CN109942950A - A kind of resistance to stress whitens, mar-proof automobile-used PP/PETG alloy material and preparation method thereof - Google Patents
A kind of resistance to stress whitens, mar-proof automobile-used PP/PETG alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of resistance to stress to whiten, mar-proof automobile-used PP/PETG alloy material and preparation method thereof.It is by the 40-70% polypropylene of weight percent, and 5-20%PETG, 10-20% is mineral-filled, 5-15% toughener, 1-4% compatilizer, 0.4% antioxidant, 0.4% lubricant, and 0.2% light stabilizer is prepared.With greatly reducing stress whitening, scratch resistant effect.
Description
Technical field
The present invention relates to technical field of polymer materials more particularly to a kind of resistance to stress to whiten, mar-proof automobile-used PP/PETG
Alloy material and preparation method thereof.
Background technique
Increasingly developed with automobile industry, light weight, beauty, energy-saving and environmental protection more become major host and produce and consumer
The target of pursuit, and have low-density, heat resistance height, performance low cost polypropylene (PP) as the maximum automobile-used macromolecule of usage amount
Material is widely used in automobile interior exterior decorations, but since it is in injection molding ejection stage easy external force or material by thimble
Expect use process collision, bending function, and stress concentration occurs, and then stress whitening occurs.Some researches show that the silver at place of whitening
The refractive index of line or crackle is different, is to generate the main reason for whitening.In addition, polypropylene material scratch resistant performance difference itself is often
Limit its further application.Traditional solves the problems, such as that PP resistance to stress is whitened, the simplest method of damage resistant is exactly to pass through addition
Damage resistant auxiliary agent, as resistance to stress is whitened auxiliary agent, silicone master batch, the lower material of erucic acid class master batch equimolecular quantity.Its principle is just
It is by the product surface of the migrations such as the molding front and back lower silicone master batch of molecular weight, forming protective layer reduces coefficient of friction, with
Improve damage resistant coefficient, but this method will also result in automobile air VOC pollution, a series of problems, such as material surface is tacky, because
A resistance to stress of exploitation is whitened, mar-proof automobile-used polypropylene material has become experts and scholars' urgent problem to be solved for this.
PETG full name is polyethylene terephthalate -1,4 cyclohexane dimethanol ester.It is by terephthalic acid (TPA)
(PTA), the product of three kinds of monomer ester-interchange method polycondensations of ethylene glycol (EG) and 1,4-CHDM (CHDM), in simple terms
It is a kind of transparent, non-crystalline type copolyesters, there is high stress-whitening resistance energy, high tenacity, high-strength and preferable resistance to shock resistance
Performance.PETG is mainly used in the fields such as cosmetic package, credit card at present.
CN104558836A discloses a kind of mar-proof and resistance to stress and whitens PP composite material and preparation method thereof, uses
Response type siloxanes and polypropylene crosslink effect and whiten and mar-proof ability to improve the resistance to stress of PP composite material,
But this method controllability is lower, is unfavorable for being mass produced.CN105037955A discloses a kind of low VOC, scratch-resistant, resistance to stress hair
White polypropene composition and preparation method thereof, using oligomeric low molecular weight polysiloxane, polypropylene grafted high molecular weight
Polysiloxane whitens to improve polypropylene material resistance to stress, but oligomer inevitably occurs and moves out tacky phenomenon.
Summary of the invention
The purpose of the present invention is to provide a kind of resistance to stress to whiten, mar-proof automobile-used PP/PETG alloy material.
To achieve the above object, the present invention provide a kind of resistance to stress whiten, mar-proof automobile-used PP/PETG alloy material,
It is characterized in that, by following weight percentage components: polypropylene 40-70%, PETG 5-20%, mineral-filled 10-20%,
Toughener 5-15%, compatilizer 1-4%, antioxidant 0.4%, lubricant 0.4%, light stabilizer 0.2% are prepared.
Further, the polypropylene is homopolypropylene or copolymer polypropylene；Preferably, the polypropylene is 2.16/230
Melting means under the conditions of DEG C is 30~60g/10min.
Further, melting means of PETG under the conditions of 2.16/230 DEG C is 20-85g/10min.
Further, it is described it is mineral-filled be superfine talcum powder, wherein SiO2Content >=56%, mesh number >=5000 mesh.
Further, melting means of toughener under the conditions of 2.16kg/190 DEG C is 5-15g/10min；Preferably, toughening
Agent is ethylene-octene copolymer, ethylene propylene diene rubber, one of Methyl Methacrylate-Butadiene-Styrene Copolymer or
More than one combination.
Further, compatilizer is ethylene-propylene copolymer grafted maleic anhydride, ethylene-octene copolymer grafted maleic
One of acid anhydride and polypropylene grafted maleic anhydride are two or more.
