CN105153556A - High-performance polypropylene material and preparation method thereof - Google Patents
High-performance polypropylene material and preparation method thereof Download PDFInfo
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- CN105153556A CN105153556A CN201510458447.8A CN201510458447A CN105153556A CN 105153556 A CN105153556 A CN 105153556A CN 201510458447 A CN201510458447 A CN 201510458447A CN 105153556 A CN105153556 A CN 105153556A
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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
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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
- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
- C08L2205/242—Beta spherulite nucleating agents
Abstract
The invention discloses a high-performance polypropylene material and a preparation method thereof. The material is composed of the following ingredients in parts by weight: 60-80 parts of polypropylene, 10-15 parts of a conjugated diene polymer, 0.1-0.5 part of an anti-oxidant, and 0.1-10 parts of a composite nucleating agent. The composite nucleating agent is composed of A: alpha/beta composite nucleating agent, and B: carbon black. The mass fraction of the A: alpha/beta composite nucleating agent is 90-99%, and the mass fraction of the B: carbon black is 1-10%. The alpha/beta composite nucleating agent is a mixture of an alpha composite nucleating agent and a beta nucleating agent. The employed composite nucleating agent integrates advantages of polypropylene with alpha and beta crystal forms, and the product mechanical properties and optical performances are substantially improved.
Description
Technical field
The present invention relates to a kind of high-performance polypropylene material and preparation method thereof, belong to technical field of composite materials.
Background technology
The crystalline structure of known isotatic polypropylene can form α, β, γ, δ and plan six side state etc. five kinds.Wherein, alpha-crystal form is oblique system, the most stable, is mainly this type of crystal formation in current commercial polypropylene, beta crystal be thermodynamics metastable state, be kinetically be unfavorable for generate a kind of crystal formation, be difficult under typical conditions obtain.Usually, use the nucleator of alpha-crystal form can induce the polypropylene producing alpha-crystal form, use the nucleator of beta crystal can induce the polypropylene producing beta crystal, alpha-crystal form nucleator can be provided as nuclear particle in crystalling propylene process, thus improve polyacrylic Tc, reduce spherocrystal temperature, spherocrystal is made to be tending towards perfect, therefore the alpha-crystal form polypropylene obtained has higher rigidity, but polyacrylic toughness can decline to some extent, and Beta-crystalline polyacrylic has higher toughness and heat-drawn wire, rigidity is not enough, due to the more difficult acquisition of beta crystal, and excellent performance, existing many technical schemes often blindly pursue the polypropylene of high beta-crystalline form content, and be not combined according to both features.
If want the polypropylene advantages of α, β two kinds of crystal formations, select suitable α/β composite nucleating agent very crucial, after adding α/β composite nucleating agent, product there will be effect has: 1. the polypropylene product obtaining wherein a kind of crystal formation or mixing crystal formation, the performance of this product is often with only to add wherein a kind of nucleator effect similar, or two kinds of nucleators simply add and effect, 2. obtain the performance enhancement type product of set two kinds of crystal formation advantages.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of high-performance polypropylene material and preparation method thereof, and the advantage of this polypropylene material set α, Beta-crystalline polyacrylic, mechanical property and the optical property of product be all significantly increased.
For solving the problem, the technical solution used in the present invention is:
A kind of high-performance polypropylene material, is made up of the component of following weight fraction meter: polypropylene 60-80 part, conjugated diene polymer 10-15 part, oxidation inhibitor 0.1-0.5 part, composite nucleator 0.1-10 part, described composite nucleator is by A: α/β composite nucleating agent, and B: carbon black forms.Wherein A: the massfraction of α/β composite nucleating agent is 90-99%, the massfraction of carbon black is 1-10%, and described α/β composite nucleating agent is the mixture of α type nucleator and β type nucleator.
Preferably, in described α/β composite nucleating agent, α type nucleator and β type nucleator mass ratio are 1/10-1/2.
Preferably, described α type nucleator is aryl carboxylic acid and metallic salt α type nucleator thereof.
Preferably, described β type nucleator is rare earth class β type nucleator.
Preferably, described conjugated diene polymer is polyhutadiene or polyisoprene.
Preferably, described oxidation inhibitor is Hinered phenols antioxidant.
Prepare a method for high-performance polypropylene material described above, the method comprises the following steps:
(1) take polypropylene, α type nucleator, β type nucleator and carbon black, and this mixture is mixed 5-15 minute in high-speed mixer;
(2) the mixture irradiation 30-60min under microwave will obtained in step (1);
(3) add conjugated diene polymer and oxidation inhibitor in the mixture after the microwave exposure obtained in step (2), mix 10-20 minute subsequently in high-speed mixer, rotating speed is: 400-800r/min;
(4) mixture that step (3) obtains is placed in twin screw extruder extruding pelletization, twin screw extruder rotating speed is: 300-500r/min, and each district temperature is 160-250 DEG C.
