CN101698736B - Modification method for enhancing polarity and flowability of polypropylene - Google Patents
Modification method for enhancing polarity and flowability of polypropylene Download PDFInfo
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- CN101698736B CN101698736B CN2009101934671A CN200910193467A CN101698736B CN 101698736 B CN101698736 B CN 101698736B CN 2009101934671 A CN2009101934671 A CN 2009101934671A CN 200910193467 A CN200910193467 A CN 200910193467A CN 101698736 B CN101698736 B CN 101698736B
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Abstract
The invention discloses a modification method for enhancing polarity and flowability of polypropylene, which is realized in a way that: raw materials of polypropylene are mixed in sequence, wherein the polypropylene comprises the following raw materials in portions by mass: 100 portions of polypropylene, 0.1-10 portions of polar monomer, 0-7 portions of phase-transformation plasticizer, 0.01-1 portion of initiator and 0.1-2 portions of antioxidant; and the sequence is realized in a way that: melting and mixing the initiator and the polar monomer before the antioxidant and the polypropylene, melting and mixing the polar monomer before the initiator and the polypropylene or simultaneously melting and mixing the polar monomer and the initiator with the polypropylene. The invention greatly increases the flow rate of the polypropylene melt without obviously affecting the impact ductility of the polypropylene; the invention can prepare modified polypropylene material with favorable melt flowability, compatibility with glass fibers, heat resistance, impact resistance and mechanical properties; and the modified polypropylene material can be used as long-glass-fiber reinforced polypropylene composite materials.
Description
Technical field
The invention belongs to the polymer modification technical field, be specifically related to the polyacrylic preparation of high flow modifier, can be used for long glass fiber reinforced polypropylene composite material.
Background technology
Polypropylene is common general-purpose plastics, compares with other general-purpose plastics to have series of advantages such as density is little, price is low, moulding is easy, mechanical property is good.Yet polyacrylic mechanical property not directly as structural part, has limited its Application Areas not as good as engineering plastics.In order to overcome the strength of PP defect of insufficient, people come Reinforced Polypropylene with glass fibre, to widen its range of application.After the glass fibre enhancing, polyacrylic physical strength, shock resistance, fatigue performance, creep-resistant property and heat-drawn wire all have significant improvement.But in the traditional glass fiber reinforced polypropylene, be subjected to the shearing action of screw rod, staple length is less than 0.5mm.Glass fibre was easily extracted out from matrix when goods were stressed, and the intensity of glass fibre is not given full play to.In order further to improve the mechanical property of glass dimension Reinforced Polypropylene, people are devoted to the exploitation of macrofiber enhancement techniques, comprise the continuous fibre tow is at high temperature passed through the dipping die head, make melt polypropylene infiltrated fiber tow produce the long glass fiber-reinforced polypropylene pellet.On the one hand, the general purpose polypropylene resin is nonpolar macromole, and is poor with the glass fibre wetting property, and it is bonding also to be difficult to directly to produce good interface; On the other hand, general polyacrylic melt viscosity height is difficult for soaking into glass fiber strand, coats each root monofilament; Therefore, produce long fibre enhanced polypropylene alkene with melt impregnation and need high mobile modified polypropene material.
Tertiary carbon atom in the polypropylene molecular chain is subject to free radical and attacks, and produces the β chain rupture, and molecular weight is reduced, and melt viscosity descends, and when fluidity of molten polypropylene improved, it is bad that its toughness becomes.Li Zhongbing etc. once studied with dicumyl peroxide and regulated polyacrylic molar mass, the acrylic resin of preparation high workability, with polypropylene melt index when 18g/10min brings up to 65g/10min, its shock strength drops to 22J/m from 26J/m, need be aided with the toughness that elastomerics improves matrix.
Industrial raising polypropylene polar method commonly used is with unsaturated carboxylic acid or its anhydride modified polypropylene.1986, Chinese patent 86103692 disclosed a kind of glass fibre enhanced polypropylene material.This material contains the acrylic resin of solution graft copolymerization carboxylic acid, to improve the compatible and bonding of polypropylene matrix and coupling processing glass.Chinese patent CN1058026 is with carboxylic acid or anhydride modified polypropylene, and the polypropylene material of preparation melting index 70-300g/10min (230 ℃ of 2.16kg) adds polypropylene as compatilizer, improves the consistency of polypropylene matrix and long glass fibres.Chinese patent CN1068358 describes with unsaturated carboxylic acid or anhydride modified polyacrylic while, also adds organosilicone compounds, makes the compatilizer of polypropylene and glass fibre.Chinese patent CN1810870 is disclosed in and adds unsaturated carboxylic acid or acid anhydrides in the polypropylene, the high flow modifier polypropylene of direct production material, and the impregnating continuous fibres tow, and with polyolefin elastomer tenacity-increased profax matrix.
