CN1566198A - Polypropylene composition and preparation process thereof - Google Patents
Polypropylene composition and preparation process thereof Download PDFInfo
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- CN1566198A CN1566198A CN 03148380 CN03148380A CN1566198A CN 1566198 A CN1566198 A CN 1566198A CN 03148380 CN03148380 CN 03148380 CN 03148380 A CN03148380 A CN 03148380A CN 1566198 A CN1566198 A CN 1566198A
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Abstract
The invention provides a polypropylene composition and preparation process thereof, wherein the polypropylene composition comprises polypropylene resin and composite powder by the total weight ratio of (1-40) : 100. The composite powder includes inorganic particles and rubber particles.
Description
Technical field
The present invention relates to a kind of polypropylene of modification, say further, relate to acrylic resin of a kind of composite powder modification and preparation method thereof.
Background technology
Polypropylene is the big kind of general-purpose plastics that is only second to polyethylene, polyvinyl chloride.Its raw material sources are abundant, and are cheap, have better comprehensive performance, are widely used.But its molding shrinkage is big, and quality is crisp, and particularly the low temperature notched shock strength is low for notched Izod impact strength, makes it be subjected to considerable restraint on using.For this reason, since middle nineteen seventies, polyacrylic tough-increased and reinforced modification has been carried out extensive and deep research both at home and abroad.
Polypropylene toughness-increasing modified have modification by copolymerization, blending and modifying and an interpolation nucleator (beta-crystal nucleator) etc.Wherein, blending and modifying (the particularly blending and modifying on the copolymerization basis) is the method that the most generally adopts, and mainly comprises (1) thermoplastic elastic body blending toughening; (2) inorganic rigid particle is toughness reinforcing; (3) inorganic nano-particle toughening or the like.
Rubber or elastic body toughening are dispersed in the polypropylene matrix as toughner with the rubber-like elastomer material usually, reach toughness reinforcing purpose, as in polypropylene, sneaking into terpolymer EP rubber (EPDM), ethylene propylene rubber (EPR), cis-1,4-polybutadiene rubber (BR), styrene-butadiene rubber(SBR) components such as (SBS).Though obtained very ten-strike with these elastic body toughening polypropylene industrial, but still existed the problem that some are difficult to overcome, all reduced significantly as rigidity, intensity, use temperature and the processing characteristics of material.
Rise the eighties, occurred the new ideas of organic rigid-particle replacement elastomerics or rubber toughened polymkeric substance abroad.Inorganic rigid particle commonly used comprises mica (Mica), talcum powder (Talc), wollastonite, CaCO
3And BaSO
4Deng.Because the high surface area that nanoparticle had and the interfacial adhesion strength advantages of higher of polymkeric substance, the particle-filled PP of nano redigity is the good matrix material of available energy also in recent years.
Performance between elastomerics and the rigid particles has very big-difference, but it is as follows to influence toughness reinforcing several main factors: the character of (1) matrix resin comprises its molecular weight, molecular weight distribution, crystal property etc.; (2) character of elastomerics or rigid particles comprises particle shape, particle diameter, size distribution and surface energy; (3) character at interface; (4) content of elastomerics and rigid particles etc.
Add rubber and can improve polyacrylic toughness, but can reduce its rigidity; Can improve the rigidity of PP and add the inflexible inorganic particulate, but it is not obvious that its toughness is improved, even descend.Therefore for obtaining rigidity and all more satisfactory matrix material of toughness, people are usually with rubber and rigid inorganic particle or glass fibre and usefulness.The shortcoming of this method is that the notched Izod impact strength raising is not obvious.
Summary of the invention
Applicant of the present invention provides a kind of in the Chinese patent application of submitting to April 18 calendar year 2001 01110730.8 (CN1381523A) be the toughness reinforcing polypropylene of rubber particles of 0.02 m～0.5 m by median size, the high-toughness polypropylene material that makes strong and unyielding balance, stable performance therefrom and have the well processed formability.
After this, applicant of the present invention provides a kind of composite powder rubber to reach the composition of being made up of this composite powder rubber and plastics in the Chinese patent application of submitting to October 12 calendar year 2001 01136382.7 (CN 1412229A).This kind composite powder rubber median size is 20～2000nm, includes rubber powder and water-soluble plastic nucleator.Wherein the gel content of rubber powder is 60% weight or higher, this composite powder rubber be by will through or mix without the rubber latex and the water-soluble plastic nucleator of radiation vulcanization, obtain after drying.Can make up with plastics, make toughened plastics.
The present inventor discovers on this basis, the composition that a kind of composite powder tenacity-increased profax that includes rubber particles and inorganic particulate that the Chinese patent application 03109108.3 of using applicant of the present invention to apply on April 3rd, 2003 is provided obtains, the tenacity-increased profax that provides than Chinese patent application 01110730.8, and the composite powder rubber that Chinese patent application 01136382.7 provides comes tenacity-increased profax, under the same umber of toughner, can improve rigidity, thermotolerance making acrylic resin significantly improve flexible simultaneously.
This composite powder that Chinese patent application 03109108.3 provided is by will be through irradiation or without rubber latex and the inorganic particulate slurries and the water-soluble plastic nucleator solution etc. of irradiation, mixed by required dry weight is even, and drying is prepared then.The composite powder that uses such preparation method to obtain, in itself and the polypropene blended composition that obtains, its powder particle has special aggregation structure: promptly composite powder is dispersed in the acrylic resin as disperse phase, this disperse phase includes the special aggregate of being made up of rubber particles and inorganic particulate, and the structure of this aggregate is single or several inorganic particulate is wrapped in the middle of the rubber particles.This special aggregation structure that is dispersed in the acrylic resin of composite powder of the present invention not only can significantly improve the toughness of acrylic resin, can also make it have rigidity and thermotolerance preferably simultaneously.Simultaneously, the contained plastics nucleator of composite powder can improve the crystal property of acrylic resin, and rubber particles and inorganic particulate synergy with in the composite powder improve toughness, rigidity and thermotolerance aspect at the same time and have positive effect.
