CN102898729B - 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 PDF

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CN102898729B
CN102898729B CN201210447086.3A CN201210447086A CN102898729B CN 102898729 B CN102898729 B CN 102898729B CN 201210447086 A CN201210447086 A CN 201210447086A CN 102898729 B CN102898729 B CN 102898729B
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nano
coupling agent
core
beta
compatilizer
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CN102898729A (en
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郭卫红
李幼辰
程艳
傅晓伟
曹二平
于云安
任佳伟
汪宇明
周玉丽
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East China University of Science and Technology
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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

A kind of nano-core-shell structure and the polyacrylic method of the brilliant coordination plasticizing of β
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 a kind of nano-core-shell structure and the polyacrylic method of the brilliant coordination plasticizing of β.
Background technology
Polypropylene (PP) as one of general-purpose plastics plays a part more and more important because it has the price of excellent over-all properties and relative moderate in life and production, but the shortcoming such as to split, goods are easily out of shape because its impelling strength is low, fragile under low temperature, significantly limit its application.Therefore, carry out toughness reinforcing to PP is the emphasis studied of people and focus to widen its Application Areas always.
At present, conventional method of modifying comprises: chemical modification, wherein comprises again: modification by copolymerization, graft modification, cross-linking modified, calcium chloride; Physically modified, comprising: elastomer blended modifier, Rigid Organic Fillers blending and modifying, stiff differential equations blending and modifying, nucleater modified etc.
PP-R is obtained by the copolymerization under heating, pressurization and catalyst action of propylene monomer and a small amount of vinyl monomer, 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 the long-term thermal stability of material, mechanical property and processing characteristics.The random performance adding degree of crystallinity and the aspect such as fusing point, the impact property improving material, long-term resistance to hydrostatic pressure, for a long time heat oxygen aging resistance reducing polymkeric substance of ethene.The distribution of vinyl monomer in 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 at different conditions.Under usual processing conditions, 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 has obvious interface, and when material generation deformation, the crackle caused by external force is easy to expand along these interfaces, makes material produce brittle rupture.And β crystalline substance belongs to hexagonal system, have unique helicoidal structure, compared with α spherocrystal, beta crystal has excellent shock resistance, obviously can improve toughness and the heat-drawn wire of material, in polypropylene, therefore add beta crystal-type nucleater is one of effective ways of polypropylene toughening.
On the other hand, in recent years, when carrying out modification to polypropylene, people often use elastomerics and inorganic rigid particle coordination plasticizing, to be formed in material matrix with inorganic rigid particle be core, take elastomerics as the nucleocapsid structure of shell, make polypropylene/elastomer/inorganic rigid particle three-component compound system, make it low intensively strengthen its toughness substantially not falling simultaneously.But only have and just can be significantly improved when elastomeric addition reaches more than 20% toughness, and this undoubtedly large increase matrix material cost and reduce rigidity and the thermotolerance of material.
Use nano-calcium carbonate for core in the present invention, heat-proof polythene is that shell makes core-shell particles, and add beta nucleater, make nano-core-shell structure and the brilliant coordination plasticizing PP-R composite material of β, make the toughness that just can significantly improve atactic copolymerized polypropene (PP-R) when reducing costs, and improve its tensile strength simultaneously, improve its thermotolerance and dimensional stability.
Summary of the invention
The object of the invention is for the deficiency in current techniques, provides a kind of low cost, can significantly improve PP-R composite material toughness and improve its tensile strength simultaneously, and increase the method for its thermotolerance and dimensional stability.
