CN1150160A - Modified polypropylene composition with low rubber content - Google Patents
Modified polypropylene composition with low rubber content Download PDFInfo
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- CN1150160A CN1150160A CN 95117929 CN95117929A CN1150160A CN 1150160 A CN1150160 A CN 1150160A CN 95117929 CN95117929 CN 95117929 CN 95117929 A CN95117929 A CN 95117929A CN 1150160 A CN1150160 A CN 1150160A
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Abstract
A modified polypropene composition with low rubber content uses copolymerized polypropene as matrix. A series of high-toughness cheap modified polypropene compositions is obtained by changing the relative contents of two kinds of copolymerized polypropene respectively with high toughness and high flowability and adding rubber (2-10 wt.%), and can be used in car, household electric appliances and thermoplastic sheet material fields.
Description
The present invention relates to polypropylene modification, specially refer to rubber and thermoplastic elastomer tenacity-increased profax and carry out the modification field.
Polypropylene is one of five big general-purpose plastics kinds.Advantages such as, resistance to chemical attack little owing to its proportion, mechanics harmony are good, easy processing obtain widespread use.But its shortcoming is low temperature brittleness and owing to shrinking percentage causes goods greatly the bent distortion of wing takes place easily.Usually can adopt polymeric modification and two kinds of methods of blending and modifying in order to improve this shortcoming.Polymeric modification is easy to scale operation and the modification quality is more stable, over particularly past 10 years, along with polymer material science and development of technology, using metalloscene catalyst to feed a certain amount of ethene in propylene polymerization processes can synthesize ethylene-propylene rubber(EPR) content and reach 40-50% in reactor, median size is the superhigh tenacity polypropylene alloy material of 0.4-0.6 μ m, Himont Co in 1994, BASF CO, DSM CO has reported this class achievement in research successively and has entered the report of commercialization stage.The shortcoming of polymeric modification is that one-time investment is big, and product grade is difficult for too much.The advantage of blending and modifying is control by the design of blend component, machining process and product structure form different, the various in style trade mark that obtains performance easily comparatively speaking.The history of rubber toughened plastics can be traced to nineteen twenty-seven U.S. Pat .Pat.1 the earliest, and 613,673, the birth of HIPS is seen US.Pat.2,694,692 but just realize commercially producing up to nineteen fifty-two.It is that second example the most successful of rubber toughened plastics seen US.Pat.2 that SAN and NBR melt blending are made ABS, 439,202 (1948), and entering the forties rubber toughened plastics has become the important technology approach that plastics industry develops rapidly.The research of rubber toughening polypropylene obtains breakthrough and obtains widespread use in industry member to start from the mid-80, sees Polym.Eng.Sci, 25 (1985), 643.Meanwhile the mechanism of rubber toughening polypropylene has also been carried out sufficient research, as rubber size and distribution thereof; The rubber volume fraction, the dependency of particle diameter and blend impact property; The dependency of matrix resin interfacial layer thickness and blend impact property etc.Has only the superhigh tenacity polypropylene blend that when the rubber volume fraction surpasses 25%, just might obtain socle girder (Izod) notched-value 〉=500J/M.The introducing of a large amount of rubber has improved polyacrylic impelling strength, has but caused the decline of blend rigidity and heat-drawn wire, has increased the cost of blend simultaneously.
In order to overcome the shortcoming of above-mentioned blend rubber tenacity-increased profax, the invention provides a kind of with the rubber toughened co-polypropylene composition of 2-10%, this modified poly propylene composition has superhigh tenacity, high-tensile, high bending strength and modulus, high heat-drawn wire, and reduced cost.
Modified poly propylene composition composition of the present invention and content are as follows:
Composition component weight percentage (%)
Co-polypropylene mixture 70-85%
Polyethylene 9-16%
Toughner 2-10%
Talcum powder 0-15%
Oxidation inhibitor 0.30-0.40%
Uv-absorbing agent 0.20-0.30%
Carbon black 0.1-2%
Superoxide 0-0.035%
Auxiliary agent 0.1-0.2%
Described Co-polypropylene mixture is the high tenacity Co-polypropylene, melting index (MI)=0.2～2.0g/10min.Izod (breach) shock strength is 360～500J/M and high workability Co-polypropylene, melting index MI=19～30g/10min.Izod (breach) shock strength is the mixture of 40-70J/M, and wherein high tenacity Co-polypropylene and high workability Co-polypropylene are 0.1-4% by weight percentage.
