CN102453274B - Viscosity reducing master batch for polyolefin and preparation method and application thereof - Google Patents
Viscosity reducing master batch for polyolefin and preparation method and application thereof Download PDFInfo
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- CN102453274B CN102453274B CN 201010522078 CN201010522078A CN102453274B CN 102453274 B CN102453274 B CN 102453274B CN 201010522078 CN201010522078 CN 201010522078 CN 201010522078 A CN201010522078 A CN 201010522078A CN 102453274 B CN102453274 B CN 102453274B
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 77
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000001603 reducing effect Effects 0.000 title abstract description 10
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 54
- 238000012545 processing Methods 0.000 claims abstract description 26
- 239000004743 Polypropylene Substances 0.000 claims abstract description 25
- 229920001155 polypropylene Polymers 0.000 claims abstract description 25
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 22
- -1 polyethylene Polymers 0.000 claims abstract description 21
- 239000004698 Polyethylene Substances 0.000 claims abstract description 4
- 229920000573 polyethylene Polymers 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims description 62
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- MOVRNJGDXREIBM-UHFFFAOYSA-N aid-1 Chemical compound O=C1NC(=O)C(C)=CN1C1OC(COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)CO)C(O)C1 MOVRNJGDXREIBM-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000008301 phosphite esters Chemical class 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 150000007519 polyprotic acids Polymers 0.000 abstract 4
- 239000000155 melt Substances 0.000 abstract 1
- 229920001903 high density polyethylene Polymers 0.000 description 23
- 239000004700 high-density polyethylene Substances 0.000 description 23
- 230000007423 decrease Effects 0.000 description 21
- 238000001125 extrusion Methods 0.000 description 19
- 239000008188 pellet Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 229920001179 medium density polyethylene Polymers 0.000 description 15
- 239000004701 medium-density polyethylene Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920002449 FKM Polymers 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 description 4
- 229920001083 polybutene Polymers 0.000 description 4
- 229940126680 traditional chinese medicines Drugs 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241001248531 Euchloe <genus> Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
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- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a viscosity reducing master batch for polyolefin and a preparation method and application thereof. The viscosity reducing master comprises the following blended components in parts by weight: 100 parts of a polyolefin resin and 1-10 parts of a processing aid, wherein the polyolefin resin is selected form polyethylene or polypropylene, and the melt flow rate is 0.01-15 g/10min; the processing aid comprises a low polymer and a polybasic acid which are blended in the molar ratio of 1:(0.1-10); the low polymer is a linear or short-chain branch low polymer of which the molecular weight is 200-20,000; at least one end in a molecular chain is provided with a terminal polar group; and the polybasic acid is an inorganic polybasic acid or an organic polybasic acid. The viscosity reducing master batch has the advantages of stable performance, small adding amount, good viscosity reducing effect and low cost, can be directly added and applied in a polyolefin processing process, and is convenient to use.
Description
Technical field
The present invention relates to a kind of master batch, furtherly, relate to a kind of novel polyolefine with viscosity reduction master batch and its preparation method, with and application in the polyolefine course of processing.
Background technology
Along with manufacturing development, polyolefinic demand rises year by year, and whole world polyethylene aggregate demand was 6,430 ten thousand tons in 2009, and the polypropylene aggregate demand is 4,434 ten thousand tons.Will be processed into plastics to a large amount of polyolefine like this and will consume a large amount of energy, the waste material amount of generation also is very surprising.Especially high molecular, narrow distribution, the polyolefin resin product of low melt index, mainly comprise high density polyethylene(HDPE) (HDPE), LLDPE (LLDPE), atactic copolymerized polypropene (PPR), polybutene (PB), metallocene PE (mPE) etc., this resinoid has excellent mechanical property, anti-cracking and creep-resistant property, the added value height, the huge market demand, but its constructional feature has determined that this class polyolefine shear viscosity is big, poor processability.Under existing technical conditions, use processing aid of polyolefine to address this problem.
Processing aid is the general name be used to a few class materials of the processing that improves high-molecular weight polymer and handling property, and mainly the molten state at polymer matrix plays a role.It is good that traditional relatively lubricant, processing aid have a viscosity reducing effect, the advantage that add-on is few.
