CN102898729A - Nano core-shell structure and method for beta-form synergistic toughening of polypropylene - Google Patents
Nano core-shell structure and method for beta-form synergistic toughening of polypropylene Download PDFInfo
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- CN102898729A CN102898729A CN2012104470863A CN201210447086A CN102898729A CN 102898729 A CN102898729 A CN 102898729A CN 2012104470863 A CN2012104470863 A CN 2012104470863A CN 201210447086 A CN201210447086 A CN 201210447086A CN 102898729 A CN102898729 A CN 102898729A
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Abstract
The invention relates to a nano core-shell structure and a method for beta-form synergistic toughening of polypropylene. The method comprises the step of proportionally adding polyethylene, a beta-nucleating agent, nano CaCO3, a compatilizer and an antioxidant into a random copolymerization polypropylene basal body to ensure that the toughness and tensile strength of a composite material are significantly improved, wherein the mass ratio of the random copolymerization polypropylene (PP-R) to heat-resistant polyethylene (PE-RT) to the nano CaCO3 to the beta-nucleating agent to the compatilizer to the antioxidant is (75-100):(0-15):(0-15):(0-0.3):(0-8):(0-1). The method achieves quite significant synergistic toughening and strengthening effects on the random copolymerization polypropylene.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of polyacrylic toughening modifying method, be specifically related to the polyacrylic method of the brilliant coordination plasticizing of a kind of nano core-shell structure and β.
Background technology
Polypropylene (PP) as one of general-purpose plastics plays a part more and more important because it has good over-all properties in life and production with relative cheap price, but because its impelling strength lowly, fragile under low temperature is split, the easy shortcoming such as distortion of goods, greatly limited its application.Therefore, carry out toughness reinforcing to PP is emphasis and the focus that people study to widen its Application Areas always.
At present, method of modifying commonly used comprises: chemical modification wherein comprises again: modification by copolymerization, graft modification, cross-linking modified, calcium chloride; Physically modified is comprising: elastomer blended modifier, Rigid Organic Fillers blending and modifying, rigid inorganic particle blending and modifying, nucleater modified etc.
PP-R is obtained by propylene monomer and a small amount of vinyl monomer copolymerization under heating, pressurization and catalyst action, and vinyl monomer is random, be distributed in the long-chain of propylene randomly.The indexs such as PP-R molecular chain structure, vinyl monomer content have direct impact to long-term thermal stability, mechanical property and the processing characteristics of material.The random adding of ethene has reduced the performance of the aspects such as degree of crystallinity and the fusing point of polymkeric substance, the impact property of having improved material, long-term resistance to hydrostatic pressure, long-term heat oxygen aging resistance.The distribution of vinyl monomer in the propylene molecules chain is more random, and the change of Properties of Polypropylene is more remarkable.
Polypropylene (PP) is the polymer that a kind of degree of crystallinity is higher, have paramorphism, can form the crystal formations such as α, β, γ under different condition.Under common processing conditions, the main crystal formation during crystalling propylene is alpha-crystal form, and beta crystal only can generate at specific crystallization condition or when having beta nucleater to exist.Alpha-crystal form coarse grains, intercrystalline have apparent in view interface, and when material generation deformation, the crackle that is caused by external force is easy to make the material production brittle rupture along these interface expansions.And the β crystalline substance belongs to hexagonal system, have unique helicoidal structure, compare with the α spherocrystal, beta crystal has excellent shock resistance, can obviously improve toughness and the heat-drawn wire of material, therefore adding beta crystal-type nucleater in polypropylene is one of effective ways of polypropylene toughening.
On the other hand, in recent years, people often use elastomerics and inorganic rigid particle coordination plasticizing when polypropylene is carried out modification, in material matrix, form the nucleocapsid structure take inorganic rigid particle as nuclear, take elastomerics as shell, make polypropylene/elastomer/inorganic rigid particle three-component compound system, make it substantially not fall low intensive its toughness that strengthens simultaneously.Reach 20% above toughness and just can be significantly improved but only have when elastomeric addition, and this undoubtedly large increase matrix material cost and reduced rigidity and the thermotolerance of material.
Use nano-calcium carbonate to be nuclear among the present invention, heat-proof polythene is that shell is made core-shell particles, and added beta nucleater, make the brilliant coordination plasticizing atactic copolymerized polypropene of nano core-shell structure and β matrix material, make in the situation that reduce the toughness that cost just can significantly improve atactic copolymerized polypropene (PP-R), and improve simultaneously its tensile strength, improve its thermotolerance and dimensional stability.
