CN107987449A - A kind of micro-foaming polypropylene composite material for bumper and preparation method thereof - Google Patents
A kind of micro-foaming polypropylene composite material for bumper and preparation method thereof Download PDFInfo
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- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
The present invention relates to technical field of macromolecules, more particularly to a kind of micro-foaming polypropylene composite material for bumper and preparation method thereof, the micro-foaming polypropylene composite material for bumper is made of feedstock composition, and the feedstock composition includes：First copolymer polypropylene powder, 85.5~93.5 parts by weight；Second copolymer polypropylene pellet, 40~65 parts by weight；5~10 parts by weight of alkyl acrylate；0.5~1.5 parts by weight of initiator；1~3 parts by weight of assistant crosslinking agent；1.5~4 parts by weight of foaming agent；10~20 parts by weight of talcum powder；10~20 parts by weight of elastomer；0.2~0.4 parts by weight of antioxidant；0.5~1 parts by weight of lubricant；Selectable 0~2 parts by weight of auxiliary agent.The present invention carries out graft modification to polypropylene, not only increase polyacrylic surface tension and high fondant-strength, also improve polyacrylic mechanical property, obtain abscess dense uniform, the micro-foaming polypropylene composite material for bumper of excellent in mechanical performance, have broad application prospects on bumper, vehicle loss of weight drop is originally had far-reaching significance.
Description
Technical field
The present invention relates to technical field of macromolecules, and in particular to a kind of micro-foaming polypropylene for bumper is compound
Material and preparation method thereof.
Background technology
With the rise and development of automobile industry, automobile just develops towards light weight, safe and environment-friendly direction, and lightweight is
So master is originally enjoyed as one of important development trend of traditional combustion engine automobile and new-energy automobile, the loss of weight drop of vehicle material
Machine factory and the concern of parts manufacturer.Bumper is that a kind of surface area is big as one of automobile large parts, product weight,
Baroque large parts, studies the technique in its loss of weight, simplified spraying process, reduces production cost, be responsive motor
Lightweight, the direction of environmental protection development, originally have far-reaching significance vehicle loss of weight drop.
The polypropylene expanded abscess for producing 10-100um in the base by being molded fretting map moulding process, can significantly drop
Low density of material, not only reduces material utilization amount, saves material cost, also eliminates internal stress, improves buckling deformation, while have matter
Amount is light, and specific strength is high, the characteristic such as sound insulation, heat-insulated, thus is widely used in the fields such as automobile, household electrical appliances, electronic apparatus.Due to poly-
Propylene is that molecular structure is regular, crystallinity is high, causes processing temperature to exceed fusing point, and viscosity drastically declines, and melt strength is low, causes
Gas is difficult to be wrapped up by melt, escapes into surface, the defects of causing a large amount of gas traces, skin lamination, floating, restricts polypropylene
Application of the micro-foaming material on bumper.Common method is sprayed to polypropylene, can cover product
Surface defect, obtains good appearance, produces fine visual effect.But spraying does not require nothing more than matrix resin with excellent
Mechanical performance and mobility, it is also necessary to which there is good paint adhesion.Polypropylene is a kind of non-polar material again, without polarity
Group, article surface can be low, are not easy to infiltrate, bind and print.Coating is poor, low with the conjugation of paint.It is pre- without surface
Processing is difficult to direct spraying paint, and parts manufacturer generally passes through following two sides to improve polyacrylic sprayable property
Method：It is a kind of article surface to be handled using flame, electric arc processing to increase the polar group on PP surfaces, but its equipment is held high
It is expensive, inconvenient, there are security risk, therefore it is subject to certain restrictions；Another kind is spraying PP priming paint, i.e., with PP bottoms before spraying
Paint carries out article surface one layer of highly polar group of pretreatment, forms the thin transition zone of 2-3um, improves PP surface polarities, but deposit
Complicated in flow, cycle length is of high cost, pollutes environment.The Chinese patent application of Application No. CN 105504529A uses ethene
Ethyl acrylate prepares a kind of polypropylene dedicated composite wood of bumper to improve the surface tension of PP composite material
Material.Polyacrylic surface polarity is improved by adding polar substances, is a kind of simple and effective method, but polar material
Matter is poor with polypropylene compatible, and polar group is difficult to realize uniformly disperse on surface.
Therefore high-performance, high surface tension how are developed, the polypropylene micro-foaming material of high fondant-strength becomes the country
The hot subject of outer extensive concern.
The content of the invention
In view of the deficiencies of the prior art, an object of the present invention is to provide a kind of fretting map for bumper and gathers
The characteristics of acrylic composite, it has, and density is small, surface-active is high, excellent in mechanical performance.