Summary of the invention
The objective of the invention is to overcome long glass fiber reinforced polypropylene produce in polypropylene polarity low, wetting property is poor, melt viscosity is big, be difficult to soak into the problem of glass fiber strand, a kind of polypropylene polarity and mobile method of modifying of improving is provided, and the present invention can prepare the excellent modified polypropene material of flowability, consistency, toughness and over-all properties.The present invention is achieved through the following technical solutions:
A kind of polypropylene polarity and mobile method of modifying of improving is characterized in that in order polypropylene being prepared burden melting mixing; Described polypropylene batching comprises following component and mass fraction: 100 parts of polypropylene, 0.1～10 part of polar monomer, 0～7 part in phase transformation softening agent, 0.1～2 part in 0.01～1 part of initiator and oxidation inhibitor; Described order is that initiator and polar monomer mix with polypropylene fusion prior to oxidation inhibitor, and polar monomer mixes with polypropylene fusion prior to initiator or polar monomer and initiator mix with polypropylene fusion simultaneously.
Described polypropylene can be homo-polypropylene or Co-polypropylene, also can be more than one mixture of homo-polypropylene and Co-polypropylene; Described polyacrylic melting index is generally 10-15g/10min at 2-20g/10min (2.16kg230 ℃).
Described polar monomer is a maleimide compound, and they contain simple function group or bifunctional; Described maleimide compound comprises N-phenylmaleimide, N-naphthyl maleimide, N-alkyl maleimide, N-cyclohexyl maleimide, diphenyl methane dimaleimide, a penylene bismaleimides, maleimide phenol, maleimide formic acid.Polar monomer is more than one of maleimide compound.The content of difunctionality maleimide is not higher than 3% of acrylic resin mass fraction, generally at 0.1-2%.Under the initiator effect, maleimide and polypropylene reaction cause grafting, degraded and crosslinked, when improving polypropylene polarity and flowability, and the polyacrylic impelling strength of not remarkably influenced.
Described phase transformation softening agent is a phthalimide compound, comprises phthalic imidine, phenyl ring substituted phthalimide and N-substituted phthalimide.Described phase transformation softening agent is a kind of in phthalic imidine, N-hydroxyphthalimide, 4-nitro phthalic imidine, the N-methyl-4-nitro phthalic imidine.Their fusing point all is higher than the polypropylene fusing point more than 10 ℃.Under the polypropylene processing temperature, can incorporate modified polypropene, play the effect of softening agent, further reduce the melt viscosity of maleimide modified polypropene; And when moulding cooled, described phthalic imidine can be separated out and recrystallize being higher than polyacrylic Tc, was present in polypropylene matrix with microcrystalline form, improved rigidity, heat-drawn wire and the shock resistance of modified polypropene.
Described initiator is ditertiary butyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2, more than one of 5-bis(t-butylperoxy) hexane.According to required polyacrylic characteristic and target, the consumption of peroxide initiator changes at 0.01-1%.
Described oxidation inhibitor is more than one of antioxidant 1010, oxidation inhibitor 168, oxidation inhibitor 412S, oxidation inhibitor 445, oxidation inhibitor 1098, oxidation inhibitor 1790, oxidation inhibitor DLTDP, oxidation inhibitor DSTP.The consumption of oxidation inhibitor is the 0.1-2% of acrylic resin mass fraction.
Described functional aid comprises lubricant, antiseptic-germicide, static inhibitor, anti ultraviolet agent; Functional aid is the alternate item according to end-use.
Above-mentioned polypropylene batching is melting mixing under 170-320 ℃ processing temperature at forcing machine or Banbury mixer, and processing temperature commonly used is 180-280 ℃.