Summary of the invention
The object of the invention is for the deficiency in the current techniques, a kind of low cost is provided, can significantly improves the atactic copolymerized polypropene composite material toughness and has improved simultaneously its tensile strength, and increased the method for its thermotolerance and dimensional stability.
Technical scheme of the present invention is
The polyacrylic method of the brilliant coordination plasticizing of a kind of nano core-shell structure and β is characterized in that, described method is: add a certain proportion of polyethylene, beta nucleater, nanometer CaCO in the atactic copolymerized polypropene matrix
3, compatilizer and oxidation inhibitor, coupling agent, to the atactic copolymerized polypropene material modification, the ratio of weight and number of above each component is as follows:
75～100 parts of atactic copolymerized polypropene PP-R;
1～15 part of heat-proof polythene PE-RT;
Nanometer CaCO
31～15 part;
0.01～0.3 part of beta nucleater;
0～8 part of compatilizer;
0～1 part in oxidation inhibitor;
0.005～0.3 part of coupling agent,
At first nano-calcium carbonate is carried out surface treatment, namely nano-calcium carbonate and coupling agent stirred 10-15 minute at 40～60 ℃;
Then take by weighing material by the said components proportion speed, surface treated nano-calcium carbonate and heat-proof polythene, compatilizer are joined extrude the preparation core-shell particles in the twin screw extruder; Again with prepared core-shell particles and atactic copolymerized polypropene, beta nucleater, oxidation inhibitor high speed mixer high speed blend 5～10 minutes, then be added to and extrude in the twin screw extruder and granulation, and will extrude in the pellet adding injection moulding machine and carry out injection moulding, make the atactic copolymerized polypropene matrix material of the brilliant coordination plasticizing of nano core-shell structure and β;
Wherein,
The melt flow rate (MFR) (MFR) of described random copolymerization poly-third be 0.3g/10min (230 ℃, 2.16kg),
Ethylene content is 1%～7%, and density is 0.90～0.91g/cm
3
The melt flow rate (MFR) of described heat-proof polythene (MFR) be 0.6g/10min (190 ℃, 2.16kg);
Described nanometer CaCO
3Diameter be 20-100nm;
Described beta nucleater is the rare earth class beta nucleater;
Described compatilizer is commercially available maleic anhydride inoculated polypropylene;
Described oxidation inhibitor is wherein a kind of or the two compound of antioxidant 1010 (four [β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester), irgasfos 168 (three [2,4-di-tert-butyl-phenyl] phosphorous acid ester);
Described coupling agent is wherein a kind of of aluminate coupling agent, titanate coupling agent, silane coupling agent.
Beneficial effect
By the invention provides the brilliant coordination plasticizing atactic copolymerized polypropene of the prepared nano core-shell structure of method of modifying and β matrix material, can be in the situation that add a small amount of nano-calcium carbonate, polyethylene and beta nucleater, significantly improve simultaneously the toughness of atactic copolymerized polypropene (PP-R), and rigidity descends less, makes matrix material have excellent over-all properties.The shock strength of the PP-R matrix material after the modification is by the 47.8KJ/m of pure PP-R
2Bring up to 69.7KJ/m
2, tensile strength is brought up to 33.1MPa by the 26.3MPa of pure PP-R, and elongation at break brings up to 1170% by 327% of pure PP-R; Nano core-shell structure and beta nucleater are quite obvious for the coordination plasticizing effect of atactic copolymerized polypropene.
Description of drawings
Fig. 1 is the microcosmic nucleocapsid structure transmission electron microscope picture (TEM) of the prepared matrix material of the embodiment of the invention 1.
Fig. 2 is the polarizing microscope photo of pure atactic copolymerized polypropene (PP-R).
Fig. 3 is the polarizing microscope photo of the prepared atactic copolymerized polypropene matrix material of the embodiment of the invention 1.
Fig. 4 is wide-angle x-ray diffraction (WAXD) figure of the embodiment of the invention 3 atactic copolymerized polypropene matrix materials and pure PP-R.
Embodiment
Below in conjunction with example content of the present invention is further set forth explanation, but content of the present invention not only is confined to following listed experiment.