Topmost processing aid is the fluororubber processing aid in the market.Patent US 3125547 reported first such processing aid when high rate of extrusion, the effect that melt fracture takes place of postponing is arranged.On this basis, people have proposed multiple modification method.Patent US 4904735 and US 4855360 have adopted the method for viton and other superpolymer blend, and patent US 5015693 and US 5688457 have adopted the method for viton and other additive compound.The mechanism of action of this analog assistant is outer lubrication mechanism, and auxiliary agent is separated out from melt in the course of processing, is attached to the metallic interior surface of processor, has reduced melt and intermetallic clinging power, and shearing stress has also had obvious decline.But this processing aid also has onset time long, and fluorine decompose to pollute, easy cleaning not, shortcomings such as cost height.
Silicon rubber also has and the viton similar effects, patent WO 9932561A1 has reported a kind of polydimethylsiloxane of high molecular and the composition of organophosphorus, can improve the surface smoothness of thermoplastics, also there is the high problem of cost in this processing aid.
Patent US 5015693 uses with having reported polyoxyethylene glycol and having contained the composite processing aid of doing of viton, can improve the critical shear rate of extrudate.
Prepared polyoxyethylene glycol/inorganic particulate the composite auxiliary for processing of patent CN 03135482 is to assisting the polyolefinic good effect that is processed with.But the large usage quantity of the described composite auxiliary for processing of this patent can influence the final use properties of goods, and does not solve the resolution problem of polyoxyethylene glycol under processing temperature.
Above patent has all been mentioned preparation and the result of use of processing aid, in actual applications, because the processing aid addition is too low, direct blend is difficult in and reaches even dispersion in the system with polyolefine, and mixing process, mass transfer process all can cause the loss of processing aid, thereby causes harm such as production process instability, auxiliary agent inefficacy.
Summary of the invention
At existing problem of the prior art, the invention provides a kind of easy preparation, low cost, high-effect, free of contamination polyolefine viscosity reduction master batch.Because most processing aid all adds by master batch, the present invention adopts a kind of novel processing aid, itself and polyolefin resin blend are prepared master batch, and this master batch can directly add in the polyolefine molding process, in order to reduce the polyolefinic shear viscosity that adds man-hour.
One of purpose of the present invention is to provide this kind viscosity reduction master batch, includes the following component of blend: polyolefin resin and processing aid; Wherein, be 100 weight parts in polyolefin resin, processing aid 1～10 weight part, preferred 1～3 weight part.
Described polyolefin resin is selected from polyethylene or polypropylene, and its molten mass flow rate (MFR) is 0.01～15g/10min.
Described processing aid includes oligopolymer and the polyprotonic acid of blend, and its ratio is oligopolymer with the molar ratio computing: polyprotonic acid is 1: (0.1～10), preferred 1: (0.25～5).
In the above-mentioned processing aid, described oligopolymer is that molecular weight is 2000～20000 linearity or short-chain branch oligopolymer, has at least an end to have terminal polar group in its molecular chain; More preferred, the terminal polar group that has in this oligomer molecules chain is selected from hydroxyl, carboxyl, at least a in the amino; Its examples of compounds is selected from least a in polyoxyethylene glycol, water-soluble polyester, the poly-silica ether.
Described polyprotonic acid is inorganic multivariate acid or organic multicomponent acid, preferred inorganic multivariate acid.More preferred, described organic acid comprises ethylenediamine tetraacetic acid (EDTA); Described mineral acid comprises boric acid, phosphoric acid.
In order to improve the antioxidant property of material, also comprise oxidation inhibitor in the processing aid of viscosity reduction master batch of the present invention, this oxidation inhibitor can be selected resin various oxidation inhibitor commonly used in the prior art for use, as: at least a in aromatic amine, sterically hindered phenolic, phosphorous acid esters/phosphiinic acid ester, sulfur-bearing synergist class, hindered amines, the azanol kind antioxidant, its consumption also is conventional amount used.Comparative optimization, described oxidation inhibitor is selected from the mixture of sterically hindered phenol kind antioxidant and phosphite ester kind antioxidant, and the weight ratio of sterically hindered phenol kind antioxidant and phosphite ester kind antioxidant is 1: 5～5: 1, preferred 2: 1～1: 1.Be 100 weight parts in the oligopolymer in the viscosity reduction master batch, oxidation inhibitor 0.1～5 weight part, preferred 0.1～1 weight part.