The melting mixing order of above-mentioned polypropylene batching has no special requirements except that oxidation inhibitor, but oxidation inhibitor must mix at initiator and polar monomer and finishes that the back is last to add mixing.Phase transformation softening agent, polar monomer can mix with polypropylene fusion simultaneously or prior to initiator; Functional aid can mix with polypropylene fusion simultaneously or prior to oxidation inhibitor.
According to used polyacrylic melting index, cooperate polar monomer and phase transformation softening agent, select suitable peroxide initiator for use, through melting mixing, can in the 30-300g/10min scope, regulate the melt-flow speed of modified polypropene.Obtain the modified polypropene material that rigidity, intensity, heat-drawn wire all are better than unmodified resin, be used for long glass fiber reinforced polypropylene composite material.
Existing relatively MODIFICATION OF POLYPROPYLENE method, the present invention has the following advantages:
1), directly prepares the modified polypropene material of continuous glass fibre melt impregnation with ultra high melt flow rate with common raw material, equipment and simple process;
2) when improving the melt polypropylene flow rate, the impelling strength of impact polypropylene material not, the modified polypropene material need not elastic body toughening;
3) the present invention is polar monomer with the maleimide, phthalic imidine is the phase transformation softening agent, under the cooperation of peroxide initiator, in forcing machine polypropylene is carried out the fusion-grafting modification, in the 30-300g/10min scope, regulate the melt-flow speed of modified polypropene.When significantly improving the melt polypropylene flow rate, the polyacrylic impelling strength of not remarkably influenced, the preparation fluidity of molten, with glass fibre consistency, goods thermotolerance, shock resistance and all excellent modified polypropene material of mechanical property.
4) when improving the melt polypropylene flow rate, improve the rigidity and the heat-drawn wire of poly-modified propylene.
Embodiment
Embodiment 1:
With melting index is 100 parts of former powder of polypropylene and 1 part of N-phenylmaleimide of 18g/10min (230 ℃ of 2.16kg), 0.5 part diphenyl methane dimaleimide, 1 part of phthalic imidine, 0.05 a part di-tert-butyl peroxide mixes, and mixes extruding pelletization on HAAKE Rheomex OS PTW16 twin screw processing forcing machine.Extruder temperature is set to 180 ℃, 220 ℃, 240 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃ and 230 ℃, and 220 ℃ of head temperatures, screw speed are 80r/min, and input speed is 12%.The modified polypropene pellet mixes with 0.1 part of oxidation inhibitor 168, is injection molded into standard test specimen on deep sharp P Series 50e injection moulding machine.Three sections temperature of injection moulding machine are set to 180 ℃, and 225 ℃ and 225 ℃, 230 ℃ at nozzle.
Embodiment 2
With melting index is 100 parts of former powder of polypropylene and 2 parts of N-phenylmaleimides of 2.5g/10min (230 ℃ of 2.16kg), 0.1 part diphenyl methane dimaleimide, 0.5 part of phthalic imidine, 0.3 a part di-tert-butyl peroxide mixes, and mixes extruding pelletization on HAAKE Rheomex OS PTW16 twin screw processing forcing machine.Extruder temperature is set to 180 ℃, 220 ℃, 240 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃ and 230 ℃, and 220 ℃ of head temperatures, screw speed are 80r/min, and input speed is 12%.The modified polypropene pellet mixes with 0.1 part of oxidation inhibitor 168, is injection molded into standard test specimen on deep sharp P Series 50e injection moulding machine.Three sections temperature of injection moulding machine are set to 180 ℃, and 225 ℃ and 225 ℃, 230 ℃ at nozzle.
Embodiment 3:
With melting index is 100 parts of former powder of polypropylene and 1 part of N-phenylmaleimide of 18g/10min (230 ℃ of 2.16kg), 0.5 part diphenyl methane dimaleimide, 1 part of phthalic imidine, 0.05 a part di-tert-butyl peroxide mixes, melting mixing on HAAKE Rheomex OS PTW16 twin screw extruder, the charging opening at the nearly head of twin screw extruder adds the granulation of glass tow simultaneously.Extruder temperature is set to 180 ℃, 220 ℃, 240 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃ and 230 ℃, and 220 ℃ of head temperatures, screw speed are 80r/min, and input speed is 12%.Strengthen pellet and mix, on deep sharp P Series 50e injection moulding machine, be injection molded into standard test specimen with 0.3 part of oxidation inhibitor 168.Three sections temperature of injection moulding machine are set to 180 ℃, and 225 ℃ and 225 ℃, 230 ℃ at nozzle.