Therefore the purpose of this invention is to provide a kind of polypropene composition, said composition has the advantage of toughness height, rigidity, good heat resistance.
Another object of the present invention provides the preparation method of described polypropene composition.
A kind of polypropene composition provided by the invention is characterized in that this kind resin combination includes the following component of blend: acrylic resin and composite powder.The weight ratio of composite powder and acrylic resin is (1～40): 100, be preferably (2～30): and 100, more preferably (3～20): 100.
Acrylic resin in the present composition comprises the disclosed various types of acrylic resins of prior art, comprises homo-polypropylene, Co-polypropylene resin etc.
Composite powder described in the present composition includes inorganic particulate, rubber particles and water-soluble plastic nucleator, and wherein the gel content of rubber particles self is 60% weight or higher, preferred 75% weight or higher.The rubber particles that composite powder is contained and the weight ratio of inorganic particulate are 90: 10～40: 60, are preferably 80: 20～40: 60.The rubber particles that composite powder is contained and the weight ratio of nucleator are 95: 5～70: 30, are preferably 90: 10～70: 30.The water-soluble plastic nucleator is preferably Sodium Benzoate in the present invention.
This composite powder can adopt the method that provides in the Chinese patent application of submitting on April 3rd, 2,003 03109108.3 according to the applicant to prepare.
Composite powder in this patent application (03109108.3) is by will be through irradiation or without the slurries of the rubber latex of irradiation and inorganic particulate and water-soluble plastic nucleator aqueous solution etc., by the mixed of required dry weight and stir, the prepared composite powder of drying then.Specifically, described composite powder is got by the method preparation that includes one of following steps:
A. the slurries of inorganic particulate, the aqueous solution and the cross-linking type synthetic rubber latex of water-soluble plastic nucleator are mixed, obtain mixed emulsion, again with this mixed emulsion drying;
B. adding or do not adding under the situation of crosslinking coagent, after adopting the energetic ray source to carry out radiation vulcanization the rubber latex, again the slurries of inorganic particulate, the aqueous solution of water-soluble plastic nucleator and the rubber latex behind the irradiation are mixed, obtain mixed emulsion, again with this mixed emulsion drying;
The slurries of the inorganic particulate in the preparation method of described composite powder are the suspension of inorganic particulate in water, can directly adopt commercial slurries product, with need before rubber latex is mixed to disperse through common dispersing apparatus (as high-shearing dispersion emulsifying machine, colloidal mill etc.), can in water, be uniformly dispersed to guarantee the solids in the slurries.If inorganic particulate does not have the slurries of commercial grade, also can make by oneself, promptly adopt common dispersing apparatus to make inorganic particulate become steady suspension, and then mix with rubber latex with an amount of water-dispersion.
Inorganic particulate described in the preparation method of described composite powder can be by synthetic or the available inorganic particulate of other various prior aries, as long as its size range can reach the needed effect of invention within the scope of the invention, be not subjected to the restriction of itself substance classes, but meet except the inorganic particulate of water unstable.Above-described its individual particle of inorganic particulate different can be sphere, elliposoidal, sheet shape, aciculiform or irregularly shaped.With three-dimensional perspective, it is 0.2～500nm that its individual particle has the one dimension mean sizes at least, is preferably 0.5～100nm.In toughened polypropylene composition provided by the invention, the inorganic particulate individual particle among the contained composite powder preparation method has one dimension mean sizes 1.0～500nm more preferably at least.
The kind of described inorganic particulate can be selected from one of following material or its combination: metal simple-substance or alloy, as gold and silver, copper, iron or its alloy separately etc.; Metal oxide is as aluminum oxide (Al
2O
3), magnesium oxide (MgO), titanium dioxide (TiO
2), ferric oxide (Fe
2O
3), Z 250 (Fe
3O
4), silver suboxide (Ag
2O), zinc oxide (ZnO) etc.; Metal or non-metal nitride are as aluminium nitride (AlN), silicon nitride (SiN
4) etc.; , non-metallic carbide, as silicon carbide (SiC) etc.; Nonmetal oxide is as silicon-dioxide (SiO
2) etc.; Metal hydroxides is as aluminium hydroxide (Al (OH)
3), magnesium hydroxide (Mg (OH)
2) etc.; Metallic salt comprises metal carbonate, silicate, vitriol etc., as lime carbonate (CaCO
3), barium sulfate (BaSO
4), calcium sulfate (CaSO
4), silver chloride (AgCl) etc.; Ore is as asbestos, talcum, kaolin, mica, feldspar, wollastonite, polynite etc.
In this patent application in rubber latex described in the preparation method of composite powder or the crosslinking-type rubber latex in the weight of contained rubber (being the solid content of rubber latex dry weight or rubber latex) and the inorganic particulate slurries ratio of the weight (dry weights of inorganic particulate slurries) of contained inorganic particulate be 99.5: 0.5～20: 80, be preferably 99: 1～50: 50.In polypropene composition provided by the invention, the rubber in the contained composite powder and the weight ratio of inorganic particulate more preferably 90: 10～40: 60 most preferably are 80: 20～40: 60.
In above-described composite powder preparation method in dry weight and the nucleator aqueous solution of the rubber latex that adopts or crosslinking-type rubber latex the ratio of the weight of nucleator be 99: 1～50: 50, be preferably 97: 3～70: 30.In polypropene composition provided by the invention, the rubber in the contained composite powder and the weight ratio of nucleator more preferably 95: 5～70: 30 most preferably are 90: 10～70: 30.Prepared like this composite powder is improving the plastics flexible simultaneously, thereby can also promote its crystallization to can further improve the rigidity and the thermotolerance of plastics at crystalline plastics.In the method for the invention the water-soluble plastic nucleator so long as water-soluble, and can play the nucleator of using in the prior art of plastics nucleogenesis and can reach the invention effect that will reach, generally use Sodium Benzoate always.