Described toughner is ethylene propylene rubber (EPR), terpolymer EP rubber (EPDM), isoprene-isobutylene rubber (BR) and SBS thermoplastic elastomer.Ethylene content is 20-70% among the EPR, and Mooney viscosity value (ML1+4,125 ℃) is 20-70, and unsaturated diene content is 2-8% among the EPDM, and ethylene content is 25-70%, and Mooney viscosity value (ML1+4,125 ℃) is 19-80.Content is the adding of 2-10% ethylene-propylene rubber(EPR), help to regulate because polypropylene and the differences in viscosity of polyethylene under processing conditions, improve mixed effect, be again polyethylene simultaneously, polypropylene good interface compatilizer, the variation by the interfacial adhesion state help to improve impelling strength and other mechanical property of composition.The impelling strength of composition increases with the increase of rubber content, but is satisfying under the situation of notched bar impact strength, and rubber content is low more economical more.
Polyethylene provided by the invention can be melting index 0.15-7g/10min, and viscosity-average molecular weight is 1.25 * 10
5-3 * 10
5Low density, middle density and high density polyethylene(HDPE).Because poly fusing point is lower about 40 ℃ than polypropylene, can becoming the out-phase nucleus when polypropene blended, and help to improve the rheological behavior that processing fluidity and blend are processed.
Described auxiliary agent is a calcium stearate.
Described superoxide can be dicumyl peroxide (DCP), ditertiary butyl peroxide (DTBP), benzoyl peroxide (BPO) and polypropylene cooling masterbatch etc.Only depend on the flowing property that final blend is regulated in the variation of two kinds of co-polypropylene component relative proportions, and the effect that reaches superhigh tenacity simultaneously is limited.The existence of a small amount of superoxide in the blend process, random free radical cracking reaction helps to remove the high high aft end portion of molecular weight in the component.On the basis that keeps mechanical property, improved the flow processability energy.Owing to the existence of superoxide, certain chemical reaction also can take place with the tertiary carbon atom among PE and the PP in the unsaturated double-bond in the rubber, helps to improve the consistency of heterogeneous system simultaneously.Because the content of superoxide is extremely low, to mix and disperse in order to help in the use, superoxide can be made into 1: superoxide acetone soln and the ethanol solution of 4-8.The polypropylene cooling masterbatch that the production of mass-producing recommends use Chinese Academy of Sciences chemistry to be invented.
Modified poly propylene composition of the present invention has superhigh tenacity, high-tensile, high bending strength, modulus and high heat-drawn wire.
The each component that the present invention is outlined mixed in high-speed mixer 1-5 minute, and granulation in twin screw extruder dewaters the pellet drying, makes the standard batten with injection moulding, used for measuring performance.
Embodiment 1-5:
With the Co-polypropylene is basestocks, and the component, content and the performance that add 2-10% (weight percentage) EPDM, its blend are listed in table 1, the table 2 respectively.
Table 1, modified polypropene blend composition component and content
| Composition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| EPDM content (%) | ????2 | ????4 | ????6 | ????8 | ??10 |
| High tenacity COPP High Flowability Polypropylene Copolymers EPDA LDPE antioxidant ultraviolet absorber carbon black auxiliary agent | ????800 ????200 ????25 ????200 ????3.5 ????2.5 ????0.6 ????2 | ????800 ????200 ????50 ????200 ????3.5 ????2.5 ????0.6 ????2 | ????800 ????200 ????77 ????200 ????3.5 ????2.5 ????0.6 ????2 | ????800 ????200 ????105 ????200 ????3.5 ????2.5 ????0.6 ????2 | ??800 ??200 ??135 ??200 ??3.5 ??2.5 ??0.6 ??2 |
Table 2, modified polypropene blend composition physicochemical property
| Composition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| EPDM content (%) | ????2 | ????4 | ????6 | ????8 | ????10 |
| MI (g/10min) σ y (MPa) ε (%) IS (lacking) is σ b (MPa) Eb (MPa) (J/M) | ????1.9 ????24.4 ????526 ????621 ????27.6 ????816 | ????1.9 ????23.7 ????525 ????691 ????26.9 ????800 | ????1.8 ????22.8 ????480 ????679 ????24.8 ????731 | ????1.8 ????21.8 ????450 ????685 ????24.0 ????676 | ????1.5 ????20.2 ????450 ????742 ????23.0 ????697 |
With the Co-polypropylene is basestocks, adds 6% SBS or EPR, the component of its blend, and content and performance are listed in respectively in the table 3,4.