Formula of the present invention utilizes melt mixing methods well known in the art also can realize, but preferably adopts above-mentioned preparation method.
Compared with prior art, the beneficial effect that the present invention reaches is:
Use composite nucleator not only to gather the advantage of α, β two kinds of crystalline polyacrylics, mechanical property and the optical property of product are all significantly increased;
Carbon black is made up of a large amount of crystallite, crystallite is in center, in spherical or roll into a ball spherical, and more or less form the chain extended to space, the interpolation of carbon black can make polyacrylic crystallization rate generation Rapid Variable Design, and then causes thermodynamic behaviour such as melt temperature, supramolecule crystalline structure to change, and finally affects the mechanical property of product, carbon black and α/β composite nucleating agent have certain synergy, the polyacrylic crystallisation process of joint effect.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.Following examples only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
Comparative example 1
Take raw material by following weight part: polypropylene 70 parts, polyisoprene 10 parts, Hinered phenols antioxidant 0.3 part, nucleator 5 parts, wherein nucleator is by A: β type nucleator, and B: carbon black forms.Wherein A: β type synthetic kernel agent is rare earth class β type nucleator, and in this nucleator, the massfraction of β type nucleator is 98%, and the massfraction of carbon black is 2%,
Preparation method is:
(1) take polypropylene, β type nucleator and carbon black by said ratio, and this mixture is mixed 10 minutes in high-speed mixer;
(2) the mixture irradiation 45min under microwave will obtained in step (1);
(3) add polyisoprene and oxidation inhibitor in the mixture after the microwave exposure obtained in step (2), mix 10-20 minute subsequently in high-speed mixer, rotating speed is: 400-800r/min;
(4) mixture that step (3) obtains is placed in twin screw extruder extruding pelletization, twin screw extruder rotating speed is: 300-500r/min, and each district temperature is 160-250 DEG C.
Comparative example 2 takes raw material by following weight part: polypropylene 70 parts, polyisoprene 10 parts, Hinered phenols antioxidant 0.3 part, α/β composite nucleating agent 5 parts, wherein α/β composite nucleating agent is the mixture of aryl carboxylic acid class α nucleator and rare earth class β type nucleator, and α type nucleator/β type nucleator mass ratio is 1/10.
Preparation method is:
(1) take polypropylene, α type nucleator, β type nucleator by said ratio, and this mixture is mixed 10 minutes in high-speed mixer;
(2) the mixture irradiation 45min under microwave will obtained in step (1);
(3) add polyisoprene and oxidation inhibitor in the mixture after the microwave exposure obtained in step (2), mix 10-20 minute subsequently in high-speed mixer, rotating speed is: 400-800r/min;
(4) mixture that step (3) obtains is placed in twin screw extruder extruding pelletization, twin screw extruder rotating speed is: 300-500r/min, and each district temperature is 160-250 DEG C.
Embodiment 1
Take raw material by following weight part: polypropylene 60 parts, polyhutadiene 15 parts, Hinered phenols antioxidant 0.1 part, composite nucleator 0.1 part, wherein composite nucleator is by A: α/β composite nucleating agent, and B: carbon black forms.Wherein A: α/β composite nucleating agent is the mixture of aryl carboxylic acid class α nucleator and rare earth class β type nucleator, the massfraction that this α/β composite nucleating agent accounts for whole composite nucleator is 90%, α type nucleator/β type nucleator is 1/10, and the massfraction of carbon black is 10%
Preparation method is:
(1) take polypropylene, α type nucleator, β type nucleator and carbon black by said ratio, and this mixture is mixed 15 minutes in high-speed mixer;
(2) the mixture irradiation 30min under microwave will obtained in step (1);
(3) add polyhutadiene and oxidation inhibitor in the mixture after the microwave exposure obtained in step (2), mix 10-20 minute subsequently in high-speed mixer, rotating speed is: 400-800r/min;
(4) mixture that step (3) obtains is placed in twin screw extruder extruding pelletization, twin screw extruder rotating speed is: 300-500r/min, and each district temperature is 160-250 DEG C.
