CN103044783A - High-fluidity and stress-resistance whitening modified polypropylene composite material and preparation method thereof - Google Patents

High-fluidity and stress-resistance whitening modified polypropylene composite material and preparation method thereof Download PDF

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Publication number
CN103044783A
CN103044783A CN2012105851345A CN201210585134A CN103044783A CN 103044783 A CN103044783 A CN 103044783A CN 2012105851345 A CN2012105851345 A CN 2012105851345A CN 201210585134 A CN201210585134 A CN 201210585134A CN 103044783 A CN103044783 A CN 103044783A
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CN
China
Prior art keywords
modified polypropylene
stress whitening
polypropylene composite
stress
polyethylene
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Pending
Application number
CN2012105851345A
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Chinese (zh)
Inventor
屈国梁
张鹰
张祥福
周文
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Shanghai Pret Composites Co Ltd
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Shanghai Pret Composites Co Ltd
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Application filed by Shanghai Pret Composites Co Ltd filed Critical Shanghai Pret Composites Co Ltd
Priority to CN2012105851345A priority Critical patent/CN103044783A/en
Publication of CN103044783A publication Critical patent/CN103044783A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • 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
    • B29C2948/92514—Pressure
    • 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
    • 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
    • B29C2948/92885—Screw or gear
    • 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

Abstract

The invention discloses a high-fluidity and stress-resistance whitening modified polypropylene composite material and a preparation method thereof. The composite material is prepared from the raw materials as follows: by weight, 79% to 94% of polypropylene, 0.5% to 5% of polyethylene wax, 5% to 15% of polyethylene and 0.1% to 2% of antioxidants. In actual applications, the prepared modified polypropylene composite material maintains the fluidity of the polyethylene wax and modifies the stress-resistance whitening performance of the polyethylene simultaneously by using the lubricity of the polyethylene wax and the good compatibility of the polypropylene and combining synergistic modification of the polyethylene. The composite material can be used for manufacturing products having high demands of the fluidity and stress-resistance whitening.