Further, the antioxidant is the mass ratio compounding gained of primary antioxidant and auxiliary anti-oxidant according to 1:1；It is preferred that
, the primary antioxidant is Hinered phenols primary antioxidant 1010 or Hinered phenols primary antioxidant 1076, the auxiliary anti-oxidant are sub-
Phosphoric acid ester auxiliary anti-oxidant 168 or phosphorous acid esters auxiliary anti-oxidant 686.
Further, the lubricant is stearates or aliphatic amide type or stearic acid class；Preferably, the tristearin
Barbiturates is zinc stearate or calcium stearate；Fat race amides are stearic acid acid amide, erucic acid acid amide or N-N ethylenebis
Stearic acid amine；The stearic acid class is stearic acid and/or hydroxy stearic acid.
Further, the light stabilizer is hindered amines, and N- is alkylated class, ultraviolet absorbing agent benzotriazole, triazine
One of benzylidene malonic acid esters or any two or more mixtures.
Further, the preparation method comprises the following steps:
Premix preparation: being added to progress high-speed stirred in high-speed mixer for load weighted all materials and be uniformly mixed,
Obtain premix；
Blending extrusion: parallel double-screw extruder is added from main feeding hopper in resulting premix, makes all components material
Shear melting blending extrusion is carried out in parallel double-screw extruder and obtains material strip, wherein each section of processing temperature of double screw extruder
For 90 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 230 DEG C, 220 DEG C, 210 DEG C, 200 DEG C of mouth mold；
The material strip is cooling, dry, pelletizing can be obtained resistance to stress whiten, mar-proof automobile-used PP/PETG alloy material.
Inventor is by creative discovery, and when weight percent is polypropylene 40-70%, PETG 5-20%, mineral are filled out
Fill 10-20%, toughener 5-15%, compatilizer 1-4%, antioxidant 0.4%, lubricant 0.4%, when light stabilizer 0.2%, system
The resistance to stress of standby obtained automobile-used PP/PETG alloy material whitens, mar-proof PP, and (Guangzhou silicon-carbon is new with scratch-resistant silicone master batch
The silicone master batch SIC-6011P of Materials Co., Ltd) compared to not only have good resistance to stress whiten, mar-proof effect, but also
Composite material machinery performance greatly improve and meanwhile avoid oligomeric molecule migration bring VOC pollution and product surface it is tacky can
Energy.This is because PETG melt strength is relatively low, for mixture when being mixed by screw rod shearing, PETG and toughener form class
Like the shell-core structure that Soft Roll is hard, the strand between polypropylene/PETG/ toughener is caused to be easy to tangle, so by
To stress, polypropylene/PETG/ toughener strand can inhibit crazing, hole to generate, together by Mobility of the chain segments deformation
When consume energy, to greatly reduce stress whitening.
Specific embodiment
The embodiment of the present invention is described below in detail, the examples of the embodiments are intended to be used to explain the present invention, and cannot
It is interpreted as limitation of the present invention.In the examples where no specific technique or condition is specified, described according to the literature in the art
Technology or conditions or carried out according to product description.Reagents or instruments used without specified manufacturer is that can lead to
Cross the conventional products of commercially available acquisition.
A kind of resistance to stress whitens, mar-proof automobile-used PP/PETG alloy material, which is characterized in that it is by following weight percent
The component of ratio: polypropylene 40-70%, PETG 5-20%, mineral-filled 10-20%, toughener 5-15%, compatilizer 1-4%,
Antioxidant 0.4%, lubricant 0.4%, light stabilizer 0.2% are prepared.
Further, the polypropylene is homopolypropylene or copolymer polypropylene；Preferably, the polypropylene is 2.16/230
Melting means under the conditions of DEG C is 30~60g/10min.
Further, melting means of PETG under the conditions of 2.16/230 DEG C is 20-85g/10min.
Further, it is described it is mineral-filled be superfine talcum powder, wherein SiO2Content >=56%, mesh number >=5000 mesh.
Further, melting means of toughener under the conditions of 2.16kg/190 DEG C is 5-15g/10min；Preferably, toughening
Agent is ethylene-octene copolymer, ethylene propylene diene rubber, one of Methyl Methacrylate-Butadiene-Styrene Copolymer or
More than one combination.
Further, compatilizer is ethylene-propylene copolymer grafted maleic anhydride, ethylene-octene copolymer grafted maleic
One of acid anhydride and polypropylene grafted maleic anhydride are two or more.
Further, the antioxidant is the mass ratio compounding gained of primary antioxidant and auxiliary anti-oxidant according to 1:1；It is preferred that
, the primary antioxidant is Hinered phenols primary antioxidant 1010 or Hinered phenols primary antioxidant 1076, the auxiliary anti-oxidant are sub-
Phosphoric acid ester auxiliary anti-oxidant 168 or phosphorous acid esters auxiliary anti-oxidant 686.
