CN101717476B - Multifunctional waste PET and polypropylene in-site fiber-forming composite material prepared by multi-component compatiblizing and toughening agent - Google Patents
Multifunctional waste PET and polypropylene in-site fiber-forming composite material prepared by multi-component compatiblizing and toughening agent Download PDFInfo
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- CN101717476B CN101717476B CN2009102274715A CN200910227471A CN101717476B CN 101717476 B CN101717476 B CN 101717476B CN 2009102274715 A CN2009102274715 A CN 2009102274715A CN 200910227471 A CN200910227471 A CN 200910227471A CN 101717476 B CN101717476 B CN 101717476B
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Abstract
The invention discloses multifunctional waste PET and polypropylene in-site fiber-forming composite material prepared from a multi-component compatiblizing and toughening agent. The multi-component controllable reactive compatiblizing and toughening agent is prepared from polypropylene, an elastomer 1, an elastomer 2, a difunctional group reactive monomer, a second monomer and a peroxide initiator. Then, multifunctional waste PET is prepared from an antioxidant and the prepared multi-component controllable reactive compatiblizing and toughening agent and waste PET; and finally, the in-site fiber-forming composite material is prepared by compounding the prepared multifunctional waste PET with polypropylene. The in-site fiber-forming composite material prepared by the technical scheme of the invention has obviously improved toughness (the notch impact strength of a cantilever beam) and rigidity (tensile yield stress and bending elastic modulus) in comparison with the raw material polypropylene and has relatively good reproducibility of mechanical performance; meanwhile, the invention also changes a great amount of waste which mainly refers to waste PET domestically generated every year into resources, thereby having remarkable economic and social benefits.
Description
One, technical field:
The present invention relates to a kind of polymer composite, what relate to particularly that a kind of multifunctional waste polyethylene terephthalate PET that utilizes polycomponent controllable type reactive compatibilization toughner preparation and polypropylene PP be prepared from has an all excellent In-situ Composite of toughness rigidity.
Two, background technology:
Big kind general-purpose plastics polypropylene is carried out modification, make its high performance, engineering plasticsization, be the hot subject of scientific worker, industry study always.One of matter of science and technology that emphasis solves is exactly toughness reinforcing (raising shock strength), but wishes simultaneously to reduce rigidity (stretching yield stress, bending elastic modulus) less or do not reduce rigidity, preferably can improve rigidity to a certain extent.In many scientific approachs of polypropylene being carried out modification, technology, strengthen the comprehensive mechanical property of the polypropylene-base matrix material that is prepared from glass fibre, comparatively speaking be preferably, fiber needs to spin in advance, glass fibre is serious to equipment attrition, extremely grind defectives such as causing the rapid deterioration of performance because of glass fibre when waste product recovery reprocessing utilizes but exist simultaneously.
Should bring into play fibre-reinforced advantage, wish again to overcome as glass fibre enhanced shortcoming the technology paid more and more attention of the thermoplastic resin of in-situ micro-fibril enhancing in recent years (In-situ Composite).The compound fiber wherein that is meant of in-situ micro-fibrilization does not just have in first being processed, but be dispersed in the matrix easy fibre-forming polymer since its be subjected to shearing, stretching action deforms, is orientated that " on the spot " fibrillation forms.If the technology that adopts is appropriate, to compare with the matrix material for preparing with macroscopic fiber, the outstanding advantage that has is: 1, Fibre diameter is little, length-to-diameter ratio is big, has dispersed preferably in matrix; 2, more help between matrix and fento, transmitting stress, can more effectively bring into play the modified effect of the good fento of obdurability; 3, can alleviate wearing and tearing to equipment, the product surface that molds is smooth; 4, fiber does not need prior spinning, has reduced the preparation section of matrix material; Fento still can " on the spot " form when 5, waste product was recycled, and the material property retention rate is more high.
With the easy fibre-forming polymer of polypropylene in-situ micro-fibril compound polyethylene terephthalate (PET), nylon 66 (PA66), nylon 6 (PA6), ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE), polyphenylene sulfide (PPS) and PEN (PEN) etc. are arranged.In recent years along with PET increases sharply at the consumption of packaging field (pure water, beverage packets bottling etc.), the generation sharp increase of waste PET (rPET), China has more than 50 ten thousand tons of various polyester bottles to be dropped every year approximately.With the technology of waste PET in-situ micro-fibril enhancing PP is the problem that PP engineering plasticsization, energy-saving and emission-reduction, changing rejected material to useful resource have important science and technology, economic worth and social effect.
