CN104945735B - A kind of electric tool fiber glass reinforced polypropylene micro-foaming material and preparation method thereof - Google Patents

A kind of electric tool fiber glass reinforced polypropylene micro-foaming material and preparation method thereof Download PDF

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Publication number
CN104945735B
CN104945735B CN201510352034.1A CN201510352034A CN104945735B CN 104945735 B CN104945735 B CN 104945735B CN 201510352034 A CN201510352034 A CN 201510352034A CN 104945735 B CN104945735 B CN 104945735B
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parts
fiber glass
glass reinforced
reinforced polypropylene
foaming
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CN104945735A (en
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王滨
吴汾
蒋顶军
周勇
汪信
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NANJING JULONG TECHNOLOGY Co Ltd
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NANJING JULONG TECHNOLOGY Co Ltd
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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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a kind of polypropylene material and preparation method thereof, especially a kind of electric tool fiber glass reinforced polypropylene micro-foaming material and preparation method thereof, belongs to technical field of polymer materials.The raw material of the present invention is made of the component of following parts by weight：40 80 parts of polypropylene, 25 parts of compatilizer, 10 50 parts of glass fibre, 2 15 parts of microporous foam composite assistant, 0.5 5 parts of foaming agent, 0.2 2 parts of antioxidant.Using injection fretting map technology, under the premise of ensureing that fiber glass reinforced polypropylene material mechanical performance is not lost substantially, mitigate part weight, improve portability, significantly reduce production cost；At the same time by using microporous foam composite assistant, hence it is evident that improve the surface quality of polypropylene micro-foaming material, solve the problems such as its article surface floating in injection moulding tool shell, gas trace, meet it in field of power tools application requirement；This material can also be used for other fields such as automobile, building, electronics, shipbuilding etc..

Description

A kind of electric tool fiber glass reinforced polypropylene micro-foaming material and preparation method thereof
Technical field
The present invention relates to a kind of PP composite material and preparation method thereof, especially a kind of electric tool fiberglass reinforced Polypropylene micro foaming composite material and preparation method thereof, belongs to technical field of polymer materials.
Background technology
Fiber glass reinforced polypropylene micro-foaming material has exclusive a dense skin and foam core structure, its feature be exactly On the premise of ensureing original modified polypropylene material mechanical performance, material utilization amount is reduced, significantly mitigates part weight, for substituting Solid injected plastics material, reduces production cost, improves production efficiency.In recent years, as electric power tool shell plastic process is continuous Accelerate, modified polypropene dosage rises year by year, has lightweight, the polypropylene micro-foaming material of inexpensive feature in electric tool Field has broad prospect of application, enjoys enterprise inside the circle to pay close attention to.
However, the defects of injection micro-foaming material generally existing article surface is of poor quality, such as a large amount of gas traces, surface point Layer, surface floating etc., this, which seriously constrains fiber glass reinforced polypropylene micro-foaming material, the electric tool of surface quality requirements Application on shell.Up to now, no effective ways can solve this technical barrier.
The content of the invention
Problem to be solved：The present invention is ensureing fiber glass reinforced polypropylene material machinery using injection fretting map technology Under the premise of performance is not lost substantially, mitigate part weight, improve instrument portability, significantly reduce production cost；Meanwhile by adopting With microporous foam composite assistant, hence it is evident that improve the surface quality of fiber glass reinforced polypropylene micro-foaming material, essentially eliminate product Surface floating, gas trace and skin lamination phenomenon, obtain excellent performance, have the electric tool fiberglass reinforced of lightweight feature Polypropylene micro-foaming material, and the preparation method of the material is provided.Technique is simple, and production cost is low, efficient, be easily achieved work Industry.
The present invention solves technical problem by the following technical programs：
A kind of electric tool special microporous foam composite assistant of fiber glass reinforced polypropylene micro-foaming material, by weight fraction Polyvinyl, 20%-30% styrene-based polymers for 40%-52%, 15-20% helping appearance agents, 10-15% nucleators composition.
Further, a kind of special microporous foam of electric tool fiber glass reinforced polypropylene micro-foaming material is compound helps Agent, the polyvinyl is high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene, ethene-vinyl acetate One kind in copolymer, Ethylene-Propylene-Diene based terpolymers；Styrene-based polymer for polystyrene, polystyrene- One kind in the fine copolymer of butadiene-styrene copolymer, styrene-propene, styrene-acrylate；Helping appearance agent is acrylic acid One kind in graft polyolefin type, cyclic acid anhydride type, epoxy type；Nucleator is benzoate, organic phosphate, sorbierite One kind in class, silica, talcum powder, montmorillonite.