In addition, in the course of processing of viscosity reduction master batch of the present invention, the needs of the concrete processing of available basis, the processing aid that in the blend material, adds other kinds commonly used in the polyolefin resin modification technology, for example: fire retardant, static inhibitor, pigment etc., its consumption is conventional amount used, or adjusts according to practical requirements.
Two of purpose of the present invention is to provide the preparation method of this kind polyolefine with the viscosity reduction master batch, is achieved through the following technical solutions:
Comprise that the component that will include polyolefin resin, processing aid makes described viscosity reduction master batch by described content melt blending.
More preferred, after can be earlier each component of described processing aid being mixed, with the polyolefin resin melt blending, may further comprise the steps again:
1. with the oligopolymer heating and melting, add other auxiliary agents that comprise polyprotonic acid by described content, heated and stirred after mix, 80～120 ℃ of Heating temperatures, preferred 80～100 ℃; Preferred 10～120 minutes of churning time.Product is taken out, grind and obtain Powdered auxiliary agent.
2. will include polyolefin resin, and above gained auxiliary agent in interior component by described content melt blending, extruding pelletization makes the viscosity reduction master batch.
In the course of processing of viscosity reduction master batch of the present invention, material melt blending temperature is used blending temperature in the common polyolefin resin processing, should select not only guaranteeing the complete fusion of matrix resin but also can not make in the scope of its decomposition, be generally 160～250 ℃, preferred 180～230 ℃.In addition, according to the processing needs, can add some auxiliary agents such as dispersion agent, surface treatment agent etc. commonly used in the polyolefin resin course of processing in right amount in the blend material, its consumption is conventional amount used, or adjusts according to practical requirements.
The mixing equipment of mixing of materials can adopt various mixing equipments used in the prior art in the preparation method of the invention described above, as stirrer, kneading machine etc.Employed melt blending equipment is the general blending equipment in the rubber and plastic processing industry in the aforesaid method of the present invention, can be twin screw extruder, the mixing unit of BUSS etc.
Three of purpose of the present invention is to provide the application of this kind polyolefine with the viscosity reduction master batch.This viscosity reduction master batch can directly add in the polyolefine course of processing, general processing temperature is 180～230 ℃, the weight ratio of addition and polyolefin resin is 1/100～10/100, is applicable to high density polyethylene(HDPE) (HDPE), LLDPE (LLDPE), atactic copolymerized polypropene (PPR), polybutene (PB), metallocene PE high-viscosity polyolefins such as (mPE).
Viscosity reduction master batch of the present invention, the composite auxiliary for processing of employing carries out modification with polyprotonic acid to the oligopolymer that contains terminal polar group of linear or short-chain branch, improves its thermotolerance and lubricant effect; Thereby the modified additive of gained is more stable than conventional lubricant, and viscosity reducing effect is better, and add-on also reduces significantly, and with respect to commercially available processing aid, cost reduces greatly.In addition, the master batch that contains this class processing aid can directly add application in the polyolefine course of processing, and easy to use, effect is remarkable.
Embodiment
The present invention will be further described below in conjunction with specific embodiment.But the present invention is not limited in following embodiment.
Experimental raw:
Polyolefin resin: high density polyethylene(HDPE) (HDPE): 2480H, Sinopec Qilu Petrochemical share has
Limit company; Melt flow rate (MFR) is 10g/10min;
High density polyethylene(HDPE) (HDPE): 4902T, Sinopec raise sub-petrochemical industry share to be had
Limit company; Melt flow rate (MFR) is 0.23g/10min;
Medium-density polyethylene (MDPE): SP980, LG Corp of South Korea; Melt flow
Speed is 0.01g/10min
Medium-density polyethylene (MDPE): XP9000, Korea S DAELIM company;
Melt flow rate (MFR) is 0.01g/10min;
Atactic copolymerized polypropene (PPR): 4220, Sinopec Qilu Petrochemical share has
Limit company; Melt flow rate (MFR) is 0.3g/10min;
Block copolymerization polypropylene (PPB): C180, Sinopec raise sub-petrochemical industry share to be had
Limit company; Melt flow rate (MFR) is 0.3g/10min;
Atactic copolymerized polypropene (PPR): RA7050, Borealis; Melt flow speed
Rate is 0.3g/10min;
Polyethylene glycol 6000: chemical reagents corporation of traditional Chinese medicines group, Japanese import packing, molecular weight 5500～7000;
Water-soluble polyester: molecular weight 12000, Xinhui Fibre Material Inst. Co., Ltd., Yangzhou;
Antioxidant 1010, oxidation inhibitor 168: Switzerland Ciba company;
The organosilicon processing aid: but upright company, LYSI-100 are thought in Chengdu;
Organosilicon master batch: Dow-Coming company, MB50-314;
Phosphoric acid: chemical pure, chemical reagents corporation of traditional Chinese medicines group;
Boric acid: chemical pure, chemical reagents corporation of traditional Chinese medicines group;
Ethylenediamine tetraacetic acid (EDTA): chemical pure, chemical reagents corporation of traditional Chinese medicines group.