Technical scheme of the present invention is
A kind of nano-core-shell structure and the polyacrylic method of the brilliant coordination plasticizing of β, it is characterized in that, described method is: in atactic copolymerized polypropene matrix, add a certain proportion of polyethylene, beta nucleater, Nano-meter CaCO3 3, compatilizer and oxidation inhibitor, coupling agent, to polypropylene random copolymer material modification, the ratio of weight and number of above each component is as follows:
Atactic copolymerized polypropene PP-R 75 ~ 100 parts;
Heat-proof polythene PE-RT 1 ~ 15 part;
Nano-meter CaCO3 31 ~ 15 part;
Beta nucleater 0.01 ~ 0.3 part;
Compatilizer 0 ~ 8 part;
0 ~ 1 part, oxidation inhibitor;
Coupling agent 0.005 ~ 0.3 part,
First nano-calcium carbonate is carried out surface treatment, namely nano-calcium carbonate and coupling agent stir 10-15 minute at 40 ~ 60 DEG C;
Then take material by said components proportion speed, surface treated nano-calcium carbonate and heat-proof polythene, compatilizer are joined in twin screw extruder and carries out extruding preparing core-shell particles; Again by prepared core-shell particles and atactic copolymerized polypropene, beta nucleater, oxidation inhibitor in high speed mixer high speed blended 5 ~ 10 minutes, then be added in twin screw extruder and carry out extruding and granulation, and pellet will be extruded add in injection moulding machine and carry out injection moulding, make the PP-R composite material of nano-core-shell structure and the brilliant coordination plasticizing of β;
Wherein,
Described random copolymerization gathers the melt flow rate (MFR) (MFR) of third for 0.3g/10min (230 DEG C, 2.16kg),
Ethylene content is 1% ~ 7%, and density is 0.90 ~ 0.91g/cm 3;
The melt flow rate (MFR) (MFR) of described heat-proof polythene is 0.6g/10min (190 DEG C, 2.16kg);
Described Nano-meter CaCO3 3diameter be 20-100nm;
Described beta nucleater is rare earth class beta nucleater;
Described compatilizer is commercially available maleic anhydride inoculated polypropylene;
Described oxidation inhibitor is antioxidant 1010 (four [β (3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester), wherein a kind of or the two compound of irgasfos 168 (three [2,4-di-tert-butyl-phenyl] phosphorous acid ester);
Described coupling agent is aluminate coupling agent, titanate coupling agent, silane coupling agent one wherein.
Beneficial effect
By the nano-core-shell structure that the invention provides prepared by method of modifying and the brilliant coordination plasticizing PP-R composite material of β, can when adding a small amount of nano-calcium carbonate, polyethylene and beta nucleater, significantly improve the toughness of atactic copolymerized polypropene (PP-R) simultaneously, and rigidity declines less, matrix material is made to have excellent over-all properties.The shock strength of modified PP-R matrix material is by the 47.8KJ/m of pure PP-R 2bring up to 69.7KJ/m 2, tensile strength brings 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 quite obvious for the coordination plasticizing effect of atactic copolymerized polypropene.
Accompanying drawing explanation
The microcosmic nucleocapsid structure transmission electron microscope picture (TEM) of the matrix material of Fig. 1 prepared by the embodiment of the present invention 1.
Fig. 2 is the polarizing microscope photo of pure atactic copolymerized polypropene (PP-R).
The polarizing microscope photo of the PP-R composite material of Fig. 3 prepared by the embodiment of the present invention 1.
Fig. 4 is Wide angle X-ray diffraction (WAXD) figure of the embodiment of the present invention 3 PP-R composite material and pure PP-R.
Embodiment
Carry out elaboration below in conjunction with example further to content of the present invention to illustrate, but content of the present invention listed experiment below being not only confined to.
Embodiment 1
Take formula material:
PP-R 85 parts;
PE-RT 7.5 parts;
Nano-meter CaCO3 37.5 part;
Rare-earth beta nucleator 0.15 part;
PP-g-MAH 5 parts;
Antioxidant 1010 0.3 part;
Irgasfos 168 0.3 part;
Silane coupling agent 0.008 part;
Inorganic filler surface process;
By Nano-meter CaCO3 3at 40 DEG C, 10 minutes are stirred, the Nano-meter CaCO3 of obtained modification with silane coupling agent 3; The preparation of core-shell particles:
By the Nano-meter CaCO3 of modification 3, PE-RT, PP-g-MAH join in twin screw extruder and carry out extruding preparing core-shell particles;
The preparation of matrix material:
By obtained core-shell particles, PP-R, rare-earth beta nucleator, antioxidant 1010, irgasfos 168 in high speed mixer high speed blended 5 ~ 10 minutes, then be added in twin screw extruder and carry out extruding and granulation, pellet will be extruded add in injection moulding machine and carry out injection moulding, make matrix material.Its performance is in table 1.
Embodiment 2
Take formula material:
PP-R 85 parts;
PE-RT 10.5 parts;
Nano-meter CaCO3 34.5 part;
Rare-earth beta nucleator 0.1 part;
PP-g-MAH 6 parts;
Antioxidant 1010 0.5 part;
Irgasfos 168 0.5 part;
Titanate coupling agent 0.009 part;
Inorganic filler surface process:
By Nano-meter CaCO3 3at 60 DEG C, 10 minutes are stirred, the Nano-meter CaCO3 of obtained modification with coupling agent 3; The preparation of core-shell particles:
By the Nano-meter CaCO3 of modification 3, PE-RT, PP-g-MAH join in twin screw extruder and carry out extruding preparing core-shell particles;
The preparation of matrix material:
By obtained core-shell particles, PP-R, rare-earth beta nucleator, antioxidant 1010, irgasfos 168 in high speed mixer high speed blended 5 ~ 10 minutes, then be added in twin screw extruder and carry out extruding and granulation,, pellet will be extruded and add in injection moulding machine and carry out injection moulding, make matrix material.Its performance is in table 1.
