CN100418991C - Porous polypropylene particle suspension solid phase graft-modification method - Google Patents
Porous polypropylene particle suspension solid phase graft-modification method Download PDFInfo
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Abstract
The present invention relates to a porous polypropylene particle suspension solid phase graft-modification method. Suspension solid phase graft-modification is carried out for polypropylene particles adsorbing with monomers and initiating agents in salt solution in order to deepen grafting depth, the degradation and the side reaction of polymers are reduced, and simultaneously, the mechanical property of polypropylene materials after modification is greatly enhanced. Products carrying out grafting modification via the method of the present invention can be used as a compatilizer for PP to mix with other polymers, the compatibility of materials is enhanced, and thus, the mechanical property of the materials is enhanced.
Description
Technical field:
The present invention relates to a kind of porous polypropylene particle suspension solid phase graft-modification method.
Background technology:
In five big general-purpose plastics, polypropylene (PP) is though developing history is short, is with fastest developing speed a kind of, and its output and production capacity are and increase progressively trend steadily, develops with the annual growth rate of 8-12%, and the throughput of states such as the U.S., West Europe and Japan accounts for 2/3 of the world.But the occupancy volume of high value added product is less relatively, and this has just caused it can not satisfy the especially needs that increase rapidly of plastic product industry of market.For this reason, new Application Areas is opened up in actively industry restructuring of PP industry both at home and abroad, increase kind, the trade mark of novel high-performance, exploitation is researched and developed PP modified product and technology energetically based on the alloy material of PP, impels PP to develop to engineering plastics and functional materials direction.
The modification of PP mainly is divided into physically modified and chemical modification.Physically modified mainly is blend, enhancing, filling, is mixed with mixing by the polymkeric substance that adds inorganic or organic filler, inorganic nano-particle, other kind, and its physics phase is changed, and reaches to reduce cost, give PP the purpose of new performance.The material blend of physically modified is relatively poor, particularly differs the intermingling material of bigger polymkeric substance for polarity, often needs to add expensive compatilizer, increases alternate affinity, just can meet the requirement of processing characteristics.
Chemical modification mainly comprises modification by copolymerization, cross-linking modified, graft modification etc., and the molecular structure by changing PP is to reach the purpose of modification.Modified product can be directly as giving the material of new capability or as blending compatilizer.
1) modification by copolymerization
Can increase impact property, the transparency and the processing fluidity of homopolymerization PP to a certain extent based on the modification by copolymerization of propylene monomer, improve PP toughness etc.Can obtain Random copolymer RCP by propylene, ethene are mixed copolymerization.Or, carry out copolymerization again with after the propylene homopolymerization, and can obtain the segmented copolymer that propylene, ethylene-propylene rubber(EPR) and ethene are formed, wherein ethylene-propylene rubber(EPR) plays a part compatilizer at the third rare and ethene between mutually.
2) cross-linking modified
The cross-linked modification method of PP has chemically crosslinked and radiation crosslinking.But for PP, it is also very serious to degrade in the time of radiation crosslinking, so the effect of radiation crosslinking is very limited.So generally adopt chemically crosslinked, by the crosslinked mechanical property and the thermotolerance that can improve PP.But this method reaction process complexity is wayward.
3) graft-modification method
The PP graft-modification method can be divided into solution grafting, fusion-grafting method, solid phase grafting method and suspension polymerization grafting method etc.
Solution graft copolymerization is meant that polyolefine carries out the method for graft polymerization reaction in dimethylbenzene, chlorobenzene equal solvent, carries out under lower temperature (100-140 ℃), and side reaction is few, percentage of grafting is high, palliating degradation degree is light.But the product postprocessing more complicated will be used a large amount of solvents and need and reclaim, the production cost height, and environmental pollution is bigger.
The temperature of reaction of fusion-grafting is more than the polyolefine fusing point, and commonly used single or two Luo bar forcing machines and Banbury mixer etc. are finished reaction, have simple to operate, solvent-free recovery, can the industrialization continuous production etc. advantage.The boiling point of the used grafted monomer of this method should be higher, and relatively suitable monomer is MAH and ester class thereof, but the temperature of reaction height, polymer degradation is serious, and residual monomer is difficult to remove, and influences quality product.