Further, the lubricant is stearates or aliphatic amide type or stearic acid class；Preferably, the tristearin
Barbiturates is zinc stearate or calcium stearate；Fat race amides are stearic acid acid amide, erucic acid acid amide or N-N ethylenebis
Stearic acid amine；The stearic acid class is stearic acid and/or hydroxy stearic acid.
Further, the light stabilizer is hindered amines, and N- is alkylated class, ultraviolet absorbing agent benzotriazole, triazine
One of benzylidene malonic acid esters or any two or more mixtures.
Further, the preparation method comprises the following steps:
Premix preparation: being added to progress high-speed stirred in high-speed mixer for load weighted all materials and be uniformly mixed,
Obtain premix；
Blending extrusion: parallel double-screw extruder is added from main feeding hopper in resulting premix, makes all components material
Shear melting blending extrusion is carried out in parallel double-screw extruder and obtains material strip, wherein each section of processing temperature of double screw extruder
For 90 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 230 DEG C, 220 DEG C, 210 DEG C, 200 DEG C of mouth mold；
The material strip is cooling, dry, pelletizing can be obtained resistance to stress whiten, mar-proof automobile-used PP/PETG alloy material.
Embodiment 1: resistance to stress whitens, the preparation of mar-proof automobile-used PP/PETG alloy material
Raw material: it is shown in Table 1.
Preparation method:
(1) PP, PETG, toughener, compatilizer, mineral-filled, antioxidant, lubricant are weighed by weight percentage；
(2) all materials in step (1) are added to progress high-speed stirred in high-speed mixer to be uniformly mixed, are premixed
Material；
(3) parallel double-screw extruder is added from main feeding hopper in the premix for obtaining step (2), makes all components material
In parallel double-screw extruder carry out shear melting blending extrusion, wherein double screw extruder processing temperature be 90,170,
180,190,200,210,215,220,230,220,210,200 DEG C of mouth mold；
(4) cooling, the dry, pelletizing by the material strip come out through parallel double-screw extruder mouth mold, obtains resistance to stress and whitens, is resistance to
The automobile-used PP/PETG alloy material of scratch.
Compliance test result: 2 are shown in Table.
Embodiment 2: resistance to stress whitens, the preparation of mar-proof automobile-used PP/PETG alloy material
Raw material: it is shown in Table 1.
Preparation method: see embodiment 1.
Compliance test result: 2 are shown in Table.
Embodiment 3: resistance to stress whitens, the preparation of mar-proof automobile-used PP/PETG alloy material
Raw material: it is shown in Table 1.
Preparation method: see embodiment 1.
Compliance test result: 2 are shown in Table.
Embodiment 4: resistance to stress whitens, the preparation of mar-proof automobile-used PP/PETG alloy material
Raw material: it is shown in Table 1.
Preparation method: see embodiment 1.
Compliance test result: 2 are shown in Table.
Embodiment 5: resistance to stress whitens, the preparation of mar-proof automobile-used PP/PETG alloy material
Raw material: it is shown in Table 1.
Preparation method: see embodiment 1.
Compliance test result: 2 are shown in Table.
Embodiment 6: resistance to stress whitens, the preparation of mar-proof automobile-used PP/PETG alloy material
Raw material: it is shown in Table 1.
Preparation method: see embodiment 1.
Compliance test result: 2 are shown in Table.
Comparative example 1: resistance to stress whitens, the preparation of mar-proof automobile-used PP/PETG alloy material
Raw material: it is shown in Table 1.
Preparation method: see embodiment 1.
Compliance test result: 2 are shown in Table.
Comparative example 2: resistance to stress whitens, the preparation of mar-proof automobile-used PP/PETG alloy material
Raw material: it is shown in Table 1.
Preparation method: see embodiment 1.
Compliance test result: 2 are shown in Table.
The raw material usage table of the comparative example 1-2 of 1 embodiment 1-6 sum of table
Each experimental group testing result list of table 2
As seen from Table 2, the resistance to stress that technical solution of the present invention is prepared whitens, mar-proof automobile-used PP/PETG alloy
The mechanical property of material includes tensile strength (being greater than 22MPa), breaking strain extends (less than 90%), bending strength (is greater than
28MPa), bending modulus (being greater than 1880MPa) and Izod notched impact strength (are greater than 27kJ/m2), it has obtained changing well
It is kind；And the effect of comparative example is poor.Another part mark levies stress-whitening resistance energy and scratch resistance, by falling sphere test and
Mar-proof test obtains modified material by mar-proof and stress-whitening resistance energy under stress, wherein scraping instrument by cross
It tests to obtain with falling sphere, Δ L indicates experiment front and back color difference, and Δ L is smaller to illustrate that stress-whitening resistance energy, scratch resistance are better.