Embodiment 3
Take formula material:
PP-R 75 parts;
PE-RT 7.5 parts;
Nano-meter CaCO3 317.5 parts;
Rare-earth beta nucleator 0.15 part;
PP-g-MAH 8 parts;
Antioxidant 1010 1 part;
Aluminate coupling agent 0.03 part;
Inorganic filler surface process:
By Nano-meter CaCO3 3at 50 DEG C, 15 minutes are stirred, the Nano-meter CaCO3 of obtained modification with coupling agent 3; The preparation of core-shell particles:
By the Nano-meter CaCO3 of modification 3, PE-RT, PP-g-MAH join in twin screw extruder and carry out extruding preparing core-shell particles;
The preparation of matrix material:
By obtained core-shell particles, PP-R, rare-earth beta nucleator, antioxidant 1010, irgasfos 168 in high speed mixer high speed blended 5 ~ 10 minutes, then be added in twin screw extruder and carry out extruding and granulation, pellet will be extruded add in injection moulding machine and carry out injection moulding, make matrix material.Its performance is in table 1.
Embodiment 4
Take formula material:
PP-R 80 parts;
PE-RT 8 parts;
Nano-meter CaCO3 312 parts;
Rare-earth beta nucleator 0.25 part;
PP-g-MAH 3 parts;
Antioxidant 1010 0.8 part;
Titanate coupling agent 0.006 part;
Inorganic filler surface process:
By Nano-meter CaCO3 3at 45 DEG C, 15 minutes are stirred, the Nano-meter CaCO3 of obtained modification with coupling agent 3; The preparation of core-shell particles:
By the Nano-meter CaCO3 of modification 3, PE-RT, PP-g-MAH join in twin screw extruder and carry out extruding preparing core-shell particles;
The preparation of matrix material:
By obtained core-shell particles, PP-R, rare-earth beta nucleator, antioxidant 1010, irgasfos 168 in high speed mixer high speed blended 5 ~ 10 minutes, then be added in twin screw extruder and carry out extruding and granulation, pellet will be extruded add in injection moulding machine and carry out injection moulding, make matrix material.Its performance is in table 1.
Nano-core-shell structure obtained by the present invention and β brilliant coordination plasticizing PP-R composite material high comprehensive performance, toughening effect particularly evident (see table 1).
The performance of table 1 nano-core-shell structure and the brilliant coordination plasticizing PP-R composite material of β
As can be seen from Table 1, through the PP-R composite 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 brings 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 and even increases after modification; Nano-core-shell structure and beta nucleater are quite obvious for the coordination plasticizing of atactic copolymerized polypropene, reinforced effects.

Claims (1)

1. nano-core-shell structure and the polyacrylic method of the brilliant coordination plasticizing of β, it is characterized in that, described method is: in atactic copolymerized polypropene matrix, add a certain proportion of polyethylene, beta nucleater, Nano-meter CaCO3 3, compatilizer and oxidation inhibitor, coupling agent, to polypropylene random copolymer material modification, the ratio of weight and number of above each component is as follows:
Atactic copolymerized polypropene PP-R 75 ~ 100 parts;
Heat-proof polythene PE-RT 1 ~ 15 part;
Nano-meter CaCO3 31 ~ 15 part;
Beta nucleater 0.01 ~ 0.3 part;
Compatilizer 0 ~ 8 part;
0 ~ 1 part, oxidation inhibitor;
Coupling agent 0.005 ~ 0.3 part,
First nano-calcium carbonate is carried out surface treatment, namely nano-calcium carbonate and coupling agent stir 10-15 minute at 40 ~ 60 DEG C;
Then take material by said components proportion speed, surface treated nano-calcium carbonate and heat-proof polythene, compatilizer are joined in twin screw extruder and carries out extruding preparing core-shell particles; Again by prepared core-shell particles and atactic copolymerized polypropene, beta nucleater, oxidation inhibitor in high speed mixer high speed blended 5 ~ 10 minutes, then be added in twin screw extruder and carry out extruding and granulation, and pellet will be extruded add in injection moulding machine and carry out injection moulding, make the PP-R composite material of nano-core-shell structure and the brilliant coordination plasticizing of 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 Nano-meter CaCO3 3diameter be 20-100nm;
Described beta nucleater is 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 168s, i.e. the compound of one or both in three [2,4-di-tert-butyl-phenyl] phosphorous acid ester;
Described coupling agent is aluminate coupling agent, titanate coupling agent, silane coupling agent one wherein.
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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
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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