Testing method:
The single screw rod torque rheometer of Haake Polylab-RC300P, the Rheomix-252P screw rod, port mould diameter 3mm, length-to-diameter ratio is close to zero, 150 ℃-200 ℃-200 ℃-200 ℃ of barrel zone temperatures, screw speed 20rpm cleans screw rod and barrel with virgin resin earlier, after torque value is stable, measure the processing torque value of the resin that contains the viscosity reduction master batch.Adopt torque value and the contrast of the torque value after balance sign viscosity reducing effect with virgin resin.
One, the preparation of viscosity reduction master batch
Embodiment 1
With 1000 the gram polyethylene glycol 6000s be heated to 80 ℃, after the polyoxyethylene glycol fusion, put into 96 the gram phosphoric acid, 4 the gram antioxidant 1010s, 2 the gram oxidation inhibitor 168.Stir after 120 minutes, product is taken out, grind and obtain Powdered processing aid.Namely get processing aid 1#, polyoxyethylene glycol: the mol ratio of phosphoric acid is 1: 5.
Be to put into homogenizer high speed at 100: 2 to mix 1 minute with HDPE 2480H pellet and processing aid 1# with weight ratio, put into the forcing machine granulation then, the forcing machine parameter setting is, barrel temperature: 190 ℃-200 ℃-200 ℃-200 ℃-200 ℃-205 ℃, feeding quantity: 7%, rotating speed: 350rpm makes viscosity reduction master batch 1#.
Embodiment 2
Replace 96 gram phosphoric acid with 2.6 gram boric acid, all the other conditions are all with embodiment 1.Make processing aid 2#, polyoxyethylene glycol: the mol ratio of boric acid 1: 0.25.
The master batch working method is with embodiment 1, but replaces processing aid 1# with equivalent processing aid 2#, makes viscosity reduction master batch 2#.
Embodiment 3
With embodiment 2, but replace HDPE 2480H with equivalent HDPE 4902T, make viscosity reduction master batch 3#.
Embodiment 4
With embodiment 2, but replace HDPE 2480H with equivalent MDPE SP980, make viscosity reduction master batch 4#.
Embodiment 5
With embodiment 2, but replace HDPE 2480H with equivalent MDPE XP9000, make viscosity reduction master batch 5#.
Embodiment 6
Be to put into homogenizer high speed at 100: 2 to mix 1 minute with PPR 4220 pellets and processing aid 1# with weight ratio, put into the forcing machine granulation then, the forcing machine parameter setting is, barrel temperature: 210 ℃-220 ℃-220 ℃-220 ℃-220 ℃-225 ℃, feeding quantity: 7%, rotating speed: 350rpm makes viscosity reduction master batch 6#.
Embodiment 7
With embodiment 6, but replace PPR 4220 with equivalent PPB C180, make viscosity reduction master batch 7#.
Embodiment 8
With embodiment 6, but replace PPR 4220 with equivalent PPR RA7050, make viscosity reduction master batch 8#.
Embodiment 9
Replace 96 gram phosphoric acid with 104 gram boric acid, all the other conditions are all with embodiment 1.Make processing aid 3#, polyoxyethylene glycol: the mol ratio of boric acid 1: 10.
The master batch working method is with embodiment 1, but replaces processing aid 1# with equivalent processing aid 3#, makes viscosity reduction master batch 9#.
Embodiment 10
Replace 96 gram phosphoric acid with 5.2 gram boric acid, 1000 all the other conditions of gram water-soluble polyester (molecular weight 12000) are all with embodiment 1.Make processing aid 4#, water-soluble polyester: the mol ratio of boric acid 1: 0.25.