A kind of electric tool fiber glass reinforced polypropylene micro-foaming material, raw material are made of the component of following parts by weight：
40-80 parts of polypropylene
5 parts of compatilizer 2-
3-10 parts of microporous foam composite assistant
10-50 parts of glass fibre
0.5-5 parts of foaming agent
0.2-2 parts of antioxidant.
Further, the polyacrylic melt index is 3-60g/10min.
Further, the compatilizer maleic anhydride stem grafting polyolefin analog copolymer.
Further, the foaming agent is ammonium hydrogen carbonate, sodium acid carbonate, azodicarbonamide, toluene sulfonephthalein amino rise abruptly, even One kind in two amine carbonate of nitrogen, preferably azodicarbonamide.
Further, the antioxidant is divided into primary antioxidant and auxiliary anti-oxidant, according to 2：3 ratio addition, the master resist The one kind of oxygen agent in Hinered phenols and sulphur ester antioxidant, preferable main anti-oxidant are 1010；Auxiliary anti-oxidant agent is selected from One kind in phosphorous acid salt and phosphite ester kind antioxidant, preferable auxiliary antioxidant are 168.
A kind of electric tool preparation method of fiber glass reinforced polypropylene micro-foaming material, comprises the following steps：
（1）By 40-80 parts of polypropylene, 2-5 parts of compatilizer, 10-50 parts of glass fibre, microporous foam composite assistant 3-10 Part, 0.2-2 parts of antioxidant are put into high-speed mixer and mix 3-6min, then by said components mixture in double screw extruder Middle extrusion is simultaneously granulated, and obtains modified polypropylene composite material；
（2）By step（1）In obtained modified polypropylene composite material 95-99.5 parts, 0.5-5 parts of foaming agent is put into Mixed in mixer, obtain homogeneous mixture；
（3）By above-mentioned steps（2）In obtained mixture be added in injection molding machine, injection molding is obtained with skinning structure Fiber glass reinforced polypropylene micro-foaming material, 200-280 DEG C of injecting machine material tube temperature, injection pressure 40-80MPa, injection speed Spend for 40-80mm/s, cooling time 10-30s；
Further, the step（1）In, twin-screw extruder barrel temperature is 180-260 DEG C, screw speed 500r/ min。
Beneficial effect：
The raw material sources of the present invention are extensive, of low cost, and product can be realized by common injection machine, easy to operate.Using Under the premise of injection fretting map technology realizes fiber glass reinforced polypropylene material lightweight, by microporous foam composite assistant, significantly change It has been apt to the surface quality of fiber glass reinforced polypropylene micro-foaming material, has solved and perplex polypropylene micro-foaming material all the time in electricity The serious surface quality problems such as article surface floating, gas trace when being applied on power driven tools, obtain excellent performance, have lightweight spy The fiber glass reinforced polypropylene micro-foaming material of sign.Product can be applied not only to electric tool, garden instrument shell etc.；Also can use In other fields, such as automobile, building, electronics, shipbuilding etc..
1 electric tool is remarkably improved micro- hair with the special microporous foam composite assistant of fiber glass reinforced polypropylene micro-foaming material The repair ability again of body during bubble.Microporous foam composite assistant constituent is readily obtained, and cost is low, is adapted to industrialization big Production.
A kind of 2 electric tools use microporous foam composite assistant with fiber glass reinforced polypropylene micro-foaming material, produce Polypropylene material using injection fretting map technology ensure fiber glass reinforced polypropylene material mechanical performance do not lose premise substantially Under, mitigate part weight, improve instrument portability, reduce production cost, significantly improve fiber glass reinforced polypropylene fretting map material The surface quality of material, solves and perplexs polypropylene micro-foaming material article surface hair when being applied on electric tool all the time The serious surface quality problems such as flower, gas trace and skin lamination phenomenon.Product has excellent dimensional stability, can be according to different need Ask, adjustment formula rate implements industrialization and reduces material utilization amount, reaches required target capabilities.
With fiber glass reinforced polypropylene micro-foaming material, preferably polyacrylic melt index is 3-60g/ to a kind of 3 electric tools 10min, scope adaptation existing equipment and instrument, can directly carry out producing the material, save production cost, can be with Multi-thread production, quantifies production.
Foaming agent described in 4, oxidant are easily to be commercially available on the market, and of low cost, are adapted to industrialization big raw Production.
A kind of preparation method of electric tool fiber glass reinforced polypropylene micro-foaming material described in 5, creative addition Microporous foam composite assistant, the polypropylene micro-foaming material surface quality produced is high, then repair ability is good.Skill of the present invention Art solution process is simple, efficient, and the process-cycle is obviously shortened, and significantly reduces production cost, and and be adapted to existing equipment, no Production line road need to be separately improved to be easily industrialized.
