CN114350074B - Low-density polypropylene composition with good appearance and preparation method thereof - Google Patents
Low-density polypropylene composition with good appearance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-density polypropylene composition with good appearance and a preparation method thereof, belonging to the field of high polymer materials. In the components of the product, the hyperbranched polymer, the coupling agent and the hollow glass beads are compounded, so that a protective buffer layer is formed on the surfaces of the hollow glass beads, the influence of external shearing action on the hollow glass beads in the processing process of the product can be effectively inhibited without pretreatment, and the product has good appearance; on the other hand, the compatibility of the formed protective buffer layer and the polypropylene resin is obviously improved, the problem that the impact strength is poor after the hollow glass beads are introduced into the polypropylene resin matrix is effectively solved, and the final product has the advantages of low density and good appearance and can maintain good impact strength. The invention also discloses a preparation method and application of the low-density polypropylene composition with good appearance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a low-density polypropylene composition with good appearance and a preparation method thereof.
Background
In recent years, with the advancement of energy saving and emission reduction, automobile weight reduction has become a research hotspot for large host factories. There are many methods for reducing the density of the parts, among which common methods include micro-foaming techniques and the addition of low density fillers such as glass beads. However, the micro-foaming technology has high equipment requirements and high equipment price, and has strict requirements on the foaming process; in contrast, the addition of glass beads is a simpler method of operation. CN 110655708A discloses a low-density polypropylene composite material with excellent comprehensive performance and a preparation method thereof, and the technical scheme adopts a high-knotThe crystalline copolymerized polypropylene is used as a base material, the surface of the hollow glass bead and the whisker is treated by a silane coupling agent, and a compatilizer with high maleic anhydride content is added, so that the bonding strength of the hollow glass bead, the whisker and the polypropylene is enhanced, the finally prepared composite material has higher strength, and the density is only 0.88-0.92 g/cm 3 . CN 108503953A discloses a modified high-crystalline polypropylene composite material, which contains special superfine talcum powder and special hollow glass beads, and the hollow glass beads are subjected to surface treatment by an aluminum-titanium coupling agent, so that the density of the material is reduced while the physical properties of the material are maintained.
However, because the compatibility of the pure glass beads and the matrix resin is poor, the impact strength of the system is greatly reduced when the pure glass beads are added into a formula system, the hollow glass beads in the technical scheme are all prepared by adopting a coupling agent to treat the surfaces in advance, and the surface treatment is carried out on the glass beads, so that the working procedures are increased and the cost is increased undoubtedly.
In addition, in the extrusion and injection molding processes of the resin composite material, hollow glass beads in the components can be subjected to strong shearing action, and once the hollow glass beads are broken, the effect of reducing the density is greatly reduced, the weight reduction effect cannot be realized, and air marks can be formed on the surface of a sample due to gas escape, so that the appearance is influenced.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide the low-density polypropylene composition with good appearance, and the components of the product are matched with the hollow glass beads by using the specific coupling agent and the hyperbranched polymer, so that the synergistic effect of the three components can be realized, the hollow glass beads can be effectively ensured not to be damaged in the processing process, the compatibility of the hollow glass beads with matrix resin can be effectively improved, and the impact strength of the product can be maintained; the product has low density, good appearance and wide application range.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a low density polypropylene composition with good appearance comprises the following components in parts by weight:
50 to 80 parts of polypropylene resin, 20 to 25 parts of hollow glass beads, 0.1 to 0.5 part of coupling agent, 2 to 12 parts of filler and 0.5 to 1.5 parts of hyperbranched polymer;
the hyperbranched polymer is linear fatty acid modified hyperbranched polyester, and the hydroxyl value is 40-70 mgKOH/g; the coupling agent is glycidyl ether oxypropyl silane coupling agent.
The hydroxyl value test method is GB/T12008.3-2009.
In the components of the low-density polypropylene composition with good appearance, the glycidyl ether oxypropyl silane coupling agent contains a relative amount of epoxy groups, and the hyperbranched polyester modified by the linear fatty acid (comprising linear saturated fatty acid and linear unsaturated fatty acid) contains a certain amount of terminal hydroxyl groups, when the glycidyl ether oxypropyl silane coupling agent and the linear saturated fatty acid are mixed with the hollow glass beads, the hyperbranched polymer and the coupling agent are fully reacted and combined and coated on the surfaces of the hollow glass beads to form a protective buffer layer with optimal thickness under the condition of a specific proportion, and the influence of external shearing action on the hollow glass beads in the processing process of the product can be effectively inhibited without pretreatment, so that the appearance of the product is good; on the other hand, the number of long carbon chains in the hyperbranched polyester modified by the linear fatty acid is increased, so that the compatibility of the formed protective buffer layer and the polypropylene resin is obviously improved, the problem of poor impact strength after hollow glass beads are introduced into a polypropylene resin matrix is effectively solved, and the final product has the advantages of low density and good appearance, and can maintain better impact strength.
In addition, the inventor also examines the hydroxyl value of the hyperbranched polymer, and as the hydroxyl in the hyperbranched polymer reacts with the epoxy group in the coupling agent, if the hydroxyl value is lower and the hydroxyl content is insufficient, more hyperbranched polyester with addition amount needs to be introduced, so that the production cost is increased; if the hydroxyl value is too high, the hydroxyl content is too high, and when a buffer protection layer with a necessary thickness is formed, more unreacted hydroxyl exists, degradation reaction with other components such as polypropylene resin and the like may occur during processing, so that the comprehensive performance of the product is reduced, the appearance performance of the product is difficult to ensure, and the impact strength of the product may be reduced.
Preferably, the number of carbon atoms of the linear fatty acid is 12 to 22.
More preferably, the linear fatty acid is any one of dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, erucic acid and behenic acid.