At present, bibliographical information about waste PET and the compound preparation In-situ Composite of PP aspect: 1, as (Composites Science and Technology such as Friedrich, 2005,65 (1): 107-116) earlier PP, recovery PET (rPET) and expanding material methyl propenoic acid glycidyl-ethylene copolymer (E-GMA) melt blending on twin screw extruder are extruded, cool off, under 75～80 ℃, stretch then, prepared PP/rPET In-situ Composite (polypropylene-base In-situ Composite).Staple length reduces much after adding expanding material, reason is that expanding material is wrapped in around the rPET particle, has stoped their each other coalescent in drawing process.The modulus in flexure of injection moulding sample is compared with common matrix material with pure PP, has improved 60%～70%, not too big effect of E-GMA.2, (Journal of AppliedPolymer Science such as Pattama Taepaiboon, 2006,102 (2): 1173-1181) adopt melt blending to extrude-thermal stretch-solid phase stretching-injection molding forming method, prepare isotactic polyprophlene (iPP)/rPET In-situ Composite, and studied the influence to compound system such as expanding material polypropylene grafted maleic anhydride (PP-g-MA), rPET content, stretch ratio.Stretch ratio is 7, rPET content is 15% o'clock, the Young's modulus of iPP/rPET, tensile strength, modulus in flexure, notched Izod impact strength are 1877MPa, 29.4MPa, 518MPa, 34.3J/m, are respectively 1.13 times, 0.95 times, 1.06 times, 0.72 times of raw material iPP; RPET content is 30% o'clock, and the Young's modulus of iPP/rPET, tensile strength, modulus in flexure, notched Izod impact strength are respectively 1681MPa, 32.0MPa, 645MPa,, 38.1J/m, be respectively 1.01 times, 1.03 times, 1.43 times, 0.80 times of raw material iPP.Though the adding of high-modulus, high strength component rPET helps improving the rigidity of matrix material, the incompatible weak bonding interface that causes is the major cause that toughness of material is starkly lower than raw material PP between the two-phase.After adding expanding material PP-g-MA, the in-situ fibrillation compound system for rPET content 15% can improve its over-all properties, is 30% in-situ fibrillation compound system for rPET content, and the every mechanical property of the adding of expanding material all descends to some extent.
At present, the mechanical property that why presents rPET in-situ micro-fibril enhancing PP matrix material is compared with raw material PP, and rigidity has improved, and toughness has reduced, or opposite situation; Add the expanding material of one-component synchronously with PP, rPET, sometimes play positive effect, sometimes play negative effect, its reason is: the consistency of rPET and PP is very poor, does not add or fail to form with the In-situ Composite that PP, rPET add synchronously the expanding material preparation that is similar to PP-g-MA, E-GMA to present the constitutional features that comprehensive good mechanical property should have.
Three, summary of the invention:
The technical problem to be solved in the present invention is: a kind of polycomponent controllable type reactive compatibilization toughner is provided, and make multifunctional waste PET with polycomponent controllable type reactive compatibilization toughner and waste PET reactively blending, multifunctional waste PET and the compound In-situ Composite that is prepared into of polypropylene in-situ fibrillation are had waste PET form special-shaped fento, form constitutional featuress such as the flexible strong bonded interface of appropriateness between waste PET fento and PP matrix resin, the In-situ Composite that realizes waste PET and the compound preparation of PP presents the toughness rigidity all than the target of the obvious raising of PP.
The technical solution used in the present invention be:
The invention provides a kind of polycomponent controllable type reactive compatibilization toughner, described compatibilization and toughening agent is to be prepared from by the following method:
A, represent with weight part, contain 55～70 parts of polypropylene in the described polycomponent controllable type reactive compatibilization toughner proportioning raw materials, 25～35 parts of elastomericss 1,5～10 parts of elastomericss 2,10～24 parts of bifunctional reactive monomers, 6～11 part of second monomer and 1.0～1.5 parts of peroxide initiators;
B, take by weighing various raw materials according to the described proportioning raw materials of step a, at first solvent is joined in the reactor, the add-on of described solvent is 7～9 times of the described raw material gross weight of step a, add the raw material elastomerics 1 that takes by weighing then, elastomerics 2 and polypropylene carry out stirring heating, when rising to 120～130 ℃, temperature slowly adds the bifunctional reactive monomer and second monomer, under 120～130 ℃ of constant temperatures, stir 2～5min, then at 120～130 ℃ of constant temperature, add the peroxide initiator under the agitation condition gradually, afterwards at 120～130 ℃ of constant temperature, agitation condition is reaction 30～40min down, and reaction after finishing is lowered the temperature reaction mixture, separate, oven dry gets final product;
Perhaps will carry out thorough mixing according to raw material polypropylene, elastomerics 1, elastomerics 2, bifunctional reactive monomer and second monomer that step a takes by weighing, after mixing raw material peroxide initiator is added, thorough mixing is even, mix the back and adopt that twin screw extruder carries out hot mechanically mixing, reacts, extrudes, cooling and dicing, at last particle is dried.
According to above-mentioned polycomponent controllable type reactive compatibilization toughner, described polypropylene is selected from any in particle shape or powdered homo-polypropylene, ethylene, propylene atactic copolymerized polypropene and the ethylene-propylene block copolymerization polypropylene;
Described elastomerics 1 is selected from any in ethylene-vinyl acetate copolymer EVA, ethylene-octene copolymer POE, bulk/emboliform ethylene propylene rubber and the bulk/emboliform terpolymer EP rubber;
Described elastomerics 2 is selected from any in linear SIS thermoplastic elastomer, linear SBS thermoplastic elastomer and the SEBS thermoplastic elastomer;
Described bifunctional reactive monomer is any in glycidyl methacrylate, glycidyl allyl ether, acrylic acid epoxy ester resin, oleic acid epoxy ester resin, linolic acid epoxy ester resin, ricinoleate acid epoxy ester resin, epoxidized polybutadiene and the methacrylic acid epoxy ester resin;
Described second monomer is any in vinylbenzene, alpha-methyl styrene, methyl methacrylate, methyl acrylate, ethyl propenoate and the butyl acrylate;
Described peroxide initiator is any in dibenzoyl peroxide BPO, dicumyl peroxide DCP, ditertiary butyl peroxide and the peroxidized t-butyl perbenzoate.
