CN104072869A - Stress whitening resisting modified polypropylene material as well as preparation method and application thereof - Google Patents
Stress whitening resisting modified polypropylene material as well as preparation method and application thereof Download PDFInfo
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- CN104072869A CN104072869A CN201410279605.9A CN201410279605A CN104072869A CN 104072869 A CN104072869 A CN 104072869A CN 201410279605 A CN201410279605 A CN 201410279605A CN 104072869 A CN104072869 A CN 104072869A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a stress whitening resisting modified polypropylene material as well as a preparation method and an application thereof, and relates to the field of automobile trim. The material comprises the following components in parts by weight: 50-70 parts of polypropylene, 2-10 parts of polyethylene, 1-10 parts of toughening agent, 1-5 parts of compatilizer, 10-30 parts of talcum powder, 0.5-2 parts of titanium dioxide, 0.2-2 parts of antioxidant and 0.2-2 parts of lubricant. On the basis that the basic mechanic properties are met, the modified polypropylene material can reduce the whitening phenomenon of the automobile trim, particularly light interior trim parts which are stressed in the injection molding or assembling process, the height testing value delta L of a 500g falling ball at 500mm is less than 0.8, and thus the material is particularly applicable to light automobile interior trim parts.
Description
Technical field
The present invention relates to automotive trim, be specifically related to a kind of proof stress turn white modified polypropylene material and the application at light automotive upholstery thereof.
Background technology
Automotive upholstery mainly contains instrument desk, door-plate, door pillar etc. at present, is all injection molded at injection moulding machine by the filled toughening polypropylene material of twin screw blending extrusion.In mould ejection or Product Assembly process, owing to being subject to stress, there will be blushing on product surface, have a strong impact on product appearance.
Publication number is CN102617935A, application number is that 201210103490.9 Chinese patent application discloses a kind of scratch-resistant anti-stress whitening polypropene composition and preparation method thereof that injures, mainly be combined on the basis that ensures certain mechanical property by compatilizer, Metallocene elastomer and superfine talcum powder, reach the effect of stress non-whitening.
Publication number is CN102382373A, application number is that 201110283014.5 Chinese patent application discloses a kind of scratch-resistant anti-stress whitening polypropene composition that injures, and reaches the effect of anti-stress whitening by adding the compatilizer of polyolefine Organosiliconcopolymere or alkyl-modified polysiloxane.
Publication number is CN103374175A, application number is that 201210107469.6 Chinese patent application discloses a kind of proof stress filling modified polypropylene material and its production and use that turns white, the dispersion effect that combines to improve material by optimizing twin screw extruder solves the problem that automotive trim turns white with material stress, but the data of the concrete anti-stress whitening of quantitative not.
Publication number is CN102863697A, and the Chinese patent application that application number is 201210401041.2 discloses a kind of proof stress modified polypropylene material and preparation method thereof that turns white, and the method mainly illustrates that titanium dioxide turns white and has covering effect material stress.The present invention is on this Research foundation, and the synergy with aspects such as the interface binding powers of rebound resilience, talcum powder and the matrix resin of material, better solves polypropylene material stress whitening problem, and provides naked eyes and whether can differentiate the criterion of turning white.
Stress whitening, is commonly called as crazing, a large amount of small internal fissure that plastics produce in the time being subject to external force, and these crackles cause that refractive power changes, and shows as and turns white.Proof stress turns white and refers to, under equal internal stress condition, produce less the ability of stress whitening.In uniform impingement or eject etc. under Conditioning, naked eyes cannot be differentiated the degree that material turns white, and the ability that this material proof stress turns white is stronger.