Embodiment 2
Take raw material by following weight part: polypropylene 70 parts, polyisoprene 10 parts, Hinered phenols antioxidant 0.3 part, composite nucleator 5 parts, wherein composite nucleator is by A: α/β composite nucleating agent, and B: carbon black forms.Wherein A: α/β composite nucleating agent is the mixture of aryl carboxylic acid class α nucleator and rare earth class β type nucleator, the massfraction that this α/β composite nucleating agent accounts for whole composite nucleator is 98%, α type nucleator/β type nucleator is 1/10, and the massfraction of carbon black is 2%
Preparation method is:
(1) take polypropylene, α type nucleator, β type nucleator and carbon black by said ratio, and this mixture is mixed 10 minutes in high-speed mixer;
(2) the mixture irradiation 45min under microwave will obtained in step (1);
(3) add polyisoprene and oxidation inhibitor in the mixture after the microwave exposure obtained in step (2), mix 10-20 minute subsequently in high-speed mixer, rotating speed is: 400-800r/min;
(4) mixture that step (3) obtains is placed in twin screw extruder extruding pelletization, twin screw extruder rotating speed is: 300-500r/min, and each district temperature is 160-250 DEG C.
Embodiment 3
Take raw material by following weight part: polypropylene 70 parts, polyhutadiene 10 parts, Hinered phenols antioxidant 0.3 part, composite nucleator 10 parts, wherein composite nucleator is by A: α/β composite nucleating agent, and B: carbon black forms.Wherein A: α/β composite nucleating agent is the metallic salt α nucleator of aryl carboxylic acid and the mixture of rare earth class β type nucleator, the massfraction that this α/β composite nucleating agent accounts for whole composite nucleator is 95%, α type nucleator/β type nucleator is 1/5, and the massfraction of carbon black is 5%
Preparation method is:
(1) take polypropylene, α type nucleator, β type nucleator and carbon black by said ratio, and this mixture is mixed 5 minutes in high-speed mixer;
(2) the mixture irradiation 60min under microwave will obtained in step (1);
(3) add polyisoprene and oxidation inhibitor in the mixture after the microwave exposure obtained in step (2), mix 10-20 minute subsequently in high-speed mixer, rotating speed is: 400-800r/min;
(4) mixture that step (3) obtains is placed in twin screw extruder extruding pelletization, twin screw extruder rotating speed is: 300-500r/min, and each district temperature is 160-250 DEG C.
Embodiment 4
Take raw material by following weight part: polypropylene 80 parts, polyisoprene 10 parts, Hinered phenols antioxidant 0.5 part, composite nucleator 0.5 part, wherein composite nucleator is by A: α/β composite nucleating agent, and B: carbon black forms.Wherein A: α/β composite nucleating agent is the mixture of aryl carboxylic acid class α nucleator and rare earth class β type nucleator, the massfraction that this α/β composite nucleating agent accounts for whole composite nucleator is 99%, α type nucleator/β type nucleator is 1/2, and the massfraction of carbon black is 1%
Preparation method is:
(1) take polypropylene, α type nucleator, β type nucleator and carbon black by said ratio, and this mixture is mixed 10 minutes in high-speed mixer;
(2) the mixture irradiation 45min under microwave will obtained in step (1);
(3) add polyisoprene and oxidation inhibitor in the mixture after the microwave exposure obtained in step (2), mix 10-20 minute subsequently in high-speed mixer, rotating speed is: 400-800r/min;
(4) mixture that step (3) obtains is placed in twin screw extruder extruding pelletization, twin screw extruder rotating speed is: 300-500r/min, and each district temperature is 160-250 DEG C.
Formula of the present invention utilizes melt mixing methods well known in the art also can realize, but preferably adopts above-mentioned preparation method.
Performance test
Melt flow rate (MFR) test is undertaken by ISO1133, and test condition is 230 DEG C × 2.16Kg, and sample bent performance test is undertaken by ISO178 standard, and specimen size is 80 × 10 × 4mm, span 64mm, rate of bending 2mm/min; Charpy Impact performance test is undertaken by ISO179-1 standard, and specimen size is 80 × 10 × 4mm, and notch depth is 1/3rd of sample thickness; Mist degree presses GB/T2410-2008, and shrinking percentage is undertaken by ISO2577, and specimen size is 150 × 100 × 3.2mm.