According to above-mentioned polycomponent controllable type reactive compatibilization toughner, described polypropylene melt flow rate (MFR) under 230 ℃, the condition of 21.168N is 1.0～7.0g/10min;
E/VA is 60/40 to be that weight ratio between ethene E and the vinyl-acetic ester VA is 60/40 among the described ethylene-vinyl acetate copolymer EVA;
Described terpolymer EP rubber is E type terpolymer EP rubber, D type terpolymer EP rubber or H type terpolymer EP rubber;
It is that 20/80 linear SIS thermoplastic elastomer, S/I are that 30/70 linear SIS thermoplastic elastomer or S/I are 40/60 linear SIS thermoplastic elastomer that described linear SIS thermoplastic elastomer is selected from S/I; It is that 20/80 linear SBS thermoplastic elastomer, S/B are that 30/70 linear SBS thermoplastic elastomer or S/B are 40/60 linear SBS thermoplastic elastomer that described linear SBS thermoplastic elastomer is selected from S/B.
According to above-mentioned polycomponent controllable type reactive compatibilization toughner, among the step b:
Described solvent is a dimethylbenzene; Described reactor is heated to be the logical steam heating of chuck; Stirring velocity when described reactor stirs is 80～200r/min; The joining day of described peroxide initiator is 25～35min; Described reaction end back cooling, sepn process are transferred in the extraction still for the reaction mixture that will react after finishing, under the speed agitation condition of 80～180r/min, carry out wet distillation, separated from solvent is come out, after the separated from solvent, adopt the chuck water flowing to make the temperature of extracting in the still reduce to 40～50 ℃ and get final product; Described oven dry is that air blast was dried 3～4 hours under 100～110 ℃ of conditions;
The rotating speed of described twin screw extruder driving screw is 80～100r/min, and forcing machine is set to 160 ℃, 180 ℃, 190 ℃, 190 ℃, 180 ℃ from the temperature that is fed to head.
A kind of multifunctional waste polyethylene terephthalate PET that utilizes above-mentioned polycomponent controllable type reactive compatibilization toughner preparation, described multifunctional waste PET is to be prepared from by the following method:
Polycomponent controllable type reactive compatibilization toughner product 15～30 weight parts and 0.2～0.5 weight part oxidation inhibitor of raw material waste PET 70～85 weight parts after the processing treatment, above-mentioned preparation are carried out thorough mixing, mix that the back adopts that twin screw extruder carries out hot automatic reaction blend, extrudes, cooling, pelletizing, obtain the product multifunctional waste PET.
According to above-mentioned multifunctional waste PET, described waste PET is the tankage or the waste PET film of waste PET bottle sheet, PET spinning;
Described oxidation inhibitor is selected from 2,6-DI-tert-butylphenol compounds, 2, the 6-di-tert-butyl-4-methy phenol is an antioxidant 264,2,6-di-t-butyl-4-normal-butyl phenol, β-positive octadecanol ester of (4-hydroxyl-3,5-DI-tert-butylphenol compounds) propionic acid be among antioxidant 1076, antioxidant 1010 and the oxidation inhibitor PKB-215 any or any two.
According to above-mentioned multifunctional waste PET, the treatment process of described waste PET: the tankage or the waste PET film of waste PET bottle, PET spinning are handled according to ordinary method sorting, removal of impurities, pulverizing, cleaning, cyclonic separation, chosen the stand-by of granularity 3～8mm after the processing; Air blast oven dry 20～24 hours under 100～120 ℃ of conditions before using;
The driving screw rotating speed of described twin screw extruder is 90～120r/min, is set to 255 ℃, 260 ℃, 265 ℃, 265 ℃, 260 ℃ from the temperature that is fed to head.
A kind of In-situ Composite of utilizing above-mentioned multifunctional waste PET and the compound preparation of polypropylene, described multifunctional waste PET and polypropylene In-situ Composite are to be prepared from by the following method:
Multifunctional waste PET 20～40 weight parts of raw material polypropylene 60～80 weight parts and above-mentioned preparation are mixed, mix that the back is adopted the hot mechanical blending of twin screw extruder, extruded, thermal stretch, cooling, pelletizing, can obtain the In-situ Composite of multifunctional waste PET and the compound preparation of polypropylene.
According to the In-situ Composite of above-mentioned multifunctional waste PET and the compound preparation of polypropylene, described polypropylene is selected from any in particle shape or powdered homo-polypropylene, ethylene-propylene atactic copolymerized polypropene and the ethylene-propylene block copolymerization polypropylene;
The driving screw rotating speed of described twin screw extruder is 90～110r/min, is set to 255 ℃, 260 ℃, 265 ℃, 265 ℃, 260 ℃ from the temperature that is fed to head, stretch ratio 5～8.
According to the In-situ Composite of above-mentioned multifunctional waste PET and the compound preparation of polypropylene, described polypropylene melt flow rate (MFR) under 230 ℃, the condition of 21.168N is 0.2～7.0g/10min.
Positive beneficial effect of the present invention:
1, polycomponent controllable type reactive compatibilization toughner of the present invention, main component is PP, elastomerics 1, elastomerics 2, has consistency with PP, by regulating the additional proportion of PP, elastomerics 1, elastomerics 2, the power of may command and polypropylene compatible; Its main component and waste PET are incompatible, but wherein be linked with can with the functional group of waste PET reaction, can form chemical bond during with the waste PET reactively blending and be connected, just make waste PET and PP have certain consistency, i.e. reactive compatibilization; Regulate the bifunctional reactive monomer and second monomeric additional proportion and the consumption during by preparation, the degree of may command and waste PET reaction is promptly controlled the compatible degree of waste PET and PP; Because the toughness of itself is fine, all has certain consistency with waste PET, PP, all can produce toughening effect to waste PET, PP.
