CN109181117A - A kind of low-density, high rigidity polypropylene material and preparation method thereof - Google Patents

A kind of low-density, high rigidity polypropylene material and preparation method thereof Download PDF

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Publication number
CN109181117A
CN109181117A CN201810989480.7A CN201810989480A CN109181117A CN 109181117 A CN109181117 A CN 109181117A CN 201810989480 A CN201810989480 A CN 201810989480A CN 109181117 A CN109181117 A CN 109181117A
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Prior art keywords
low
high rigidity
polypropylene material
density
parts
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CN201810989480.7A
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Chinese (zh)
Inventor
于致远
黄志杰
王海华
沈岳新
杨仓先
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Nakahiro Junl (shanghai) New Material Co Ltd
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Nakahiro Junl (shanghai) New Material Co Ltd
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Priority to CN201810989480.7A priority Critical patent/CN109181117A/en
Publication of CN109181117A publication Critical patent/CN109181117A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/14Copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/24Crystallisation aids

Abstract

The present invention provides a kind of low-density, high rigidity polypropylene material and preparation method thereof, by 50~80 parts of polypropylene, 5~20 parts of elastomer flexibilizer, 0.1~3 part of reinforcement nucleating agent and 1~5 part of interfacial compatibilizer, it is added in agitated kettle and is uniformly mixed, then 5~30 parts of modified talc powder, 0.1~1 part of antioxidant and 1~3 part of processing aid are added, it is sent into double screw extruder after mixing, obtains low-density of the invention, high rigidity polypropylene material through melt blending, extrusion, cooling, granulation.Compared with traditional polypropylene, the density for the polypropylene material that the present invention obtains reduces by 10% or more, and bending modulus improves 60%, while having good notch impact toughness and mobility.