As can be seen that whitened using the resistance to stress that technical solution of the present invention is prepared, mar-proof automobile-used PP/PETG alloy material it is resistance to
It scrapes scratching Δ L and is respectively less than 2, and comparative example is then much larger than 3.The whitening resistance Δ L of falling sphere is respectively less than 3.5, and comparative example is then much larger than
4.Illustrate the resistance to stress being prepared using technical solution of the present invention whiten, mar-proof automobile-used PP/PETG alloy material resistance to stress
Performance, the scratch resistance of whitening are good.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art are not departing from the principle of the present invention and objective
In the case where can make changes, modifications, alterations, and variations to the above described embodiments within the scope of the invention.
Claims (10)
1. a kind of resistance to stress is whitened, mar-proof automobile-used PP/PETG alloy material, which is characterized in that it is by following weight percent
Component: polypropylene 40-70%, PETG5-20%, mineral-filled 10-20%, toughener 5-15%, compatilizer 1-4%, antioxygen
Agent 0.4%, lubricant 0.4%, light stabilizer 0.2% are prepared.
2. according to claim 1 a kind of resistance to stress whiten, mar-proof automobile-used PP/PETG alloy material, which is characterized in that institute
Stating polypropylene is homopolypropylene or copolymer polypropylene；Preferably, melting means of polypropylene under the conditions of 2.16/230 DEG C is
30~60g/10min.
3. according to claim 1 a kind of resistance to stress whiten, mar-proof automobile-used PP/PETG alloy material, which is characterized in that institute
Stating melting means of PETG under the conditions of 2.16/230 DEG C is 20-85g/10min.
4. according to claim 1 a kind of resistance to stress whiten, mar-proof automobile-used PP/PETG alloy material, which is characterized in that institute
Stating mineral-filled is superfine talcum powder, wherein SiO2Content >=56%, mesh number >=5000 mesh.
5. according to claim 1 resistance to stress whiten, mar-proof automobile-used PP/PETG alloy material, which is characterized in that the increasing
Tough dose of melting means under the conditions of 2.16kg/190 DEG C is 5-15g/10min；Preferably, toughener is ethylene-octene copolymer, three
First EP rubbers, one of Methyl Methacrylate-Butadiene-Styrene Copolymer or more than one combination.
6. according to claim 1 a kind of resistance to stress whiten, mar-proof automobile-used PP/PETG alloy material, which is characterized in that phase
Appearance agent is ethylene-propylene copolymer grafted maleic anhydride, ethylene-octene copolymer grafted maleic anhydride and polypropylene grafted Malaysia
One of acid anhydrides is two or more.
7. according to claim 1 a kind of resistance to stress whiten, mar-proof automobile-used PP/PETG alloy material, which is characterized in that institute
Stating antioxidant is the mass ratio compounding gained of primary antioxidant and auxiliary anti-oxidant according to 1:1；Preferably, the primary antioxidant be by
Phenols primary antioxidant 1010 or Hinered phenols primary antioxidant 1076 are hindered, the auxiliary anti-oxidant is phosphorous acid esters auxiliary anti-oxidant 168
Or phosphorous acid esters auxiliary anti-oxidant 686.
8. a kind of anti-stress whitening, mar-proof automobile-used PP/PETG alloy material according to claim 1, which is characterized in that institute
Stating lubricant is stearates or aliphatic amide type or stearic acid class；Preferably, the stearates are zinc stearate
Or calcium stearate；Fat race amides are stearic acid acid amide, erucic acid acid amide or N-N ethylenebis stearic acid amine；The hard ester
Acids is stearic acid and/or hydroxy stearic acid.
9. a kind of anti-stress whitening, mar-proof automobile-used PP/PETG alloy material according to claim 1, which is characterized in that institute
Light stabilizer is stated as in hindered amines, N- alkylation class, ultraviolet absorbing agent benzotriazole, triazine benzylidene malonic acid esters
A kind of or any two or more mixtures.
10. a kind of any resistance to stress of claim 1-9 is whitened, mar-proof automobile-used PP/PETG alloy material, feature exists
In, the preparation method comprises the following steps:
Premix preparation: load weighted all materials are added to progress high-speed stirred in high-speed mixer and are uniformly mixed, are obtained
Premix；
Blending extrusion: parallel double-screw extruder is added from main feeding hopper in resulting premix, makes all components material flat
Shear melting blending extrusion is carried out in row double screw extruder and obtains material strip, and wherein each section of processing temperature of double screw extruder is 90
DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 230 DEG C, 220 DEG C, 210 DEG C, 200 DEG C of mouth mold；
The material strip is cooling, dry, pelletizing can be obtained resistance to stress whiten, mar-proof automobile-used PP/PETG alloy material.
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