CN105330957A - Polypropylene composition and preparation method thereof - Google Patents
Polypropylene composition and preparation method thereof Download PDFInfo
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- CN105330957A CN105330957A CN201410393456.9A CN201410393456A CN105330957A CN 105330957 A CN105330957 A CN 105330957A CN 201410393456 A CN201410393456 A CN 201410393456A CN 105330957 A CN105330957 A CN 105330957A
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Abstract
The invention relates to a polypropylene composition and preparation method thereof. The polypropylene composition contains polypropylene resin, a polymer composition and a damage resistant master batch; the polymer composition contains 40wt%-70wt% of crystallized polypropylene A and 30wt%-60wt% of a ethane-propylene elastic copolymer B, the molecular weight distribution indices of the polymer composition and the crystallized polypropylene A are more than 4, and ratio between a fusion index of the polymer composition to a fusion index of the crystallized polypropylene A is 0.7-1.3. Products prepared by the polypropylene composition have a good anti-stress whitening property and a higher damage resistant performance, and the products are especially suitable for industries of automobile, household electrical appliance, etc.
Description
Technical field
The present invention relates to a kind of polypropene composition, prepare the method for this polypropene composition, and the polypropene composition prepared by the method.
Background technology
In recent years, along with people in use keep the requirement of good appearance day by day to improve to goods, preparation has favorable comprehensive mechanical property, can in use keep again the polypropylene material of good appearance to become the development trend of polypropylene in automobile, field of household appliances application simultaneously.
In order to improve polyacrylic shock resistance to meet service requirements, conventional method is undertaken blended by polypropylene and rubber or elastomerics (as ethylene-propylene rubber(EPR), polyolefin elastomer etc.).But this method has some limitations, one of them is exactly produce detrimentally affect to modified polypropene surface property (as scratch resistant, stress whitening etc.).
As everyone knows, studies on scratch resistance of PP can be poor, and be easy under external force be scratched, toughner such as adding of rubber, elastomerics etc. then can further deteriorated polyacrylic scratch resistance.Therefore, can be restricted during the field that appearance requirement is higher when this type of tenacity-increased profax is applied to electric appliance casing, automotive upholstery etc., particularly be applied to automotive upholstery, as dashboard, door-plate etc.
For solving the problem, US6541568B1 discloses a kind of by adding the formula improving polyacrylic scratch resistance containing a large amount of cinnamic multipolymer.But the manufacturing expense of styrene copolymer is expensive, the cost of polypropylene blend significantly can be increased.In addition, this styrene copolymer is limited to polyacrylic scratch resistance improvement result.
CN101173074A discloses a kind of by adding aliphatic amide lubricant polypropylene composite improving its scratch resistance and preparation method thereof; CN1580115A discloses a kind of by adding mar-proof talcum powder polypropylene composite improving scratch resistance and preparation method thereof; CN1631960A disclose a kind of by adding high rigidity, high tenacity is mar-proof talcum powder polypropylene composite improving its scratch resistance and preparation method thereof.But these methods need the consumption strengthening lubricant along with the increase of rubber content, and the simple improvement of consumption to scratch resistance by increasing lubricant is limited.In addition, the increase of lubricant quantity also can cause the problems such as lubricant precipitation, surfaces of tacky frostization, life-time service lubricant effect variation.
In addition, because polypropylene own structural characteristics causes polypropylene to there is stress whitening problem.When being subject to External Force Acting, as Shooting Technique eject link or goods are subject to external force collision etc., material can produce crazing in corresponding position and expand crazing region to absorb energy, and crazing region produces and expansion will cause product to turn white, and affects outward appearance or produces unacceptable product.In addition, when being subject to external force scraping, stress whitening can cause the decline of scratch resistant performance further.Adding of rubber or filler, the further reduction of stress-whitening resistance may be caused.
For solving the problem, CN101709124A discloses a kind of polypropylene material and manufacture method thereof of anti-folding stress whitening resistant, improves toughness and the stress-whitening resistance energy of material by adding elastomerics and the homemade resistance to stress master batch that turns white in high impact resistance polypropylene base material.Although described material demonstrates very high shock resistance, Co-polypropylene consumption is too many, causes the rigidity of material to decline, while stress-whitening resistance also do not expect so high.CN101058655B discloses a kind of resistance to stress and turns white and the filling modified polypropylene material of stress cracking, stress whitening problem is improved by polyethylene, but what it adopted is block copolymerization polypropylene, and Co-polypropylene consumption is too much, causes improving the standard of material stress-whitening resistance limited.
Therefore, for how to improve its stress-whitening resistance while Reinforced Polypropylene scratch resistance, still there is no good method at present.
Summary of the invention
The object of the invention is to improve the scratch resistance of polypropylene articles prepared therefrom and the problem of stress-whitening resistance to overcome existing polypropene composition simultaneously, a kind of polypropene composition and preparation method thereof is provided.
The invention provides a kind of polypropene composition, this polypropene composition contains acrylic resin, polymer composition and damage resistant master batch, and described polymer composition contains:
The crystalline polypropylene A of (a) 40-70 % by weight, this crystalline polypropylene A is selected from alfon and/or random copolymer of propylene, with the gross weight of propylene random co-polymer for benchmark, this propylene random co-polymer contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 82-99.9 % by weight, the ethylene unit unit of 0-6 % by weight and 0-12 % by weight, and ethylene unit unit is 0.1-18 % by weight with the total content of the alpha-olefin structural unit with 4-10 carbon atom, and
The ethylene-propylene elastomeric multipolymer B of (b) 30-60 % by weight, with the gross weight of ethylene-propylene elastomeric multipolymer B for benchmark, this ethylene-propylene elastomeric multipolymer B contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 60-92 % by weight, the ethylene unit unit of 8-25 % by weight and 0-15 % by weight
Wherein, the molecular weight distributing index of described polymer composition and described crystalline polypropylene A is all greater than 4; The melting index of described polymer composition is 0.7-1.3 with the ratio of the melting index of described crystalline polypropylene A.