2, multifunctional waste PET of the present invention, be when utilizing polycomponent controllable type reactive compatibilization toughner of the present invention and waste PET reactively blending, the characteristic " transplanting " of polycomponent controllable type reactive compatibilization toughner has arrived in the waste PET, it is multi-functional to give waste PET: multifunctional waste PET still can form fento owing to PP appropriate consistency is arranged smoothly with PP compound tense waste PET; Contained polycomponent controllable type reactive compatibilization toughner and PP have consistency preferably, must from waste PET, in PP, spread with PP compound tense polycomponent controllable type reactive compatibilization toughner, but there is chemical bond to be connected with waste PET, the energy state that polycomponent controllable type reactive compatibilization toughner only is enriched in waste PET fento and PP matrix resin interface region compound system is just minimum, entropy is just maximum, be that limited diffusion group is loaded on the interface region, make the interface have stronger bonding force; Again because the modular ratio waste PET of polycomponent controllable type reactive compatibilization toughner, PP low, it is flexible that the interface that is built into has appropriateness, the hoop stress that the paired waste PET fento of radial shrinkage transformation for stress that waste PET fento and PP matrix resin interface region produce in the time of can be with forming process is swept along, both avoid string stress to cause tiny crack, further strengthened the bonding force at interface again; Though contained polycomponent controllable type reactive compatibilization toughner has chemical bond to be connected with waste PET, but consistency has determined that right and wrong are homodisperse in multifunctional waste PET, limited diffusion will cause forming the uneven waste PET fento of diameter thickness to the interface region, promptly forms special-shaped fento.That is to say, can form the constitutional features that the toughness rigidity all should have than the obvious raising of PP with the In-situ Composite of multifunctional waste PET of the present invention and the compound preparation of PP.
3, having adopted the annual a large amount of wastes that produce of China in the present invention is waste PET; not only make waste obtain recycling; help the environment protection of society; and the toughness rigidity of utilizing the In-situ Composite that multifunctional waste PET and PP prepare is all than the obvious improve of raw material PP; be a kind of engineering plastics of high comprehensive performance, have remarkable economical, social benefit.
The mechanical property of enumerating (seeing Table one) from embodiment shows, the present invention has solved matrix resin and fibre-forming polymer consistency preferably and has formed the contradiction of fento, be built into In-situ Composite and formed special-shaped fento, the constitutional features that the flexible strong bonding force interface of appropriateness etc. is optimized, multifunctional waste PET of preparing and polypropylene In-situ Composite just can present and the general visibly different mechanical property of polypropylene-base In-situ Composite, toughness not only, rigidity is all than the polyacrylic obvious improve of raw material, and the circulation ratio of mechanical property is fairly good, the socle girder notched Izod impact strength, stretching yield stress, bending elastic modulus is brought up to polyacrylic 1.75～2.75 times of raw material respectively, 1.02～1.13 times, 1.19～1.35 times.
Four, embodiment:
Following examples only in order to further specify the present invention, do not limit content of the present invention.
Embodiment 1:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 70 parts of particle shape homo-polypropylene PP, 24.0 parts of E type terpolymer EP rubbers with weight part, 6.0 parts of linear SBS thermoplastic elastomers (S/B is 20/80), 17.0 parts of glycidyl methacrylate, 6.0 parts of vinylbenzene, 1.1 parts of dibenzoyl peroxide;
Polypropylene melt flow rate (MFR) under 230 ℃, the condition of 21.168N is 6.5g/10min.
B, take by weighing various raw materials according to step a, at first solvent xylene is joined in the reactor, the add-on of described dimethylbenzene is 8.5 times of above-mentioned raw materials gross weight, add the raw material polypropylene that takes by weighing then, elastomerics 1 and elastomerics 2, stir, chuck leads to steam heating, stirring velocity is 80～200r/min, when rising to 125 ℃, temperature slowly adds the bifunctional reactive monomer and second monomer, under 125 ± 2 ℃ of conditions, stir 2～5min, then under this temperature, add the peroxide initiator gradually, and constantly stir, the joining day of described peroxide initiator is 25～35min, afterwards at this constant temperature, agitation condition is reaction 40min down, after reaction finishes reaction mixture is transferred in the extraction still, under the stirring velocity condition of 80～180r/min, carry out wet distillation, solvent xylene is separated, adopt the chuck water flowing to make the temperature of extracting in the still reduce to 40～50 ℃ after the separated from solvent, the product centrifugation except that anhydrating, was got final product products obtained therefrom air blast oven dry under 100～110 ℃ of conditions in 3～4 hours at last.
(2) preparation of multifunctional waste PET:
Anticipating of waste PET: the tankage or the waste PET film of waste PET bottle, PET spinning are handled according to ordinary method sorting, removal of impurities, pulverizing, cleaning, cyclonic separation, choose the stand-by of granularity 3～8mm after the processing, with preceding air blast oven dry 20～24 hours under 100～120 ℃ of conditions;
Polycomponent controllable type reactive compatibilization toughner 25 weight parts and the 0.3 weight part antioxidant 1010 of raw material waste PET 75 weight parts of anticipating, above-mentioned preparation are carried out thorough mixing, mix that the back adopts that twin screw extruder carries out hot automatic reaction blend, extrudes, cooling, granulation make multifunctional waste PET; The driving screw rotating speed of twin screw extruder is 120r/min, and forcing machine is set to 255 ℃, 260 ℃, 265 ℃, 265 ℃, 260 ℃ from the temperature that is fed to head.