The color of automotive upholstery is generally black, grey or beige, black is because carbon black covering effect generally there will not be the white phenomenon in top, grey and beige are easy to occur that top is white, therefore more meaningful for the stress whitening research of the inside gadget of grey and beige.The domestic patent for polypropylene material stress whitening is mainly also present in naked eyes sees the qualitative examination of the level that whether turns white, although the Chinese patent that publication number is CN102382373A has done comparatively quantitative research, but it is mainly to rely on to add siliceous class compatilizer, reduce and adopt falling sphere stress whitening front and back aberration △ L value, for formula in other various different componentss as the composite synergistic effect of the components such as titanium dioxide, compatilizer, linear low density polyethylene LLDPE, reduce stress whitening effect, also need to do a large amount of further investigations.
The applicant is devoted to find the stress whitening modified polypropylene material for automotive upholstery always.
Summary of the invention
The object of the invention is to prepare a kind of proof stress modified polypropylene material that turns white, another object of the present invention is to the application of modified polypropylene material on light automotive upholstery of turning white of this proof stress.
Technical problem to be solved by this invention: titanium dioxide has certain covering effect for stress whitening, but titanium dioxide consumption reaches a certain amount of rear DeGrain, then the aspect synergy such as matrix resin is combined with the interface of filler systems by improving, material is received rebound resilience after stress.Generally turn white and lack checking means for material stress, can be more succinct by falling sphere mode find out the situation that material proof stress turns white.With 500g falling sphere 500mm height drop impact 3mm disk, before and after falling sphere, △ L value size is carried out the evaluating material proof stress degree of turning white.General △ L value is below 0.8, and the more difficult resolution of naked eyes, thereby screening formula, improve the white phenomenon in top that material occurs in injection moulding or assembling process.
Modified polypropylene material provided by the invention, is made up of following component:
Wherein screening formulation is:
Wherein optimization formula is:
Or optimization formula is:
According to preference of the present invention, described polypropylene, refers to one or more in the high-crystallinity polypropylene of 1-50g/10min, block copolymerization polypropylene, homo-polypropylene of melt flow rate (MFR) under 230 DEG C × 2.16kg test condition.
Described polypropylene can adopt commercially available prod, as Yanshan Petrochemical K8303, platform K8025, oil of SPC M700R, Yanshan Petrochemical K7726, raises sub-petrochemical industry SP179, Dushanzi T30S, oil of SPC Y2600T, middle husky 511MK40T etc.
According to preference of the present invention, described linear low density polyethylene LLDPE, its side chain is hexene, and/or octene, as raises sub-petrochemical industry LLDPE7042 etc.
According to preference of the present invention, described toughner is ethylene-octene copolymer, and density is 0.86g/cm
3～0.88g/cm
3, under 190 DEG C × 2.16kg test condition, melt flow rate (MFR) is at 0.5g/10min～1g/10min.Can adopt the POE8150 of DOW company, the DF610 of Mitsui, DF605, the LC175 of LG company, LC165 etc.
According to preference of the present invention, described compatilizer is maleic anhydride inoculated polypropylene, can adopt commercially available prod, rises CMG5001, the FUS P353 of Du Pont, Bondyram1001 etc. as Shanghai day.
According to preference of the present invention, described talcum powder, order number is at least 1250 orders, 750 DEG C of loss on ignition≤10%, hydrochloric acid insoluble substance >=90%, silicone content >=50%.
According to preference of the present invention, described titanium dioxide is Rutile type Titanium Dioxide, and its particle diameter is at 0.1～0.35 μ m.
According to preference of the present invention, described oxidation inhibitor is composite antioxidant system, be four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), tricresyl phosphite (2,4-di-tert-butyl) the two octadecyl esters (oxidation inhibitor DSTP) of ester (irgasfos 168), thio-2 acid, the two lauryls, 1 of thio-2 acid, 3, one or more in 5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide.
According to preference of the present invention, described lubricant is one or more in stearate, silicone powder, erucicamide.