In above-described method, inorganic particulate slurries, the equilateral stirring of nucleator aqueous solution limit can be added in the rubber latex or crosslinking-type rubber latex behind the irradiation, make it to mix through fully stirring.The concentration of rubber latex and the concentration of the inorganic nano-particle slurries and the nucleator aqueous solution are had no special requirements.Drying means when preparing fully vulcanized powder rubber in the Chinese patent 00109217.0 of the drying means that in described drying process, is adopted with Chinese patent application 99125530.5 (publication number of its international patent application is WO01/40356) and application on June 15th, 2000, be that drying process can be carried out with spray-dryer, inlet temperature can be controlled at 100～200 ℃, and temperature out can be controlled at 20～80 ℃.Gel content by the contained rubber of the composite powder of above two kinds of method gained is consistent with the gel content of cross-linking type synthetic rubber latex in step a, and is consistent with the gel content of rubber latex behind the irradiation in step b.
In the preparation method's of described composite powder step a, cross-linking type synthetic rubber latex described in the Chinese patent application 00130386.4 that the cross-linking type synthetic rubber latex that uses is submitted on November 3rd, 2000 as the applicant, the gel content of this cross-linking type synthetic rubber latex (cross-linking type synthetic rubber latex) should be 80% weight or higher, is preferably 85% weight or higher.For this crosslinking-type rubber latex,, need not further cross-linking radiation and get final product drying and obtain rubber powder because the crosslinking degree of self is higher.The kind of cross-linking type synthetic rubber latex is selected from cross-linking type butylbenzene rubber latex, cross-linking type carboxylic styrene-butadiene rubber latex, cross-linking type content of polybutadiene rubber latex, crosslinking butadiene nitrile rubber latex, cross-linking type carboxy nitrile rubber latex, cross-linking type chloroprene rubber latex, crosslinking acrylate rubber latex etc.
Among the preparation method's of described composite powder the step b, to used rubber latex raw material without any restriction, rubber latex with middle preparation fully vulcanized powder rubber in the Chinese patent 00109217.0 of Chinese patent application 99125530.5 (publication number of its international patent application is WO01/40356) and application on June 15th, 2000 can be selected from natural rubber latex; styrene butadiene rubber latex; carboxylic styrene-butadiene rubber latex; paracril latex; carboxy nitrile rubber latex; content of polybutadiene rubber latex; chloroprene rubber latex; silicone rubber latex; the esters of acrylic acid rubber latex; vinylpyridiene-styrene-butadiene rubber latex; polyisoprene rubber latex; isoprene-isobutylene rubber latex; ethylene-propylene rubber(EPR) latex; thiorubber latex; Acrylester Butadiene Rubber latex; urethanes latex and fluoroelastomer latex etc.
In fact used rubber latex comprises the crosslinking-type rubber latex among the above-described step a among the described composite powder preparation process b, that is to say that crosslinking-type rubber latex can prepare composite powder of the present invention (as described in step a) without irradiation, also can prepare composite powder of the present invention (as step b) through irradiation.Just the gel content of rubber is higher than the former in the composite powder that obtains of the latter.
Solid content (drc) to rubber latex in two kinds of preparation processes of described composite powder is not particularly limited, and is generally 20～70% weight, is preferably 30～60% weight, more preferably 40～50% weight.
Among preparation method's step b of described composite powder, for the irradiance method of the irradiance method of rubber latex (comprise energetic ray source that crosslinking coagent, irradiation dose, irradiation are used etc.) with preparation fully vulcanized powder rubber in the Chinese patent 00109217.0 of Chinese patent application 99125530.5 (publication number of its international patent application is WO01/40356) and application on June 15th, 2000.In rubber latex, crosslinking coagent can be do not used, also crosslinking coagent can be used.Used crosslinking coagent is selected from simple function group crosslinking coagent, two functional group's crosslinking coagents, trifunctional crosslinking coagent, four-functional group crosslinking coagent or polyfunctional group crosslinking coagent and arbitrary combination thereof.The example of described simple function group crosslinking coagent includes, but is not limited to: (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate; The example of described two functional group's crosslinking coagents includes, but is not limited to: 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Vinylstyrene; The example of described trifunctional crosslinking coagent includes, but is not limited to: trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate; The example of described four-functional group crosslinking coagent includes, but is not limited to: tetramethylolmethane four (methyl) acrylate, ethoxyquin tetramethylolmethane four (methyl) acrylate; The example of described polyfunctional group crosslinking coagent includes, but is not limited to: Dipentaerythritol five (methyl) acrylate.In this article, " (methyl) acrylate " refers to acrylate or methacrylic ester.These crosslinking coagents can use in the mode of arbitrary combination, as long as they help sulfuration under irradiation.
The add-on of the above crosslinking coagent is generally the 0.1-10% weight into dried glue weight in the latex with the kind and different variation of prescription of rubber latex, is preferably 0.5-9% weight, more preferably 0.7-7% weight.
The energetic ray source is selected from cobalt source, ultraviolet or high-energy electron accelerator among preparation method's step b of described composite powder, preferred cobalt source.The dosage of irradiation can be 0.1～30Mrad, preferred 0.5～20Mrad.The dosage of irradiation is relevant with prescription with the kind of rubber latex.Generally speaking, irradiation dose should make the gel content behind the rubber latex radiation vulcanization reach 60% weight or higher, preferred 75% weight or higher, most preferably 80% weight or higher.