Embodiment
Embodiment one
By 2 parts of 40 parts of polypropylene, the compatilizer that melt index is 60g/10min, 42 parts, 9 parts microporous foams of glass fibre Composite assistant（Its component includes:40% polyvinyl, 30% styrene-based polymer, 20% helping appearance agent, 10% nucleator, institute The polyvinyl stated is ethylene-vinyl acetate copolymer, the styrene-based polymer for styrene-butadiene- Styrol copolymer, the helping appearance agent are cyclic acid anhydride type, and the nucleator is montmorillonite）, described compatilizer be horse Maleic anhydride grafted polyolefin copolymers, cooxidant are irgasfos 168 phosphorous acid three (2,4- di-tert-butyl-phenyl) ester 1.2 Part, primary oxidant for antioxidant 1010 four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester, 0.8 part Oxidant mixture is put into high-speed mixer, mixes 6 minutes, then, said components mixture is squeezed in double screw extruder Go out and be granulated.Twin-screw extruder barrel temperature setting is 180-260 DEG C, screw speed 500r/min；Finally by 5 parts of foaming agents It is uniformly mixed with 95 parts of above-mentioned extrusion pellets, the foaming agent is azodicarbonamide, is added in injection molding machine, injection molding obtains To electric tool fiber glass reinforced polypropylene micro foaming composite material.Injecting machine material tube temperature is arranged to 200-280 DEG C, injection pressure Power is 70MPa, injection speed 60mm/s, cooling time 15s.The contrast of gained composite property is as shown in the table：
1 embodiment one of table and unexpanded fiber glass reinforced polypropylene material performance comparison
Detection project Standard It is unexpanded Embodiment one
Density/g/cm3 ISO 1183 1.27 1.10
Tensile strength/MPa ISO 527 102.1 97.2
Bending modulus/MPa ISO 178 8500 8700
Simply supported beam unnotched impact strength/kJ/m2 ISO 180 45 47
Heat distortion temperature/DEG C ISO 75 150 151
Embodiment two
By 5 parts of 80 parts of polypropylene, the compatilizer that melt index is 26g/10min, 10 parts, 4.3 parts micropore hairs of glass fibre Steep composite assistant（Its component includes：40% polyvinyl, 25% styrene-based polymer, 20% helping appearance agent, 15% nucleation Agent, the polyvinyl are linear low density polyethylene, and the styrene-based polymer is fine common for styrene-propene Polymers, the helping appearance agent are acrylic acid-grafted polyolefin-type, and the nucleator is talcum powder）；The compatilizer is horse Maleic anhydride grafted polyolefin copolymers；The auxiliary anti-oxidant is 0.12 part of phosphite ester kind antioxidant, primary antioxidant is sulphur 0.08 part of esters antioxidant；
Said mixture is put into high-speed mixer, mixes 3 minutes, then, said components mixture is squeezed in twin-screw Go out in machine and extrude and be granulated.Twin-screw extruder barrel temperature setting is 180-260 DEG C, screw speed 500r/min；Finally will 0.5 part of foaming agent is uniformly mixed with 99.5 parts of above-mentioned extrusion pellets, and the foaming agent is sodium acid carbonate, is added in injection molding machine, Injection molding obtains great surface quality polypropylene micro foaming composite material.Injecting machine material tube temperature is arranged to 200-280 DEG C, injection Pressure is 50MPa, injection speed 80mm/s, cooling time 30s.The contrast of gained composite property is as shown in the table：
2 embodiment two of table and unexpanded fiber glass reinforced polypropylene material performance comparison
Detection project Standard It is unexpanded Embodiment two
Density/g/cm3 ISO 1183 0.98 0.93
Tensile strength/MPa ISO 527 47.2 43.2
Bending modulus/MPa ISO 178 2400 2500
Simply supported beam unnotched impact strength/kJ/m2 ISO 180 36 38
Heat distortion temperature/DEG C ISO 75 132 131
Embodiment three
By 3 parts of 50 parts of polypropylene, the compatilizer that melt index is 40g/10min, 30 parts, 10 parts microporous foams of glass fibre Composite assistant（Its component includes:42% polyvinyl, 28% styrene-based polymer, 15% helping appearance agent, 15% nucleator, institute The polyvinyl stated is Ethylene-Propylene-Diene based terpolymers, and the styrene-based polymer is styrene-the third The fine copolymer of alkene, the helping appearance agent are epoxy type, and the nucleator is glucitols）, the compatilizer is maleic acid Acid anhydride grafted polyolefin hydrocarbon type copolymer, the auxiliary anti-oxidant is 1.2 parts of phosphorous acid salt, primary antioxidant is that Hinered phenols are anti-oxidant The mixture that 0.8 part of agent is put into high-speed mixer, mixes 3 minutes, then, by said components mixture in double screw extruder Extrude and be granulated.Twin-screw extruder barrel temperature setting is 180-260 DEG C, screw speed 500r/min；Finally by 5 parts of foaming Agent is uniformly mixed with 95 parts of above-mentioned extrusion pellets, and the foaming agent rises abruptly for toluene sulfonephthalein amino, is added in injection molding machine, is molded into Type obtains great surface quality polypropylene micro foaming composite material.Injecting machine material tube temperature is arranged to 200-280 DEG C, and injection pressure is 80MPa, injection speed 70mm/s, cooling time 30s.The contrast of gained composite property is as shown in the table：