The preparation method of modified polypropene of the present invention, comprises the following steps:
(A) take raw material by above-mentioned formula;
(B) raw material step (A) being obtained stirring at low speed more than 10 minutes in agitator kettle;
(C) mixture that adopts twin screw extruder that step (B) is obtained melt extrudes, granulation, its technique is: 120 ± 10 DEG C, a district, two 200 ± 10 DEG C, districts, three 220 ± 10 DEG C, districts, four-nine 230 ± 10 DEG C, districts, engine speed 500 ± 50rpm, main feeding 20 ± 5Hz, obtains described modified polypropylene material.
Modified polypropylene material of the present invention, can be for the preparation of light automotive upholstery.
Compared with prior art, tool of the present invention has the following advantages:
The invention provides a kind of proof stress for automotive trim modified polypropylene material that turns white, ensureing under the prerequisite of basic mechanical performance, be combined with the interface of filler systems by improving matrix resin, the rebound resilience of matrix resin and suitable defect are covered the synergies such as means, reaching 3mm disk highly falls at 500g falling sphere 500mm, front and back △ L value (placing the L value of 24h and the difference of the front L value of falling sphere after falling sphere) is below 0.8, reach naked eyes to distinguishing the degree of whether turning white, in injection moulding and assembling process, there will not be the white phenomenon in top, improve injection moulding and assembling yield rate, the product performance of preparation meet main engine plants' requirement, have a extensive future.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can combining mutually between specifically described each technical characterictic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tire out and state no longer one by one at this.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.
Embodiment 1
As shown in table 1, weigh polypropylene platform K8025 (melt flow rate (MFR) 25g/10min), 51.5 weight parts; Polypropylene Yanshan Petrochemical K8303 (melt flow rate (MFR) 2.5g/10min), 10 weight parts; Linear low density polyethylene LLDPE raises sub-petrochemical industry LLDPE7042,8 weight parts; The toughner DOW POE8150 of company, 5 weight parts; The maleic anhydride inoculated polypropylene CMG5001 of compatilizer Shanghai Zhi Sheng company (MAH percentage of grafting >=1%), 3 weight parts; 1250 order talcum powder, 20 weight parts; Rutile type Titanium Dioxide, 1.5 weight parts; Antioxidant 1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester), 0.2 weight part; Irgasfos 168 (tricresyl phosphite (2,4-di-tert-butyl) ester), 0.2 weight part; Oxidation inhibitor DSTP (the two octadecyl esters of thio-2 acid), 0.2 weight part; Lubricant stearic acid calcium, 0.4 weight part.Each component stirring at low speed in agitator kettle more than 10 minutes, after mixing, is put into forcing machine hopper, by twin screw extruder melt blending, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packagings.
Described twin screw extruder temperature arranges, 120 ± 10 DEG C, a district, two 200 ± 10 DEG C, districts, three 220 ± 10 DEG C, districts, four-nine 230 ± 10 DEG C, districts, engine speed 500 ± 50rpm, main feeding 20 ± 5Hz, the molten how of temperature control adjustment, at 75-85g/10min, obtains described modified polypropylene material.
Embodiment 2
As shown in table 1, weigh polypropylene platform K8025,55.5 weight parts; Polypropylene Yanshan Petrochemical K8303,10 weight parts; Linear low density polyethylene LLDPE raises sub-petrochemical industry LLDPE7042,5 weight parts; The toughner DOW POE8150 of company, 5 weight parts; The maleic anhydride inoculated polypropylene CMG5001 of compatilizer Shanghai Zhi Sheng company, 2 weight parts; 1250 order talcum powder, 20 weight parts; Rutile type Titanium Dioxide, 1.5 weight parts; Antioxidant 1010,0.2 weight part; Irgasfos 168,0.2 weight part; Oxidation inhibitor DSTP, 0.2 weight part; Lubricant stearic acid calcium, 0.4 weight part.Each component stirring at low speed in agitator kettle more than 10 minutes, after mixing, is put into forcing machine hopper, by twin screw extruder melt blending, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packagings.
Processing parameter, batten preparation condition are with embodiment 1.