(3) the compound preparation In-situ Composite of multifunctional waste PET and polypropylene:
Raw material polypropylene 75 weight parts (polypropylene melt flow rate (MFR) under 230 ℃, the condition of 21.168N is 1.0g/10min) and multifunctional waste PET 25 weight parts of above-mentioned preparation are mixed, mix that the back is adopted the hot mechanical blending of twin screw extruder, extruded, thermal stretch, cooling, granulation make multifunctional waste PET and polypropylene In-situ Composite; Twin screw extruder is set to 255 ℃, 260 ℃, 265 ℃, 265 ℃, 260 ℃ from the temperature that is fed to head, and the driving screw rotating speed of forcing machine is 110r/min, stretch ratio 5～8.
Mainly be to adopt injection molding technique when at present the polypropylene-base In-situ Composite being molded into goods, so the present invention becomes the standard strip with the multifunctional waste PET that makes with the injection molding of polypropylene In-situ Composite, press GB/T 1040.2-2006, GB/T 9341-2000, GB/T 1843-1996 test stretching yield stress, bending elastic modulus, socle girder notched Izod impact strength respectively, probe temperature is 25 ± 1 ℃.Concrete mechanical property experimental data sees attached list one.
Embodiment 2: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 64 parts of particle shape homo-polypropylene PP, 28 parts of ethylene-octene copolymer POE with weight part, 8 parts of linear SBS thermoplastic elastomers (S/B is 20/80), 17.0 parts of glycidyl allyl ethers, 6.0 parts of vinylbenzene, 1.1 parts of dibenzoyl peroxide;
The add-on of b, dimethylbenzene is 8 times of above-mentioned raw materials gross weight, and temperature of reaction is 128 ± 2 ℃.
Other are with embodiment 1.
Embodiment 3: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 60 parts of powdery homo-polypropylene PP, 32 parts of D type terpolymer EP rubbers with weight part, 8 parts of linear SBS thermoplastic elastomers (S/B is 30/70), 22.0 parts of acrylic acid epoxy ester resins, 7.5 parts of vinylbenzene, 1.5 parts of dibenzoyl peroxide;
The add-on of b, dimethylbenzene is 9 times of above-mentioned raw materials gross weight, and temperature of reaction is 122 ± 2 ℃.
Other are with embodiment 1.
Embodiment 4: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 55 parts of particle shape homo-polypropylene PP, 36 parts of H type terpolymer EP rubbers with weight part, 9 parts of linear SBS thermoplastic elastomers (S/B is 40/60), 24.0 parts of acrylic acid epoxy ester resins, 6 parts of vinylbenzene, 1.0 parts of dibenzoyl peroxide.
The add-on of b, dimethylbenzene is 9 times of above-mentioned raw materials gross weight.
Other are with embodiment 1.
Embodiment 5: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 55 parts of particle shape homo-polypropylene PP, 35 parts of H type terpolymer EP rubbers with weight part, 10 parts of linear SIS thermoplastic elastomers (S/I is 20/80), 24.0 parts of oleic acid epoxy ester resins, 7.5 parts of vinylbenzene, 1.3 parts of dibenzoyl peroxide.
The add-on of b, dimethylbenzene is 9 times of above-mentioned raw materials gross weight.
Other are with embodiment 1.
Embodiment 6: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 68 parts of particle shape homo-polypropylene PP, 25 parts of H type terpolymer EP rubbers with weight part, 7.0 parts of linear SIS thermoplastic elastomers (S/I is 30/70), 24.0 parts of oleic acid epoxy ester resins, 9.0 parts of alpha-methyl styrenes, 1.2 parts of dibenzoyl peroxide.
Other are with embodiment 1.
Embodiment 7: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 68 parts of particle shape homo-polypropylene PP, 25.6 parts of H type terpolymer EP rubbers with weight part, 6.4 parts of linear SIS thermoplastic elastomers (S/I is 40/60), 24.0 parts of linolic acid epoxy ester resins, 8.0 parts of alpha-methyl styrenes, 1.1 parts of dibenzoyl peroxide.
Other are with embodiment 1.
Embodiment 8: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent with weight part, 68 parts of particle shape homo-polypropylene PP, 25.6 parts of ethylene-vinyl acetate copolymer EVA (E/VA is 60/40), 6.4 parts of linear SIS thermoplastic elastomers (S/I is 30/70), 24.0 parts of linolic acid epoxy ester resins, 7.5 parts of vinylbenzene, 1.1 parts of dibenzoyl peroxide.
The add-on of b, dimethylbenzene is 7 times of above-mentioned raw materials gross weight.
Other are with embodiment 1.
Embodiment 9: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent with weight part, 68 parts of particle shape homo-polypropylene PP, 25.6 parts of ethylene-octene copolymer POE, 6.4 parts of linear SIS thermoplastic elastomers (S/I is 30/70), 17.0 parts of glycidyl methacrylate, 7.5 parts of methyl methacrylates, 1.1 parts of dibenzoyl peroxide.
Polypropylene melt flow rate (MFR) under 230 ℃, the condition of 21.168N is 1.0g/10min.
Other are with embodiment 1.
Embodiment 10: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 68 parts of particle shape homo-polypropylene PP, 25.6 parts of E type terpolymer EP rubbers with weight part, 6.4 parts of linear SBS thermoplastic elastomers (S/B is 30/70), 24.0 parts of ricinoleate acid epoxy ester resins, 7.5 parts of ethyl propenoates, 1.1 parts of dibenzoyl peroxide.
Other are with embodiment 1.