The master batch working method is with embodiment 9, but replaces processing aid 3# with equivalent processing aid 4#, makes viscosity reduction master batch 10#.
Embodiment 11
Replace 96 gram phosphoric acid with 12.5 gram ethylenediamine tetraacetic acid (EDTA)s, all the other conditions are all with embodiment 9.Make processing aid 5#, polyoxyethylene glycol: the mol ratio of ethylenediamine tetraacetic acid (EDTA) 1: 0.25.
The master batch working method is with embodiment 9, but replaces processing aid 3# with equivalent processing aid 5#, makes viscosity reduction master batch 11#.
Embodiment 12
Adopt HDPE2480H pellet and 100: 8 proportioning of processing aid 2# weight ratio, with the preparation technology of viscosity reduction master batch 2#, make viscosity reduction master batch 12#.
Comparative Examples 1
Be to put into homogenizer high speed at 100: 2 to mix 1 minute with MDPE SP980 pellet and silicoorganic compound with weight ratio, put into the forcing machine granulation then, the forcing machine parameter setting is, barrel temperature: 190 ℃-200 ℃-200 ℃-200 ℃-200 ℃-205 ℃, feeding quantity: 7%, rotating speed: 350rpm makes and falls contrast viscosity reduction master batch 1#.
Comparative Examples 2
Be to put into homogenizer high speed at 100: 2 to mix 1 minute with PPR 4220 pellets and organosilicon processing aid with weight ratio, put into the forcing machine granulation then, the forcing machine parameter setting is, barrel temperature: 210 ℃-220 ℃-220 ℃-220 ℃-220 ℃-225 ℃, feeding quantity: 7%, rotating speed: 350rpm makes contrast viscosity reduction master batch 2#.
2. the application of viscosity reduction master batch
Embodiment 13
HDPE 2480H pellet is put into the homogenizer high speed with viscosity reduction master batch 2# with weight ratio at 20: 1 mixed 1 minute, put into single screw rod Haake rheometer then and extrude, 150 ℃-200 ℃-200 ℃-200 ℃ of barrel zone temperatures, screw speed 20rpm.Extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure HDPE 2480H.
Embodiment 14
MDPE SP980 pellet is put into the homogenizer high speed with viscosity reduction master batch 4# with weight ratio at 20: 1 mixed 1 minute, put into single screw rod Haake rheometer then and extrude, 150 ℃-200 ℃-200 ℃-200 ℃ of barrel zone temperatures, rotating speed 20rpm.Extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure MDPE SP980.
Embodiment 15
MDPE SP980 pellet is put into the homogenizer high speed with viscosity reduction master batch 2# with weight ratio at 20: 1 mixed 1 minute, put into single screw rod Haake rheometer then and extrude, 150 ℃-200 ℃-200 ℃-200 ℃ of barrel zone temperatures, rotating speed 20rpm.Extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure MDPE SP980/HDPE2480H alloy (weight ratio 20: 1).
Embodiment 16
PPR 4220 pellets are put into the homogenizer high speed with viscosity reduction master batch 6# with weight ratio at 20: 1 mixed 1 minute, put into single screw rod Haake rheometer then and extrude, 170 ℃-220 ℃-220 ℃-220 ℃ of barrel zone temperatures, rotating speed 20rpm.Extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure PPR 4220.
Embodiment 17
With embodiment 13, but replace viscosity reduction master batch 1# with viscosity reduction master batch 5#, extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure 2480H.
Embodiment 18
HDPE 4902T pellet is put into the homogenizer high speed with viscosity reduction master batch 3# with weight ratio at 20: 1 mixed 1 minute, put into single screw rod Haake rheometer then and extrude, 150 ℃-200 ℃-200 ℃-200 ℃ of barrel zone temperatures, screw speed 20rpm.Extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure HDPE4902T.
Embodiment 19
MDPE XP9000 pellet is put into the homogenizer high speed with viscosity reduction master batch 5# with weight ratio at 20: 1 mixed 1 minute, put into single screw rod Haake rheometer then and extrude, 150 ℃-200 ℃-200 ℃-200 ℃ of barrel zone temperatures, screw speed 20rpm.Extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure MDPE XP9000.
