CN104592628A - High-toughness high-rigidity modified polypropylene material and preparation method thereof - Google Patents
High-toughness high-rigidity modified polypropylene material and preparation method thereof Download PDFInfo
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- CN104592628A CN104592628A CN201410829021.4A CN201410829021A CN104592628A CN 104592628 A CN104592628 A CN 104592628A CN 201410829021 A CN201410829021 A CN 201410829021A CN 104592628 A CN104592628 A CN 104592628A
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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
- C08L23/14—Copolymers of propene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-toughness high-rigidity modified polypropylene material and a preparation method thereof. The high-toughness high-rigidity modified polypropylene material mainly comprises the following components in percentage by weight: 47.0%-99.8% of polypropylene, 0%-20% of talcum powder, 0.2%-1% of antioxidants, 0%-30% of elastomers, 0.1%-1.5% of cross-linking agents and 0.1%-0.5% of auxiliary cross-linking agents. By being different from a general principle of toughening polypropylene by adding the elastomers, the modified polypropylene material disclosed by the invention realizes the dynamic vulcanization in the melt blending process of the elastomers and the polypropylene by using the cross-linking agents and the auxiliary cross-linking agents on the basis that the elastomers are added to a formula which takes the polypropylene as a substrate, so the high-toughness high-rigidity modified polypropylene material is different from the characteristic that TPV appears as rubber at normal temperature. The modified polypropylene material disclosed by the invention appears as the physical property of a thermoplastic plastic at normal temperature, not only has the rigidity of a thermoplastic material, but also has high toughness, so that the high-toughness high-rigidity modified polypropylene material is obtained.
Description
Technical field
The present invention relates to a kind of high tenacity, high rigidity modified polypropylene material, particularly relate to a kind of high tenacity, high rigidity modified polypropylene material and preparation method thereof.
Background technology
In recent years, the development of automotive industry is swift and violent, as the main force of automotive interior material, and the sharp increase of polypropylene composite material demand.For door-plate, dashboard, decorations post etc., some require higher automotive upholstery to safety coefficient, need that except requiring component there is enough intensity, both other component be arranged on dashboard or door-plate can have been carried, there is again enough abilities and produce distortion to resist external stress, also require part to have is enough to resist the toughness of external impacts simultaneously, can can not produce when automobile collides and significantly break or sharp fragments, and then injure the safety of driver and conductor.Wherein carrying is the most directly impacted when vehicle generation side impact by door-plate, seamless gasbag dashboard then needs to ensure that when collision happens air bag is opened smoothly and promptly, all can not produce any hard fragments that may hurt sb.'s feelings in above process, especially, under limit cold condition, more high requirement is proposed to polypropylene material.
General for copolymerized type propene polymer material, the polypropylene material using elastomerics to carry out toughening modifying can possess reasonable normal temperature impact property, but because polypropylene material has higher second-order transition temperature, cause it under-30 DEG C even environment of-40 DEG C, show very poor toughness, can be improved by elastic body toughening modification, but increasing elastomeric consumption simply to improve the result of toughness is exactly that the impatient play of rigidity of material and thermal deformation resistant declines, thus cannot meet the requirement of strength of relatively large part.Therefore toughness how is balanced and rigidity becomes the key point needing to break through.
In order to solve the problem, the present invention is while employing weighting agent ensures rigidity, select ethylene-octene copolymer elastomerics, make its under the synergy of linking agent and additional crosslinker with polypropylene fusion process in produce crosslinked, but because elastomerics consumption is less, determine the relatively whole material system of its cross-linking density lower, the winding arrangement produced owing to being cross-linked so is just not enough to produce larger impact to the processibility of material, but it is apparent to the raising of material monolithic toughness, the high tenacity obtained like this, high rigidity modified polypropylene material can well meet the demand to the higher automobile component of safety index requirement.
Summary of the invention
The object of the invention is to develop a kind of high tenacity, high rigidity modified polypropylene material, to meet the higher component of demand automotive upholstery to require to(for) safety coefficient.
The present invention can be achieved through the following technical solutions:
A kind of high tenacity, high rigidity modified polypropylene material, is characterized in that: by weight percentage, and its composition and proportioning are:
Preferably,
A kind of high tenacity, high rigidity modified polypropylene material, is characterized in that: by weight percentage, and its composition and proportioning are:
The present invention in the polypropylene composite material system that is suitable for,
One or both compositions in the homo-polypropylene that described polypropylene is melt flow rate (MFR) (230 DEG C × 2.16Kg) is 0.5-60g/10min and Co-polypropylene.