Embodiment 11: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 68 parts of particle shape homo-polypropylene PP, 25.6 parts of D type terpolymer EP rubbers with weight part, 6.4 parts of linear SBS thermoplastic elastomers (S/B is 30/70), 24.0 parts of ricinoleate acid epoxy ester resins, 7.5 parts of ethyl propenoates, 1.1 parts of dibenzoyl peroxide.
Other are with embodiment 1.
Embodiment 12: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 68 parts of particle shape homo-polypropylene PP, 25.6 parts of D type terpolymer EP rubbers with weight part, 6.4 parts of linear SBS thermoplastic elastomers (S/B is 20/80), 24.0 parts of epoxidized polybutadienes, 7.5 parts of vinylbenzene, 1.1 parts of dibenzoyl peroxide.
Other are with embodiment 1.
Embodiment 13: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 68 parts of particle shape homo-polypropylene PP, 25.6 parts of D type terpolymer EP rubbers with weight part, 6.4 parts of linear SBS thermoplastic elastomers (S/B is 20/80), 24.0 parts of methacrylic acid epoxy ester resins, 7.5 parts of vinylbenzene, 1.2 parts of dibenzoyl peroxide.
Other are with embodiment 1.
Embodiment 14: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 68 parts of particle shape homo-polypropylene PP, 25.6 parts of D type terpolymer EP rubbers with weight part, 6.4 parts of linear SBS thermoplastic elastomers (S/B is 20/80), 17.0 parts of glycidyl methacrylate, 7.5 parts of butyl acrylates, 1.1 parts of dibenzoyl peroxide.
Other are with embodiment 1.
Embodiment 15: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 64 parts of particle shape homo-polypropylene PP, 28.8 parts of E type terpolymer EP rubbers with weight part, 7.2 parts of linear SBS thermoplastic elastomers (S/B is 20/80), 17.0 parts of glycidyl methacrylate, 7.0 parts of vinylbenzene, 1.1 parts of dibenzoyl peroxide.
Other are with embodiment 1.
Embodiment 16: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 60 parts of particle shape homo-polypropylene PP, 32.0 parts of E type terpolymer EP rubbers with weight part, 8.0 parts of linear SBS thermoplastic elastomers (S/B is 20/80), 17.0 parts of glycidyl methacrylate, 7.0 parts of vinylbenzene, 1.1 parts of dibenzoyl peroxide.
Other are with embodiment 1.
Embodiment 17: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 55 parts of particle shape homo-polypropylene PP, 35.0 parts of E type terpolymer EP rubbers with weight part, 10.0 parts of linear SBS thermoplastic elastomers (S/B is 20/80), 17.0 parts of glycidyl methacrylate, 7.0 parts of vinylbenzene, 1.1 parts of dibenzoyl peroxide.
The add-on of b, dimethylbenzene is 9 times of above-mentioned raw materials gross weight.
Other are with embodiment 1.
Embodiment 18: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 64 parts of particle shape homo-polypropylene, 28.8 parts of E type terpolymer EP rubbers with weight part, 7.2 parts of linear SBS thermoplastic elastomers (S/B is 20/80), 17.0 parts of glycidyl methacrylate, 7.0 parts of vinylbenzene, 1.2 parts of dicumyl peroxides.
B, will carry out thorough mixing according to raw material polypropylene, elastomerics 1, elastomerics 2, bifunctional reactive monomer and second monomer that step a takes by weighing, after mixing the dicumyl peroxide initiator is added, thorough mixing is even, mix the back and adopt that twin screw extruder carries out hot mechanically mixing, reacts, extrudes, cooling and dicing, particle air blast oven dry under 100～110 ℃ of conditions was got final product in 3～4 hours; Twin screw extruder is set to 160 ℃, 180 ℃, 190 ℃, 190 ℃, 180 ℃ from the temperature that is fed to head; The driving screw rotating speed of forcing machine is 80r/min.
Other are with embodiment 1.
Embodiment 19: be with embodiment 18 differences:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 64 parts of particle shape homo-polypropylene, 28.8 parts of E type terpolymer EP rubbers with weight part, 7.2 parts of linear SBS thermoplastic elastomers (S/B is 20/80), 17.0 parts of glycidyl methacrylate, 7.0 parts of vinylbenzene, 1.2 parts of ditertiary butyl peroxides.
The driving screw rotating speed of b, forcing machine is 90r/min.
Other are with embodiment 18.
Embodiment 20: be with embodiment 18 differences:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 64 parts of particle shape homo-polypropylene, 28.8 parts of ethylene-octene copolymer POE with weight part, 7.2 parts of linear SBS thermoplastic elastomers (S/B is 20/80), 17.0 parts of glycidyl methacrylate, 7.0 parts of vinylbenzene, 1.2 parts of peroxidized t-butyl perbenzoates.
The driving screw rotating speed of b, forcing machine is 100r/min.
Other are with embodiment 18.
Embodiment 21: difference from Example 1 is:
(1) preparation of polycomponent controllable type reactive compatibilization toughner:
A, proportioning raw materials: represent 68 parts of particle shape homo-polypropylene PP, 25.6 parts of E type terpolymer EP rubbers with weight part, 6.4 parts of linear SBS thermoplastic elastomers (S/B is 20/80), 10.0 parts of glycidyl methacrylate, 11.0 parts of vinylbenzene, 1.1 parts of dibenzoyl peroxide;
(2) preparation of multifunctional waste PET:
To anticipate (with embodiment 1) good raw material waste PET 70 weight parts, polycomponent controllable type reactive compatibilization toughner 30 weight parts and 0.2 weight part 2 of above-mentioned preparation, the 6-DI-tert-butylphenol compounds is carried out thorough mixing, mixes that the back adopts that twin screw extruder carries out hot automatic reaction blend, extrudes, cooling, granulation make multifunctional waste PET; The driving screw rotating speed of twin screw extruder is 100r/min.