The second object of the present invention is to provide a kind of preparation of the micro-foaming polypropylene composite material for bumper
Method, it has the characteristics that process stabilizing, easy to operate, production cost is low, is adapted to industrialization continuous production.
To achieve these goals, it is described the present invention is provided to the micro-foaming polypropylene composite material of bumper
Micro-foaming polypropylene composite material for bumper is made of feedstock composition, and the feedstock composition includes：
The present invention also provides a kind of preparation method of the micro-foaming polypropylene composite material for bumper,
Comprise the following steps：
(1) the first copolymer polypropylene powder is stirred to complete swelling in organic solvent, then adds acrylic acid alkyl
After ester monomer and assistant crosslinking agent stir evenly, initiator is added, then in atmosphere of inert gases, is stirred at 100~130 DEG C
2~4h, is then cooled to room temperature, after centrifuge washing, drying, obtains modified polypropene；
(2) by modified polypropene, the second copolymer polypropylene pellet, talcum powder, elastomer, antioxidant, lubricant and auxiliary agent
After mixing, put into double screw extruder, through melting, being granulated, PP composite material is made；
(3) PP composite material and foaming agent are added into injection molding machine after mixing, carries out twice-die-opening injection, obtain
Micro-foaming polypropylene composite material for bumper.
Through the above technical solutions, the present invention has following technique effect：
1st, the present invention uses acrylate to carry out graft modification to the first copolymer polypropylene powder for grafted monomers, not only exists
Polar group and hydrophobic fat clan elder's main chain are introduced on polypropylene backbone, while alkyl group of drawing money on credit forms branched structure, with the
Two copolymer polypropylene segments mutually tangle, and form three-dimensional netted three-dimensional-structure, so as to improve polyacrylic surface tension, change
It is apt to polyacrylic adhesive force, strengthens the combination power of matrix and paint film.
2nd, modified polypropene can mutually tangle under the high shear forces of twin-screw with the second copolymer polypropylene, and first
The branched segment of copolymer polypropylene and the second copolymer polypropylene segment form crosslinking points, and the melt for improving the second copolymer polypropylene is strong
Degree, effectively supports the growth of carbon dioxide bubble.
3rd, micro-foaming polypropylene composite material of the invention has density small, and surface-active is high, can be directly on its surface
Spray paint, cost-effective and resource, has broad application prospects on bumper, and to vehicle loss of weight drop, this has deep
Remote meaning.
4th, the present invention in micro-foaming polypropylene composite material stable preparation process, easy to operate, production cost is low, be adapted to
Industrialize continuous production.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
It is described to be used for car insurance the present invention provides a kind of micro-foaming polypropylene composite material for bumper
The micro-foaming polypropylene composite material of thick stick is made of feedstock composition, and the feedstock composition includes：
In order to optimize the mobility of the micro-foaming polypropylene composite material, under optimum condition, at 230 DEG C, 2.16kg's
Under test condition, the melt flow rate (MFR) (MI) of the second copolymer polypropylene pellet is 30~100g/10min.
In order to optimize the impact strength of the micro-foaming polypropylene composite material, under optimum condition, the elastomer is
Polyolefin elastomer (POE), it is further preferred that under 190 DEG C, the test condition of 2.16kg, the polyolefin elastomer
Melt flow rate (MFR) (MI) is 5~30g/10min.
In order to optimize the rigidity of the micro-foaming polypropylene composite material, heat resistance and shrinking percentage, carried using talcum powder
High polypropylene rigidity and heat resistance, reduce its shrinking percentage.
Graft modification is carried out to the first copolymer polypropylene powder by alkyl acrylate in the present invention, it is poly- in the first copolymerization
The surface of propylene introduces fatty clan elder's main chain, so as to improve the mechanical property and Surface Polarization of micro-foaming polypropylene composite material
Can, under optimum condition, the alkyl acrylate is selected from lauryl ester, octadecyl methacrylate and third
At least one of olefin(e) acid docosane ester.
By adding initiator and assistant crosslinking agent in the present invention, promote and improve the grafting effect of the first copolymer polypropylene powder
Rate, under optimum condition, the initiator is dibenzoyl peroxide and/or azodiisobutyronitrile；The assistant crosslinking agent is diethyl
Alkenyl benzene, rosin ester, triallyl cyanurate, iso-cyanuric acid triallyl ester.
In order to further optimize the inoxidizability of micro-foaming polypropylene composite material, under optimum condition, the antioxidant choosing
From at least one of Hinered phenols antioxidant, thiosulfates kind antioxidant and phosphite ester kind antioxidant, further preferably
, the Hinered phenols antioxidant is antioxidant 1010, and the thiosulfates kind antioxidant is anti-oxidant DLTP, the phosphorous
Acid esters kind antioxidant is irgasfos 168.