Description

A kind of low-density, high rigidity polypropylene material and preparation method thereof
Technical field
The invention belongs to field of polypropylene modification, and in particular to a kind of low-density, high rigidity for bumper is poly- Propylene material and preparation method thereof.
Background technique
Polypropylene material has many merits such as light, resistant to chemical etching, processing performance is good, cost performance is high, extensive It is current fastest-rising thermoplasticity general-purpose plastics applied to fields such as automobile, household electrical appliances, building, electronic apparatus.Especially in vapour Polyacrylic usage amount alreadys exceed 80% on vehicle bumper, and from the point of view of current trend, the following polypropylene makes bumper Dosage can further increase.
However as the development of auto industry, the lightweights of automobile plastic components, environmental protection, high-performance, low cost at For the main trend of current development.By taking PP composite material bumper as an example, article surface product is big, and structure is complicated, single For part weight in 4~6kg, 1 meter of length or more, be that current automotive light weight technology studies more popular auto parts and components.Wherein realize The lightweight of product, the more of current research is being thinning design and reach light-weighted effect by product, still The problems such as reduction of product wall thickness will lead to mechanical properties decrease, and the size of product is unstable under high/low temperature condition.So protecting It, can be by the density of reduction material, to reach light-weighted mesh under the premise of the mechanical property and dimensional stability of demonstrate,proving product 's.A kind of automobile bumper material for high-impact that patent application CN201510365616 is previously mentioned, it compares weighting and improves material The notch impact strength of material, but the rigidity of material shows slightly insufficient.Patent application CN201611216311 discloses a kind of use The high modified talc powder of big radius-thickness ratio, lamella integrity degree is modified polypropylene material, is obviously improved although rigidity has, But the toughness of material is insufficient, and dimensional stability is not good enough.101838423 A of Chinese patent CN discloses one kind and passes through inorganic mineral Modified polypropylene material, the rigidity of material are significantly improved with the mode of inorfil compounding, but surface is in the presence of floating Fibre influences the appearance of product.
It, cannot only being thinning design and reach the effect of loss of weight from product in conclusion for the lightweight for realizing product Fruit, but should be under the premise of guaranteeing toughness of material and dimensionally stable, by reducing the density of material, improving the rigid of material Property, guarantee product appearance, to meet the requirement of lightweight and high performance.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of low-density for bumper, height Rigid polypropylene material and preparation method thereof.
What the purpose of the present invention was achieved through the following technical solutions:
The first object of the present invention is to provide a kind of low-density for bumper, high rigidity polypropylene material, It is made using the raw material for including following weight percent:
Wherein: the polypropylene be copolymer polypropylene, under 230 DEG C, 2.16Kg test condition, melting means be 25~ 100g/10min;
The modified talc powder selection is 5000~10000 mesh, draw ratio >=10, silicone content >=70wt%, drying It is mixed afterwards with silane coupling agent high-speed stirred;The silane coupling agent is commercial product, and preferably epoxy silane is coupled One of agent, amino silicane coupling agent and acyloxy silane coupling agent are a variety of;
The reinforcement nucleating agent is the one or several kinds of aryl amide, carboxylic acid metal's salt;
The elastomer flexibilizer is one of polyolefin elastomer, TPO, TPV or several, density 0.8 ~1.0g/cm3, under 190 DEG C and 5kg test condition, melt index is 0.5~40g/10min;
The antioxidant is antioxidant 1010 (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythrites Ester), irgasfos 168 (phosphorous acid three (2,4- di-tert-butyl-phenyl) ester), antioxidant 3114 ((the 3,5- di-t-butyl-of 1,3,5- tri- 4- hydroxybenzyl) isocyanuric acid), one of DLTP (thio-2 acid double lauryls) or several;
The interfacial compatibilizer is polypropylene grafted maleic anhydride, and wherein the grafting rate of maleic anhydride is 1%~2%;
Further, a kind of low-density for bumper of the invention, high rigidity polypropylene material further include 1%~3% processing aid, effect are the rigidity for increasing polypropylene material, the drop for reducing material mechanical performance in process Mobility that is low, improving material, such as selection calcium stearate and/or powdered whiting.
The second object of the present invention is the provision of a kind of low-density for bumper, high rigidity polypropylene material Preparation method include the following steps: according to 100 parts of meters are added up to
By 50~80 parts of polypropylene, 5~20 parts of elastomer flexibilizer, 0.1~3 part of reinforcement nucleating agent and interfacial compatibilizer 1 It~5 parts, is added in agitated kettle and is uniformly mixed, then add 5~30 parts of modified talc powder, 0.1~1 part of antioxidant and processing It 1~3 part of auxiliary agent, is sent into double screw extruder, is obtained through melt blending, extrusion, cooling, granulation of the invention after mixing Low-density, high rigidity polypropylene material.
Compared with prior art, the present invention has the advantage that
The present invention for it is low it is mineral-filled under conditions of insufficient rigidity of material, it is high it is mineral-filled under conditions of product weight The shortcomings that weighting, the talcum powder conduct high using lamella integrity degree, draw ratio is big and modified through special process through silane analog assistant Packing material, and cooperate reinforcement nucleating agent, under the auxiliary of interfacial compatibilizer, makes polypropylene material compared under low-density, have The characteristics of high rigidity, high tenacity, high fluidity.Compared with traditional polypropylene, the density for the polypropylene material that the present invention obtains 10% or more is reduced, about 0.93~0.99g/cm3;Bending modulus improves 60%, reaches 2100MPa or more;Have simultaneously good Good notch impact toughness and mobility.In addition the simple production process of material, manufacturing cost is low to have very strong competitive advantage.
Specific embodiment
Below by specific embodiment, the present invention will be further described, and the embodiment is only limitted to illustrate the present invention Rather than limiting the invention.
The explanation of raw material used in the present invention:
PP K8025: copolymer polypropylene, Taiwan chemical fibre, melt index are 30g/10min (230 DEG C, 2.16kg);
PP 1124: polypropylene, Taiwan plastic cement, melting means index 15g/10min (230 DEG C, 2.16);
POE 8407: polyolefine toughener, DOW Chemical, melt index 30g/10min (190 DEG C, 2.16kg);
TPO CA7320: polyolefine toughener, Basel, melt index 6.5g/10min (230 DEG C, 5kg);
TPV W600NS: polyolefine toughener, Mitsui, melt index 2.6g/10min (230 DEG C, 5kg);
Reinforcement nucleating agent 1: nucleating agent, be in and science and technology, trade mark NAP-50;
Reinforcement nucleating agent 2: nucleating agent, Shanxi chemical research institute, trade mark TMA-3;
Modified talc powder: 10000 mesh talcum powder are stirred with KH-560 silane coupling agent to the special process system such as be blended by height ?;
Interfacial compatibilizer: maleic anhydride inoculated polypropylene CMG5001, the liter new material Co., Ltd of Shanghai day, chemistry connect Branch rate 1%;
Calcium stearate: Hangzhou Wangjiang oil and fat chemical Co., Ltd, calcium content 6-7%, free acid≤0.5%;
10000 mesh talcum powder: AIHAI-IMI production, trade mark HTPO5.
Embodiment 1
By 80 parts of polypropylene PP K8025,0.3 part of reinforcement nucleating agent NAP-50,10 parts of POE toughener 8407 and 1 Part interfacial compatibilizer CMG-5001, which is added in agitated kettle, to be uniformly mixed, and 5 parts of modified talc powders, 0.3 part of antioxidant are then added 1010 and 3 parts of calcium stearates are sent into extruding pelletization in double screw extruder after mixing, and wherein the technological parameter of twin-screw is 80 DEG C are followed successively by from temperature of the feed opening to from head, 170 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, 180 DEG C, 170 DEG C, is led Machine revolving speed is 350 turns/min.
Embodiment 2
By 71 parts of polypropylene PP K8025,6 parts of 1124,0.3 parts of polypropylene PP of reinforcement nucleating agent NAP-50,0.7 The reinforcement nucleating agent TMA-3,5 parts of toughener POE8407,3 parts of toughener TPO CA7320 and 2 parts of interfacial compatibilizers of part CMG-5001 is added in agitated kettle and is uniformly mixed, and then adds 10 parts of modified talc powders, 0.3 part of irgasfos 168 and 1.7 parts of weights Matter calcium carbonate is sent into extruding pelletization in double screw extruder after mixing, and wherein the technological parameter of twin-screw is from feed opening Temperature at head is followed successively by 80 DEG C, and 170 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 190 DEG C, 180 DEG C, 170 DEG C, engine speed is 350 turns/min.
Embodiment 3
By 50 parts of polypropylene PP K8025,3 parts of reinforcement nucleating agent TMA-3,3 parts of toughener POE8407,8.7 parts Toughener TPO CA7320 and 4 parts of interfacial compatibilizer CMG-5001 be added in agitated kettles and be uniformly mixed, then add 30 parts Modified talc powder, 0.3 part of antioxidant 3114 and 1 part of calcium stearate are sent into extruding pelletization in double screw extruder after mixing, Wherein the technological parameter of twin-screw is to be followed successively by 80 DEG C from temperature of the feed opening to from head, 170 DEG C, 200 DEG C, and 200 DEG C, 200 DEG C, 190 DEG C, 180 DEG C, 170 DEG C, engine speed is 350 turns/min.
Embodiment 4
By 60 parts of polypropylene PP K8025,1124,5 parts of PP of reinforcement nucleating agent NAP-50 of 5 parts by weight, 5 parts of increasing It is equal that mixing in agitated kettle is added in tough dose of POE8407,15 parts of toughener TPV W600NS and 2 parts of interfacial compatibilizer CMG-5001 It is even, 7 parts of modified talc powders, 1 part of anti-oxidant DLTP are then added, is sent into double screw extruder to squeeze out after mixing and make Grain, wherein the technological parameter of twin-screw is to be followed successively by 80 DEG C from temperature of the feed opening to from head, 170 DEG C, 200 DEG C, and 200 DEG C, 200 DEG C, 190 DEG C, 180 DEG C, 170 DEG C, engine speed is 350 turns/min.
Comparative example 1
By the common talcum powder of 10 part of 10000 mesh, 9 parts of 8407,80 parts of POE toughener of PP K8025,0.3 part of antioxidant 1010,0.7 part of calcium stearate is added in agitated kettle stirs evenly together, is adding twin-screw extrude, extruding pelletization, wherein The technological parameter of twin-screw is to be followed successively by 80 DEG C from temperature of the feed opening to from head, 170 DEG C, 200 DEG C, and 200 DEG C, 200 DEG C, 190 DEG C, 180 DEG C, 170 DEG C, engine speed is 350 turns/min.
Comparative example 2
By 20 part of 10000 common talcum powder of mesh, 8 parts of 8407,71 parts of POE toughener of PP K8025,0.3 part of antioxidant 1010,0.7 part of calcium stearate is added in agitated kettle stirs evenly together, is adding twin-screw extrude, extruding pelletization, wherein The technological parameter of twin-screw is to be followed successively by 80 DEG C from temperature of the feed opening to from head, 170 DEG C, 200 DEG C, and 200 DEG C, 200 DEG C, 190 DEG C, 180 DEG C, 170 DEG C, engine speed is 350 turns/min.
One properties of product testing standard of table and condition
Serial number Detection project Examination criteria Unit Test condition
1 Density ISO 1183-1 g/cm3
2 Bending modulus ISO 178 MPa 14mm/min
3 Notch impact strength ISO 179-1 KJ/m2 23 DEG C, 50RH
4 Melting means ISO 1133-1 g/10min 230 DEG C, 2.16kg
Examples 1 to 4 is a kind of low-density, high rigidity poly- third for bumper of patent according to the present invention in table two The test result of the embodiment of part of representative in alkene material, it is of the invention a kind of for bumper in order to protrude Low-density, high rigidity polypropylene material and preparation method thereof the characteristics of advantage, use two conventional formulation comparative examples 1 and right Ratio 2 and Examples 1 to 4 carry out performance test.It is obtained by the data comparison of table two as drawn a conclusion:
Two Examples 1 to 4 of table and 1~2 the performance test results of comparative example
Being used in compounding using modified talc powder and reinforcement nucleating agent of the present invention, makes material in the item compared with low-density Under part, the bending modulus of material can be made to be greatly improved.Under equal densities, the present invention compares conventional formulation, bending die Amount is increased to 2138.7MPa by 1349.7MPa, and increase rate is close to 800MPa.In situation similar in modulus, the present invention and biography The formula of system is compared, and density is by 1.0521g/cm3It is reduced to 0.9586g/cm3.In general, low-density of the present invention, height Rigid material, can have the function that reduce bumper product, meet the standard of major main engine plants, meet current environmental protection, Light-weighted trend creates good social value and market value.
The present invention is not limited to the above embodiments, and the above embodiments and description only describe of the invention Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these change and change Into all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claims and its equivalent It defines.