3 embodiment three of table and unexpanded fiber glass reinforced polypropylene material performance comparison
Detection project Standard It is unexpanded Embodiment three
Density/g/cm3 ISO 1183 1.16 1.02
Tensile strength/MPa ISO 527 72.2 68.6
Bending modulus/MPa ISO 178 5600 5800
Simply supported beam unnotched impact strength/kJ/m2 ISO 180 57 60
Heat distortion temperature/DEG C ISO 75 152 153
Example IV
By 2 parts of 50 parts of 40 parts of polypropylene, glass fibre, the compatilizer that melt index is 3g/10min, 3 parts of microporous foams are answered Close auxiliary agent（Its component includes:48% polyvinyl, 27% styrene-based polymer, 17.5% helping appearance agent, 12.5% nucleator, The polyvinyl is ethylene-vinyl acetate copolymer, and the styrene copolymer is styrene-acrylate Copolymer, the helping appearance agent are acrylic acid-grafted polyolefin-type, and the nucleator is benzoate）, described is compatible Agent is maleic anhydride stem grafting polyolefin analog copolymer, and the auxiliary anti-oxidant is 0.9 part of phosphorous acid salt, the primary antioxidant High-speed mixer is put into for 0.6 part of mixture of sulphur ester antioxidant, is mixed 5 minutes, then, by said components mixture in double Extrude and be granulated in screw extruder.Twin-screw extruder barrel temperature setting is 180-260 DEG C, screw speed 500r/min； Finally 3.5 parts of foaming agents are uniformly mixed with 96.5 parts of above-mentioned extrusion pellets, the foaming agent rises abruptly for toluene sulfonephthalein amino, adds Enter in injection molding machine, injection molding obtains great surface quality polypropylene micro foaming composite material.Injecting machine material tube temperature is arranged to 200-280 DEG C, injection pressure 40MPa, injection speed 40mm/s, cooling time 10s.Gained composite property contrasts It is as shown in the table：
4 example IV of table and unexpanded fiber glass reinforced polypropylene material performance comparison
Detection project Standard It is unexpanded Example IV
Density/g/cm3 ISO 1183 1.36 1.17
Tensile strength/MPa ISO 527 105.2 102.3
Bending modulus/MPa ISO 178 10400 10600
Simply supported beam unnotched impact strength/kJ/m2 ISO 180 38 36
Heat distortion temperature/DEG C ISO 75 155 158
The present invention is can be seen that using the micro- hair of injection from above example and unexpanded modified polypropylene material performance comparison Bubble technology, under the premise of ensureing that fiber glass reinforced polypropylene material mechanical performance is not lost substantially, is greatly reduced product weight, reduces Material utilization amount, significantly reduces production cost；Meanwhile using combined type microporous foam composite assistant, it can obtain and unexpanded glass The visual almost consistent great surface quality of fiber reinforced polypropylene material, eliminates the floating of polypropylene fretting map product surface, gas trace The problems such as, can substitute existing solid injection modified polypropylene material in the application of housing of electric tool, improve instrument portability, Reduce cost.Another feature of the present invention is to be obviously shortened the process-cycle, can also reduce production cost, improve production efficiency. Product has excellent dimensional stability.In addition, it can adjust formula rate according to different demands, reach required target capabilities, subtract Few material utilization amount.
This product can be realized by common Shooting Technique, easy to operate, highly practical.Product is except suitable for electric tool Outside housing product, it may also be used for the industry field such as garden instrument, automobile building, electronics, sports equipment.
The foregoing is merely the embodiment of the present invention, but protection scope of the present invention is not limited thereto, any Those skilled in the art are in the technical scope of the present invention, changes or substitutions that can be made without creative work, It should be covered by the protection scope of the present invention.