Present invention also offers the preparation method of above-mentioned polypropene composition, the method comprises the following steps:
(1) under the first olefin polymerization conditions, by the first monomer a and the ziegler natta catalyst contact reacts with high stereoselective, and remove unreacted monomer the mixture obtained after contact reacts, obtain the first mixture containing crystalline polypropylene A, wherein, described first monomer a contains propylene and optional ethene and/or has the alpha-olefin of 4-10 carbon atom;
(2) under alkene gas-phase polymerization condition, described the first mixture contact reacts containing crystalline polypropylene A that second comonomer b and step (1) are obtained, obtain the second mixture containing crystalline polypropylene A and ethylene-propylene elastomeric multipolymer B, and unreacted monomer is removed from this second mixture, obtain polymer composition, wherein, described second comonomer b contains propylene and ethene and/or has the alpha-olefin of 4-10 carbon atom;
(3) polymer composition, the damage resistant master batch that will obtain in acrylic resin, step (2), and optional polyethylene, mineral filler and toughner are dry mixed, and carry out melt blending by being dry mixed the mixture obtained.
In polypropene composition provided by the invention, the rubber phase particle diameter in polymer composition is less and be uniformly dispersed, and presents good consistency, make the goods anti-impact successful formed by polypropene composition of the present invention with acrylic resin; Damage resistant master batch also can be dispersed in acrylic resin, and there is not the problem that sample surfaces is clamminess.The goods that polypropene composition of the present invention is made not only have good stress-whitening resistance and also have higher scratch resistant performance, thus are specially adapted to the industry such as automobile, household electrical appliances.
In addition, the preparation technology of polypropene composition of the present invention is simple, easy handling, is suitable for industrial applications.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing 1 is the dynamic mechanical analysis curve of the polymer composition with reference to preparation example 1 preparation, and characteristic feature is at the temperature of-60 DEG C to 20 DEG C, have two glass transition points (Tg);
Accompanying drawing 2 is the dynamic mechanical analysis curve of polymer composition prepared by preparation example 1, and characteristic feature is at the temperature of-60 DEG C to 20 DEG C, have a glass transition point (Tg);
Accompanying drawing 3 is the atomic force microscope images of polymer composition prepared by preparation example 1, shows that component (b) is highly dispersed in composition with the particle diameter of 0.3 micron.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of polypropene composition, this polypropene composition contains acrylic resin, polymer composition and damage resistant master batch, and described polymer composition contains:
The crystalline polypropylene A of (a) 40-70 % by weight, this crystalline polypropylene A is selected from alfon and/or random copolymer of propylene, with the gross weight of propylene random co-polymer for benchmark, this propylene random co-polymer contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 82-99.9 % by weight, the ethylene unit unit of 0-6 % by weight and 0-12 % by weight, and ethylene unit unit is 0.1-18 % by weight with the total content of the alpha-olefin structural unit with 4-10 carbon atom, and
The ethylene-propylene elastomeric multipolymer B of (b) 30-60 % by weight, with the gross weight of ethylene-propylene elastomeric multipolymer B for benchmark, this ethylene-propylene elastomeric multipolymer B contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 60-92 % by weight, the ethylene unit unit of 8-25 % by weight and 0-15 % by weight
Wherein, the molecular weight distributing index of described polymer composition and described crystalline polypropylene A is all greater than 4; The melting index of described polymer composition is 0.7-1.3 with the ratio of the melting index of described crystalline polypropylene A.
In the preferred case, described polymer composition obtains with continuous polymerization under existing at the ziegler natta catalyst with high stereoselective.Described continuous polymerization refers to the step that preparation process comprises at least two orders and carries out, wherein, component (a) (i.e. crystalline polypropylene A) and component (b) (i.e. ethylene-propylene elastomeric multipolymer B) are prepared separately in a separate step, and, except the first step, a rear step is carried out under the established polymkeric substance of previous step and the existence of catalyzer that uses in a previous step.
Under above-mentioned preferable case, because described polymer composition adopts the ziegler natta catalyst with high stereoselective to obtain, the molecular weight distribution of its molecular weight distribution and its component (a) is all greater than 4, be preferably greater than 4.5, be more preferably 4.5-20 (" polypropylene handbook " (Chemical Industry Press, in June, 2008 first version, the 15th page).In the present invention, molecular weight distribution represents with the ratio of weight-average molecular weight with number-average molecular weight.
In the present invention, the alpha-olefin of the described 4-10 of a having carbon atom can for this area commonly use various can with the compound of propylene and ethene generation copolymerization, the example can be but be not limited to: at least one in butylene (as 1-butylene), amylene (as 1-amylene), 4-methyl-1-pentene, hexene (as 1-hexene), heptene (as 1-heptene) and octene (as 1-octene), most preferably is 1-butylene.
In described polymer composition, described crystalline polypropylene A is at least one in alfon and random copolymer of propylene.With the gross weight of propylene random co-polymer for benchmark, the alpha-olefin structural unit with 4-10 carbon atom of this propylene random co-polymer preferably containing the propylene structural unit of 97-99.9 % by weight, the ethylene unit unit of 0-1 % by weight and 0-2 % by weight, and ethylene unit unit is 0.1-3 % by weight with the total content of the alpha-olefin structural unit with 4-10 carbon atom.Under above-mentioned preferable case, the fusing point of described crystalline polypropylene A is greater than 150 DEG C, makes described polymer composition have the fusing point being greater than 150 DEG C, thus demonstrates good resistance toheat.Further preferably, described crystalline polypropylene A is alfon, and under this preferable case, described polymer composition has good rigidity and resistance toheat concurrently.
In described polymer composition, described crystalline polypropylene A can, containing the more structural unit derived to other olefin comonomers, can make described polymer composition demonstrate better toughness like this.In described polymer composition, described ethylene-propylene elastomeric multipolymer B can containing a small amount of alpha-olefin structural unit with 4-10 carbon atom, such as, with the gross weight of ethylene-propylene elastomeric multipolymer B for benchmark, described ethylene-propylene elastomeric multipolymer B can contain the alpha-olefin structural unit with 4-10 carbon atom of 0.1-15 % by weight, 0.1-5 % by weight or 0.1-3 % by weight.Under preferable case, described ethylene-propylene elastomeric multipolymer B does not comprise the alpha-olefin structural unit with 4-10 carbon atom substantially; Further preferably, with the gross weight of described ethylene-propylene elastomeric multipolymer B for benchmark, described ethylene-propylene elastomeric multipolymer B contains the propylene structural unit of 75-92 % by weight and the ethylene unit unit of 8-25 % by weight; Still more preferably, described ethylene-propylene elastomeric multipolymer B contains the ethylene unit unit of 10-18 % by weight and the propylene structural unit of 82-90 % by weight.