In order to simplify the expressing technique of micro-foaming polypropylene composite material, also added in the present invention in copolymer polypropylene
Lubricant, under optimum condition, the lubricant is Tissuemat E, calcium stearate, zinc stearate, lignite wax, pentaerythrite are stearic
At least one of acid esters.
In order to further improve the comprehensive performance of micro-foaming polypropylene composite material, the present invention also adds in the composite
Auxiliary agent, the auxiliary agent in UV absorbers, light stabilizer, finishing agent, antistatic additive and the colouring agent at least
One kind, it is further preferred that the ultra-violet absorber is selected from least one of UV-9, UV-531 and UVP-327；The light
Stabilizer is selected from least one of light stabilizer 292, light stabilizer 622, light stabilizer 770 and light stabilizer 944；The table
The one kind of face brightener in erucyl amide, glycerin monostearate, oleamide；The antistatic additive is selected from polyether ester acyl
At least one of amine, epoxypropane copolymerization thing and polyethylene glycol oxide；The colouring agent is selected from carbon black, lemon yellow, indigo, phthalein
Cyanines are at least one of green.
In order to reduce harm of the foaming agent to environment, under optimum condition, the present invention uses environmentally protective micro-foaming material,
For example, the chemical foaming agent be foaming agent using LDPE as carrier, sodium acid carbonate parcel LDPE carrier insides.
The present invention also provides a kind of preparation method of the micro-foaming polypropylene composite material for bumper, including with
Lower step：
(1) the first copolymer polypropylene powder is stirred to complete swelling in organic solvent, then adds acrylic acid alkyl
After ester monomer and assistant crosslinking agent stir evenly, initiator is added, then in atmosphere of inert gases, is stirred at 100~130 DEG C
2~4h, is then cooled to room temperature, after centrifuge washing, drying, obtains modified polypropene；
(2) by modified polypropene, the second copolymer polypropylene pellet, talcum powder, elastomer, antioxidant, lubricant and auxiliary agent
After mixing, put into double screw extruder, through melting, being granulated, PP composite material is made；
(3) PP composite material and foaming agent are added into injection molding machine after mixing, carries out twice-die-opening injection, obtain
Micro-foaming polypropylene composite material for bumper.
Under optimum condition, the organic solvent is selected from dimethylbenzene.
In step (1), the technique of the stirring to complete swelling is that 24~36h is stirred at 40~50 DEG C.
In order to improve the grafting efficiency of the first copolymer polypropylene powder, under optimum condition, in step (1), the initiation
Agent is divided into be added three times, and the interval time added every time is 10~15min.
Under the conditions of, according to the invention it is preferred to, in step (2), the technique of the melting extrusion is：The extrusion temperature of extruder
Spend for 180~200 DEG C, screw speed is 350~400r/min, and vacuum is -0.06~-0.08MPa.
In order to improve the uniformity of stomata in micro-foaming polypropylene composite material, under optimum condition, under optimum condition, in step
Suddenly in (3), the temperature of the injection molding is 180~200 DEG C.
The present invention will be described in detail by way of examples below.In following embodiments, copolymer polypropylene powder
(M350R) it is purchased from oil of SPC；Second copolymer polypropylene pellet (K7100) is purchased from Yanshan Petrochemical；Second copolymer polypropylene pellet
(K6760) it is purchased from Yanshan Petrochemical；Second copolymer polypropylene pellet (M30RHC) is purchased from Zhenghai refinery；Foaming agent (EE207) is purchased from
Japanese Yonghe County's chemical conversion industry Co., Ltd., POE (8407) are purchased from the U.S. DOW, POE (8200) purchased from the U.S. DOW, POE (8137)
Purchased from U.S. DOW.
Embodiment 1
A kind of micro-foaming polypropylene composite material for bumper, is made of following material：
The preparation method of the micro-foaming polypropylene composite material for bumper, step are as follows：
(1) 93.5 parts by weight copolymer polypropylene M350R powders are stirred into 24h at 40 DEG C in dimethylbenzene, then adds 5 weights
After amount part lauryl methacrylate monomer and 1 parts by weight divinylbenzene stir evenly, 0.5 parts by weight peroxidating is added
Dibenzoyl, then in nitrogen atmosphere, stirs 2h, then cooled to room temperature, after centrifuge washing, 40 at 100 DEG C
24h is dried in vacuo at DEG C, obtains modified polypropene；
(2) 10 part by weight modified polypropylene, 65 parts by weight copolymer polypropylene M30RHC pellets, 10 parts by weight talcums are weighed
Powder, 10 parts by weight POE 8407,0.1 parts by weight antioxidant 1010,0.1 parts by weight irgasfos 168 and 0.5 parts by weight of calcium stearate
After mixing, put into parallel dual-screw extruding machine, through melting, being granulated, PP composite material is made；The melting extrusion
Technique be：The extrusion temperature of extruder is 190 DEG C, screw speed 400r/min, and vacuum is -0.08MPa.