Above-described this composite powder, in the composition that itself and acrylic resin blend obtain, its powder particle presents special aggregation structure: promptly composite powder is dispersed in the acrylic resin as disperse phase, this disperse phase includes the special aggregate of being made up of rubber particles and inorganic particulate, and the structure of this aggregate is single or several inorganic particulate is wrapped in the middle of the rubber particles.The disperse phase of the composite powder in the acrylic resin also might include the rubber particles that disperses outside aggregate except including the aggregate of being made up of rubber particles and inorganic particulate, perhaps also include the inorganic particulate of discrete (not being wrapped in the rubber particles).These are dispersed in rubber particles discrete in the acrylic resin matrix and/or the aggregate of inorganic particulate and special construction also can produce certain synergistic effect, obtain result preferably.The composition that composite powder and acrylic resin blend are obtained solidifies the back section, and direct viewing can obtain reflecting the photo (as accompanying drawing 1) of this aggregation structure under transmission electron microscope.
This special aggregate (being that the inflexible inorganic particulate is wrapped in the aggregate of forming in the elastic rubber particles) that is dispersed in the acrylic resin, simultaneously because the synergy of nucleator, can significantly improve the acrylic resin flexible simultaneously, can also make it have good rigidity and thermotolerance.
For toughened polypropylene composition of the present invention, contained rubber and the inorganic particulate of composite powder wherein, no matter assemble or do not assemble, the particle diameter of its single particle is very little, as according to the described content of Chinese patent application 99125530.5 (publication number of its international patent application is WO01/40356), the particle diameter of single particle that can infer rubber is between 20～2000nm, and to have the one dimension mean sizes at least be 0.2～500nm to the single particle of inorganic particulate as mentioned above.The flexibility of rubber, the rigidity of inorganic particulate and the minimum size of single particle thereof probably are to cause composite powder to be dispersed into the reason of special state of aggregation in polypropylene, and concern little with rubber and inorganic particulate kind separately.The outstanding toughening effect that toughened polypropylene composition of the present invention can reach mainly is that composite powder is dispersed in special state of aggregation in the polypropylene matrix and the synergy of nucleator is brought, and does not lie in the kind of rubber or inorganic particulate.Therefore the rubber kind and/or the inorganic particulate kind of composite powder are unrestricted in the present invention.If but took into account consistency, the composite powder in the toughened polypropylene composition of the present invention is more excellent would be selected from the composite powder that contains styrene-butadiene rubber(SBR), Sodium Benzoate and inorganic particulate.
The preparation method of tenacity-increased profax resin of the present invention is: the polypropene composition that acrylic plastering and above-described composite powder is made high tenacity by melt blending.The weight ratio of composite powder and acrylic resin is (1～40): 100, be preferably (2～30): and 100, more preferably (3～20): 100.
In preparation process, the blending temperature of material is the temperature that acrylic plastering is processed used melt blending in the prior art, can decide according to the melt temperature of matrix acrylic plastering, should in the scope that not only guarantees the complete fusion of matrix acrylic plastering but also acrylic plastering is decomposed, select.In addition, according to the processing needs, can in the blend material, add the conventional auxiliary agent and the expanding material of acrylic plastering processing in right amount.
The employed melt blending equipment of present method is the general blending equipment in the rubber and plastic processing industry, can be mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.
Toughened polypropylene composition of the present invention by the toughness reinforcing acrylic resin of composite powder, has rigidity and thermotolerance preferably when having excellent shock resistance.Operating procedure is simple in this polypropene composition preparation process, and cost is lower.
Description of drawings
Accompanying drawing 1 is the transmission electron microscope Photomicrograph of the polypropene composition section of embodiment 5.Its magnification is 5,000 times.Bigger among the figure, erose dash area is to be dispersed in the styrene-butadiene rubber(SBR) particle in the plastic substrate and the aggregate of calcium carbonate particles, and point dark in the shade is the calcium carbonate particles that contains in styrene-butadiene rubber(SBR).
Embodiment
Further describe the present invention below in conjunction with embodiment, scope of the present invention is not subjected to the restriction of these embodiment.Scope of the present invention proposes in claims.
One, the preparation of toughner
Embodiment 1
Get solid content and be commercially available styrene-butadiene emulsion (Lanhua Latex Research and Development Centre of 45 weight %, the trade mark: butylbenzene-50, the rubber particles gel content is 82% weight in the emulsion) 3Kg places a container, nano-calcium carbonate slurries (nano Tyke, Beijing nanosecond science and technology company limited that adds 47.3 weight %, mean sizes 40～60nm) 715g and Sodium Benzoate on its granular one dimension of calcium carbonate particles are (commercially available, chemical pure) 169g stirs one hour until stirring.Mixed emulsion is by the spray-dryer spraying drying, and the inlet temperature of spray-dryer is 125 ℃～145 ℃, and temperature out is 45 ℃～60 ℃, collection dried butylbenzene-lime carbonate-Sodium Benzoate composite powder in cyclonic separator (
Composite powder 1).
Composite powder 1The weight ratio of middle styrene-butadiene rubber(SBR) and lime carbonate is 80: 20; The weight ratio of styrene-butadiene rubber(SBR) and Sodium Benzoate is 89: 11; Wherein Sodium Benzoate and (gross dry weight of styrene-butadiene rubber(SBR) and lime carbonate) are than being 10: 100.
Embodiment 2
Except the consumption of styrene-butadiene emulsion, lime carbonate and Sodium Benzoate was different, all the other conditions were all with embodiment 1.The consumption of styrene-butadiene emulsion is 1.2kg, and the calcium carbonate serosity consumption is 1.7kg, and the Sodium Benzoate consumption is 135g, spray-dried
Composite powder 2The weight ratio of styrene-butadiene rubber(SBR) and lime carbonate is 40: 60 in this sample, and the weight ratio of styrene-butadiene rubber(SBR) and Sodium Benzoate is 80: 20; Wherein Sodium Benzoate and (gross dry weight of styrene-butadiene rubber(SBR) and lime carbonate) are than being 10: 100.