Embodiment 4:
With melting index is 100 parts of former powder of polypropylene and 1 part of N-phenylmaleimide of 18g/10min (230 ℃ of 2.16kg), 0.5 part diphenyl methane dimaleimide, 0.05 a part di-tert-butyl peroxide mixes, and mixes extruding pelletization on HAAKE Rheomex OS PTW16 twin screw processing forcing machine.Extruder temperature is set to 180 ℃, 220 ℃, 240 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃ and 230 ℃, and 220 ℃ of head temperatures, screw speed are 80r/min, and input speed is 12%.The modified polypropene pellet mixes with 0.1 part of oxidation inhibitor 168, is injection molded into standard test specimen on deep sharp P Series 50e injection moulding machine.Three sections temperature of injection moulding machine are set to 180 ℃, and 225 ℃ and 225 ℃, 230 ℃ at nozzle.
Embodiment 5:
With melting index is 100 parts of former powder of polypropylene and 7 parts of N-phenylmaleimides of 2.5g/10min (230 ℃ of 2.16kg), 0.1 penylene bismaleimides, 3 parts of phthalic imidines between part, 0.6 a part di-tert-butyl peroxide mixes, and mixes extruding pelletization on HAAKE Rheomex OS PTW16 twin screw processing forcing machine.Extruder temperature is set to 180 ℃, 220 ℃, 240 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃ and 230 ℃, and 220 ℃ of head temperatures, screw speed are 80r/min, and input speed is 12%.The modified polypropene pellet mixes with 0.1 part of oxidation inhibitor 168, is injection molded into standard test specimen on deep sharp P Series 50e injection moulding machine.Three sections temperature of injection moulding machine are set to 180 ℃, and 225 ℃ and 225 ℃, 230 ℃ at nozzle.
Embodiment 6:
With melting index is 100 parts of former powder of polypropylene and 1 part of N-phenylmaleimide of 2.5g/10min (230 ℃ of 2.16kg), 0.5 part diphenyl methane dimaleimide, 5 parts of phthalic imidines, 0.5 a part di-tert-butyl peroxide mixes, and mixes extruding pelletization on HAAKE Rheomex OS PTW16 twin screw processing forcing machine.Extruder temperature is set to 180 ℃, 220 ℃, 240 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃ and 230 ℃, and 220 ℃ of head temperatures, screw speed are 80r/min, and input speed is 12%.The modified polypropene pellet mixes with 0.1 part of oxidation inhibitor 168, is injection molded into standard test specimen on deep sharp P Series 50e injection moulding machine.Three sections temperature of injection moulding machine are set to 180 ℃, and 225 ℃ and 225 ℃, 230 ℃ at nozzle.
Table 1 has comprehensively been listed the test result of above-mentioned embodiment sample.Table 1 has also provided the performance of common medium viscosity homo-polypropylene product P P 140.
Table 1
| Project | Glass fiber content | Melting index | Modulus in flexure | Flexural strength | Tensile strength | Notched Izod impact strength | Heat-drawn wire |
| Method | Roasting | GB3682- 83 | GB/T104 0-92 | GB/T104 0-92 | ASTM-D 638 | ASTM-D 256 | GB/T1634 |
| ％ | g/10min | GPa | MPa | MPa | J/m | ℃ | |
| PP140 | 19 | 1.3 | 48 | 35 | 22 | 91 | |
| Example 1 | 53 | 1.5 | 53 | 34 | 27 | 102 | |
| Example 2 | 250 | 1.4 | 49 | 31 | 22 | 100 | |
| Example 3 | 30 | 5.6 | 110 | 70 | 70 | 140 | |
| Example 4 | 38 | 1.4 | 50 | 36 | 26 | 99 |
| Example 5 | 95 | 1.3 | 53 | 33 | 23 | 98 | |
| Example 6 | 37 | 1.6 | 51 | 33 | 26 | 110 |
General medium viscosity polypropylene product, as PP 140, its melt flow rate (MFR), flexural strength, shock strength, heat-drawn wire is respectively 19g/10min, 48.5MPa, 22J/m and 90 ℃.In embodiment 1, polypropylene is after modification, and its melt flow rate (MFR) reaches 53g/10min, improves nearly 2 times, and flexural strength, and shock strength and heat-drawn wire are respectively 53MPa, and 27J/m and 102 ℃ are all higher than virgin resin PP140.In embodiment 2, polypropylene is after modification, and its melt flow rate (MFR) is brought up to 250g/10min from 2.5g/10min, and shock strength maintains 22J/m.In 30% glass enhancing modified polypropylene example 3, its modulus in flexure, flexural strength, shock strength and heat-drawn wire are respectively 5.6GPa, 110MPa, 70J/m and 140 ℃.And be 4.8GPa with 30% short glass fiber Reinforced Polypropylene generally, 60MPa, 55J/m and 127 ℃.Example 3 performance of composites are far above the performance of general fiber glass reinforced polypropylene.