Other are with embodiment 1.
Embodiment 22: difference from Example 1 is:
(2) preparation of multifunctional waste PET:
To handle polycomponent controllable type reactive compatibilization toughner 15 weight parts and 0.5 weight part 2 of (same) good raw material waste PET 85 weight parts, embodiment 1 preparation in advance with embodiment 1, the 6-di-tert-butyl-4-methy phenol carries out thorough mixing, mixes that the back adopts that twin screw extruder carries out hot automatic reaction blend, extrudes, cooling, granulation make multifunctional waste PET; The driving screw rotating speed of twin screw extruder is 110r/min.
Other are with embodiment 1.
Embodiment 23: difference from Example 1 is:
(3) preparation of multifunctional waste PET and polypropylene In-situ Composite:
At first multifunctional waste PET 40 weight parts with raw material polypropylene 60 weight parts and embodiment 1 preparation mix, and mix that the back is adopted the hot mechanical blending of twin screw extruder, extruded, thermal stretch, cooling, granulation make multifunctional waste PET and polypropylene In-situ Composite; The driving screw rotating speed of forcing machine is 100r/min.
Other are with embodiment 1.
Embodiment 24: difference from Example 1 is:
(3) preparation of multifunctional waste PET and polypropylene In-situ Composite:
At first multifunctional waste PET 20 weight parts with raw material polypropylene 80 weight parts and embodiment 1 preparation mix, and mix that the back is adopted the hot mechanical blending of twin screw extruder, extruded, thermal stretch, cooling, granulation make multifunctional waste PET and polypropylene In-situ Composite; The driving screw rotating speed of forcing machine is 90r/min.
Other are with embodiment 1.
Embodiment 25: difference from Example 1 is:
(1) polypropylene that adopts in the preparation process of polycomponent controllable type reactive compatibilization toughner is the ethylene-propylene block copolymerization polypropylene.
(3) polypropylene that adopts in the preparation process of multifunctional waste PET and polypropylene In-situ Composite is the ethylene-propylene block copolymerization polypropylene.
Other are with embodiment 1.
Embodiment 26: difference from Example 1 is:
(1) polypropylene that adopts in the preparation process of polycomponent controllable type reactive compatibilization toughner is the ethylene, propylene atactic copolymerized polypropene.
(3) polypropylene that adopts in the preparation process of multifunctional waste PET and polypropylene In-situ Composite is the ethylene, propylene atactic copolymerized polypropene.
Other are with embodiment 1.
The mechanical property experimental data of table one multifunctional waste PET and polypropylene In-situ Composite
Indicate: TYS---stretch yielding stress; FM---bending elastic modulus; NIIS---socle girder notched Izod impact strength.
Claims (10)
1. polycomponent controllable type reactive compatibilization toughner is characterized in that described compatibilization and toughening agent is to be prepared from by the following method:
A, represent with weight part, contain 55～70 parts of polypropylene in the described polycomponent controllable type reactive compatibilization toughner proportioning raw materials, 25～35 parts of elastomericss 1,5～10 parts of elastomericss 2,10～24 parts of bifunctional reactive monomers, 6～11 part of second monomer and 1.0～1.5 parts of peroxide initiators;
Described elastomerics 1 is selected from any in ethylene-vinyl acetate copolymer EVA, ethylene-octene copolymer POE, bulk/emboliform ethylene propylene rubber and the bulk/emboliform terpolymer EP rubber;
Described elastomerics 2 is selected from any in linear SIS thermoplastic elastomer, linear SBS thermoplastic elastomer and the SEBS thermoplastic elastomer;
Described bifunctional reactive monomer is any in glycidyl methacrylate, glycidyl allyl ether, acrylic acid epoxy ester resin, oleic acid epoxy ester resin, linolic acid epoxy ester resin, ricinoleate acid epoxy ester resin, epoxidized polybutadiene and the methacrylic acid epoxy ester resin;
Described second monomer is any in vinylbenzene, alpha-methyl styrene, methyl methacrylate, methyl acrylate, ethyl propenoate and the butyl acrylate;
B, take by weighing various raw materials according to the described proportioning raw materials of step a, at first solvent is joined in the reactor, the add-on of described solvent is 7～9 times of the described raw material gross weight of step a, add the raw material elastomerics 1 that takes by weighing then, elastomerics 2 and polypropylene carry out stirring heating, when rising to 120～130 ℃, temperature slowly adds the bifunctional reactive monomer and second monomer, under 120～130 ℃ of constant temperatures, stir 2～5min, then at 120～130 ℃ of constant temperature, add the peroxide initiator under the agitation condition gradually, afterwards at 120～130 ℃ of constant temperature, agitation condition is reaction 30～40min down, and reaction after finishing is lowered the temperature reaction mixture, separate, oven dry gets final product;
Perhaps will carry out thorough mixing according to raw material polypropylene, elastomerics 1, elastomerics 2, bifunctional reactive monomer and second monomer that step a takes by weighing, after mixing raw material peroxide initiator is added, thorough mixing is even, mix the back and adopt that twin screw extruder carries out hot mechanically mixing, reacts, extrudes, cooling and dicing, at last particle is dried.