Table 3, modified polypropene blend composition component and content
| Composition | Embodiment 6 SBS | Embodiment 7 EPR |
| Toughner content % | ???6 | ???6 |
| High tenacity COPP High Flowability Polypropylene Copolymers SBS or EPR LDPE antioxidant ultraviolet absorber carbon black auxiliary agent | ???800 ???200 ???77 ???200 ???3.5 ???2.5 ???0.6 ???2 | ???800 ???200 ???77 ???200 ???3.5 ???2.5 ???0.6 ???2 |
Table 4, modified polypropene blend composition physicochemical property
In the formula: MI-melting index, σ y-tensile yield strength, ε-elongation at break, IS (lacking)-socle girder notched Izod impact strength, σ b-flexural strength, the result of Eb-modulus in flexure embodiment 1-5 has shown the economy of this low rubber content superhigh tenacity blend composition and good comprehensive mechanical property.But flowability is lower, slightly dislikes not enough.Embodiment 8-11 has done improvement to this.
| Composition | Embodiment 1 SBS | Embodiment 2 EPR |
| Toughner content % | ????6 | ????6 |
| MI (g/10min) σ y (MPa) ε (%) IS (lacking) is σ b (MPa) Eb (MPa) (J/M) | ????1.0 ????24.9 ????324 ????657.5 ????26.0 ????790 | ????1.1 ????23.2 ????409 ????647.6 ????24.0 ????760 |
Embodiment 8-11 blend composition component, content and performance are respectively in table 5, in the table 6.
Table 5, modified polypropene blend composition component and content
| Composition | Example 8 | Example 9 | Example 10 | Example 11 |
| High tenacity COPP High Flowability Polypropylene Copolymers EPDM LDPE talcum powder antioxidant ultraviolet absorber carbon black auxiliary agent (calcium stearate) DCP solution (ml) | ????550 ????300 ????50??? ????100 ????- ????3.5 ????2.5 ????0.6 ????2 ????- | ????400 ????450 ????50 ????100 ????- ????3.5 ????2.5 ????0.6 ????2 ????- | ??800 ??200 ??50 ??200 ??160 ??3.5 ??2.5 ??0.6 ??2 ??1 | ??800 ??200 ??50 ??200 ??160 ??3.5 ??2.5 ??0.6 ??2 ??2 |
In the DCP acetone soln, the concentration expressed in percentage by weight of DCP is 20%.
Table 6, modified polypropene blend composition physicochemical property
| Physicochemical property | Example 8 | Example 9 | Example 10 | Example 11 |
| MI (G/10Min) σ y (MPa) ε (%) Is (lacking) is σ b (MPa) Eb (MPa) (J/M) | ????3.0 ????22.6 ????550 ????625 ????30.1 ????966 | ????5.1 ????22.5 ????595 ????472 ????31.7 ????1060 | ????3.4 ????21.3 ????530 ????556 ????29.1 ????1375 | ????4.5 ????20.7 ????600 ????501 ????29.1 ????1118 |
Claims (9)
1, a kind of modified poly propylene composition contains polypropylene, polyethylene, toughner, oxidation inhibitor, uv-absorbing agent, processing aid, talcum powder, carbon black and superoxide, it is characterized in that described component and weight percentage are as follows:
Composition component weight percentage (%)
Co-polypropylene mixture 70-85%
Polyethylene 9-16%
Toughner 2-10%
Talcum powder 0-15%
Oxidation inhibitor 0.30-0.40%
Uv-absorbing agent 0.20-0.30%
Carbon black 0.1-2%
Superoxide 0-0.035%
The described Co-polypropylene mixture of auxiliary agent 0.1-0.2% is that melting index MI=0.2～2.0g/10min.Izod (breach) shock strength is that high tenacity Co-polypropylene and melting index MI=19～30g/10min.Izod (breach) shock strength of 360～500J/M is the mixture of 40-70J/M high workability Co-polypropylene.