Table 1 is the performance test results of above embodiment and comparative example:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| MI value (g/10min) | 29 | 35 | 30 | 31 | 26 | 27 |
| Mist degree, % | 10.0 | 8.9 | 9.1 | 9.7 | 14.8 | 9.8 |
| Modulus in flexure, MPa | 1907 | 2150 | 1928 | 1997 | 1788 | 1801 |
| Notched Izod impact strength, 23 DEG C of (KJ/m 2） | 30 | 35 | 31 | 29 | 26 | 24 |
| After shrinking (%) 24h | 0.88 | 0.68 | 0.77 | 0.91 | 0.69 | 0.89 |
As seen from Table 1, the relatively existing acrylic resin formula of the same type of acrylic resin of the present invention's formula has better mechanical property and optical property, modulus in flexure all remains on more than 1850Mpa, mist degree is minimum is down to 8.9%, toughness of products is also very good, and shrinking percentage is within the scope of 0.68-0.91%.Not enough without product rigidity during α type nucleator in composite nucleator, but toughness is maintained, as compared for 1 and embodiment 2, when adding without carbon black, product rigidity is also poor, by the 2150MPa in comparative example 2, be down to 1801MPa, do not use the solution flow rate of composite nucleator product in the present invention and other performances all to decrease.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and distortion, these improve and distortion also should be considered as protection scope of the present invention.
Claims (7)
1. a high-performance polypropylene material, it is characterized in that: be made up of the component of following weight parts: polypropylene 60-80 part, conjugated diene polymer 10-15 part, oxidation inhibitor 0.1-0.5 part, composite nucleator 0.1-10 part, described composite nucleator is made up of the carbon black of massfraction to be the α/β composite nucleating agent of 90-99% and massfraction be 1-10%, and described α/β composite nucleating agent is the mixture of α type nucleator and β type nucleator.
2. a kind of high-performance polypropylene material according to claim 1, is characterized in that: in described α/β composite nucleating agent, α type nucleator and β type nucleator mass ratio are 1/10-1/2.
3. a kind of high-performance polypropylene material according to claim 2, is characterized in that: described α type nucleator is aryl carboxylic acid and metallic salt α type nucleator thereof.
4. a kind of high-performance polypropylene material according to claim 3, is characterized in that: described β type nucleator is rare earth class β type nucleator.
5. a kind of high-performance polypropylene material according to claim 1, is characterized in that: described conjugated diene polymer is polyhutadiene or polyisoprene.
6. a kind of high-performance polypropylene material according to claim 1, is characterized in that: described oxidation inhibitor is Hinered phenols antioxidant.
7. prepare a method for high-performance polypropylene material described in any one of claim 1-6, it is characterized in that: comprise the following steps:
(1) take polypropylene, α type nucleator, β type nucleator and carbon black, and this mixture is mixed 5-15 minute in high-speed mixer;
(2) the mixture irradiation 30-60min under microwave will obtained in step (1);
(3) add conjugated diene polymer and oxidation inhibitor in the mixture after the microwave exposure obtained in step (2), mix 10-20 minute subsequently in high-speed mixer, rotating speed is: 400-800r/min;
(4) mixture that step (3) obtains is placed in twin screw extruder extruding pelletization, twin screw extruder rotating speed is: 300-500r/min, and each district temperature is 160-250 DEG C.
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| CN201510458447.8A CN105153556A (en) | 2015-07-30 | 2015-07-30 | High-performance polypropylene material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107793635A (en) * | 2016-08-30 | 2018-03-13 | 李长荣化学工业股份有限公司 | Polypropylene expanded body and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250787A (en) * | 1998-10-12 | 2000-04-19 | 四川联合大学 | Interface compatibilizing method for polyolefin filler mixture |
| CN101704974A (en) * | 2009-11-05 | 2010-05-12 | 上海金发科技发展有限公司 | High-gloss polypropylene material containing carbon black colorant and preparation method thereof |
| CN102040772A (en) * | 2010-12-06 | 2011-05-04 | 华东理工大学 | Method for regulating mechanical property of polypropylene based on alpha/beta complex nucleating agent |
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- 2015-07-30 CN CN201510458447.8A patent/CN105153556A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250787A (en) * | 1998-10-12 | 2000-04-19 | 四川联合大学 | Interface compatibilizing method for polyolefin filler mixture |
| CN101704974A (en) * | 2009-11-05 | 2010-05-12 | 上海金发科技发展有限公司 | High-gloss polypropylene material containing carbon black colorant and preparation method thereof |
| CN102040772A (en) * | 2010-12-06 | 2011-05-04 | 华东理工大学 | Method for regulating mechanical property of polypropylene based on alpha/beta complex nucleating agent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107793635A (en) * | 2016-08-30 | 2018-03-13 | 李长荣化学工业股份有限公司 | Polypropylene expanded body and preparation method thereof |
| US10882968B2 (en) | 2016-08-30 | 2021-01-05 | Lcy Chemical Corporation | Polypropylene foams and processes of making |
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