Embodiment 3
Except the consumption of styrene-butadiene emulsion, lime carbonate and Sodium Benzoate was different, all the other conditions were all with embodiment 1.The styrene-butadiene emulsion consumption is 750g, and the calcium carbonate serosity consumption of 47.3 weight % is 178.4g, and the Sodium Benzoate consumption is 93.8g, spray-dried
Composite powder 3The weight ratio of styrene-butadiene rubber(SBR) and lime carbonate is 80: 20 in this sample; The weight ratio of styrene-butadiene rubber(SBR) and Sodium Benzoate is 78: 22; Wherein Sodium Benzoate and (gross dry weight of styrene-butadiene rubber(SBR) and lime carbonate) are than being 22: 100.
Embodiment 4
Commercially available styrene-butadiene emulsion (with the embodiment 1) 1.5Kg that gets solid content and be 45 weight % places a container, under agitation drips 2% weight Viscoat 295 13.5g, after being added dropwise to complete, continues to stir one hour.Latex cobalt-60 radiosterilize, dosage are 2.0Mrad.Rubber particles gel content 91% weight in the emulsion behind the irradiation.To add while stirring in the latex of calcium carbonate serosity (with embodiment 1) behind irradiation of Sodium Benzoate (with embodiment 1) and solid content 47.3% weight, after adding, continue to stir one hour.Wherein the consumption of Sodium Benzoate is 84.4g, and the consumption of the calcium carbonate serosity of 47.3% weight is 357g.Mixed latex is by the spray-dryer spraying drying, and the inlet temperature of spray-dryer is 125 ℃～145 ℃, and temperature out is 45 ℃～60 ℃, collection dried butylbenzene-lime carbonate-Sodium Benzoate composite powder in cyclonic separator (
Compound Powder 4).The weight ratio of styrene-butadiene rubber(SBR) and lime carbonate is 80: 20 in this sample; The weight ratio of styrene-butadiene rubber(SBR) and Sodium Benzoate is 89: 11; Wherein Sodium Benzoate and (gross dry weight of styrene-butadiene rubber(SBR) and lime carbonate) are than being 10: 100.
Comparative example 1
Getting solid content is commercially available styrene-butadiene emulsion (with the embodiment 1) 1kg of 45 weight %, add Sodium Benzoate 45g, the back continues to stir one hour, mixed emulsion is by the spray-dryer spraying drying, the inlet temperature of spray-dryer is 125 ℃～145 ℃, temperature out is 45 ℃～60 ℃, collection dried compound butylbenzene-Sodium Benzoate powdered rubber in cyclonic separator (
Powder 1).The weight ratio of styrene-butadiene rubber(SBR) and Sodium Benzoate is 100: 10 (91: 9) in this sample.
Two, the preparation of polypropene composition
Embodiment 5
Adopt
Composite powder 1With polypropylene powder (Daqing Huake Co., Ltd., the trade mark: B-200) and antioxidant 1010 (Switzerland vapour Ba Jiaji production) mix, be 100 parts in the parts by weight of plastics, it specifically consists of: 100 parts of polypropylene,
Composite powder 110 parts, other sneaks in polypropylene and composite powder gross weight is the antioxidant 1010 of 100 part of 0.25 weight part, in high speed agitator, mixed one minute, with the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively 165 ℃, 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ (head temperature).Pellet is made the standard batten with injection, and the performance of polypropene composition that obtains the composite powder modification after tested is as shown in table 1.
Embodiment 6
With among the embodiment 5
Composite powder 1Change into
Composite powder 2, all the other conditions are identical with embodiment 5, and the pellet that melt blending obtains is made the standard batten through injection moulding, carries out various Mechanics Performance Testings, the results are shown in table 1.
Comparative example 2
After polypropylene powder (with embodiment 5) and antioxidant 1010 (Switzerland vapour Ba Jiaji production) mix with 100: 0.25 weight ratio, by with the same melt blending condition granulation of embodiment 5, pellet is extruded injection moulding make the standard batten, carry out various Mechanics Performance Testings, the results are shown in table 1.
Comparative example 3
Adopt in the comparative example 1
Powder 1Replace
Composite powder 1, all the other conditions are identical with embodiment 5.The pellet that melt blending obtains is made the standard batten with injection, carry out various Mechanics Performance Testings, the results are shown in table 1.
Table 1
| Project | Polypropylene | Composite powder * | ? Powder 1 * | Tensile strength MPa | Tension fracture elongation rate % | Izod notched Izod impact strength (23 ℃) J/m | Flexural strength MPa | Modulus in flexure GPa | Heat-drawn wire ℃ |
| Embodiment 5 | ?100 | ????10 | ????- | ??34.6 | ????120 | ????221 | ??36.0 | ??1.57 | ??116.4 |
| Embodiment 6 | ?100 | ????10 | ????- | ??36.5 | ????109 | ????236 | ??38.9 | ??1.70 | ??120.5 |
| Comparative example 2 | ?100 | ????-- | ????- | ??36.5 | ????145 | ????64.4 | ??36.2 | ??1.54 | ??106.8 |
| Comparative example 3 | ?100 | ????-- | ????10 | ??33.9 | ????119 | ????186 | ??35.9 | ??1.53 | ??116.0 |
| Testing standard | ?- | ????-- | ????＝ | ??GB/T ??1040 | ????GB/T ????1040 | ????GB ????1843 | ??GB/T ??9341 | ??GB/T ??9341 | ??GB ??1634 |
Annotate: each component content is parts by weight in the table 1; Wherein the weight ratio of nucleator and (styrene-butadiene rubber(SBR) and lime carbonate gross dry weight) is 10: 100 in the composite powder;
Powdered rubber 1The weight ratio of middle nucleator and styrene-butadiene rubber(SBR) is 10: 100.