Solid phase grafting is equipped with in the churned mechanically batch reactor in the laboratory, N
2Protection adds monomer, initiator, catalyzer and interfacial agent, the graft polymerization reaction that carries out down between 100-120 ℃.This method temperature of reaction is low, solvent-free recovery, and expense is also lower, but its grafting degree of depth is wayward, and monomer is also had certain selectivity.
The suspension grafting causes with monomer, initiator polyolefin masterbatch in suspension medium water graft polymerization reaction.Usually make polymkeric substance contact the swelling certain hour with monomer before the reaction at a lower temperature, temperature reaction then, after reaction for some time, elevated temperature again, slaking for some time, filtration drying can obtain product.
The advantage of this method is that the grafting matrix reacts (less than the boiling point of water) at low temperatures with solid-state form, polymer degradation is few, side reaction is few, with water for the dispersion medium temperature of reaction is easy to control, system viscosity is low, need not solvent recuperation, percentage of grafting, grafting efficiency are all very high, can be used for the graftomer of synthesizing new, conversion unit is simple, expense is low, is easy to industry and amplifies.Suspension grafting method more and more is subject to people's attention.
But, since this method be with pure water as reaction medium, thereby certain restriction is arranged for grafted monomer, not being suitable for has bigger deliquescent monomer in water.And exist reactant to separate and problems such as the grafting degree of depth is low with the product difficulty.
Summary of the invention:
The present invention is directed to the deficiency of existing suspension crosslinking technology, a kind of method to porous polypropylene particle suspension solid phase graft-modification is provided, employing is carried out the suspension solid phase grafting modification to the polypropylene particles of having adsorbed monomer and initiator in salt brine solution, to improve the grafting degree of depth, reduce the degraded of polymkeric substance and the generation of side reaction, improve the mechanical property of polypropylene material after the modification simultaneously.
The present invention is a kind of porous polypropylene particle suspension solid phase graft-modification method, with porosity is that 0.14～0.44 porous polypropylene particle soaks in the mixing solutions of grafted monomer and initiator, treat that monomer and initiator are fully adsorbed the aqueous solution that places salt afterwards by the hole of polypropylene particles, at 70-90 ℃, agitation condition reacted 1-7 hour down, discharging, drying obtain the polypropylene particles of graft modification.
Being used for above-mentioned suspension grafted monomer is the monomer that can be used for radical polymerization, is preferably any in the following material or their mixture: vinylformic acid, methacrylic acid, acrylic ester compound, methyl acrylic ester compound, maleic anhydride, vinyl acetate, vinylbenzene, vinyl cyanide, acrylamide etc.
Used salt is water soluble and the inorganic salt that do not participate in graft reaction in the aqueous solution of above-mentioned salt, is preferably any in hydrochloride, hydrophosphate, dihydrogen phosphate, vitriol or the nitrate of sodium, potassium or their mixture.The mass percentage concentration of salt brine solution is preferably 5～40%.
The initiator that the suspension grafting is used is superoxide or azo compound, is preferably any in the following material or their mixture: benzoyl peroxide, dicumyl peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).The consumption of initiator is 0.1～3% of a monomer mass.
An amount of suspension dispersive agent can also when handling, be added in the suspension grafting among the present invention, to avoid the adhesion between the PP particle.
The porous polypropylene of porosity between 0.14～0.44 that the present invention is selected, under scanning electronic microscope, observe, its inside is made up of less than 1 micron spherical particle aggregate many diameters, so contain a large amount of linked holes, this just means that the contained inner ratio surface area of this macrobead PP can be 100～1000 times of common PP, provides possibility for carrying out effective surface grafting polymerization modification.Spherical porous polypropylene can be as reaction bed and in surface and the reaction of internal implementation free yl graft polymerization.After graft modification of the present invention, novel polymer and former PP matrix resin that graft polymerization generates link with chemical bond, can not separate; The characteristics of radical polymerization make most of monomers can be used for grafting homopolymerization or graft copolymerization, can realize designing as required synthetic materials; Method technology of the present invention is simple and pollution-free, is easy to realize suitability for industrialized production.