Described talcum powder, its particle size range is 1 ~ 10 micron.
Described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, and primary antioxidant selects one or more in Hinered phenols antioxidant; Auxiliary anti-oxidant selects the mixture of one or more in phosphite ester kind antioxidant.
Described primary antioxidant is selected from one or more in 1010,3114 and DSTP; Auxiliary anti-oxidant be selected from 618 and 168 one or both.
Described elastomerics is the multipolymer of ethylene-octene, and melt flow rate (MFR) (230 DEG C × 2.16Kg) is 0.5-10g/10min.
Described linking agent is DCP (dicumyl peroxide).
Described additional crosslinker is TAIC (iso-cyanuric acid triallyl ester).
The preparation method of above-mentioned high tenacity, high rigidity modified polypropylene material, its step is as follows:
1) raw material is taken according to weight proportion.
2) polypropylene, weighting agent, elastomerics, oxidation inhibitor, linking agent and additional crosslinker are dry mixed 3-5 minute in high speed mixer.
3) raw material of mixing is placed in twin screw extruder through melt extruding, granulation, its concrete technology is: extruder temperature controller one district 160-180 DEG C, two district 200-210 DEG C, three district 210-220 DEG C, four district 210-220 DEG C, five district 210-220 DEG C, six district 205-215, seven district 200-210, pressure 12-18MPa.
Be matrix with polypropylene in the present invention, add on elastomeric basis in formula, by using linking agent, additional crosslinker, make elastomerics with polyacrylic melt blending process implementation dynamic vulcanization, be different from the characteristic that TPV shows as rubber at normal temperatures, the present invention shows as the physical property of thermoplastics at normal temperatures, has namely both had the rigidity of thermoplastic material, there is again higher toughness, thus obtain the modified polypropylene material of high tenacity, high rigidity.
Embodiment
By the following examples implementation method of the present invention is specifically described, but does not limit interest field of the present invention.
In the material prescription of embodiment and comparative example, the block copolymerization third that the melt flow rate (MFR) (230 DEG C × 2.16KG) that polypropylene selects oil of SPC to produce is 30g/10min gathers, and trade names are M2600R; Talcum powder median size is 2.5 μm, commercially available; Primary antioxidant is the DSTP that ICE company of Britain produces, and trade names are Negonox DSTP, and chemical name is thio-2 acid octadecyl ester, and 3114 of the production of Ciba company, trade names are Irganox3114, and chemical name is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid.Auxiliary anti-oxidant is 168 of the production of Ciba company, and trade names are Irgafox168, and chemical name is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester; Linking agent is selected from the DCP that Shanghai Fang Rui reaches company, chemical name dicumyl peroxide; Additional crosslinker is selected from the TAIC that Shanghai Fang Rui reaches company, and chemical name is iso-cyanuric acid triallyl ester; Elastomerics is the ethylene-octene copolymer 8180 that DOW company produces.
Comparative example one:
Polypropylene 79.0%, weighting agent 10%, thermo-stabilizer 1.0%, elastomerics 10.0% are dry mixed 3-5 minute in high speed mixer, afterwards, then through melt extruding in twin screw extruder, granulation, its technique is: a district 160-180 DEG C, two district 200-210 DEG C, three district 210-220 DEG C, four district 210-220 DEG C, five district 210-220 DEG C, six district 205-215, seven district 200-210, pressure 12-18MPa.
Comparative example two:
Polypropylene 64.5%, weighting agent 15%, thermo-stabilizer 0.5%, elastomerics 20.0% are dry mixed 3-5 minute in high speed mixer, afterwards, then through melt extruding in twin screw extruder, granulation, its technique is: a district 160-180 DEG C, two district 200-210 DEG C, three district 210-220 DEG C, four district 210-220 DEG C, five district 210-220 DEG C, six district 205-215, seven district 200-210, pressure 12-18MPa.
Comparative example three:
Polypropylene 49.8%, weighting agent 20%, thermo-stabilizer 0.2%, elastomerics 30.0% are dry mixed 3-5 minute in high speed mixer, afterwards, then through melt extruding in twin screw extruder, granulation, its technique is: a district 160-180 DEG C, two district 200-210 DEG C, three district 210-220 DEG C, four district 210-220 DEG C, five district 210-220 DEG C, six district 205-215, seven district 200-210, pressure 12-18MPa
Embodiment one:
By polypropylene 83.65%, weighting agent 10%, thermo-stabilizer 1.0%, elastomerics 5.0%, linking agent 0.25%, additional crosslinker 0.1%, in high speed mixer, be dry mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technique is: a district 160-180 DEG C, two district 200-210 DEG C, three district 210-220 DEG C, four district 210-220 DEG C, five district 210-220 DEG C, six district 205-215, seven district 200-210, pressure 12-18MPa.