Description

A kind ofly highly flow, anti-stress whitening modified polypropylene composite material and preparation method thereof
Technical field
The present invention relates to a kind ofly highly flow, anti-stress whitening modified polypropylene composite material, be the modified polypropylene material that a kind of technique is simple, over-all properties is good, can for the preparation of some have highly flow, the goods of anti-stress whitening requirement.
Background technology
Polypropylene is one of five large class general-purpose plastics, because its raw material sources are abundant, low price, be easy to machine-shaping, product high comprehensive performance, therefore purposes is very extensive, has become kind with fastest developing speed in the resins for universal use, is widely used in the inner and outer decorative parts of automobile product.When being applied to the automotive trims such as fascia, door-plate, because being easy to the scuffing meeting, the surface directly affects the attractive in appearance of automobile, and this has had a strong impact on its application in automobile decoration piece; Simultaneously polypropylene articles is in injection moulding process, easily to eject the position stressed more concentrated, produces blushing in the force part, namely pushes up white phenomenon, causes products appearance defective; Some polypropylene articles in use some special construction such as card base etc. is easily stressed and produce the situation of stress whitening, cracking.
Summary of the invention
The object of the present invention is to provide a kind of high mobile, anti-stress whitening modified polypropylene composite material, to solve the problems referred to above of prior art.
Purpose of the present invention mainly is achieved through the following technical solutions.
A kind ofly highly flow, anti-stress whitening modified polypropylene composite material, form by the preparation of raw material of following weight percent meter:
Polypropylene of the present invention is under the test condition of 230 ℃ * 2.16Kg, and melt flow rate (MFR) is the Co-polypropylene of 5～30g/10min.
Described ethylene waxes is unoxidized high density polyethylene waxes, and its density is at 0.90-0.98g/cm 3
Described polyethylene is linear low density of polyethylene, and under the test condition of 230 ℃ * 2.16Kg, its molten finger is 0.5～10g/10min.
Described oxidation inhibitor is primary antioxidant and auxiliary anti-oxidant, and wherein primary antioxidant is selected from one or more in hindered phenol and the sulphur ester antioxidant.Be 3114,1010 and DSTP in one or more; Auxiliary anti-oxidant is selected one or more of phosphite and ester kind antioxidant.Be in 618 and 168 one or both.
Also comprise being no more than other auxiliary agents of 3%, described other main frames are one or more the mixtures in various lubricants, anti UV agent and the pigment.
Prepare that this height flows, the method for anti-stress whitening modified polypropene, its step is as follows:
(take by weighing by weight ratio raw material;
2 place super mixer to be dry mixed 3～5 minutes the raw material;
3 put into the twin screw extruder extruding pelletization with the raw material that mixes, and screw speed is 180～600 rev/mins, and temperature is 190～200 ℃ in a district, 200～220 ℃ in two districts, 220～235 ℃ in three districts, 215～220 ℃ in four districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18MPa.
The present invention in actual applications, utilize the oilness of polyethylene wax and the consistency good with polypropylene, in conjunction with poly modified synergic, prepared modified polypropylene material has also improved polyacrylic anti-stress whitening performance when keeping the polypropylene flowability.Can be used for making flow and the demanding goods of anti-stress whitening.
Concrete embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
In embodiment and Comparative Examples composite-material formula, polypropylene is the Co-polypropylene that Shanghai Petrochemical Co. Ltd. produces, and commodity are called M2600R, and its melt flow rate (MFR) is 26g/10min (test condition: 230 ℃ * 2.16Kg); Described polyethylene wax is the CERALENE high-efficiency polyethylene wax that Polish EUROCERAS company produces, and commodity are by name 882, and density is at 0.93g/cm 3Described polyethylene is the LLDPE7042 that Qilu Petrochemical Company is produced, and it is molten to refer to the (test condition: 230 ℃ * 2.16Kg) for 2.0g/10min.The DSTP that primary antioxidant selects Britain ICE company to produce, chemistry thio-2 acid octadecyl ester by name, and Ciba company produce 3114, chemistry 3,5-di-t-butyl-4 hydroxybenzyl diethyl phosphoric acid by name.Auxiliary anti-oxidant is 168 of Ciba company production, and chemical name is three (2,4-di-t-butyl benzyl) phosphorous acid ester.
All components are added in the super mixer, be dry mixed 3～5 minutes with the rotating speed that is higher than 600r/min.The raw material that mixes is put into the twin screw extruder extruding pelletization, and screw speed is 180～600 rev/mins, and temperature is 190～200 ℃ in a district, 200～220 ℃ in two districts, 220～235 ℃ in three districts, 215～220 ℃ in four districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18MPa.
Performance evaluation and implementation standard:
As in 100 ℃ the air dry oven dry 2～3 hours, and then the pellet that drying is good carried out the injection molding sample preparation at injection moulding machine with the particulate material of finishing as stated above granulation.
The melt flow rate (MFR) test is carried out according to ISO1133, and test condition is 230 ℃ * 2.16Kg; Tensile property carries out according to ISO527, and specimen size is 170 * 10 * 4, and draw speed is 50mm/min; The bending property test is carried out according to ISO178, and specimen size is 80 * 10 * 4, and rate of bending is 2mm/min, and span is 64mm; Simply supported beam impacts and is undertaken by ISO180, and specimen size is 80 * 10 * 4, and notch depth is 1/3rd of sample thickness;
Anti-stress whitening performance is carried out according to popular PV3966, is divided into Three Estate: A, the unstressed B of turning white, slight stress turn white C, obvious stress whitening.
The over-all properties of material is passed judgment on by notched Izod impact strength, tensile strength, modulus in flexure and the stress whitening grade of test gained.Example formulations and properties test result are seen following each table:
Table 1 embodiment 1～6 and Comparative Examples 1～5 prescription (% by weight).
? Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative Examples 1 Comparative Examples 2 Comparative Examples 3
Polypropylene 93.6 916 89.6 84.6 79.6 99.6 84.6 946
Polyethylene wax 1 3 5 5 5 - - 5
Polyethylene 5 5 5 10 15 - 15 -
3114 01 01 01 01 01 01 01 01
168 02 02 02 02 02 02 02 02
DSTP 01 01 01 01 01 01 01 01
Table 2 embodiment 1～7 and Comparative Examples 1～4 test result
Can find out from embodiment 1～3 Comparative Examples 1,3 contrast, in polypropylene material, add the melt flow rate (MFR) that polyethylene wax can obviously improve material; Can find out from the contrast of embodiment 3～5 Comparative Examples 1～2, the adding of linear low density polyethylene can improve the anti-stress whitening performance of material, with the acting in conjunction of polyethylene wax under, can access all good modified polypropylene materials of flowability and stress whitening performance.