2, a kind of modified poly propylene composition according to claim 1 is characterized in that described high tenacity Co-polypropylene and high workability Co-polypropylene are 0.1-4% by weight percentage.
3, a kind of modified poly propylene composition according to claim 1 is characterized in that described toughner is terpolymer EP rubber EPDM.
4, a kind of modified poly propylene composition according to claim 3 is characterized in that unsaturated diene content is 2-8% among the described EPDM, and ethylene content is 25-70%, and Mooney viscosity value is 19-80.
5, a kind of modified poly propylene composition according to claim 1 is characterized in that described toughner is the SBS thermoplastic elastomer.
6, a kind of modified poly propylene composition according to claim 1 is characterized in that described toughner is ethylene propylene rubber EPR.
7, a kind of modified poly propylene composition according to claim 1 is characterized in that ethylene content is 20-70% among the described ethylene propylene rubber EPR, and Mooney viscosity value is 20-70%.
8, a kind of modified poly propylene composition according to claim 1 is characterized in that described poly melting index is 0.15-7g/10min, and viscosity-average molecular weight is 1.25 * 10
5-3 * 10
5
9, a kind of modified poly propylene composition according to claim 1 is characterized in that described superoxide is DCP, BPO or DTBP.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117929A CN1062880C (en) | 1995-11-01 | 1995-11-01 | Modified polypropylene composition with low rubber content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95117929A CN1062880C (en) | 1995-11-01 | 1995-11-01 | Modified polypropylene composition with low rubber content |
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|---|---|
| CN1150160A true CN1150160A (en) | 1997-05-21 |
| CN1062880C CN1062880C (en) | 2001-03-07 |
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|---|---|---|---|
| CN95117929A Expired - Fee Related CN1062880C (en) | 1995-11-01 | 1995-11-01 | Modified polypropylene composition with low rubber content |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002026869A1 (en) * | 2000-08-22 | 2002-04-04 | China Petroleum & Chemical Corporation | Tenacity plastic and its preparation method |
| CN106633401A (en) * | 2016-12-20 | 2017-05-10 | 太仓市天丝利塑化有限公司 | PP material for infant car seat and injection molding process of PP material |
| CN110577699A (en) * | 2018-06-07 | 2019-12-17 | 深圳科创新源新材料股份有限公司 | Polypropylene composite material and preparation method and application thereof |
| CN113978078A (en) * | 2021-09-27 | 2022-01-28 | 宁波瑞成包装材料有限公司 | Antibacterial CPP film and production method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ222492A3 (en) * | 1991-07-19 | 1993-02-17 | Hoechst Ag | Stiffened polypropylene starting materials |
-
1995
- 1995-11-01 CN CN95117929A patent/CN1062880C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002026869A1 (en) * | 2000-08-22 | 2002-04-04 | China Petroleum & Chemical Corporation | Tenacity plastic and its preparation method |
| US6998438B2 (en) | 2000-08-22 | 2006-02-14 | China Petroleum & Chemical Corporation | Toughened plastics and preparation thereof |
| CN106633401A (en) * | 2016-12-20 | 2017-05-10 | 太仓市天丝利塑化有限公司 | PP material for infant car seat and injection molding process of PP material |
| CN110577699A (en) * | 2018-06-07 | 2019-12-17 | 深圳科创新源新材料股份有限公司 | Polypropylene composite material and preparation method and application thereof |
| CN113978078A (en) * | 2021-09-27 | 2022-01-28 | 宁波瑞成包装材料有限公司 | Antibacterial CPP film and production method thereof |
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| Publication number | Publication date |
|---|---|
| CN1062880C (en) | 2001-03-07 |
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