The product that carries out graft modification through method of the present invention can also improve the consistency of material as the compatilizer of PP and other polymer blending, thereby improves the mechanical property of material.
Description of drawings:
Fig. 1: scanning electronic microscope (SEM) photo of the impact section of PA6/PP co-mixing system
Fig. 2: the SEM photo of the impact section of PA6/PP/ embodiment 4 grafts co-mixing systems
As can be seen from the figure: do not add compatilizer (graft product) and add the compatilizer co-mixing system Impact fracture surface difference is very big. Fig. 1 does not add in the photo of compatilizer and shows bigger hole, the PP grain Son is dispersed in the PA6 particle with large-size, the interface out-of-flatness, and these holes, hole are when fracture, PP Due to particle is extracted from matrix PA6, and the edge, hole is very smooth. This shows and does not add compatilizer The Miscibility of PA6 and PP is poor, causes a little less than the two-phase interface power, when being subjected to external shock, The boundary fracture of weakness, the PP particle is extracted from the PA6 matrix more easily, so that limit, hole, hole Edge is smooth.
Fig. 2 adds the then different of compatilizer, and the hole, hole disappears substantially, and PP particles dispersed therein phase size diminishes, The interface is smooth, shows that the compatilizer that adds has greatly improved the compatibility of system, has improved two phase boundaries The adhesion strength of face. Therefore can improve to a great extent the mechanical performance of co-mixing system, system stiffness Be greatly improved with hardness.
Embodiment 1:
The initiator benzoyl peroxide is dissolved in the Acrylic Acid Monomer by 0.5% of monomer mass, be that porous polypropylene (PP) particle of 0.14-0.44 was soaked in the solution of above-mentioned monomers/initiator 30 minutes again with porosity, monomer and initiator fully are adsorbed onto in the hole of PP particle.Compound concentration is 20% sodium chloride brine, place reactor, open and stir and heat riser, when treating that temperature reaches 85 ℃, put into the PP particle that is soaked with monomer and initiator, react after 2 hours, discharging through distilled water and washing with acetone, is removed unreacted monomer, initiator, drying again obtains the product of graft modification.
Embodiment 2:
The initiator benzoyl peroxide is dissolved in the methacrylate monomer by 1% of monomer mass, be that porous polypropylene (PP) particle of 0.14-0.44 was soaked in the solution of above-mentioned monomers/initiator 20 minutes again with porosity, monomer and initiator are fully absorbed in the hole of PP particle.Compound concentration is 35% sodium chloride brine, places reactor, opens and stirs and heat riser.When treating that temperature reaches 85 ℃, put into the PP particle that is soaked with monomer and initiator, react after 3 hours, discharging is washed respectively through distilled water and acetone, removes unreacted monomer, initiator, and drying again obtains the product of graft modification.
Embodiment 3:
The initiator benzoyl peroxide is dissolved in vinylformic acid and the methacrylate monomer (mass ratio is 1: 1) by 1.5% of monomer mass, be that porous polypropylene (PP) particle of 0.14-0.44 was soaked in the solution of above-mentioned monomers/initiator 30 minutes again with porosity, monomer and initiator are fully absorbed in the hole of PP particle.Compound concentration is 25% sodium chloride brine, places reactor, opens and stirs and heat riser.When treating that temperature reaches 85 ℃, put into the PP particle that is soaked with monomer and initiator, react after 3 hours, discharging is washed respectively through distilled water and acetone, removes unreacted monomer, initiator, and drying again obtains the product of graft modification.Make batten with graft product through injection, record notched Izod impact strength (kJ/M
2) be 5.44, tensile strength (Mpa) is 37.54, yielding stress (Mpa) 31.99.