Embodiment 7
With among the embodiment 1
Composite powder 1With polypropylene powder (the Luoyang petroleum chemical plant trade mark: B200) and the oxidation inhibitor mix, count with weight part concrete the composition: 100 parts of polypropylene,
Composite powder 15 parts, other sneaks in polypropylene and composite powder gross weight is the antioxidant 1010 of 100 part of 0.25 weight part, uses the ZSK-25 twin screw extruder blend granulation of German WP company respectively, each section of forcing machine temperature is respectively 165 ℃, and 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ (head temperature).The pellet that melt blending obtains is made the standard batten with injection, and the performance of polypropene composition that obtains the composite powder modification after tested is as shown in table 2.
Embodiment 8
With among the embodiment 7
Composite powder 1Consumption change 10 parts into, all the other conditions are identical with embodiment 7, the pellet that melt blending obtains is made the standard batten through injection moulding, carries out various Mechanics Performance Testings, the results are shown in table 2.
Comparative example 4
After polypropylene powder (with embodiment 7) and oxidation inhibitor (with embodiment 7) mixed with weight ratio at 100: 0.25, through with embodiment 7 identical extrude, injecting condition makes the standard batten, carries out various Mechanics Performance Testings, the results are shown in table 2.
Table 2
| Project | ? Composite powder?? End 1 | Tensile strength MPa | Tension fracture elongation rate % | Izod notched Izod impact strength (23 ℃) J/m | Flexural strength MPa | Modulus in flexure GPa | Heat-drawn wire ℃ |
| Embodiment 7 | ????5 | ??36.6 | ????138 | ????413 | ??33.9 | ??1.46 | ??121.7 |
| Embodiment 8 | ????10 | ??35.0 | ????130 | ????414 | ??34.3 | ??1.55 | ??114.6 |
| Comparative example 4 | ????0 | ??35.9 | ????223 | ????86.9 | ??31.2 | ??1.36 | ??109.8 |
| Testing standard | ????- | ??GB/T ??1040 | ?GB/T?1040 | ????GB?1843 | ??GB/T ??9341 | ??GB/T ??9341 | ??GB?1634 |
Annotate: each component content is parts by weight in the table 2;
Composite powder 1The weight ratio of middle styrene-butadiene rubber(SBR) and lime carbonate is 80: 20, and the weight ratio of styrene-butadiene rubber(SBR) and Sodium Benzoate is 89: 11.
Embodiment 9
With among the embodiment 4
Composite powder 4With polypropylene powder (with embodiment 7) and oxidation inhibitor mix, count with weight part concrete the composition: 100 parts of polypropylene,
Composite powder 45 parts, other sneaks in polypropylene and composite powder gross weight is the antioxidant 1010 of 100 part of 0.25 weight part, uses the ZSK-25 twin screw extruder blend granulation of German WP company respectively, each section of forcing machine temperature is respectively 165 ℃, and 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ (head temperature).The pellet that melt blending obtains is made the standard batten with injection, and the performance of polypropene composition that obtains the composite powder modification after tested is as shown in table 3.
Embodiment 10
With among the embodiment 9
Composite powder 4Consumption change 10 parts into, all the other conditions are identical with embodiment 9, the pellet that melt blending obtains is made the standard batten through injection moulding, carries out various Mechanics Performance Testings, the results are shown in table 3.
Table 3
| Project | ? Composite powder?? End 8 | Tensile strength | Tension fracture elongation rate | Izod notched Izod impact strength (23 ℃) | Izod notched Izod impact strength (20 ℃) | Flexural strength | Modulus in flexure | Heat-drawn wire |
| Unit | MPa | ????％ | ????J/m | ????J/m | ??MPa | ??GPa | ??℃ | |
| Embodiment 9 | ????5 | 36.6 | ????166 | ????451 | ????27.5 | ??35.2 | ??1.54 | ??119.8 |
| Embodiment 10 | ????10 | 34.4 | ????163 | ????416 | ????28.7 | ??32.9 | ??1.48 | ??119.3 |
| Comparative example 4 | ????0 | 35.9 | ????223 | ????86.9 | ????27.1 | ??31.2 | ??1.36 | ??109.8 |
| Testing standard | ????- | GB/T 1040 | ????GB/T ????1040 | ???GB?1843 | ???GB?1843 | ??GB/T ??9341 | ??GB/T ??9341 | ??GB ??1634 |
Annotate: each component content is parts by weight in the table 3;
Composite powder 4The weight ratio of middle styrene-butadiene rubber(SBR) and lime carbonate is 80: 20, and the weight ratio of styrene-butadiene rubber(SBR) and Sodium Benzoate is 89: 11.
Embodiment 11
With among the embodiment 3
Composite powder 3With polypropylene powder (with embodiment 7) and oxidation inhibitor mix, count with weight part concrete the composition: 100 parts of polypropylene,
Composite powder 310 parts, other sneaks in polypropylene and composite powder gross weight is the antioxidant 1010 of 100 part of 0.25 weight part, use the ZSK-25 twin screw extruder blend granulation of German WP company respectively, each section of forcing machine temperature is respectively 165 ℃, 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ (head temperature).The pellet that melt blending obtains is made the standard batten with injection, and the performance of polypropene composition that obtains the composite powder modification after tested is as shown in table 4.