Embodiment 3
As shown in table 1, weigh polypropylene platform K8025,60 weight parts; Polypropylene Yanshan Petrochemical K8303,10 weight parts; Linear low density polyethylene LLDPE raises sub-petrochemical industry LLDPE7042,10 weight parts; The toughner DOW POE8150 of company, 5 weight parts; The maleic anhydride inoculated polypropylene CMG5001 of compatilizer Shanghai Zhi Sheng company, 1 weight part; 1250 order talcum powder, 10 weight parts; Rutile type Titanium Dioxide, 3 weight parts; Antioxidant 1010,0.2 weight part; Irgasfos 168,0.2 weight part; Oxidation inhibitor DSTP, 0.2 weight part; Lubricant stearic acid calcium, 0.4 weight part.Each component stirring at low speed in agitator kettle more than 10 minutes, after mixing, is put into forcing machine hopper, by twin screw extruder melt blending, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packagings.
Processing parameter, batten preparation condition are with embodiment 1.
Embodiment 4
As shown in table 1, weigh polypropylene platform K8025,43 weight parts; Polypropylene Yanshan Petrochemical K8303,10 weight parts; Linear low density polyethylene LLDPE raises sub-petrochemical industry LLDPE7042,3 weight parts; The toughner DOW POE8150 of company, 5 weight parts; The maleic anhydride inoculated polypropylene CMG5001 of compatilizer Shanghai Zhi Sheng company, 5 weight parts; 1250 order talcum powder, 30 weight parts; Rutile type Titanium Dioxide, 3 weight parts; Antioxidant 1010,0.2 weight part; Irgasfos 168,0.2 weight part; Oxidation inhibitor DSTP, 0.2 weight part; Lubricant stearic acid calcium, 0.4 weight part.Each component stirring at low speed in agitator kettle more than 10 minutes, after mixing, is put into forcing machine hopper, by twin screw extruder melt blending, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packagings.
Processing parameter, batten preparation condition are with embodiment 1.
Comparative example 1
As shown in table 1, weigh polypropylene platform K8025,59 weight parts; Polypropylene Yanshan Petrochemical K8303,10 weight parts; High density polyethylene Daqing petrochemical HDPE5000S, 5 weight parts; The toughner DOW POE8150 of company, 5 weight parts; 1250 order talcum powder, 20 weight parts; Antioxidant 1010,0.2 weight part; Irgasfos 168,0.2 weight part; Oxidation inhibitor DSTP, 0.2 weight part; Lubricant stearic acid calcium, 0.4 weight part.Each component stirring at low speed in agitator kettle more than 10 minutes, after mixing, is put into forcing machine hopper, by twin screw extruder melt blending, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packagings.
Processing parameter, batten preparation condition are with embodiment 1.
Comparative example 2
As shown in table 1, weigh polypropylene platform K8025,57.5 weight parts; Polypropylene Yanshan Petrochemical K8303,10 weight parts; High density polyethylene Daqing petrochemical HDPE5000S, 5 weight parts; The toughner DOW POE8150 of company, 5 weight parts; 1250 order talcum powder, 20 weight parts; Rutile type Titanium Dioxide, 1.5 weight parts; Antioxidant 1010,0.2 weight part; Irgasfos 168,0.2 weight part; Oxidation inhibitor DSTP, 0.2 weight part; Lubricant stearic acid calcium, 0.4 weight part.Each component stirring at low speed in agitator kettle more than 10 minutes, after mixing, is put into forcing machine hopper, by twin screw extruder melt blending, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packagings.
Processing parameter, batten preparation condition are with embodiment 1.
Comparative example 3
As shown in table 1, weigh polypropylene platform K8025,56 weight parts; Polypropylene Yanshan Petrochemical K8303,10 weight parts; High density polyethylene Daqing petrochemical HDPE5000S, 5 weight parts; The toughner DOW POE8150 of company, 5 weight parts; 1250 order talcum powder, 20 weight parts; Rutile type Titanium Dioxide, 3 weight parts; Antioxidant 1010,0.2 weight part; Irgasfos 168,0.2 weight part; Oxidation inhibitor DSTP, 0.2 weight part; Lubricant stearic acid calcium, 0.4 weight part.Each component stirring at low speed in agitator kettle more than 10 minutes, after mixing, is put into forcing machine hopper, by twin screw extruder melt blending, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packagings.