Embodiment 1
Take by weighing formula material:
85 parts of PP-R;
7.5 parts of PE-RT;
Nanometer CaCO
37.5 part;
0.15 part of rare-earth beta nucleator;
5 parts of PP-g-MAH;
0.3 part of antioxidant 1010;
0.3 part of irgasfos 168;
0.008 part of silane coupling agent;
Inorganic filler surface is processed;
With nanometer CaCO
3Stirred 10 minutes under 40 ℃ with silane coupling agent, make the nanometer CaCO of modification
3The preparation of core-shell particles:
Nanometer CaCO with modification
3, PE-RT, PP-g-MAH join and extrude the preparation core-shell particles in the twin screw extruder;
Composite manufacture:
With the core-shell particles that makes, PP-R, rare-earth beta nucleator, antioxidant 1010, irgasfos 168 high speed mixer high speed blend 5～10 minutes, then be added to and extrude in the twin screw extruder and granulation, to extrude in the pellet adding injection moulding machine and carry out injection moulding, make matrix material.Its performance sees Table 1.
Embodiment 2
Take by weighing formula material:
85 parts of PP-R;
10.5 parts of PE-RT;
Nanometer CaCO
34.5 part;
0.1 part of rare-earth beta nucleator;
6 parts of PP-g-MAH;
0.5 part of antioxidant 1010;
0.5 part of irgasfos 168;
0.009 part of titanate coupling agent;
Inorganic filler surface is processed:
With nanometer CaCO
3Stirred 10 minutes under 60 ℃ with coupling agent, make the nanometer CaCO of modification
3The preparation of core-shell particles:
Nanometer CaCO with modification
3, PE-RT, PP-g-MAH join and extrude the preparation core-shell particles in the twin screw extruder;
Composite manufacture:
With the core-shell particles that makes, PP-R, rare-earth beta nucleator, antioxidant 1010, irgasfos 168 high speed mixer high speed blend 5～10 minutes, then be added to and extrude in the twin screw extruder and granulation,, will extrude in the pellet adding injection moulding machine and carry out injection moulding, make matrix material.Its performance sees Table 1.
Take by weighing formula material:
75 parts of PP-R;
7.5 parts of PE-RT;
Nanometer CaCO
317.5 part;
0.15 part of rare-earth beta nucleator;
8 parts of PP-g-MAH;
1 part of antioxidant 1010;
0.03 part of aluminate coupling agent;
Inorganic filler surface is processed:
With nanometer CaCO
3Stirred 15 minutes under 50 ℃ with coupling agent, make the nanometer CaCO of modification
3The preparation of core-shell particles:
Nanometer CaCO with modification
3, PE-RT, PP-g-MAH join and extrude the preparation core-shell particles in the twin screw extruder;
Composite manufacture:
With the core-shell particles that makes, PP-R, rare-earth beta nucleator, antioxidant 1010, irgasfos 168 high speed mixer high speed blend 5～10 minutes, then be added to and extrude in the twin screw extruder and granulation, to extrude in the pellet adding injection moulding machine and carry out injection moulding, make matrix material.Its performance sees Table 1.
Embodiment 4
Take by weighing formula material:
80 parts of PP-R;
8 parts of PE-RT;
Nanometer CaCO
312 parts;
0.25 part of rare-earth beta nucleator;
3 parts of PP-g-MAH;
0.8 part of antioxidant 1010;
0.006 part of titanate coupling agent;
Inorganic filler surface is processed:
With nanometer CaCO
3Stirred 15 minutes under 45 ℃ with coupling agent, make the nanometer CaCO of modification
3The preparation of core-shell particles:
Nanometer CaCO with modification
3, PE-RT, PP-g-MAH join and extrude the preparation core-shell particles in the twin screw extruder;
Composite manufacture:
With the core-shell particles that makes, PP-R, rare-earth beta nucleator, antioxidant 1010, irgasfos 168 high speed mixer high speed blend 5～10 minutes, then be added to and extrude in the twin screw extruder and granulation, to extrude in the pellet adding injection moulding machine and carry out injection moulding, make matrix material.Its performance sees Table 1.
The brilliant coordination plasticizing atactic copolymerized polypropene of the prepared nano core-shell structure of the present invention and β composite material combination property is good, toughening effect particularly evident (seeing Table 1).
The performance of the brilliant coordination plasticizing atactic copolymerized polypropene of table 1 nano core-shell structure and β matrix material
As can be seen from Table 1, through the atactic copolymerized polypropene matrix material of method modification of the present invention, its shock strength is by the 47.8KJ/m of pure PP-R
2Bring up to 69.7KJ/m
2, tensile strength is brought up to 33.1MPa by the 26.3MPa of pure PP-R, and elongation at break brings up to 1170% by 327% of pure PP-R, and Young's modulus then substantially remains unchanged even increases after modification; Nano core-shell structure and beta nucleater are quite obvious for coordination plasticizing, the reinforced effects of atactic copolymerized polypropene.