Claims (7)

  1. A kind of 1. electric tool fiber glass reinforced polypropylene micro-foaming material, it is characterised in that raw material by following parts by weight group It is grouped into：
    40-80 parts of polypropylene
    2-5 parts of compatilizer
    3-10 parts of microporous foam composite assistant
    10-50 parts of glass fibre
    0.5-5 parts of foaming agent
    0.2-2 parts of antioxidant；
    Polyvinyl, 20%-30% styrene of the microporous foam composite assistant by weight fraction for 40%-52% Based polyalcohol, 15-20% helping appearance agents, 10-15% nucleators composition；The polyvinyl is high density polyethylene (HDPE), low In density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, Ethylene-Propylene-Diene based terpolymers One kind；Styrene-based polymer is polystyrene, styrene-butadiene-styrol copolymer, styrene-propene are fine common One kind in polymers, styrene-acrylate；Helping appearance agent is acrylic acid-grafted polyolefin-type, in cyclic acid anhydride type, epoxy type It is a kind of；Nucleator is one kind in benzoate, organic phosphate, glucitols, silica, talcum powder, montmorillonite.
  2. 2. electric tool fiber glass reinforced polypropylene micro-foaming material according to claim 1, it is characterised in that：Described poly- third The melt index of alkene is 3-60g/10min.
  3. 3. electric tool fiber glass reinforced polypropylene micro-foaming material according to claim 1, it is characterised in that：It is described compatible Agent maleic anhydride stem grafting polyolefin analog copolymer.
  4. 4. electric tool fiber glass reinforced polypropylene micro-foaming material according to claim 1, it is characterised in that：The foaming Agent is ammonium hydrogen carbonate, sodium acid carbonate, azodicarbonamide, toluene sulfonephthalein amino rise abruptly, one kind in two amine carbonate of azo, described Foaming agent is azodicarbonamide.
  5. 5. electric tool fiber glass reinforced polypropylene micro-foaming material according to claim 1, it is characterised in that：The antioxygen Agent is divided into primary antioxidant and auxiliary anti-oxidant, according to 2：3 ratio addition, the primary antioxidant is selected from Hinered phenols and thioesters class resists One kind in oxygen agent, the main anti-oxidant are 1010；Auxiliary anti-oxidant is selected from phosphorous acid salt and phosphite ester kind antioxidant In one kind, the auxiliary antioxidant be 168.
  6. 6. according to claim 1-5, the preparation method of any electric tool fiber glass reinforced polypropylene micro-foaming material, bag Include following steps：
    By 40-80 parts of polypropylene, 2-5 parts of compatilizer, 10-50 parts of glass fibre, 3-10 parts of microporous foam composite assistant, antioxidant 0.2-2 parts are put into high-speed mixer and mix 3-6min, then extrude said components mixture simultaneously in double screw extruder It is granulated, obtains modified polypropylene composite material；
    By obtained modified polypropylene composite material 95-99.5 parts in step (1), 0.5-5 parts of foaming agent is put into mixer Mixing, obtains homogeneous mixture；
    The mixture obtained in above-mentioned steps (2) is added in injection molding machine, injection molding obtains the glass with skinning structure Reinforced polypropylene micro-foaming material, 200-280 DEG C of injecting machine material tube temperature, injection pressure 40-80MPa, injection speed 40- 80mm/s, cooling time 10-30s.
  7. 7. the preparation method of electric tool fiber glass reinforced polypropylene micro-foaming material, its feature exist according to claim 6 In：In the step (1), twin-screw extruder barrel temperature is 180-260 DEG C, screw speed 500r/min.
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CN105504509A (en) * 2016-01-05 2016-04-20 苏州润佳工程塑料股份有限公司 Wall-shrink-resisting modified polypropylene material
CN109233112A (en) * 2017-07-10 2019-01-18 合肥杰事杰新材料股份有限公司 A kind of foaming automobile inside gadget material and preparation method thereof
CN110105673A (en) * 2019-02-03 2019-08-09 南京聚隆科技股份有限公司 Automobile-used wear-resisting plant fiber reinforced polypropylene micro-foaming material of one kind and preparation method thereof
CN113831632B (en) * 2020-06-24 2024-06-14 合肥杰事杰新材料股份有限公司 Foaming polypropylene board and preparation method thereof
CN115960415A (en) * 2022-12-30 2023-04-14 武汉金发科技有限公司 Micro-foaming reinforced polyolefin composite material and preparation method and application thereof

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CN104140591A (en) * 2014-07-24 2014-11-12 南京聚隆科技股份有限公司 Highly filled micro foamed polypropylene composite material and preparation method thereof

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