Embodiment two:
By polypropylene 78.3%, weighting agent 10%, thermo-stabilizer 1.0%, elastomerics 10.0%, linking agent 0.5%, additional crosslinker 0.2%, in high speed mixer, be dry mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technique is: a district 160-180 DEG C, two district 200-210 DEG C, three district 210-220 DEG C, four district 210-220 DEG C, five district 210-220 DEG C, six district 205-215, seven district 200-210, pressure 12-18MPa.
Embodiment three:
By polypropylene 73.65%, weighting agent 15%, thermo-stabilizer 0.5%, elastomerics 10.0%, linking agent 0.6%, additional crosslinker 0.25%, in high speed mixer, be dry mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technique is: a district 160-180 DEG C, two district 200-210 DEG C, three district 210-220 DEG C, four district 210-220 DEG C, five district 210-220 DEG C, six district 205-215, seven district 200-210, pressure 12-18MPa.
Embodiment four:
By polypropylene 63.4%, weighting agent 15%, thermo-stabilizer 0.5%, elastomerics 20.0%, linking agent 0.8%, additional crosslinker 0.3%, in high speed mixer, be dry mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technique is: a district 160-180 DEG C, two district 200-210 DEG C, three district 210-220 DEG C, four district 210-220 DEG C, five district 210-220 DEG C, six district 205-215, seven district 200-210, pressure 12-18MPa.
Embodiment five:
By polypropylene 58.4%, weighting agent 20%, thermo-stabilizer 0.2%, elastomerics 20.0%, linking agent 1.0%, additional crosslinker 0.4%, in high speed mixer, be dry mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technique is: a district 160-180 DEG C, two district 200-210 DEG C, three district 210-220 DEG C, four district 210-220 DEG C, five district 210-220 DEG C, six district 205-215, seven district 200-210, pressure 12-18MPa.
Embodiment six:
By polypropylene 48.1%, weighting agent 20%, thermo-stabilizer 0.2%, elastomerics 30.0%, linking agent 1.2%, additional crosslinker 0.5%, in high speed mixer, be dry mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technique is: a district 160-180 DEG C, two district 200-210 DEG C, three district 210-220 DEG C, four district 210-220 DEG C, five district 210-220 DEG C, six district 205-215, seven district 200-210, pressure 12-18MPa.
The list of table one experimental formula
Table two experimental data contrast table
Performance evaluation mode
As can be seen from the contrast of embodiment 1 and 2,3 and 4,5 and 6, increase elastomeric consumption, the toughness of polypropylene material, namely shock resistance can improve, rigidity, namely Young's modulus can reduce, and contrasts situation from comparative example 1,2,3, better by adding elastomeric modified polypropylene material normal temperature Toughness Ratio, and the low-temperature impact property entirety of-30 DEG C is on the low side; Comparative example 1,2 and comparative example 1, embodiment 3,4 and comparative example 2, embodiment 5,6 and comparative example 3 known, carry out polypropylene material modification by elastomer crosslinked, can when not increasing elastomerics consumption, toughness is significantly improved, rigidity is but substantially unaffected, in other words, by elastomer crosslinked principle, suitably can reduce elastomerics consumption to improve rigidity, and toughness of material be affected less.In sum, by carrying out vulcanization crosslinking to elastomerics, carry out polypropylene modification, can the toughness of balancing material and rigidity effectively, thus obtain strong and unyielding excellent polypropylene material of holding concurrently.
Claims (10)
1. high tenacity, a high rigidity modified polypropylene material, is characterized in that: by weight percentage, and its composition and proportioning are:
2. a kind of high tenacity according to claim 1, high rigidity modified polypropylene material, is characterized in that: by weight percentage, and its composition and optimum ratio are:
3. a kind of high tenacity according to claim 1 and 2, high rigidity modified polypropylene material, it is characterized in that: under 230 DEG C × 2.16Kg test condition, one or both compositions in the homo-polypropylene of described polypropylene to be melt flow rate (MFR) be 0.5-60g/10min and Co-polypropylene.
4. a kind of high tenacity according to claim 1 and 2, high rigidity modified polypropylene material, it is characterized in that: described talcum powder, its particle size range is 1 ~ 10 micron.