Claims (1)
1. the polyacrylic method of the brilliant coordination plasticizing of a nano core-shell structure and β is characterized in that, described method is: add a certain proportion of polyethylene, beta nucleater, nanometer CaCO in the atactic copolymerized polypropene matrix
3, compatilizer and oxidation inhibitor, coupling agent, to the atactic copolymerized polypropene material modification, the ratio of weight and number of above each component is as follows:
75～100 parts of atactic copolymerized polypropene PP-R;
1～15 part of heat-proof polythene PE-RT;
Nanometer CaCO
31～15 part;
0.01～0.3 part of beta nucleater;
0～8 part of compatilizer;
0～1 part in oxidation inhibitor;
0.005～0.3 part of coupling agent,
At first nano-calcium carbonate is carried out surface treatment, namely nano-calcium carbonate and coupling agent stirred 10-15 minute at 40～60 ℃;
Then take by weighing material by the said components proportion speed, surface treated nano-calcium carbonate and heat-proof polythene, compatilizer are joined extrude the preparation core-shell particles in the twin screw extruder; Again with prepared core-shell particles and atactic copolymerized polypropene, beta nucleater, oxidation inhibitor high speed mixer high speed blend 5～10 minutes, then be added to and extrude in the twin screw extruder and granulation, and will extrude in the pellet adding injection moulding machine and carry out injection moulding, make the atactic copolymerized polypropene matrix material of the brilliant coordination plasticizing of nano core-shell structure and β;
Wherein, the melt flow rate (MFR) of described atactic copolymerized polypropene is 0.3g/10min, and ethylene content is
1%～7%, density is 0.90～0.91g/cm
3
The melt flow rate (MFR) of described heat-proof polythene is 0.6g/10min;
Described nanometer CaCO
3Diameter be 20-100nm;
Described beta nucleater is the rare earth class beta nucleater;
Described compatilizer is commercially available maleic anhydride inoculated polypropylene;
Described oxidation inhibitor is antioxidant 1010, i.e. four [β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and irgasfos 168, the i.e. compound of one or both in three [2,4-di-tert-butyl-phenyl] phosphorous acid ester;
Described coupling agent is wherein a kind of of aluminate coupling agent, titanate coupling agent, silane coupling agent.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103172933A (en) * | 2013-02-19 | 2013-06-26 | 江阴爱科森通信材料有限公司 | Secondary coating modified PP (polypropylene) material for optical fiber and manufacturing method thereof |
| CN108976589A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | Polypropylene toughening master batch and preparation method thereof |
| CN112175293A (en) * | 2020-10-22 | 2021-01-05 | 武汉金牛经济发展有限公司 | High-impact PP-R pipe and preparation method thereof |
| CN115181364A (en) * | 2022-07-29 | 2022-10-14 | 广西雄塑科技发展有限公司 | Modified core-shell master batch toughened PPR pipe |
| CN115851150A (en) * | 2021-09-26 | 2023-03-28 | 大正新型材料(肇庆)有限公司 | High-toughness polypropylene decorative film and preparation method and application thereof |
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| CN107903505A (en) * | 2017-11-14 | 2018-04-13 | 陕西省石油化工研究设计院 | A kind of method for compounding nucleator tenacity-increased profax |
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Cited By (8)
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|---|---|---|---|---|
| CN103172933A (en) * | 2013-02-19 | 2013-06-26 | 江阴爱科森通信材料有限公司 | Secondary coating modified PP (polypropylene) material for optical fiber and manufacturing method thereof |
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| CN108976589A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | Polypropylene toughening master batch and preparation method thereof |
| CN108976589B (en) * | 2017-05-31 | 2021-03-02 | 中国石油化工股份有限公司 | Polypropylene toughening master batch and preparation method thereof |
| CN112175293A (en) * | 2020-10-22 | 2021-01-05 | 武汉金牛经济发展有限公司 | High-impact PP-R pipe and preparation method thereof |
| CN115851150A (en) * | 2021-09-26 | 2023-03-28 | 大正新型材料(肇庆)有限公司 | High-toughness polypropylene decorative film and preparation method and application thereof |
| CN115181364A (en) * | 2022-07-29 | 2022-10-14 | 广西雄塑科技发展有限公司 | Modified core-shell master batch toughened PPR pipe |
| CN115181364B (en) * | 2022-07-29 | 2023-08-15 | 广西雄塑科技发展有限公司 | Modified core-shell master batch toughened PPR pipe |
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