In the present invention, the melting index of described polymer composition is 0.7-1.3 with the ratio of the melting index of described crystalline polypropylene A, is preferably 0.75-1.2.Particularly, the melting index of described polymer composition can be 0.1-100g/10min, is preferably 0.5-50g/10min.In the present invention, melting index measures according to ASTMD1238-99 method.
In described polymer composition, described polymer composition can be observed by atomic force microscope and there is two phase structure.Described ethylene-propylene elastomeric multipolymer B is preferably less than the Granular composite of 0.5 μm in described polymer composition with median size.In the present invention, described median size (i.e. granular size) is determined by atomic force microscopy.
In the present invention, the mist degree of described polymer composition is preferably less than 60%, is more preferably less than 40%, is preferably less than 30% further.Described mist degree records according to ASTMD1003 method, the result namely recorded on the injected sample thin slice of 1mm.
In the present invention, described polymer composition has a glass transition point at the temperature of-60 DEG C to 20 DEG C.
In the present invention, with the gross weight of polymer composition for benchmark, this polymer composition can also contain the nucleator of 0.1-1 % by weight.Described nucleator can be the nucleator that various this area routine uses, such as: two (2,4-di-tert-butyl-phenyl) sodium phosphate, 2,2 ’ ?methylene radical-two (4,6-di-n-butyl phenol) the aryl phosphoric acids salt nucleator such as sodium phosphate, methylene-bis (2,4-di-tert-butyl-phenyl) aluminum phosphate; The Sorbitol Nucleators such as the derivative that two benzal sorbyl alcohols or its alkyl replace, can enumerate Millad3905, Millad3940 and Millad3988 etc. of Milliken company as commercially available product; Carboxylic acid metal's salt nucleators such as Sodium Benzoate, p-tert-butyl benzoic acid carboxyl aluminium.Polymer composition containing nucleator has higher modulus in flexure and the transparency.
Those skilled in the art should be understood that, the content increasing ethylene-propylene elastomeric multipolymer can increase the shock resistance of polymer composition, but under ziegler natta catalyst exists, during the polypropene composition of the high ethylene-propylene elastomeric multipolymer content obtained with continuous polymerization, usually all can run into the situation that ethylene-propylene elastomeric copolymer particle is clamminess.And the performance in order to make the performance of multipolymer reach transparent anti-impact, the ethylene-propylene elastomeric molecular weight of copolymer that multipolymer uses is all smaller, this makes ethylene-propylene elastomeric copolymer particle more easily occur situation about being clamminess, so adopt continuous polymerization to be difficult to obtain the polymer composition that ethylene-propylene elastomeric multipolymer content accounts for polymer composition gross weight more than 30 % by weight.For this reason, usually need at present to adopt the melt blending of high cost to prepare transparent impact product.But the present inventor is found by research, the polymer composition with continuous polymerization synthesis with higher ethylene-propylene elastomeric multipolymer content can be realized by selecting specific ziegler natta catalyst.
In the present invention, described polymer composition contains the ethylene-propylene elastomeric multipolymer B more than 30 % by weight, and polymer composition can be made like this to demonstrate good toughness.
In described polypropene composition of the present invention, in order to improve scratch resistance and the stress-whitening resistance of the goods be made up of this polypropene composition further, relative to the described acrylic resin of 100 weight parts, the content of described polymer composition can be 1-30 weight part, is preferably 5-20 weight part.
In described polypropene composition of the present invention, described acrylic resin can be the various acrylic resins that this area routine uses.Under preferable case, for the scratch resistance and stress-whitening resistance that make the goods be made up of this polypropene composition are further improved, it is at least one in the Co-polypropylene of 3-60g/10min that described acrylic resin is selected from homo-polypropylene that melting index is 3-60g/10min and melting index, is more preferably the Co-polypropylene that melting index is 3-60g/10min.
Described damage resistant master batch is preferably from the ultra-high molecular weight siloxanes master batch taking polypropylene as carrier, and described polyacrylic melting index (MI, g/10min) can be 10-15.Due to described siloxanes master batch, there is higher concentration and ultra-high molecular weight structure and be carrier with polypropylene, so not only can ensure not to be clamminess in the surface of described Polypropylene compositions Tetramune, and the scratch resistant performance of goods can also be improved further and reduce the generation of stress whitening.Described damage resistant master batch can by commercially available acquisition, and such as, the trade mark purchased from Dow Corning Corporation is the product of MB50-001.
The content of the present invention to described damage resistant master batch is not particularly limited, and usually, for the described acrylic resin of 100 weight parts, the content of described damage resistant master batch can be 0.5-15 weight part, is preferably 1-10 weight part.
In a preferred embodiment, in order to improve scratch resistance and the stress-whitening resistance of the goods prepared by this polypropene composition further, described polypropene composition is preferably also containing polyethylene, and described poly crystallization can improve stress whitening further to the relexation of rubber grain.Relative to the described acrylic resin of 100 weight parts, described poly content can be 0.1-30 weight part, is preferably 5-15 weight part.
Described polyethylene can be the polyethylene that this area routine uses, and preferably, it is at least one in the Low Density Polyethylene of 0.2-40g/10min that described polyethylene is selected from high density polyethylene(HDPE) that melting index is 0.2-40g/10min and melting index.In the present invention, described high density polyethylene(HDPE) refers to that density is 0.946-0.976g/cm
3polyethylene, described Low Density Polyethylene refers to that density is 0.945g/cm
3following polyethylene.
In the present invention, described polypropene composition can also contain mineral filler and/or toughner.Relative to the described acrylic resin of 100 weight parts, the content of described mineral filler can be 0-50 weight part, is preferably 0.1-20 weight part; The content of described toughner can be 0-30 weight part, is preferably 0.1-15 weight part; And the total content of described mineral filler and described toughner is at least 0.1 weight part.
Described mineral filler can be the mineral filler that this area routine uses, such as, can be at least one in talcum powder, wollastonite and calcium carbonate.The particle diameter of described mineral filler can be 300 ~ 5000 orders.Described toughner can be the toughner that this area routine uses, such as, can be at least one in amorphous ethylene-alpha-olefin copolymer (as ethylene-propylene rubber(EPR)) and styrenic based thermoplastic elastomer.