Claims (8)

  1. One kind high flow, anti-stress whitening modified polypropylene composite material, it is characterized in that: the preparation of raw material by following weight percent meter forms:
  2. 2. according to claim 1ly a kind ofly highly flow, anti-stress whitening modified polypropylene composite material, it is characterized in that: polypropylene of the present invention is under the test condition of 230 ℃ * 2.16Kg, and melt flow rate (MFR) is the Co-polypropylene of 5～30g/10min.
  3. 3. according to claim 1ly a kind ofly highly flow, anti-stress whitening modified polypropylene composite material, it is characterized in that: described ethylene waxes is unoxidized high density polyethylene waxes, and its density is at 0.90-0.98g/cm 3
  4. 4. according to claim 1ly a kind ofly highly flow, anti-stress whitening modified polypropylene composite material, it is characterized in that: described polyethylene is linear low density of polyethylene, under the test condition of 230 ℃ * 2.16Kg, its molten finger is 0.5～10g/10min.
  5. 5. according to claim 1ly a kind ofly highly flow, anti-stress whitening modified polypropylene composite material, it is characterized in that: described oxidation inhibitor is primary antioxidant and auxiliary anti-oxidant, and wherein primary antioxidant is selected from one or more in hindered phenol and the sulphur ester antioxidant; Auxiliary anti-oxidant is selected one or more in phosphite and the ester kind antioxidant.
  6. 6. according to claim 5ly a kind ofly highly flow, anti-stress whitening modified polypropylene composite material, it is characterized in that: primary antioxidant be 3114,1010 and DSTP in one or more; Auxiliary anti-oxidant is one or both in 618 and 168.
  7. 7. according to claim 1ly a kind ofly highly flow, anti-stress whitening modified polypropylene composite material, it is characterized in that: also comprise being no more than other auxiliary agents of 3% mixture of one or more that described other main frames are various lubricants, anti UV agent and pigment.
  8. 8. one kind prepares that the described height of claim 1 flows, the method for anti-stress whitening modified polypropene, and it is characterized in that: its step is as follows:
    (take by weighing by weight ratio raw material;
    2 place super mixer to be dry mixed 3～5 minutes the raw material;
    3 put into the twin screw extruder extruding pelletization with the raw material that mixes, and screw speed is 180～600 rev/mins, and temperature is 190～200 ℃ in a district, 200～220 ℃ in two districts, 220～235 ℃ in three districts, 215～220 ℃ in four districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18MPa.
CN2012105851345A 2012-12-28 2012-12-28 High-fluidity and stress-resistance whitening modified polypropylene composite material and preparation method thereof Pending CN103044783A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103756132A (en) * 2013-12-28 2014-04-30 重庆普利特新材料有限公司 Wear-resisting polypropylene composite material and preparation method thereof
CN105219072A (en) * 2015-10-30 2016-01-06 无锡市长安曙光手套厂 A kind of electroconductive nylon, preparation method and its usage
CN105504647A (en) * 2015-12-30 2016-04-20 上海普利特复合材料股份有限公司 Stress-whitening-resistant imitated-metal-effect polypropylene composite material and preparation method thereof
CN106700386A (en) * 2015-11-15 2017-05-24 合肥杰事杰新材料股份有限公司 Stress whitening resistant styrene-based resin, and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101759934A (en) * 2008-12-23 2010-06-30 上海普利特复合材料股份有限公司 High-flowing high-tenacity and low-contractibility rate filling modified polypropylene material
CN101759918A (en) * 2008-12-23 2010-06-30 上海普利特复合材料股份有限公司 Conductive polypropylene composite material and preparation method thereof
CN102558676A (en) * 2011-12-21 2012-07-11 上海普利特复合材料股份有限公司 Highly-antibacterial polypropylene composite material and preparation method thereof
CN102649854A (en) * 2011-02-23 2012-08-29 中国科学院化学研究所 Polypropylene composition and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101759934A (en) * 2008-12-23 2010-06-30 上海普利特复合材料股份有限公司 High-flowing high-tenacity and low-contractibility rate filling modified polypropylene material
CN101759918A (en) * 2008-12-23 2010-06-30 上海普利特复合材料股份有限公司 Conductive polypropylene composite material and preparation method thereof
CN102649854A (en) * 2011-02-23 2012-08-29 中国科学院化学研究所 Polypropylene composition and preparation method thereof
CN102558676A (en) * 2011-12-21 2012-07-11 上海普利特复合材料股份有限公司 Highly-antibacterial polypropylene composite material and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103756132A (en) * 2013-12-28 2014-04-30 重庆普利特新材料有限公司 Wear-resisting polypropylene composite material and preparation method thereof
CN103756132B (en) * 2013-12-28 2016-09-21 重庆普利特新材料有限公司 A kind of wear-resisting polypropene composite material and preparation method thereof
CN105219072A (en) * 2015-10-30 2016-01-06 无锡市长安曙光手套厂 A kind of electroconductive nylon, preparation method and its usage
CN106700386A (en) * 2015-11-15 2017-05-24 合肥杰事杰新材料股份有限公司 Stress whitening resistant styrene-based resin, and preparation method thereof
CN105504647A (en) * 2015-12-30 2016-04-20 上海普利特复合材料股份有限公司 Stress-whitening-resistant imitated-metal-effect polypropylene composite material and preparation method thereof

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