Embodiment 4:
The initiator benzoyl peroxide is dissolved in vinylformic acid and the Hydroxyethyl acrylate monomer (mass ratio is 1: 1) by 2% of monomer mass, be that porous polypropylene (PP) particle of 0.14-0.44 was soaked in the solution of above-mentioned monomers/initiator 20 minutes again with porosity, monomer and initiator are fully absorbed in the hole of PP particle.Compound concentration is 20% sodium chloride brine, places reactor, opens and stirs and heat riser.When treating that temperature reaches 90 ℃, put into the PP particle that is soaked with monomer and initiator, react after 7 hours, discharging is washed respectively through distilled water and acetone, removes unreacted monomer, initiator, and drying again obtains the product of graft modification.Make batten with graft product through injection, record notched Izod impact strength (kJ/M
2) be 4.62, tensile strength (Mpa) is 34.56, yielding stress (Mpa) 31.67.
Embodiment 5:
Initiator Diisopropyl azodicarboxylate and benzoyl peroxide (mass ratio is 1: 1) are dissolved in the Vinyl Acetate Monomer by 1.5% of monomer mass, be that porous polypropylene (PP) particle of 0.14-0.44 was soaked in the solution of above-mentioned monomers/initiator 10 minutes again with porosity, monomer and initiator are fully absorbed in the hole of PP particle.Compound concentration is 10% Repone K salt solution, and adds the polyethylene of dispersing agent alcohol of monomer mass 2%, places reactor, opens and stirs and heat riser.When treating that temperature reaches 70 ℃, put into the PP particle that is soaked with monomer and initiator, react after 4 hours, discharging is washed respectively through distilled water and acetone, removes unreacted monomer, initiator, and drying again obtains the product of graft modification.
Embodiment 6:
The initiator benzoyl peroxide is dissolved in the Vinyl Acetate Monomer by 2% of monomer mass, be that porous polypropylene (PP) particle of 0.14-0.44 was soaked in the solution of above-mentioned monomers/initiator 10 minutes again with porosity, monomer and initiator are fully absorbed in the hole of PP particle.Compound concentration is 10% sodium chloride brine, and adds the polyethylene of dispersing agent alcohol of monomer mass 2%, places reactor, charges into the nitrogen of 1.2-1.5MPa, opens and stirs and heat riser.When treating that temperature rises to 90 ℃, put into the PP particle that is soaked with monomer and initiator, react after 1.5 hours, discharging is washed respectively through distilled water and acetone, removes unreacted monomer, initiator, and drying again obtains the product of graft modification.
Embodiment 7:
The initiator benzoyl peroxide is dissolved in the styrene monomer by 1% of monomer mass, be that porous polypropylene (PP) particle of 0.14-0.44 was soaked in the solution of above-mentioned monomers/initiator 20 minutes again with porosity, monomer and initiator are fully absorbed in the hole of PP particle.Compound concentration is 5% sodium hydrogen phosphate salt solution, places reactor, opens and stirs and heat riser.When treating that temperature rises to 85 ℃, put into the PP particle that is soaked with monomer and initiator, react after 2 hours, discharging is washed respectively through distilled water and acetone, uses the acetone extracting again 24 hours, removes unreacted monomer, initiator, and drying again obtains the product of graft modification.
Application examples:
Use embodiment 3, embodiment 4 resulting graft products as the blending compatilizer of polypropylene (PP) and nylon (PA6), to obtain good result respectively, the result is as shown in table 1.Because PA6 and PP are the very poor resins of consistency, the blend process can not produce the chemical reaction key, and intermolecular interface interaction power also very a little less than, form slick cavity, cause tensile strength very low thereby be very easy to make the PP particle from the PA6 particle, to pull out in the effect of external force.Be the good PA6/PP blend of processability, need solve dispersion and the key issue such as interface compatibility of PP in the PA6 resin.Make original position in the blend process generate multipolymer, realize the consistency blend of PA6 and PP with compatibilization.