Table 4
| Project unit | Polypropylene | Composite powder | Tensile strength MPa | Tension fracture elongation rate % | Izod notched Izod impact strength (23 ℃) J/m | Izod notched Izod impact strength (20 ℃) J/m | Flexural strength MPa | Modulus in flexure GPa | Heat-drawn wire ℃ | |
| Rubber: inorganic particulate | Rubber: nucleator | |||||||||
| Embodiment 11 | ?100 | ?80∶20 | ?78∶22 | ??34.6 | ??134 | ??309 | ????30.0 | ??34.1 | ????1.53 | ??120.4 |
| Embodiment 8 | ?100 | ?80∶20 | ?89∶11 | ??35.0 | ??130 | ??414 | ????31.5 | ??34.3 | ????1.55 | ??114.6 |
| Comparative example 4 | ?100 | ?-- | ?-- | ??35.9 | ??223 | ??86.9 | ????27.1 | ??31.2 | ????1.36 | ??109.8 |
| Testing standard | ?- | ?-- | ?-- | ??GB/T ??1040 | ??GB/T ??1040 | ??GB ??1843 | ????GB ????1843 | ??GB/T ??9341 | ????GB/T ????9341 | ??GB ??1634 |
Annotate: each component content is parts by weight in the table 4; The composite powder addition is 10 weight parts among the embodiment.
Comparative example 5
With in the comparative example 1
Powder 1(cover westernization factory with the nano-calcium carbonate calcium powder, mean sizes 40～60nm) on its granular one dimension of calcium carbonate particles and polypropylene powder (with embodiment 7) and antioxidant 1010 (Switzerland vapour Ba Jiaji production) mix, weight fraction in plastics is 100 parts, it specifically consists of: 100 parts of polypropylene
Powder 18 parts, 2 parts of nano-calcium carbonates, other sneaks in polypropylene and powdered rubber gross weight is the antioxidant 1010 of 100 part of 0.25 weight part, mixes in high speed agitator one minute, with the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively 165 ℃, 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ (head temperature).Pellet is made the standard batten with injection, and the performance that obtains modified polypropylene plastic after tested is as shown in table 5.
Comparative example 6
Adopt nano-calcium carbonate calcium powder (with comparative example 5) to replace
Composite powder 1, all the other conditions are identical with embodiment 8.Pellet is made the standard batten with injection, and the performance that obtains modified polypropylene plastic after tested is as shown in table 5.
Table 5
| Project | Embodiment 8 | Embodiment 10 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Testing standard | ||
| Polypropylene | ????100 | ????100 | ????100 | ????100 | ????100 | ?-- | ||
| Composite powder | Rubber: inorganic particulate | ????80∶20 | ????80∶20 | ????-- | ????-- | ????-- | ?-- | |
| Rubber: nucleator | ????89∶11 | ????89∶11 | ????-- | ????-- | ????-- | ?-- | ||
| Powder 1 (rubber: nucleator) | ????-- | ????-- | ????-- | ????8 | ????-- | ?-- | ||
| Inorganic particulate | ????-- | ????-- | ????-- | ????2 | ????10 | ?-- | ||
| Tensile strength | MPa | ????35.0 | ????34.4 | ????35.9 | ????34.9 | ????35.9 | ?GB/T1040 | |
| Tension fracture elongation rate | ％ | ????130 | ????163 | ????223 | ????66 | ????191 | ?GB/T1040 | |
| Izod notched Izod impact strength (23 ℃) | J/m | ????414 | ????416 | ????86.9 | ????265 | ????273 | ?GB/T1843 | |
| Flexural strength | MPa | ????34.3 | ????32.9 | ????31.2 | ????30.5 | ????30.4 | ?GB/T9341 | |
| Modulus in flexure | GPa | ????1.55 | ????1.48 | ????1.36 | ????1.34 | ????1.29 | ?GB/T9341 | |
| Heat-drawn wire | ℃ | ????114.6 | ????119.3 | ????109.8 | ????121.4 | ????105.9 | ?GB?1634 | |
Annotate: each component content is parts by weight in the table 5; The composite powder addition is 10 weight parts among the embodiment.In the table in the composite powder weight ratio of nucleator and (styrene-butadiene rubber(SBR) and lime carbonate gross dry weight) be 10: 100;
Powder 1The weight ratio of middle nucleator and styrene-butadiene rubber(SBR) is 10: 100.
As can be seen, utilize composite powder tenacity-increased profax resin, contain the powdered rubber of nucleator, use the simple blend of inorganic particulate or use powdered rubber and inorganic particulate to come modified polypropylene resin merely than simple use under same consumption, can make acrylic resin obtain higher toughness, also can improve rigidity and thermotolerance simultaneously.
Claims (15)
1. a polypropene composition is characterized in that it includes the following component of blend: acrylic resin and composite powder; The ratio of composite powder gross weight and acrylic resin gross weight is (1～40): 100; Wherein said composite powder is got by the method preparation that includes one of following steps:
A. the slurries of inorganic particulate, the aqueous solution and the cross-linking type synthetic rubber latex of water-soluble plastic nucleator are mixed, obtain mixed emulsion, again with this mixed emulsion drying;
B. adding or do not adding under the situation of crosslinking coagent, after adopting the energetic ray source to carry out radiation vulcanization the rubber latex, again the slurries of inorganic particulate, the aqueous solution of water-soluble plastic nucleator and the rubber latex behind the irradiation are mixed, obtain mixed emulsion, again with this mixed emulsion drying;
Above-described inorganic particulate slurries are the suspension of inorganic particulate in water; Described inorganic particulate is selected from one of following material or its combination: metal simple-substance, metal alloy, metal oxide, metal or non-metal nitride, non-metallic carbide, nonmetal oxide, metal hydroxides, metallic salt and ore;
It is 0.2～500nm that its particle has the one dimension mean sizes at least;
In described rubber latex or the cross-linking type synthetic rubber latex in the weight of contained rubber and the inorganic particulate slurries weight ratio of contained inorganic particulate be 90: 10～40: 60;
In described rubber latex or the cross-linking type synthetic rubber latex in the weight of contained rubber and the described nucleator aqueous solution weight ratio of contained nucleator be 95: 5～70: 30.
2. polypropene composition according to claim 1 is characterized in that the water-soluble plastic nucleator among the described composite powder preparation method is a Sodium Benzoate.
3. polypropene composition according to claim 1 is characterized in that the weight ratio of contained nucleator in the weight of contained rubber in rubber latex among the described composite powder preparation method or the cross-linking type synthetic rubber latex and the described nucleator aqueous solution is 90: 10～70: 30.