(3) above-mentioned PP composite material and 1.5 parts by weight of blowing agent (EE207) are added into injection molding machine after mixing,
Twice-die-opening injection is carried out, forming temperature is 190 DEG C, obtains the micro-foaming polypropylene composite material for bumper.
Embodiment 2
A kind of micro-foaming polypropylene composite material for bumper, is made of following material：
The preparation method of the micro-foaming polypropylene composite material for bumper, step are as follows：
(1) 85.5 parts by weight copolymer polypropylene M350R powders are stirred into 36h at 50 DEG C in dimethylbenzene, then adds 10
After weight parts of methacrylic acid octadecyl ester monomer and 3 parts by weight triallyl cyanurates stir evenly, 1.5 weights are added
Amount part azodiisobutyronitrile (is divided into 2 additions, interval time 15min), then in nitrogen atmosphere, at 130 DEG C
4h is stirred, then cooled to room temperature, after centrifuge washing, be dried in vacuo 48h at 60 DEG C, obtain modified polypropene；
(2) weigh 15 part by weight modified polypropylene, 50 parts by weight copolymer polypropylene K6760 pellets, 20 parts by weight talcum powder,
15 parts by weight POE 8137,0.2 parts by weight antioxidant 1010,0.2 parts by weight irgasfos 168 and the mixing of 1 weight account polyethylene wax
After uniformly, put into parallel dual-screw extruding machine, through melting, being granulated, PP composite material is made；The work of the melting extrusion
Skill is：The extrusion temperature of extruder is 200 DEG C, screw speed 400r/min, and vacuum is -0.06MPa.
(3) above-mentioned PP composite material and 4 parts by weight of blowing agent (EE207) are added into injection molding machine after mixing, into
Row twice-die-opening is molded, and forming temperature is 180~200 DEG C, obtains the micro-foaming polypropylene composite material for bumper.
Embodiment 3
A kind of micro-foaming polypropylene composite material for bumper, is made of following material：
The preparation method of the micro-foaming polypropylene composite material for bumper, step are as follows：
(1) 89.5 parts by weight copolymer polypropylene M350R powders are stirred into 30h at 45 DEG C in dimethylbenzene, then adds 7.5
After weight parts of methacrylic acid octadecyl ester monomer and 2 parts by weight divinylbenzenes stir evenly, 1 parts by weight azo two is added
Isobutyronitrile (is divided into 3 additions, interval time 15min), then in nitrogen atmosphere, 2h is stirred at 120 DEG C, then
Cooled to room temperature, after centrifuge washing, is dried in vacuo 36h at 55 DEG C, obtains modified polypropene；
(2) 20 part by weight modified polypropylene, 40 parts by weight copolymer polypropylene K7170 pellets pellets, 20 parts by weight are weighed to slide
Mountain flour, 20 parts by weight POE 8200,0.15 parts by weight anti-oxidant DLTP, 0.15 parts by weight irgasfos 168,0.75 parts by weight are stearic
Sour calcium, 0.5 parts by weight UV-531,0.5 parts by weight light stabilizer 944 and 1 parts by weight of lemon Huang after mixing, are put into double in the same direction
In screw extruder, through melting, being granulated, PP composite material is made；The technique of the melting extrusion is：The extrusion of extruder
Temperature is 180 DEG C, screw speed 350r/min, and vacuum is -0.08MPa.
(3) above-mentioned PP composite material and 1.5 parts by weight of blowing agent (EE207) are added into injection molding machine after mixing,
Twice-die-opening injection is carried out, forming temperature is 180 DEG C, obtains the micro-foaming polypropylene composite material for bumper.
Embodiment 4
A kind of micro-foaming polypropylene composite material for bumper, is made of following material：
The preparation method of the micro-foaming polypropylene composite material for bumper, step is the same as embodiment 3.
Comparative example 1
According to the method for embodiment 3, the difference is that, graft modification processing is not carried out to the first copolymer polypropylene, (made
Step (1) is not included during standby).
Comparative example 2
According to the method for embodiment 3, the difference is that, do not contain the first copolymer polypropylene.