In the present invention, described polypropene composition can also contain oxidation inhibitor.Relative to the described acrylic resin of 100 weight parts, the content of described oxidation inhibitor can be 0.1-3 weight part.Described oxidation inhibitor can be the oxidation inhibitor that this area routine uses, such as, can be antioxidant 1076, antioxidant 1010, irgasfos 168, sulphur ester antioxidant (as DLTP, DSTP) etc.
In the present invention, the processing aid that described polypropene composition can also use containing this area routine, such as, lubricant, static inhibitor, dispersion agent, pigment etc.Relative to the described acrylic resin of 100 weight parts, the content of described processing aid can be 0.1-5 weight part.
In the present invention, described polypropene composition can be prepared according to the method for routine, such as, its preparation method can comprise acrylic resin, polymer composition, damage resistant master batch, and optional polyethylene, mineral filler, toughner, oxidation inhibitor and other processing aids carry out melt blending.
In a preferred embodiment, the preparation method of described polypropene composition comprises: first prepare polymer composition, again by the polymer composition of acrylic resin, preparation, damage resistant master batch, and optional polyethylene, mineral filler, toughner, oxidation inhibitor and other processing aids carry out melt blending.
Particularly, the preparation method of described polypropene composition comprises the following steps:
(1) under the first olefin polymerization conditions, by the first monomer a and the ziegler natta catalyst contact reacts with high stereoselective, and remove unreacted monomer the mixture obtained after contact reacts, obtain the first mixture containing crystalline polypropylene A, wherein, described first monomer a contains propylene and optional ethene and/or has the alpha-olefin of 4-10 carbon atom;
(2) under alkene gas-phase polymerization condition, described the first mixture contact reacts containing crystalline polypropylene A that second comonomer b and step (1) are obtained, obtain the second mixture containing crystalline polypropylene A and ethylene-propylene elastomeric multipolymer B, and unreacted monomer is removed from this second mixture, obtain polymer composition, wherein, described second comonomer b contains propylene and ethene and/or has the alpha-olefin of 4-10 carbon atom;
(3) polymer composition, the damage resistant master batch that will obtain in acrylic resin, step (2), and optional polyethylene, mineral filler and toughner are dry mixed, and carry out melt blending and extruding pelletization by being dry mixed the mixture obtained.
In the above-mentioned methods, have described in the alpha-olefin of 4-10 carbon atom, described acrylic resin, described damage resistant master batch, described polyethylene, described mineral filler and described toughner all can with describe above identical.
The present inventor finds in research process: when adopting ziegler natta catalyst at least to comprise the propylene polymerization of two sequential steps, by controlling polymerizing condition, make the melting index of polymer composition and crystalline polypropylene A than in specified range and by the specific composition of crystallization control polypropylene A and ethylene-propylene elastomeric multipolymer B and content, the polymer composition of formation can have the high transparency and resistance to impact shock.
In one embodiment, described first monomer a is propylene, makes the crystalline polypropylene A obtained under the first olefin polymerization conditions be alfon.
In a preferred embodiment, described second comonomer b is propylene and ethene, makes the ethylene-propylene elastomeric multipolymer B obtained under alkene gas-phase polymerization condition contain the propylene structural unit of 75-92 % by weight and the ethylene unit unit of 8-25 % by weight; Further preferably, ethylene-propylene elastomeric multipolymer B is made to contain the propylene structural unit of 82-90 % by weight and the ethylene unit unit of 10-18 % by weight.
In the present invention, " there is the ziegler natta catalyst of high stereoselective " and refer to the catalyzer can prepared isotactic index and be greater than the alfon of 95%.
The described ziegler natta catalyst with high stereoselective can contain:
(i) ingredient of solid catalyst, its main component is magnesium, titanium, halogen and internal electron donor;
(ii) organo-aluminium compound; And
(iii) optional external donor compound,
The described median size with the ziegler natta catalyst of high stereoselective can be greater than 30 microns, is preferably greater than 40 microns.
Preferably, the ziegler natta catalyst adopting magnesium diaikoxide compound to prepare as carrier has advantage for the present invention.Adopt the catalyzer described in CN102453150A, especially there is advantage for the present invention.
Described ingredient of solid catalyst obtains preferably by following steps:
A (), under protection of inert gas, with magnesium and alcohol for raw material, back flow reaction under the existence of halogenating agent, obtains magnesium diaikoxide compound;
B (), under inert diluent exists, magnesium diaikoxide compound step (a) obtained and titanium compound and internal electron donor compound carry out contact reacts;
Described magnesium diaikoxide compound is spherical particle, and median size is 10 ~ 150 microns, size distribution index SPAN<1.1.
The preparation process of above-mentioned preferred ziegler natta catalyst and described ingredient of solid catalyst with describe in patent application CN102453150A identical.
The described ziegler natta catalyst with high stereoselective can directly use, and also can add after pre-complexing and prepolymerization.
Organo-aluminium compound as the cocatalyst component of catalyzer is preferably alkylaluminium cpd, is more preferably selected from least one in trialkylaluminium (as: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, trioctylaluminum), aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, dichloro one aluminium triethyl and ethyl aluminum dichloride.
With Ti/Al molar ratio computing, described ingredient of solid catalyst can be 1:25 to 1:1000 with the ratio of described organo-aluminium compound cocatalyst component.
The external donor compound of catalyst component is optionally preferably silicoorganic compound, and its general formula is R
nsi (OR')
4-n, 0 < n≤3 in formula, wherein, R and R' is identical or different, and is selected from alkyl, cycloalkyl, aryl and haloalkyl independently of one another, and R also can be halogen or hydrogen atom.Particularly, described silicoorganic compound can be but be not limited only to: tetramethoxy-silicane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, isopropyl methyl dimethoxysilane, two phenoxy group dimethoxysilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, Cyclohexyl Methyl Dimethoxysilane, dicyclopentyl dimethoxyl silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, 2-ethyl piperidine base-2-t-butyldimethoxysilane, (1, 1, the fluoro-2-propyl group of 1-tri-)-2-ethyl piperidine base dimethoxysilane, (1, 1, the fluoro-2-propyl group of 1-tri-)-methyl dimethoxysilane etc.
With Al/Si molar ratio computing, described alkylaluminium cpd can be 3:1 to 100:1 with the ratio of described silicoorganic compound.