4. polypropene composition according to claim 1 is characterized in that the weight ratio of contained inorganic particulate in the weight of contained rubber in rubber latex among the described composite powder preparation method or the cross-linking type synthetic rubber latex and the described inorganic particulate slurries is 80: 20～40: 60.
5. polypropene composition according to claim 1 is characterized in that among the described composite powder preparation method that it is 1.0～100nm that its particle of inorganic particulate has the one dimension mean sizes at least.
6. polypropene composition according to claim 1 is characterized in that the inorganic particulate among the described composite powder preparation method is selected from one of following material or its combination: gold, silver, copper, iron, au-alloy, silver alloys, copper alloy, iron alloy, aluminum oxide, magnesium oxide, titanium dioxide, ferric oxide, Z 250, silver suboxide, zinc oxide, aluminium nitride, silicon nitride, silicon carbide, silicon-dioxide, aluminium hydroxide, magnesium hydroxide, lime carbonate, barium sulfate, calcium sulfate, silver chloride, asbestos, talcum, kaolin, mica, feldspar, wollastonite or polynite.
7. polypropene composition according to claim 1, the gel content that it is characterized in that the cross-linking type synthetic rubber latex described in the step a among the described composite powder preparation method is 80% weight or higher.
8. polypropene composition according to claim 7 is characterized in that the described cross-linking type synthetic rubber of step a latex is selected from cross-linking type butylbenzene rubber latex, cross-linking type carboxylic styrene-butadiene rubber latex, cross-linking type content of polybutadiene rubber latex, crosslinking butadiene nitrile rubber latex, cross-linking type carboxy nitrile rubber latex, cross-linking type chloroprene rubber latex or crosslinking acrylate rubber latex among the described composite powder preparation method.
9. polypropene composition according to claim 1 is characterized in that the described rubber latex of step b is selected from natural rubber latex among the described composite powder preparation method; styrene butadiene rubber latex; carboxylic styrene-butadiene rubber latex; paracril latex; carboxy nitrile rubber latex; content of polybutadiene rubber latex; chloroprene rubber latex; silicone rubber latex; esters of acrylic acid rubber latex; vinylpyridiene-styrene-butadiene rubber latex; polyisoprene rubber latex; isoprene-isobutylene rubber latex; ethylene-propylene rubber(EPR) latex; thiorubber latex; Acrylester Butadiene Rubber latex; urethanes latex or fluoroelastomer latex.
10. polypropene composition according to claim 1, the gel content that it is characterized in that rubber in the described composite powder is 60% weight or higher.
11. polypropene composition according to claim 10, the gel content that it is characterized in that rubber in the described composite powder is 75% weight or higher.
12. polypropene composition according to claim 1 is characterized in that the described composite powder gross weight and the ratio of acrylic resin gross weight are (2～30): 100.
13. polypropene composition according to claim 1 is characterized in that contained rubber is styrene-butadiene rubber(SBR) in described rubber latex or the cross-linking type synthetic rubber latex.
14. according to the described polypropene composition of one of claim 1～13, it is characterized in that being dispersed with in the acrylic resin aggregate of being made up of rubber particles and inorganic particulate, the structure of this aggregate is single or several inorganic particulates are wrapped in the middle of the rubber particles.
15. a preparation method who prepares the described polypropene composition of one of claim 1～14 is characterized in that described acrylic plastering and described composite powder melt blending are made polypropene composition.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423636B (en) * | 2007-10-31 | 2011-08-03 | 中国石油化工股份有限公司 | High rigid and high heat tolerant polypropylene composition and preparation method thereof |
| CN101412828B (en) * | 2007-10-19 | 2011-12-28 | 中国石油化工股份有限公司 | Modified polypropylene composition and preparation thereof |
| CN103304897A (en) * | 2013-06-24 | 2013-09-18 | 苏州新区佳合塑胶有限公司 | Plastic for vacuum flask housing, and preparation method thereof |
| CN103788474A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Binary composite polypropylene nucleating agent, preparation method of binary composite polypropylene nucleating agent and polypropylene composition prepared from binary composite polypropylene nucleating agent |
| CN107118448A (en) * | 2017-05-08 | 2017-09-01 | 安徽省中车科技有限公司 | A kind of elastomeric material for traffic indication board shell |
| CN107565501A (en) * | 2017-08-16 | 2018-01-09 | 国网天津市电力公司电力科学研究院 | The implementation method at high-performance polypropylene/silicon rubber interface in cable connector |
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2003
- 2003-07-02 CN CN 03148380 patent/CN1233722C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412828B (en) * | 2007-10-19 | 2011-12-28 | 中国石油化工股份有限公司 | Modified polypropylene composition and preparation thereof |
| CN101423636B (en) * | 2007-10-31 | 2011-08-03 | 中国石油化工股份有限公司 | High rigid and high heat tolerant polypropylene composition and preparation method thereof |
| CN103788474A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Binary composite polypropylene nucleating agent, preparation method of binary composite polypropylene nucleating agent and polypropylene composition prepared from binary composite polypropylene nucleating agent |
| CN103788474B (en) * | 2012-10-30 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of binary composite polypropylene nucleator, preparation method and polypropene composition prepared therefrom |
| CN103304897A (en) * | 2013-06-24 | 2013-09-18 | 苏州新区佳合塑胶有限公司 | Plastic for vacuum flask housing, and preparation method thereof |
| CN107118448A (en) * | 2017-05-08 | 2017-09-01 | 安徽省中车科技有限公司 | A kind of elastomeric material for traffic indication board shell |
| CN107565501A (en) * | 2017-08-16 | 2018-01-09 | 国网天津市电力公司电力科学研究院 | The implementation method at high-performance polypropylene/silicon rubber interface in cable connector |
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