Processing parameter, batten preparation condition are with embodiment 1.
Comparative example 4
As shown in table 1, weigh polypropylene platform K8025,57.5 weight parts; Polypropylene Yanshan Petrochemical K8303,10 weight parts; Linear low density polyethylene LLDPE raises sub-petrochemical industry LLDPE7042,5 weight parts; The toughner DOW POE8150 of company, 5 weight parts; 1250 order talcum powder, 20 weight parts; Rutile type Titanium Dioxide, 1.5 weight parts; Antioxidant 1010,0.2 weight part; Irgasfos 168,0.2 weight part; Oxidation inhibitor DSTP, 0.2 weight part; Lubricant stearic acid calcium, 0.4 weight part.Each component stirring at low speed in agitator kettle more than 10 minutes, after mixing, is put into forcing machine hopper, by twin screw extruder melt blending, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packagings.
Processing parameter, batten preparation condition are with embodiment 1.
Comparative example 5
As shown in table 1, weigh polypropylene platform K8025,57 weight parts; Polypropylene Yanshan Petrochemical K8303,10 weight parts; Linear low density polyethylene LLDPE raises sub-petrochemical industry LLDPE7042,5 weight parts; The toughner DOW POE8150 of company, 5 weight parts; The maleic anhydride inoculated polypropylene CMG5001 of compatilizer Shanghai Zhi Sheng company, 2 weight parts; 1250 order talcum powder, 20 weight parts; Rutile type Titanium Dioxide, 3 weight parts; Antioxidant 1010,0.2 weight part; Irgasfos 168,0.2 weight part; Oxidation inhibitor DSTP, 0.2 weight part; Lubricant stearic acid calcium, 0.4 weight part.Each component stirring at low speed in agitator kettle more than 10 minutes, after mixing, is put into forcing machine hopper, by twin screw extruder melt blending, extrude that material strip is cooling, air-dry, pelletizing, equal mixed, packagings.
Processing parameter, batten preparation condition are with embodiment 1.
Performance test
By the modified polypropylene material making, at air dry oven, 90 DEG C are dried 1 hour, then by injection moulding machine injection moulding test bars.Density measurement is pressed DIN EN ISO1183-1 standard and is carried out; Tensile strength and elongation at break amount are pressed DIN EN ISO527-2 standard and are carried out, speed 50mm/min; Flexural strength and modulus in flexure test are pressed DIN EN ISO178 standard and are carried out, and speed is 2mm/min; Simply supported beam notched Izod impact strength is pressed DIN EN ISO179-1/1eA standard and is carried out; Melt flow rate (MFR) is pressed DIN EN ISO1133 standard and is carried out, 230 DEG C, 2.16kg; Thermal distortion is pressed DIN EN ISO75-2 standard and is carried out, 0.45MPa; Falling sphere test reference PV3966 standard, the heavy 500g of ball, height of the fall ball 500mm, 3mm thickness disk, places the L value of 24h and the difference of the front L value of falling sphere after contrast falling sphere, and in the time that this difference of repetition test is below 0.8, whether naked eyes cannot be distinguished and turn white.
The turn white proportioning (weight part) of the each component of modified polypropylene material of table 1 proof stress
The polypropylene material test result of table 2 for making, from table, the data of embodiment 1-4 and comparative example 1-5 can be found out, 3mm disk highly falls at 500g falling sphere 500mm, and front and back △ L value (placing the L value of 24h and the difference of the front L value of falling sphere after falling sphere) aspect difference is still larger.
From comparative example 1-3, along with the introducing of titanium dioxide and the increase of consumption, △ L value presents downtrending, illustrates that titanium dioxide has certain covering effect in vain to pushing up, but that consumption reaches a certain amount of variation is little.