Described three kinds of components with the ziegler natta catalyst of high stereoselective can directly join in polymerization reactor, also after the known pre-complexing of industry and/or prepolymerization, then can join in reactor.Prepolymerization can be carried out continuously under liquid-phase bulk condition, also can carry out in inert solvent discontinuous.Pre-polymerization reactor can be continuous stirred tank, annular-pipe reactor etc.Prepolymerized temperature can control between-10 to 60 DEG C, and preferred temperature is 0 to 40 DEG C.Prepolymerized multiple can control at 0.5 to 1000 times, and preferred multiple is 1.0 to 500 times.
In the above-mentioned methods, the first olefinic polymerization and alkene gas-phase polymerization can carry out continuously, also may be carried out batchwise.Successive polymerization can use plural tandem reactor to carry out.
First olefinic polymerization can be carried out in liquid phase, also can carry out in gas phase.First olefinic polymerization reactor used can be Liquid-phase reactor, also can be Gas-phase reactor.Liquid-phase reactor can be annular-pipe reactor and stirred-tank reactor etc., and Gas-phase reactor can be horizontal type agitated bed reactor, vertical mixing bed bioreactor and fluidized-bed reactor etc., and above Liquid-phase reactor and Gas-phase reactor also can at random matched combined.
In the above-mentioned methods, described first olefin polymerization conditions can comprise: temperature is 50-100 DEG C, is preferably 60-95 DEG C; Pressure is 1-8MPa, is preferably 1.2-5.5MPa; Time is 30-180 minute, is preferably 45-120 minute.In the present invention, pressure refers to reactor gauge pressure.
The reactor of alkene gas-phase polymerization can be horizontal type agitated bed reactor, vertical mixing bed bioreactor, fluidized-bed reactor etc., and above Gas-phase reactor can at random matched combined.
In the above-mentioned methods, described alkene gas-phase polymerization condition can comprise: temperature is 50-100 DEG C, is preferably 60-95 DEG C; Pressure is 1-4MPa, is preferably 1.2-3.5MPa; Time is 10-180 minute, is preferably 10-90 minute.
In the present invention, the preparation method of described polypropene composition can also comprise: by described polymer composition together with other components before melt blending, granulation is carried out to the polymer composition that step (2) obtains, and adds nucleator when polymer composition granulation.Preferably, the nucleator of 0.1-1 % by weight (preferred 0.2-0.5 % by weight) is contained in the polymer composition that the consumption of described nucleator obtains after making granulation.Described nucleator can with describe above identical.
In the present invention, the temperature of described melt blending can be blending temperature used in the processing of usual polypropylene, should not only ensureing the complete melting of acrylic resin but also can not make to select in its scope of decomposing.Particularly, the temperature of described melt blending can be 190-230 DEG C, is preferably 200-230 DEG C.
In the present invention, the preparation method of described polypropene composition can also comprise: after melt blending, carry out extruding pelletization.Preferably, the process of described melt blending and described extruding pelletization is carried out in twin screw extruder or the mixing unit of BUSS.
Present invention also offers the polypropene composition prepared by aforesaid method.
Described polypropene composition has damage resistant master batch on the one hand, and described damage resistant master batch can be effectively dispersed in acrylic resin, can significantly improve polyacrylic scratch resistant performance and there is not the problem that sample surfaces is clamminess; Have on the other hand the less and finely dispersed rubber phase of particle diameter, the structure that described polypropene composition is formed effectively can absorb the impact energy in the external world when being subject to external impacts, anti-impact successful and can effectively improve polyacrylic stress whitening.
Therefore, the goods that the polypropene composition adopting method of the present invention to prepare is formed have good scratch resistant performance and stress-whitening resistance energy, thus are specially adapted to the industry such as automobile, household electrical appliances.
The invention will be further described by the following examples.
Corresponding testing method is as follows:
The invention will be further described by the following examples.
Corresponding testing method is as follows:
Melting index (MFR): according to ASTMD1238-99,230 DEG C, measure under 2.16kg load.
Monomeric building blocks content in multipolymer: measure by fourier infrared method.
Xylene soluble content: measure by ASTMD5492-98.
Melting temperature (Tm): use the DSC7 type differential scanning calorimeter instrument of PerkinElmer company to measure, test specification is from 50 DEG C to 200 DEG C, first sample is risen to 200 DEG C to eliminate thermal history by the speed of 10 DEG C/min, 50 DEG C are down to again by the speed of 10 DEG C/min, record its Tc and crystallization enthalpy, rise to 200 DEG C by the speed of 10 DEG C/min again, record its fusing point and melting enthalpy.
Tensile strength: measure injected sample according to ASTMD638.
Modulus in flexure: measure injected sample according to ASTMD790.
Cantilever beam impact strength (Izod notch shock): according to ASTDD256, measures injected sample respectively at 23 DEG C and-20 DEG C.
Heat-drawn wire (HDT): measure according to ASTMD648.
Mist degree: according to ASTMD1003, measures the mist degree of the injected sample of 1 mm thick.
Transmittance: according to ASTMD1003, measures the transmittance of the injected sample of 1 mm thick.
Catalyzer median size: adopt MalvernMastersizerTM2000 laser particle analyzer, normal hexane dispersion agent laser diffractometry measures the average particle diameter size of catalyzer.
Second-order transition temperature (Tg): adopt dynamic mechanical analysis (DMA), TARSAIII type solid rheometer test temperature scope is-90 DEG C to 50 DEG C, and test sample is injection moulding batten, temperature rise rate 3 DEG C/min, frequency 1Hz, three-point bending pattern.
Atomic force microscopy: polypropylene injection moulding batten is ultrathin section(ing) after cryogenic freezing is to subzero 50 degrees Celsius, observes tangent plane.U.S. Vecco company NaonscopeIIIa type multiple mode scanning force microscope, J scanner head, tapping-mode, sweep limit 5 μm × 5 μm, gathers phasor.
Molecular weight distributing index (Mw/Mn): adopt PolymerLaboratories company of Britain to produce the molecular weight distribution of PL-GPC220 gel permeation chromatograph working sample, chromatographic column is 3 series connection Plgel10 μm of MIXED-B post, solvent and moving phase are 1,2,4-trichlorobenzene, column temperature 150 DEG C, adopt PL company EasiCalPS-1 Narrow distribution polystyrene standard specimen to carry out universal calibration, detector adopts the infrared concentration detector of IR5 of POLYCHAR company.
Preparation example: prepare polymer composition
Following preparation example and obtaining by the following method with reference to the polymer composition in preparation example, material amounts wherein and polymeric reaction condition are listed in table 1.