Embodiment 20
PPB C180 pellet is put into the homogenizer high speed with viscosity reduction master batch 7# with weight ratio at 20: 1 mixed 1 minute, put into single screw rod Haake rheometer then and extrude, 170 ℃-220 ℃-220 ℃-220 ℃ of barrel zone temperatures, rotating speed 20rpm.Extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure PPB C180.
Embodiment 21
PPR RA7050 pellet is put into the homogenizer high speed with viscosity reduction master batch 8# with weight ratio at 20: 1 mixed 1 minute, put into single screw rod Haake rheometer then and extrude, 170 ℃-220 ℃-220 ℃-220 ℃ of barrel zone temperatures, rotating speed 20rpm.Extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure PPR RA7050.
Embodiment 22
With embodiment 13, but replace viscosity reduction master batch 1# with viscosity reduction master batch 9#, extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure 2480H.
Embodiment 23
With embodiment 13, but replace viscosity reduction master batch 1# with viscosity reduction master batch 10#, extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure 2480H.
Embodiment 24
With embodiment 13, but replace viscosity reduction master batch 1# with viscosity reduction master batch 11#, extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure 2480H.
Embodiment 25
With embodiment 13, but viscosity reduction master batch 2# was increased to 10: 8 with respect to the weight ratio of 2480H pellet, and extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure 2480H.
Comparative Examples 3
HDPE 2480H pellet is put into the homogenizer high speed with commercially available HDPE/ organosilicon master batch (organosilicon content 2phr) weight ratio at 20: 1 to be mixed 1 minute, putting into single screw rod Haake rheometer then extrudes, 150 ℃-200 ℃-200 ℃-200 ℃ of barrel zone temperatures, rotating speed 20rpm.Extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure HDPE2480H.
Comparative Examples 4
After HDPE 2480H pellet soaked into surface with a little white oil, putting into the homogenizer high speed at 1000: 1 with commercially available organosilicon processing aid weight ratio mixed 1 minute, put into single screw rod Haake rheometer then and extrude, 150 ℃-200 ℃-200 ℃-200 ℃ of barrel zone temperatures, rotating speed 20rpm.Extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure HDPE2480H.
Comparative Examples 5
After PPR 4220 pellets are soaked into surface with a little white oil, putting into the homogenizer high speed with processing aid 2# at 1000: 1 with weight ratio mixed 1 minute, put into single screw rod Haake rheometer then and extrude, 170 ℃-220 ℃-220 ℃-220 ℃ of barrel zone temperatures, rotating speed 20rpm.Extrusion sees Table 1 with respect to pure 4220 the moment of torsion range of decrease.
Comparative Examples 6
MDPE SP980 pellet is put into the homogenizer high speed with contrast viscosity reduction master batch 1# with weight ratio at 20: 1 mixed 1 minute, put into single screw rod Haake rheometer then and extrude, 150 ℃-200 ℃-200 ℃-200 ℃ of barrel zone temperatures, rotating speed 20rpm.Extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure MDPE SP980.
Comparative Examples 7
PPR 4220 pellets are put into the homogenizer high speed with contrast viscosity reduction master batch 2# with weight ratio at 20: 1 mixed 1 minute, put into single screw rod Haake rheometer then and extrude, 170 ℃-220 ℃-220 ℃-220 ℃ of barrel zone temperatures, rotating speed 20rpm.Extrusion sees Table 1 with respect to the moment of torsion range of decrease of pure PPR 4220.
Each embodiment of table 1 is with respect to the screw torque range of decrease of pure material
| Routine number | The screw torque range of decrease (%) with respect to pure material |
| Embodiment 13 | 29 |
| Embodiment 14 | 17 |
| Embodiment 15 | 26 |
| Embodiment 16 | 18 |
| Embodiment 17 | 26 |
| Embodiment 18 | 22 |
| Embodiment 19 | 25 |
| Embodiment 20 | 19 |
| Embodiment 21 | 23 |
| Embodiment 22 | 27 |
| Embodiment 23 | 29 |
| Embodiment 24 | 29 |
| Embodiment 25 | 25 |
| Comparative Examples 3 | 20 |
| Comparative Examples 4 | 12 |
| Comparative Examples 5 | 8 |
| Comparative Examples 6 | 15 |
| Comparative Examples 7 | 16 |
By 13～25 data of embodiment in the table 1 as seen, the present invention add in the polyolefin resin through the oligopolymer of modified by polyacid and composite auxiliary for processing, its master batch that makes can directly add in the course of processing, and can reduce the processing moment of torsion of material significantly, and then reach and cut down the consumption of energy, improve the purpose of processing characteristics.