Claims (12)

1. a kind of low-density, high rigidity polypropylene material, which is characterized in that using the raw material system for including following weight percent :
Polypropylene: 50%~80%
Modified talc powder: 5%~30%
Reinforcement nucleating agent: 0.1%~3%
Elastomer flexibilizer: 5%~20%
Antioxidant: 0.1%~1%
Interfacial compatibilizer: 1%~5%.
2. a kind of low-density according to claim 1, high rigidity polypropylene material, which is characterized in that the polypropylene For copolymer polypropylene, under 230 DEG C, 2.16Kg test condition, melting means is 25~100g/10min.
3. a kind of low-density according to claim 1, high rigidity polypropylene material, which is characterized in that the modified cunning Mountain flour selection is 5000~10000 mesh, draw ratio >=10, silicone content >=70wt%, with silane coupling agent height mixes conjunction after dry It forms.
4. a kind of low-density according to claim 3, high rigidity polypropylene material, which is characterized in that the silane is even Connection agent is one of epoxy silane coupling agent, amino silicane coupling agent and acyloxy silane coupling agent or a variety of.
5. a kind of low-density according to claim 1, high rigidity polypropylene material, which is characterized in that the increasing just at Core agent is the one or several kinds of aryl amide, carboxylic acid metal's salt.
6. a kind of low-density according to claim 1, high rigidity polypropylene material, which is characterized in that the elastomer Toughener is one of polyolefin elastomer, TPO, TPV or several.
7. a kind of low-density according to claim 6, high rigidity polypropylene material, which is characterized in that the elastomer The density of toughener is 0.8~1.0g/cm3, under 190 DEG C and 5kg test condition, melt index is 0.5~40g/10min.
8. a kind of low-density according to claim 1, high rigidity polypropylene material, which is characterized in that the antioxidant For one of antioxidant 1010, irgasfos 168, antioxidant 3114, DLTP or several.
9. a kind of low-density according to claim 1, high rigidity polypropylene material, which is characterized in that the interface phase Appearance agent is polypropylene grafted maleic anhydride, and wherein the grafting rate of maleic anhydride is 1%~2%.
10. a kind of low-density according to claim 1, high rigidity polypropylene material, which is characterized in that further include 1%~3% Processing aid.
11. a kind of low-density according to claim 9, high rigidity polypropylene material, which is characterized in that the processing helps Agent is calcium stearate and/or powdered whiting.
12. the preparation side of a kind of any one low-density prepared as described in claim 1~11, high rigidity polypropylene material Method, according to adding up to 100 parts of meters, which comprises the steps of:
By 50~80 parts of polypropylene, 5~20 parts of elastomer flexibilizer, 0.1~3 part of reinforcement nucleating agent and interfacial compatibilizer 1~5 Part, it is added in agitated kettle and is uniformly mixed, then add 5~30 parts of modified talc powder, 0.1~1 part of antioxidant and processing and help It 1~3 part of agent, is sent into double screw extruder, is obtained through melt blending, extrusion, cooling, granulation of the invention low after mixing Density, high rigidity polypropylene material.
CN201810989480.7A 2018-08-28 2018-08-28 A kind of low-density, high rigidity polypropylene material and preparation method thereof Pending CN109181117A (en)