Claims (6)
1. one kind is improved polypropylene polarity and mobile method of modifying, it is characterized in that in order polypropylene being prepared burden melting mixing; Described polypropylene batching comprises following component and mass fraction: 100 parts of polypropylene, 0.1～10 part of polar monomer, 0～7 part in phase transformation softening agent, 0.1～2 part in 0.01～1 part of initiator and oxidation inhibitor; Described order is that initiator and polar monomer mix with polypropylene fusion prior to oxidation inhibitor, and polar monomer mixes with polypropylene fusion prior to initiator or polar monomer and initiator mix with polypropylene fusion simultaneously; Described polypropylene is more than one in homo-polypropylene, the Co-polypropylene; Described polar monomer is a maleimide compound, and they contain simple function group or bifunctional; Described maleimide compound comprises N-phenylmaleimide, N-naphthyl maleimide, N-alkyl maleimide, N-cyclohexyl maleimide, diphenyl methane dimaleimide, a penylene bismaleimides, maleimide phenol, maleimide formic acid; Described maleimide contains simple function group or bifunctional; The content of difunctionality maleimide is the 0.1-2% of acrylic resin mass fraction in the described polar monomer; Described phase transformation softening agent is a kind of in phthalic imidine, N-hydroxyphthalimide, 4-nitro phthalic imidine, the N-methyl-4-nitro phthalic imidine.
2. method according to claim 1 is characterized in that described polypropylene batching comprises also that functional aid, functional aid mix with polypropylene fusion prior to oxidation inhibitor or functional aid and oxidation inhibitor while mix with polypropylene fusion.
3. method according to claim 2 is characterized in that described functional aid comprises more than one in lubricant, antiseptic-germicide, static inhibitor, the anti ultraviolet agent.
4. method according to claim 1 is characterized in that described initiator is ditertiary butyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2, more than one of 5-bis(t-butylperoxy) hexane.
5. method according to claim 1 is characterized in that described oxidation inhibitor is more than one of antioxidant 1010, oxidation inhibitor 168, oxidation inhibitor 412S, oxidation inhibitor 445, oxidation inhibitor 1098, oxidation inhibitor 1790, oxidation inhibitor DLTDP, oxidation inhibitor DSTP.
6. according to each described method of claim 1～5, it is characterized in that described melting mixing is for mixing described polypropylene batching in 170～320 ℃ temperature by described order at forcing machine or Banbury mixer.
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| CN102051038A (en) * | 2011-01-18 | 2011-05-11 | 华南理工大学 | High-liquidity modified polyphenyl ether plastics and production method thereof |
| CN103146062A (en) * | 2013-03-19 | 2013-06-12 | 太仓市佳玲塑料制品有限公司 | Preparation technology of flame resistant polypropylene |
| CN111393786A (en) * | 2020-04-01 | 2020-07-10 | 湖北亿纬动力有限公司 | Insulating plastic under battery top cover, preparation method and application thereof |
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| CN1834145A (en) * | 2005-03-18 | 2006-09-20 | 上海金发科技发展有限公司 | Polypropylene composite material for automobile bumper and prepn. thereof |
| CN101338053A (en) * | 2008-08-12 | 2009-01-07 | 苏州工业园区华通科技有限公司 | Polyolefine core tube and method for preparing same |
| CN101423590A (en) * | 2008-12-12 | 2009-05-06 | 江苏工业学院 | Method for preparing polypropylene/maleic anhydride melt grafting high condensing pre-mixed master batch |
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