Polyreaction is carried out on set of horizontal type gas phase polypropylene pilot plant, polymerization reactor be two series connection Horizontal stirring reactors, polymerization process and step as follows:
Primary Catalysts (ingredient of solid catalyst) adopts the method that in CN102453150A, embodiment 1 describes to obtain, and internal electron donor compound wherein adopts n-butyl phthalate.
Primary Catalysts, promotor (triethyl aluminum), external electron donor add Horizontal stirring reactor continuously and carry out polyreaction under the carrying of propylene.Catalyzer enters from first stirring tank front end, and under the condition of gas phase, polymerization generates crystalline polypropylene A, and reaction heat is vaporized by the propylene sprayed and taken away.The polymkeric substance generated is discharged by the end of stirring tank.Catalyzer and polymkeric substance move in reactor in the mode close to plug flow, and polymerization temperature is 66 DEG C or assigned temperature, reaction pressure 2.3MPa, and the residence time is 90 minutes.
Polymkeric substance is discharged from first reactor, by being equipped with the equipment of transfer between two reactors, polymkeric substance is transferred to second Horizontal stirring reactor.Polymkeric substance enters from second stirring tank front end, and under the condition of gas phase, polymerization generates ethylene-propylene elastomeric multipolymer B, and reaction heat is vaporized by the propylene sprayed and taken away.The polymkeric substance generated is discharged by the end of stirring tank.Catalyzer and polymkeric substance move in reactor in the mode close to plug flow, and polymerization temperature is 66 DEG C or assigned temperature, reaction pressure 2.2MPa, are 60 minutes during stop.
The polymkeric substance be obtained by reacting, after degassed, wet nitrogen deactivation process, obtains polymer composition.
Adopt hydrogen as molecular weight regulator in two reactors, use the composition (ethene, propylene, butylene and hydrogen) of gas in the continuous analysis reactor of gas-chromatography.
The calcium stearate (purchased from Ciba company limited) of the IRGAFOS168 additive (purchased from Ciba company limited) of 0.1 weight part, the IRGANOX1010 additive (purchased from Ciba company limited) of 0.1 weight part and 0.05 weight part is added respectively in powder according to obtained polymer composition 100 weight part, and the Millad3988 additive (concrete consumption is see table 2) added purchased from Milliken company, use twin screw extruder granulation.
Injection moulding machine preparation meets the injected sample of ASTM standard, and measures its physical properties, and measurement result is as shown in table 2.
With reference to preparation example 1
Polyreaction is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot plant, and the catalyst particle size of use is 59 microns, and reaction is carried out according to the method described above.The external electron donor adopted is diisopropyl dimethoxy silane, and the first reactor polyreaction is propylene homo, and polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the residence time is about 90 minutes.Second reactor is that copolymerization of propylene prepares component (b), adds ethene, propylene in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa, and the residence time is 60 minutes.The polymkeric substance be obtained by reacting, after degassed, wet nitrogen deactivation process, obtains product.Reaction conditions and product property as shown in table 1.Product adds additive granulation, but non-Added Nucleating Agents, make the injected sample DP1 of polymer composition, its test performance is as shown in table 2.The dynamic mechanical analysis curve of the polymer composition of preparation as shown in Figure 1, as can be seen from the figure, has two glass transition points (Tg) at the temperature of-60 DEG C to 20 DEG C.
With reference to preparation example 2
Use with reference to preparation example 1 catalyzer used, prepare polymer composition according to the method described above, the polymerization temperature unlike the first reactor is 85 DEG C, changes added hydrogen, and changes composition and the content of component (b).Reaction conditions and product property as shown in table 1.Product adds additive granulation, makes the injected sample DP2 of polymer composition, and its test performance is as shown in table 2.
Preparation example 1
Use with reference to preparation example 1 catalyzer used, prepare polymer composition according to the method described above, unlike change added hydrogen, the polymerization temperature of the second reactor is 85 DEG C, changes composition and the content of component (b).Reaction conditions and product property as shown in table 1.Product adds additive granulation, makes the injected sample P1 of polymer composition, and its test performance is as shown in table 2.The dynamic mechanical analysis curve of the polymer composition of preparation as shown in Figure 2, as can be seen from the figure, has a glass transition point (Tg) at the temperature of-60 DEG C to 20 DEG C.As shown in Figure 3, as can be seen from the figure, described polymer composition has two phase structure to the atomic force microscopy of the polymer composition of preparation, and shows that component (b) is highly dispersed in composition with the particle diameter of about 0.3 micron.
Preparation example 2
Use with reference to preparation example 1 catalyzer used, prepare polymer composition according to the method described above, unlike change added hydrogen, the polymerization temperature of the second reactor is 85 DEG C, changes composition and the content of component (b).Reaction conditions and product property as shown in table 1.Product adds additive granulation, makes the injected sample P2 of polymer composition, and its test performance is as shown in table 2.
Preparation example 3
Polyreaction is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot plant, and the catalyst particle size of use is 35 microns, and reaction is carried out according to the method described above.The external electron donor adopted is diisopropyl dimethoxy silane, and the first reactor polyreaction is propylene and ethylene random copolymerization, and polymerization temperature is 66 DEG C, reaction pressure 2.3MPa, and the residence time is 90 minutes.Second reactor is that copolymerization of propylene prepares component (b), adds ethene, propylene in reactor, and polymerization temperature is 66 DEG C, reaction pressure 2.2MPa, and the residence time is about 60 minutes.The polymkeric substance be obtained by reacting, after degassed, wet nitrogen deactivation process, obtains product.Reaction conditions and product property as shown in table 1.Product adds additive granulation, but non-Added Nucleating Agents, make the injected sample P3 of polymer composition, its test performance is as shown in table 2.
Preparation example 4
Polyreaction is carried out on above-mentioned horizontal pneumatic heterophasic polypropylene pilot plant, and the catalyst particle size of use is 30 microns, and reaction is carried out according to the method described above.The external electron donor adopted is second, isobutyl dimethoxy silane, and the first reactor polyreaction is propylene homo, and polymerization temperature is 75 DEG C, reaction pressure 2.3MPa, and the residence time is 90 minutes.Second reactor is that copolymerization of propylene prepares component (b), adds ethene, propylene in reactor, and polymerization temperature is 75 DEG C, reaction pressure 2.2MPa, and the residence time is about 60 minutes.The polymkeric substance be obtained by reacting, after degassed, wet nitrogen deactivation process, obtains polymer composition.Reaction conditions and product property as shown in table 1.Product adds additive granulation, but non-Added Nucleating Agents, make the injected sample P4 of polymer composition, its test performance is as shown in table 2.
