotating speeds, 40～400 rev/mins of twin screw extruder rotating speeds, single screw extrusion machine or twin screw extruder feeding section temperature are 160～190 ℃, single screw extrusion machine or the twin screw extruder temperature from melt zone to the mouth mould is 180～260 ℃, extruding pelletization obtains a kind of high melt strength, propylene.
3. the preparation method of a kind of high melt strength, propylene as claimed in claim 1 or 2 is characterized in that, described polypropylene weight-average molecular weight is 100000～600000g/mol.
4. the preparation method of a kind of high melt strength, propylene as claimed in claim 1 or 2 is characterized in that, the described monomer consumption that contains two keys is 10～60mmol/kg polypropylene.
5. the preparation method of a kind of high melt strength, propylene as claimed in claim 1 or 2 is characterized in that, described amount of peroxide is 2～4mmol/kg polypropylene;
6. the preparation method of a kind of high melt strength, propylene as claimed in claim 1 or 2 is characterized in that, described superoxide is 0.5～1.2 minute 160～260 ℃ of half-life.
7. the preparation method of a kind of high melt strength, propylene as claimed in claim 1 or 2, it is characterized in that described dithiocarbamate(s) auxiliary agent is cupric dimethyldithiocarbamate, zinc-ethylphenyl dithiocarbamate, zinc diethyldithiocarbamate, ziram, zinc dibutyl dithiocarbamate or ferric dimethyl dithiocarbamate.
8. the preparation method of a kind of high melt strength, propylene as claimed in claim 1 or 2 is characterized in that, described dithiocarbamate(s) auxiliary agent is a cupric dimethyldithiocarbamate.
9. the preparation method of a kind of high melt strength, propylene as claimed in claim 1 or 2 is characterized in that, described dithiocarbamate(s) consumption is 0.5～3mmol/kg polypropylene.
10. the preparation method of a kind of high melt strength, propylene as claimed in claim 1 or 2 is characterized in that, the consumption of described oxidation inhibitor is 0.6～4g/kg polypropylene.
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