Comparative example 3
According to the method for embodiment 3, the difference is that, do not contain elastomer POE.
Test 1：By the main thing of micro-foaming polypropylene composite material made from above-described embodiment 1~4 and comparative example 1~3
Property index is according to coherent detection standard testing, its apparent density, loss of weight ratio, melt strength, surface tension and mean cell diameter
Examination criteria and testing result it is as shown in table 1.
Wherein, loss of weight than computational methods：The loss of weight ratio=(weight of the weight of unexpanded bumper-foaming rear bumper
Amount)/unexpanded bumper weight * 100%.
Table 1：Micro-foaming polypropylene composite material performance indicator in embodiment 1~4 and comparative example 1~3
From table 1 it follows that adding the polypropylene of graft modification in the second copolymer polypropylene pellet matrix, not only may be used
To improve the adhesive force of paint, strengthen the combination power of basis material and paint film, moreover it is possible to improve polyacrylic melt strength this poly- third
Alkene composite material after tested material surface tension up to 48mN/N, melt strength up to 7.3CN, after twice-die-opening foams its
Density as low as 0.68g/cm3, abscess average diameter as low as 58um.
Test 2：By the main power of micro-foaming polypropylene composite material made from above-described embodiment 1~4 and comparative example 1~3
Performance indicator is learned according to coherent detection standard testing, its tensile strength, 23 DEG C of notch impact strengths, bending strength, bending moduluses
Examination criteria and testing result it is as shown in table 2.
Table 2：Micro-foaming polypropylene composite material mechanical performance index in embodiment 1~4 and comparative example 1~3
From Table 2, it can be seen that adding cross-linking modified polypropylene in the second copolymer polypropylene pellet matrix, significantly carry
The high tensile strength of PP composite material, notch impact strength and bending property.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of micro-foaming polypropylene composite material for bumper, it is characterised in that be made of feedstock composition, institute
Stating feedstock composition includes：
2. the micro-foaming polypropylene composite material according to claim 1 for bumper, wherein, described second is common
The melt flow rate (MFR) of poly- polypropylene granules is 30~100g/10min.
3. the micro-foaming polypropylene composite material according to claim 1 for bumper, wherein, the elastomer
For polyolefin elastomer.
4. the micro-foaming polypropylene composite material according to claim 3 for bumper, wherein, the polyolefin
The melt flow rate (MFR) of elastomer is 5~30g/10min.
5. the micro-foaming polypropylene composite material according to claim 1 for bumper, wherein, the acrylic acid
Arrcostab in lauryl ester, octadecyl methacrylate and behenyl ester at least one
Kind；And/or
The initiator is dibenzoyl peroxide and/or azodiisobutyronitrile；And/or
The assistant crosslinking agent is selected from divinylbenzene, rosin ester, triallyl cyanurate, iso-cyanuric acid triallyl ester
It is at least one.
6. the micro-foaming polypropylene composite material according to claim 1 for bumper, wherein, the antioxidant
Selected from least one of Hinered phenols antioxidant, thiosulfates kind antioxidant and phosphite ester kind antioxidant.
7. the micro-foaming polypropylene composite material according to claim 1 for bumper, wherein, the auxiliary agent choosing
From at least one of UV absorbers, finishing agent, light stabilizer, antistatic additive and colouring agent.
8. the micro-foaming polypropylene composite material for bumper according to any one in claim 1~7
Preparation method, it is characterised in that comprise the following steps：
(1) the first copolymer polypropylene powder is stirred to complete swelling in organic solvent, then adds alkyl acrylate list
After body and assistant crosslinking agent stir evenly, add initiator, then in atmosphere of inert gases, at 100~130 DEG C stir 2~
4h, is then cooled to room temperature, after centrifuge washing, drying, obtains modified polypropene；
(2) modified polypropene, the second copolymer polypropylene pellet, talcum powder, elastomer, antioxidant, lubricant and auxiliary agent are mixed
After uniformly, put into double screw extruder, through melting, being granulated, PP composite material is made；
(3) PP composite material and foaming agent are added into injection molding machine after mixing, carries out twice-die-opening injection, be used for
The micro-foaming polypropylene composite material of bumper.
9. preparation method according to claim 8, wherein, in step (1), the initiator is divided into be added three times
Enter, the interval time added every time is 10~15min.
10. preparation method according to claim 8 or claim 9, wherein, in step (2), the technique of the melting extrusion is：
The extrusion temperature of extruder is 180~200 DEG C, and screw speed is 350~400r/min, and vacuum is -0.06~-0.08MPa；
And/or
In step (3), the temperature of the injection molding is 180~200 DEG C.
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