By Comparative Examples 3,6,7 as can be seen, the viscosity reducing effect of viscosity reduction master batch of the present invention is better than commercially available silicone based viscosity reduction master batch.Can find out that by Comparative Examples 4～5 in reality processing, processing aid directly adds, and can't demonstrate fully viscosity reducing effect.Using viscosity reduction master batch of the present invention is can be economical, improves polyolefinic processing characteristics effectively.
Claims (7)
1. polyolefine viscosity reduction master batch includes the following component of blend:
Polyolefin resin and processing aid; Wherein, be 100 weight parts in polyolefin resin, processing aid 1～10 weight part;
Described polyolefin resin is selected from polyethylene or polypropylene; Its melt flow rate (MFR) is 0.01～15g/10min;
Described processing aid includes oligopolymer and the polyprotonic acid of blend, and the mol ratio of oligopolymer and polyprotonic acid is 1:(0.1～10); Wherein, described oligopolymer is that molecular weight is 2000～20000 linearity or short-chain branch oligopolymer, has at least an end to have terminal polar group in its molecular chain, is selected from least a in polyoxyethylene glycol, the water-soluble polyester; Described polyprotonic acid is at least a in ethylenediamine tetraacetic acid (EDTA), boric acid, the phosphoric acid.
2. viscosity reduction master batch as claimed in claim 1 is characterized in that, includes the following component of blend:
Be 100 weight parts in polyolefin resin, processing aid 1～3 weight part.
3. viscosity reduction master batch as claimed in claim 1 is characterized in that:
The mol ratio of oligopolymer and polyprotonic acid is 1:(0.25～5 in the described processing aid).
4. as each described viscosity reduction master batch of claim 1～3, it is characterized in that:
Comprise oxidation inhibitor; Be 100 weight parts in described oligopolymer, oxidation inhibitor 0.1～5 weight part;
Described oxidation inhibitor is selected from the mixture of sterically hindered phenol kind antioxidant and phosphite ester kind antioxidant, and the weight ratio of sterically hindered phenol kind antioxidant and phosphite ester kind antioxidant is 1:5～5:1.
5. as the preparation method of each described polyolefine of claim 1～4 with the viscosity reduction master batch, it is characterized in that:
Comprise that the component that will include polyolefin resin, processing aid makes described viscosity reduction master batch by described content melt blending.
6. preparation method as claimed in claim 5 is characterized in that may further comprise the steps:
(1) with described oligopolymer heating and melting, add other auxiliary agents that comprise polyprotonic acid by described content, heated and stirred is taken out product after mix, and grinds and obtains Powdered auxiliary agent; 80～120 ℃ of Heating temperatures;
(2) will include polyolefin resin, and above gained auxiliary agent in interior component by described content melt blending, extruding pelletization makes the viscosity reduction master batch.
7. as each described polyolefine viscosity reduction master batch application in the polyolefine course of processing of claim 1～4.
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| CN106554553B (en) * | 2015-09-30 | 2019-07-30 | 中国石油化工股份有限公司 | Easy processing metallocene PE composition and preparation method thereof |
| CN113372587B (en) * | 2021-06-22 | 2022-10-18 | 普信氟硅新材料（衢州）有限公司 | Preparation method of organic-inorganic nano-doped polymer material processing aid master batch |
| CN114801049B (en) * | 2022-04-22 | 2024-03-19 | 联塑科技发展(贵阳)有限公司 | Raw material screening device for PE water supply pipe production and manufacturing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1155153A (en) * | 1996-11-25 | 1997-07-23 | 四川联合大学 | Special material for outer protective sleeve of communication cable and optical cable |
| CN1234515A (en) * | 1998-04-24 | 1999-11-10 | 四川联合大学 | Communication cable, optical cable protecting casing material of high-density polyethylene |
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| CN1155153A (en) * | 1996-11-25 | 1997-07-23 | 四川联合大学 | Special material for outer protective sleeve of communication cable and optical cable |
| CN1234515A (en) * | 1998-04-24 | 1999-11-10 | 四川联合大学 | Communication cable, optical cable protecting casing material of high-density polyethylene |
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