Contrast comparative example 2 and comparative example 4, for reducing △ L value, linear low density polyethylene LLDPE is because the many rebound resiliences of side chain are good, and successful is better than high density polyethylene.
Comparative example 2 and comparative example 4, the introducing of compatilizer, has strengthened the combination degree of filler and matrix resin, can obviously reduce △ L value.
Comprehensive Correlation embodiment 1-4 and comparative example 1-5, introduce the poly rebound resilience of covering effect, polyteny of titanium dioxide, the interface keying action that compatilizer improves talcum powder and matrix resin, the collaborative stress whitening problem that can reduce preferably modified polypropylene material of three.Due to the existence of titanium dioxide, be not suitable for doing black inside gadget, but at light color as grey, beige automotive upholstery successful Application, in injection moulding and assembling process, do not occur again pushing up white phenomenon, ensured the yield rate of injection moulding and assembling.
The polypropylene material test result that table 2 makes
All documents of mentioning in the present invention are all quoted as a reference in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (14)
1. the proof stress modified polypropylene material that turns white, is made up of following component:
2. the proof stress as claimed in claim 1 modified polypropylene material that turns white, is characterized in that, is made up of following component:
3. the proof stress as claimed in claim 1 modified polypropylene material that turns white, is characterized in that, is made up of following component:
4. the proof stress as claimed in claim 1 modified polypropylene material that turns white, is characterized in that, is made up of following component:
5. the proof stress as claimed in claim 1 modified polypropylene material that turns white, it is characterized in that, described polypropylene, refers to one or more in the high-crystallinity polypropylene of 1-50g/10min, block copolymerization polypropylene, homo-polypropylene of melt flow rate (MFR) under 230 DEG C × 2.16kg test condition.
6. the proof stress as claimed in claim 1 modified polypropylene material that turns white, is characterized in that, described linear low density polyethylene, and its side chain is selected from the arbitrary or combination of hexene, octene.
7. the proof stress as claimed in claim 1 modified polypropylene material that turns white, is characterized in that, described toughner is ethylene-octene copolymer, and density is 0.86g/cm
3～0.88g/cm
3, under 190 DEG C × 2.16kg test condition, melt flow rate (MFR) is at 0.5g/10min～1g/10min.
8. the proof stress as claimed in claim 1 modified polypropylene material that turns white, is characterized in that, described compatilizer is maleic anhydride inoculated polypropylene.
9. the proof stress as claimed in claim 1 modified polypropylene material that turns white, is characterized in that, described talcum powder, and order number is at least 1250 orders, 750 DEG C of loss on ignition≤10%, hydrochloric acid insoluble substance >=90%, silicone content >=50%.
10. the proof stress as claimed in claim 1 modified polypropylene material that turns white, is characterized in that, described titanium dioxide is Rutile type Titanium Dioxide, and its particle diameter is at 0.1～0.35 μ m.
The 11. proof stresss as claimed in claim 1 modified polypropylene material that turns white, it is characterized in that, described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2,4-di-tert-butyl) the two octadecyl esters of ester, thio-2 acid, the two lauryls, 1 of thio-2 acid, one or more in 3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide.
The 12. proof stresss as claimed in claim 1 modified polypropylene material that turns white, is characterized in that, described lubricant is one or more in stearate, silicone powder, erucicamide.
The turn white preparation method of modified polypropylene material of proof stress described in 13. claim 1-9, is characterized in that, preparation method comprises the steps:
(A) take raw material by formula;
(B) raw material step (A) being obtained stirring at low speed more than 10 minutes in agitator kettle;
(C) mixture that adopts twin screw extruder that step (B) is obtained melt extrudes, granulation, its technique is: 120 ± 10 DEG C, a district, two 180 ± 10 DEG C, districts, three 200 ± 10 DEG C, districts, four-nine 210 ± 10 DEG C, districts, engine speed 500 ± 50rpm, main feeding 20 ± 5Hz, obtains modified polypropylene material.