5. a kind of high tenacity according to claim 1 and 2, high rigidity modified polypropylene material, is characterized in that: described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, and primary antioxidant selects one or more in Hinered phenols antioxidant; Auxiliary anti-oxidant selects the mixture of one or more in phosphite ester kind antioxidant.
6. a kind of high tenacity according to claim 5, high rigidity modified polypropylene material, is characterized in that: described primary antioxidant is selected from one or more in 1010,3114 and DSTP; Auxiliary anti-oxidant be selected from 618 and 168 one or both.
7. a kind of high tenacity according to claim 1 and 2, high rigidity modified polypropylene material, is characterized in that: described elastomerics is the multipolymer of ethylene-octene, under 230 DEG C × 2.16Kg test condition, melt flow rate (MFR) is 0.5-10g/10min.
8. a kind of high tenacity according to claim 1 and 2, high rigidity modified polypropylene material, is characterized in that: described linking agent is dicumyl peroxide.
9. a kind of high tenacity according to claim 1 and 2, high rigidity modified polypropylene material, is characterized in that: described additional crosslinker is iso-cyanuric acid triallyl ester.
10. prepare a method for a kind of novel renewable modified polypropylene material described in claim 1 or 2, it is characterized in that: its step is as follows:
1) raw material is taken according to weight proportion.
2) raw material is placed in high speed mixer and is dry mixed 3-5 minute.
3) raw material of mixing is placed in twin screw extruder through melt extruding, granulation, its concrete technology is: extruder temperature controller one district 160-180 DEG C, two district 200-210 DEG C, three district 210-220 DEG C, four district 210-220 DEG C, five district 210-220 DEG C, six district 205-215, seven district 200-210, pressure 12-18MPa.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482265A (en) * | 2015-12-22 | 2016-04-13 | 合肥仲农生物科技有限公司 | Polypropylene composite material for washing machine |
| CN105754219A (en) * | 2016-03-31 | 2016-07-13 | 安徽纽麦特新材料科技股份有限公司 | Polypropylene composite material with high toughness under ultralow temperature and preparation method and application thereof |
| CN107383583A (en) * | 2017-09-15 | 2017-11-24 | 广州市合诚化学有限公司 | A kind of outer cover material of the low opening force of high rigidity and preparation method and application |
| CN108164647A (en) * | 2018-01-16 | 2018-06-15 | 鲁东大学 | A kind of dynamic vulcanization flexibilized polypropylene material and preparation method thereof |
| CN111844673A (en) * | 2020-07-08 | 2020-10-30 | 上海叶心材料科技有限公司 | Application method of high-strength propylene elastomer applied to TPV (thermoplastic vulcanizate) automobile instrument panel |
| CN112409690A (en) * | 2020-11-19 | 2021-02-26 | 上海金发科技发展有限公司 | High-melt-strength in-situ reinforced polypropylene composite material and preparation method 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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| CN103254507A (en) * | 2012-02-16 | 2013-08-21 | 合肥杰事杰新材料股份有限公司 | Stress-whitening-resistant filling-modified polypropylene composite material and preparation method thereof |
| CN103739946A (en) * | 2013-12-07 | 2014-04-23 | 天津市华鑫达投资有限公司 | High-impact high-stiffness polypropylene rotational molding material and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482265A (en) * | 2015-12-22 | 2016-04-13 | 合肥仲农生物科技有限公司 | Polypropylene composite material for washing machine |
| CN105754219A (en) * | 2016-03-31 | 2016-07-13 | 安徽纽麦特新材料科技股份有限公司 | Polypropylene composite material with high toughness under ultralow temperature and preparation method and application thereof |
| CN107383583A (en) * | 2017-09-15 | 2017-11-24 | 广州市合诚化学有限公司 | A kind of outer cover material of the low opening force of high rigidity and preparation method and application |
| CN107383583B (en) * | 2017-09-15 | 2020-10-13 | 广州市合诚化学有限公司 | Outer cover material with high rigidity and low opening force, and preparation method and application thereof |
| CN108164647A (en) * | 2018-01-16 | 2018-06-15 | 鲁东大学 | A kind of dynamic vulcanization flexibilized polypropylene material and preparation method thereof |
| CN111844673A (en) * | 2020-07-08 | 2020-10-30 | 上海叶心材料科技有限公司 | Application method of high-strength propylene elastomer applied to TPV (thermoplastic vulcanizate) automobile instrument panel |
| CN112409690A (en) * | 2020-11-19 | 2021-02-26 | 上海金发科技发展有限公司 | High-melt-strength in-situ reinforced polypropylene composite material and preparation method 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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Application publication date: 20150506 |