Preparation example 5
Polymer composition is prepared, unlike the content increasing component (b) according to the method for preparation example 4.Reaction conditions and product property as shown in table 1.Final polymer particle is clamminess, and test can not be carried out continuously.Visible, when above-mentioned ziegler natta catalyst particle diameter is 30 microns, during the polypropene composition of the high ethylene-propylene elastomeric multipolymer content prepared with continuous polymerization, be difficult to obtain the polymer composition that ethylene-propylene elastomeric multipolymer content accounts for polymer composition gross weight more than 30 % by weight.
Table 1
Note: P is diisopropyl dimethoxy silane; B is second, isobutyl dimethoxy silane; MFR
a+b/ MFR
arefer to the melting index ratio of polymer composition and crystalline polypropylene A.
Table 2
Embodiment
The corresponding detection method of following examples and comparative example is as follows:
The scratch resistant performance of polypropene composition is according to germany volkswagen PV3952 standard testing.Probe temperature: 23 ± 5 DEG C; Anchorage force: 10N; Scuffing speed: 1000mm/min.In same sample region, scratch front and rear surfaces scattering of light value by spectral photometric colour measuring other measure sample of scoring, to scratch the quality of front and back scattering of light difference DELTA E tolerance studies on scratch resistance of PP, Δ E value is less, shows that the scratch resistance of goods is better.
The stress-whitening resistance of polypropene composition can according to germany volkswagen PV3966 standard testing.Height of the fall ball selects 500mm standard.Measure the quality of polypropylene stress-whitening resistance with the scattering difference DELTA E ' of ball falling impact sample front and rear surfaces, Δ E ' value is less, shows that the stress-whitening resistance of goods is better.
The source of the raw material used in following examples and comparative example is as follows:
Acrylic resin: purchased from Sinopec Beijing Yanshan Petrochemical Co., the trade mark is K7726, is 26g/10min according to the melting index that ASTMD1238-99 measures.
Talcum powder: purchased from mining industry company limited of Dalian Fuji, particle diameter is 2500 orders.
Ethylene-propylene rubber(EPR): purchased from Dow Chemical, the trade mark is NORDELIP.
Damage resistant master batch: purchased from Dow Corning Corporation, the trade mark is MB50-001.
Polyethylene: purchased from Sinopec Beijing Yanshan Petrochemical Co., the trade mark is 3300J, is 2.5g/10min according to the melting index that ASTMD1238-99 measures.
Oxidation inhibitor: purchased from Ciba fine chemicals, the trade mark is B225.
Calcium stearate: purchased from Ciba fine chemicals.
The mixing unit of BUSS as melt blending equipment is purchased from BUSS company of Switzerland, and the trade mark is MKD-30.
Embodiment 1-6 and comparative example 1-3
Each component shown in table 3 is put into homogenizer respectively, stirs 3 minutes under the rotating speed of 300 revs/min, each component is fully mixed; Subsequently mixture is carried out melt blending and extruding pelletization, then through injector injection sample preparation, obtain the goods of polypropene composition.Then the polypropylene articles of preparation is carried out scratch resistant performance and resistance to stress the test of performance such as to turn white, it the results are shown in Table 3.
Table 3
As can be seen from the data of table 3, goods prepared by polypropene composition according to the present invention have good scratch resistant performance and stress-whitening resistance.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (19)
1. a polypropene composition, is characterized in that, this polypropene composition contains acrylic resin, polymer composition and damage resistant master batch, and described polymer composition contains:
The crystalline polypropylene A of (a) 40-70 % by weight, this crystalline polypropylene A is selected from alfon and/or random copolymer of propylene, with the gross weight of propylene random co-polymer for benchmark, this propylene random co-polymer contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 82-99.9 % by weight, the ethylene unit unit of 0-6 % by weight and 0-12 % by weight, and ethylene unit unit is 0.1-18 % by weight with the total content of the alpha-olefin structural unit with 4-10 carbon atom, and
The ethylene-propylene elastomeric multipolymer B of (b) 30-60 % by weight, with the gross weight of ethylene-propylene elastomeric multipolymer B for benchmark, this ethylene-propylene elastomeric multipolymer B contains the alpha-olefin structural unit with 4-10 carbon atom of the propylene structural unit of 60-92 % by weight, the ethylene unit unit of 8-25 % by weight and 0-15 % by weight
Wherein, the molecular weight distributing index of described polymer composition and described crystalline polypropylene A is all greater than 4; The melting index of described polymer composition is 0.7-1.3 with the ratio of the melting index of described crystalline polypropylene A.
2. polypropene composition according to claim 1, wherein, described polymer composition obtains with continuous polymerization under existing at the ziegler natta catalyst with high stereoselective.
3. polypropene composition according to claim 2, wherein, the molecular weight distribution of described polymer composition and crystalline polypropylene A is all greater than 4, is preferably 4.5-20.
4. according to the polypropene composition in claim 1-3 described in any one, wherein, described crystalline polypropylene A is alfon; Described ethylene-propylene elastomeric multipolymer B contains the ethylene unit unit of 10-18 % by weight and the propylene structural unit of 82-90 % by weight.
5. according to the polypropene composition in claim 1-4 described in any one, wherein, the melting index of described polymer composition is 0.1-100g/10min, is preferably 0.5-50g/10min.
6. according to the polypropene composition in claim 1-5 described in any one, wherein, described ethylene-propylene elastomeric multipolymer B is less than the Granular composite of 0.5 μm in described polymer composition with median size.
7. the mist degree that according to the polypropene composition in claim 1-6 described in any one, wherein, described polymer composition measures according to ASTMD1003 method is less than 60%.
8. according to the polypropene composition in claim 1-7 described in any one, wherein, described polymer composition has a glass transition point at the temperature of-60 DEG C to 20 DEG C.
9. according to the polypropene composition in claim 1-8 described in any one, wherein, relative to the described acrylic resin of 100 weight parts, the content of described polymer composition is 1-30 weight part, is preferably 5-20 weight part.