The application of 14. modified polypropylene materials as described in claim 1-9 any one in the light automotive upholstery of preparation.
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| CN105646996A (en) * | 2016-02-19 | 2016-06-08 | 太仓市晨洲塑业有限公司 | Multifunctional plastic basin |
| CN106633334A (en) * | 2016-09-21 | 2017-05-10 | 惠州市纳米金塑胶科技有限公司 | High-elasticity composite material for gloves |
| CN106700385A (en) * | 2015-11-15 | 2017-05-24 | 合肥杰事杰新材料股份有限公司 | Stress-whitening-resisting modified styrene-based resin and preparation method thereof |
| CN106750922A (en) * | 2016-12-12 | 2017-05-31 | 广东威林工程塑料股份有限公司 | A kind of proof stress turns white, high elastic modified PP composite material and preparation method thereof |
| CN106995551A (en) * | 2016-01-26 | 2017-08-01 | 合肥杰事杰新材料股份有限公司 | A kind of low VOC, low migration PP composite material and preparation method thereof |
| CN108727684A (en) * | 2017-04-18 | 2018-11-02 | 广东金发科技有限公司 | PP composite material and preparation method thereof, sheet material prepared therefrom or profile shapes and application |
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| CN110903549A (en) * | 2019-12-04 | 2020-03-24 | 联泓(江苏)新材料研究院有限公司 | Polypropylene composite material and preparation method and application thereof |
| CN111592710A (en) * | 2020-07-01 | 2020-08-28 | 东莞市鑫创新材料科技有限公司 | Nose bridge strip material of all-plastic mask and preparation method thereof |
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| CN105646996A (en) * | 2016-02-19 | 2016-06-08 | 太仓市晨洲塑业有限公司 | Multifunctional plastic basin |
| CN109071893A (en) * | 2016-03-25 | 2018-12-21 | 陶氏环球技术有限责任公司 | Separator tube for fiber optic cables |
| CN109071893B (en) * | 2016-03-25 | 2021-06-01 | 陶氏环球技术有限责任公司 | Buffer tube for optical fiber cable |
| CN106633334A (en) * | 2016-09-21 | 2017-05-10 | 惠州市纳米金塑胶科技有限公司 | High-elasticity composite material for gloves |
| CN106750922A (en) * | 2016-12-12 | 2017-05-31 | 广东威林工程塑料股份有限公司 | A kind of proof stress turns white, high elastic modified PP composite material and preparation method thereof |
| CN108727684B (en) * | 2017-04-18 | 2020-09-04 | 广东金发科技有限公司 | Polypropylene composite material, preparation method thereof, sheet or profiled bar prepared from polypropylene composite material and application of polypropylene composite material |
| CN108727684A (en) * | 2017-04-18 | 2018-11-02 | 广东金发科技有限公司 | PP composite material and preparation method thereof, sheet material prepared therefrom or profile shapes and application |
| CN110903549A (en) * | 2019-12-04 | 2020-03-24 | 联泓(江苏)新材料研究院有限公司 | Polypropylene composite material and preparation method and application thereof |
| CN110903549B (en) * | 2019-12-04 | 2023-10-13 | 联泓(江苏)新材料研究院有限公司 | Polypropylene composite material and preparation method and application thereof |
| CN111592710A (en) * | 2020-07-01 | 2020-08-28 | 东莞市鑫创新材料科技有限公司 | Nose bridge strip material of all-plastic mask and preparation method thereof |
| CN112724502A (en) * | 2020-12-31 | 2021-04-30 | 常州威材新材料科技有限公司 | Anti-blushing auxiliary agent and application method thereof |
| CN112724502B (en) * | 2020-12-31 | 2021-09-07 | 常州威材新材料科技有限公司 | Anti-blushing auxiliary agent and application method thereof |
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Application publication date: 20141001 |