2. polycomponent controllable type reactive compatibilization toughner according to claim 1 is characterized in that:
Described polypropylene is selected from any in particle shape or powdered homo-polypropylene, ethylene, propylene atactic copolymerized polypropene and the ethylene-propylene block copolymerization polypropylene;
Described peroxide initiator is any in dibenzoyl peroxide BPO, dicumyl peroxide DCP, ditertiary butyl peroxide and the peroxidized t-butyl perbenzoate.
3. polycomponent controllable type reactive compatibilization toughner according to claim 2 is characterized in that:
Described polypropylene melt flow rate (MFR) under 230 ℃, the condition of 21.168N is 1.0～7.0g/10min;
E/VA is 60/40 to be that weight ratio between ethene E and the vinyl-acetic ester VA is 60/40 among the described ethylene-vinyl acetate copolymer EVA;
Described terpolymer EP rubber is E type terpolymer EP rubber, D type terpolymer EP rubber or H type terpolymer EP rubber;
It is that 20/80 linear SIS thermoplastic elastomer, S/I are that 30/70 linear SIS thermoplastic elastomer or S/I are 40/60 linear SIS thermoplastic elastomer that described linear SIS thermoplastic elastomer is selected from S/I; It is that 20/80 linear SBS thermoplastic elastomer, S/B are that 30/70 linear SBS thermoplastic elastomer or S/B are 40/60 linear SBS thermoplastic elastomer that described linear SBS thermoplastic elastomer is selected from S/B.
4. polycomponent controllable type reactive compatibilization toughner according to claim 1 is characterized in that, among the step b:
Described solvent is a dimethylbenzene; Described reactor is heated to be the logical steam heating of chuck; Stirring velocity when described reactor stirs is 80～200r/min; The joining day of described peroxide initiator is 25～35min; Described reaction end back cooling, sepn process are transferred in the extraction still for the reaction mixture that will react after finishing, under the speed agitation condition of 80～180r/min, carry out wet distillation, separated from solvent is come out, after the separated from solvent, adopt the chuck water flowing to make the temperature of extracting in the still reduce to 40～50 ℃ and get final product; Described oven dry is that air blast was dried 3～4 hours under 100～110 ℃ of conditions;
The rotating speed of described twin screw extruder driving screw is 80～100r/min, and forcing machine is set to 160 ℃, 180 ℃, 190 ℃, 190 ℃, 180 ℃ from the temperature that is fed to head.
5. multifunctional waste polyethylene terephthalate PET who utilizes the described polycomponent controllable type of claim 1 reactive compatibilization toughner preparation is characterized in that described multifunctional waste PET is to be prepared from by the following method:
Raw material waste PET 70～85 weight parts after the processing treatment, the described polycomponent controllable type of claim 1 reactive compatibilization toughner product 15～30 weight parts and 0.2～0.5 weight part oxidation inhibitor are carried out thorough mixing, mix that the back adopts that twin screw extruder carries out hot automatic reaction blend, extrudes, cooling, pelletizing, obtain the product multifunctional waste PET.
6. multifunctional waste PET according to claim 5 is characterized in that: described waste PET is the tankage or the waste PET film of waste PET bottle sheet, PET spinning;
Described oxidation inhibitor is selected from 2,6-DI-tert-butylphenol compounds, 2, the 6-di-tert-butyl-4-methy phenol is an antioxidant 264,2,6-di-t-butyl-4-normal-butyl phenol, β-positive octadecanol ester of (4-hydroxyl-3,5-DI-tert-butylphenol compounds) propionic acid be among antioxidant 1076, antioxidant 1010 and the oxidation inhibitor PKB-215 any or any two.
7. multifunctional waste PET according to claim 6, it is characterized in that: the treatment process of described waste PET is chosen the stand-by of granularity 3～8mm for the tankage or the waste PET film of waste PET bottle, PET spinning are handled according to ordinary method sorting, removal of impurities, pulverizing, cleaning, cyclonic separation after the processing; Air blast oven dry 20～24 hours under 100～120 ℃ of conditions before using;
The driving screw rotating speed of described twin screw extruder is 90～120r/min, is set to 255 ℃, 260 ℃, 265 ℃, 265 ℃, 260 ℃ from the temperature that is fed to head.
8. an In-situ Composite of utilizing described multifunctional waste PET of claim 5 and the compound preparation of polypropylene is characterized in that, described multifunctional waste PET and polypropylene In-situ Composite are to be prepared from by the following method:
Multifunctional waste PET 20～40 weight parts of raw material polypropylene 60～80 weight parts and the described preparation of claim 5 are mixed, mix that the back is adopted the hot mechanical blending of twin screw extruder, extruded, thermal stretch, cooling, pelletizing, can obtain the In-situ Composite of multifunctional waste PET and the compound preparation of polypropylene.
9. the In-situ Composite of multifunctional waste PET according to claim 8 and the compound preparation of polypropylene is characterized in that: described polypropylene is selected from any in particle shape or powdered homo-polypropylene, ethylene-propylene atactic copolymerized polypropene and the ethylene-propylene block copolymerization polypropylene;
The driving screw rotating speed of described twin screw extruder is 90～110r/min, is set to 255 ℃, 260 ℃, 265 ℃, 265 ℃, 260 ℃ from the temperature that is fed to head, stretch ratio 5～8.
10. the In-situ Composite of multifunctional waste PET according to claim 8 and the compound preparation of polypropylene is characterized in that: described polypropylene melt flow rate (MFR) under 230 ℃, the condition of 21.168N is 0.2～7.0g/10min.
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| CN103113707B (en) * | 2011-11-16 | 2015-09-02 | 深圳金大全科技有限公司 | A kind of plastic liquid, powder or toughener and working method thereof |
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