10. according to the polypropene composition in claim 1-9 described in any one, wherein, relative to the described acrylic resin of 100 weight parts, the content of described damage resistant master batch is 0.5-15 weight part, is preferably 1-10 weight part.
11. according to the polypropene composition in claim 1-10 described in any one, wherein, described polypropene composition also contains polyethylene, relative to the described acrylic resin of 100 weight parts, described poly content is 0.1-30 weight part, is preferably 5-15 weight part.
12. according to the polypropene composition in claim 1-11 described in any one, wherein, described polypropene composition is also containing mineral filler and/or toughner, relative to the described acrylic resin of 100 weight parts, the content of described mineral filler is 0-50 weight part, the content of described toughner is 0-30 weight part, and the total content of described mineral filler and described toughner is at least 0.1 weight part.
The preparation method of the polypropene composition in 13. claim 1-12 described in any one, the method comprises the following steps:
(1) under the first olefin polymerization conditions, by the first monomer a and the ziegler natta catalyst contact reacts with high stereoselective, and remove unreacted monomer the mixture obtained after contact reacts, obtain the first mixture containing crystalline polypropylene A, wherein, described first monomer a contains propylene and optional ethene and/or has the alpha-olefin of 4-10 carbon atom;
(2) under alkene gas-phase polymerization condition, described the first mixture contact reacts containing crystalline polypropylene A that second comonomer b and step (1) are obtained, obtain the second mixture containing crystalline polypropylene A and ethylene-propylene elastomeric multipolymer B, and unreacted monomer is removed from this second mixture, obtain polymer composition, wherein, described second comonomer b contains propylene and ethene and/or has the alpha-olefin of 4-10 carbon atom;
(3) polymer composition, the damage resistant master batch that will obtain in acrylic resin, step (2), and optional polyethylene, mineral filler and toughner are dry mixed, and carry out melt blending by being dry mixed the mixture obtained.
14. methods according to claim 13, wherein, described in there is the ziegler natta catalyst of high stereoselective particle diameter be greater than 30 microns.
15. methods according to claim 13, wherein, described in there is the ziegler natta catalyst of high stereoselective carrier be magnesium diaikoxide compound.
16. according to the method in claim 13-15 described in any one, wherein, described in there is high stereoselective ziegler natta catalyst contain:
(i) ingredient of solid catalyst;
(ii) organo-aluminium compound; And
(iii) optional external donor compound,
Described ingredient of solid catalyst is obtained by following steps:
A (), under protection of inert gas, with magnesium and alcohol for raw material, back flow reaction under the existence of halogenating agent, obtains magnesium diaikoxide compound;
B (), under inert diluent exists, magnesium diaikoxide compound step (a) obtained and titanium compound and internal electron donor compound carry out contact reacts;
Described magnesium diaikoxide compound is spherical particle, and median size is 10 ~ 150 microns, size distribution index SPAN<1.1.
17. methods according to claim 13, wherein, described first olefin polymerization conditions comprises: temperature is 50-100 DEG C, and pressure is 1-8MPa, and the time is 30-180 minute; Preferably, described first olefin polymerization conditions comprises: temperature is 60-95 DEG C, and pressure is 1.2-5.5MPa, and the time is 45-120 minute.
18. methods according to claim 13, wherein, described alkene gas-phase polymerization condition comprises: temperature is 50-100 DEG C, and pressure is 1-4MPa, and the time is 10-180 minute; Preferably, described alkene gas-phase polymerization condition comprises: temperature is 60-95 DEG C, and pressure is 1.2-3.5MPa, and the time is 10-90 minute.
19. polypropene compositions prepared by the method in claim 13-18 described in any one.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107629308A (en) * | 2016-07-19 | 2018-01-26 | 大韩道恩高分子材料(上海)有限公司 | A kind of low-density Polypropylene composite resin composition for automobile |
| CN112063054A (en) * | 2019-06-10 | 2020-12-11 | 中国石油化工股份有限公司 | Thermoplastic resin composition and application thereof in medium-voltage alternating-current cable insulation layer |
| CN112694678A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Polypropylene composition for power pipe and preparation method thereof |
| CN113667225A (en) * | 2020-05-13 | 2021-11-19 | 中韩(武汉)石油化工有限公司 | Special material for polypropylene waterproof coiled material and production method thereof |
| CN113667221A (en) * | 2020-05-13 | 2021-11-19 | 中韩(武汉)石油化工有限公司 | Polypropylene resin for producing waterproof coiled material |
| CN116063789A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Heterophasic polypropylene composition, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030944A (en) * | 2009-09-25 | 2011-04-27 | 中国石油化工股份有限公司 | Scratch-resistant polypropylene composition and preparation method thereof |
| CN102372874A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Stress whitening resistant and scratch resistant polypropylene composition, and preparation method thereof |
| CN103201339A (en) * | 2010-11-12 | 2013-07-10 | 博里利斯股份公司 | Heterophasic propylene copolymers with improved stiffness/impact/flowability balance |
-
2014
- 2014-08-12 CN CN201410393456.9A patent/CN105330957B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030944A (en) * | 2009-09-25 | 2011-04-27 | 中国石油化工股份有限公司 | Scratch-resistant polypropylene composition and preparation method thereof |
| CN102372874A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Stress whitening resistant and scratch resistant polypropylene composition, and preparation method thereof |
| CN103201339A (en) * | 2010-11-12 | 2013-07-10 | 博里利斯股份公司 | Heterophasic propylene copolymers with improved stiffness/impact/flowability balance |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107629308A (en) * | 2016-07-19 | 2018-01-26 | 大韩道恩高分子材料(上海)有限公司 | A kind of low-density Polypropylene composite resin composition for automobile |
| CN112063054A (en) * | 2019-06-10 | 2020-12-11 | 中国石油化工股份有限公司 | Thermoplastic resin composition and application thereof in medium-voltage alternating-current cable insulation layer |
| CN112694678A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Polypropylene composition for power pipe and preparation method thereof |
| CN113667225A (en) * | 2020-05-13 | 2021-11-19 | 中韩(武汉)石油化工有限公司 | Special material for polypropylene waterproof coiled material and production method thereof |
| CN113667221A (en) * | 2020-05-13 | 2021-11-19 | 中韩(武汉)石油化工有限公司 | Polypropylene resin for producing waterproof coiled material |
| CN116063789A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Heterophasic polypropylene composition, and preparation method and application thereof |
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