As can be seen from Table 1, in co-mixing system, add 6 parts of graft products after, compare shock strength, tensile strength all be greatly improved (about 3-4 times) with barren PP/PA6 co-mixing system.This mainly is that the co-mixing system consistency increases after adding grafts, and disperse phase is mutually switching little, and interfacial adhesion increases, and makes mechanical property improve.
The composition of table 1 co-mixing system and main mechanical property
Claims (4)
1. porous polypropylene particle suspension solid phase graft-modification method, be that 0.14～0.44 porous polypropylene particle soaks in the mixing solutions of suspension grafted monomer that can be used for radical polymerization and initiator with porosity, treat that monomer and initiator are fully adsorbed the aqueous solution that places salt afterwards by the hole of polypropylene particles, used salt is sodium, the hydrochloride of potassium, hydrophosphate, dihydrogen phosphate, any in vitriol or the nitrate or their mixture, at 70-90 ℃, agitation condition reacted 1-7 hour down, discharging, drying obtain the polypropylene particles of graft modification;
The said suspension grafted monomer that can be used for radical polymerization is any in the following material or their mixture: vinylformic acid, methacrylic acid, acrylic ester compound, methyl acrylic ester compound, maleic anhydride, vinyl acetate, vinylbenzene, vinyl cyanide, acrylamide.
2. according to the method for modifying of claim 1, it is characterized in that: the initiator that the suspension grafting is used is superoxide or azo compound, and the consumption of initiator is 0.1～3% of a monomer mass.
3. according to the method for modifying of claim 1 or 2, it is characterized in that: the mass percentage concentration of the aqueous solution of salt is 5～40%.
4. according to the method for modifying of claim 2, it is characterized in that: the initiator that the suspension grafting is used is any in the following material: benzoyl peroxide, dicumyl peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile).
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| CN103772615B (en) * | 2013-11-22 | 2016-03-16 | 南京工业大学 | Method for improving grafting rate of polypropylene suspension grafted acrylic acid |
| CN105504171A (en) * | 2014-10-20 | 2016-04-20 | 中国石化扬子石油化工有限公司 | Polypropylene graft and preparation method thereof |
| CN106519123A (en) * | 2016-09-26 | 2017-03-22 | 北京化工大学 | High-impact polypropylene grafted polymer and preparation method thereof |
| CN107915806B (en) * | 2016-10-10 | 2020-11-10 | 中国石油化工股份有限公司 | Method for grafting polar monomer onto polypropylene particles |
| CN109142136B (en) * | 2018-07-25 | 2021-02-02 | 同济大学 | Device and method for measuring loading depth of functional group on surface of pore channel of modified porous material |
| JP2023523069A (en) | 2020-04-29 | 2023-06-01 | 中国石油化工股▲ふん▼有限公司 | Anhydride group-containing polypropylene graft and method for preparing polypropylene graft |
| TW202323424A (en) | 2021-08-04 | 2023-06-16 | 大陸商中國石油化工科技開發有限公司 | Flexible polypropylene modified insulation material, preparation method therefor, and application thereof |
| KR20240149394A (en) | 2022-01-06 | 2024-10-14 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Biaxially oriented polypropylene dielectric film, modified polypropylene material and uses thereof |
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| CN1199743A (en) * | 1997-05-15 | 1998-11-25 | 住友化学工业株式会社 | Method for producing graft copolymer rubber and polypropylene-based resin composition |
| JP2003183336A (en) * | 2001-12-20 | 2003-07-03 | Japan Polychem Corp | Acid-modified polypropylene resin, its production process and resin composition made by using it |
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Patent Citations (5)
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| US3919178A (en) * | 1972-02-24 | 1975-11-11 | Lion Fat Oil Co Ltd | Method of manufacturing polymer graft-polymerized onto water soluble inorganic substance |
| CN1100441A (en) * | 1993-06-10 | 1995-03-22 | 钟渊化学工业株式会社 | Modified polyolefin and composition containing the same |
| CN1199743A (en) * | 1997-05-15 | 1998-11-25 | 住友化学工业株式会社 | Method for producing graft copolymer rubber and polypropylene-based resin composition |
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