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CN109942963A (en) * 2019-04-16 2019-06-28 国合绿材科技(江苏)有限公司 A kind of formula and preparation method of the PP modified material applied to high-intensitive rainwater module
CN110698769A (en) * 2019-10-17 2020-01-17 中广核俊尔(浙江)新材料有限公司 High-fluidity low-gloss impact-resistant polypropylene composite material and preparation method and application thereof
CN110878159A (en) * 2019-11-14 2020-03-13 中广核俊尔(上海)新材料有限公司 Low-density polypropylene composite material and preparation method thereof
CN111004442A (en) * 2019-12-23 2020-04-14 广东道生科技股份有限公司 High-strength low-specific gravity foamed polypropylene material using plastic instead of steel and preparation method thereof
CN114381068A (en) * 2022-01-12 2022-04-22 上海金发科技发展有限公司 Talcum powder filled polypropylene material and preparation method and application thereof
CN114702754A (en) * 2022-03-31 2022-07-05 金发科技股份有限公司 Low-density high-rigidity high-toughness polypropylene material and preparation method and application thereof
CN115418055A (en) * 2022-10-17 2022-12-02 北京天罡助剂有限责任公司 High-fluidity polypropylene plastic and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN109942963A (en) * 2019-04-16 2019-06-28 国合绿材科技(江苏)有限公司 A kind of formula and preparation method of the PP modified material applied to high-intensitive rainwater module
CN110698769A (en) * 2019-10-17 2020-01-17 中广核俊尔(浙江)新材料有限公司 High-fluidity low-gloss impact-resistant polypropylene composite material and preparation method and application thereof
CN110698769B (en) * 2019-10-17 2022-03-15 中广核俊尔(浙江)新材料有限公司 High-fluidity low-gloss impact-resistant polypropylene composite material and preparation method and application thereof
CN110878159A (en) * 2019-11-14 2020-03-13 中广核俊尔(上海)新材料有限公司 Low-density polypropylene composite material and preparation method thereof
CN111004442A (en) * 2019-12-23 2020-04-14 广东道生科技股份有限公司 High-strength low-specific gravity foamed polypropylene material using plastic instead of steel and preparation method thereof
CN114381068A (en) * 2022-01-12 2022-04-22 上海金发科技发展有限公司 Talcum powder filled polypropylene material and preparation method and application thereof
CN114702754A (en) * 2022-03-31 2022-07-05 金发科技股份有限公司 Low-density high-rigidity high-toughness polypropylene material and preparation method and application thereof
CN115418055A (en) * 2022-10-17 2022-12-02 北京天罡助剂有限责任公司 High-fluidity polypropylene plastic and preparation method thereof

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