Preferably, the particle diameter D50 of the hollow glass beads is 25-40 mu m, and the density is 0.5-0.65 g/cm 3 The compressive strength is more than or equal to 50MPa.
More preferably, the compressive strength of the hollow glass beads is more than or equal to 100MPa.
According to the method for testing the compressive strength, according to the reference of the method and principle for testing the compressive strength of hollow glass beads, namely new variety glass, a gas isostatic pressure method commonly used in quality inspection of 3M company in the United states is adopted, and gas is used as a pressure medium for testing.
The particle size and the density of the hollow glass beads can influence the surface coating effect of the hyperbranched polymer combined with the coupling agent, so that the dispersibility of the hyperbranched polymer in a polypropylene resin matrix is influenced, and the product shows different flexural modulus and impact strength; in addition, the higher the intrinsic compressive strength of the hollow glass microsphere, the better the anti-damage capability of the hollow glass microsphere in the processing injection molding process. Preferably, when the hollow glass beads with the particle size and the density range are used as components, the compressive strength is more than or equal to 50MPa (preferably more than or equal to 100MPa, but the higher the compressive strength of the hollow glass beads in the prior art is, the higher the production difficulty and the cost are, and the compressive strength of the prepared product is basically not more than 200 MPa), the product can have excellent appearance and mechanical properties.
Preferably, the polypropylene resin is at least one of homo-polypropylene and co-polypropylene;
more preferably, the polypropylene resin has a density of 0.894 to 0.914g/cm as measured according to ASTM D792-2013 3 The polypropylene resin has a melt mass flow rate of 0.5-100 g/10min at 230 ℃ under 2.16kg test conditions according to ASTM D1238-2013.
Different polypropylene resins are selected as the matrix in the range, so that products meeting different actual performance requirements can be obtained.
Preferably, 0 to 6 parts of toughening agent is also included in the components of the low density polypropylene composition with good appearance.
The toughness and rigidity of the product can be effectively improved by introducing the toughening agent and the filler, and the prepared product can meet the requirements of practical application better by different addition ratios.
Preferably, the toughening agent is at least one of ethylene-alpha olefin copolymer and styrene elastomer; the melt mass flow rate of the toughening agent under the test condition of 2.16kg at 190 ℃ according to ASTM D1238-2013 is 0.1-30 g/10min;
preferably, the other filler is at least one of talcum powder and whisker.
Preferably, a processing aid is also included in the components of the good appearance low density polypropylene composition;
more preferably, the processing aid comprises 0.1 to 0.5 part of antioxidant, 0 to 0.5 part of nucleating agent, 0 to 2 parts of toner and 0 to 0.5 part of lubricant.
Another object of the present invention is to provide a method for preparing the good appearance low density polypropylene composition, comprising the steps of:
(1) Uniformly mixing other components except the hollow glass beads to obtain a premix;
(2) And (3) feeding the premix into a main feeding port of a double-screw extruder, adding hollow glass beads into a side feeding port, uniformly mixing, and granulating by vacuum melting extrusion to obtain the low-density polypropylene composition with good appearance.
The preparation method of the low-density polypropylene composition with good appearance has simple operation steps, does not need any surface pretreatment on the hollow glass beads, and can realize industrial mass production.
Preferably, the mixing in the step (1) is performed by a high-speed mixer, wherein the stirring speed of the mixing is 1000-2000 r/min, and the time is 1-3 min;
preferably, the temperature of the vacuum melt extrusion granulation in the step (2) is 190-230 ℃.
It is a further object of the present invention to provide the use of the low density polypropylene composition of good appearance for the preparation of low density articles, including automotive trim parts or smart wear products.
The low-density polypropylene composition with good appearance has the advantages that the hollow glass beads are adopted as a main filler system, so that compared with the existing polypropylene products with the same type, the density is obviously reduced, the special coupling agent and the hyperbranched polymer are introduced to match with the hollow glass beads, the compatibility of the hollow glass beads and a polypropylene resin matrix is improved, meanwhile, the damage condition of the hollow glass beads caused by external shearing force in the processing process of the product is obviously relieved, and the obtained product has good impact strength and bending modulus and good appearance, and is particularly suitable for preparing low-density products with certain requirements on density and impact resistance.
The invention has the beneficial effects that the invention provides the low-density polypropylene composition with good appearance, the hyperbranched polymer, the coupling agent and the hollow glass beads are compounded in the components of the product, so that the surfaces of the hollow glass beads form a protective buffer layer, the influence of external shearing action on the hollow glass beads in the processing process of the product can be effectively inhibited without pretreatment, and the appearance of the product is good; on the other hand, the compatibility of the formed protective buffer layer and the polypropylene resin is obviously improved, the problem that the impact strength is poor after the hollow glass beads are introduced into the polypropylene resin matrix is effectively solved, and the final product has the advantages of low density and good appearance and can maintain good impact strength. The invention also provides a preparation method and application of the low-density polypropylene composition with good appearance.
Drawings
FIG. 1 is a classification standard of the low density polypropylene composition of the present invention with good appearance in judging the mark grade.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present invention, and the object of the present invention is to be understood in detail, not to limit the present invention. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments designed for the implementation of the invention are common reagents and instruments unless otherwise specified.
The reagent raw materials used in each example and comparative example are as follows:
polypropylene resin 1: the copolymerized polypropylene, BX3900, has a melt mass flow rate of 55.5g/10min at 230℃under 2.16kg test conditions, according to ASTM D1238-2013; its density is 0.905g/cm according to ASTM D792-2013 3 The method comprises the steps of carrying out a first treatment on the surface of the Korea SK;
polypropylene resin 2: the polypropylene copolymer, B8101, has a melt mass flow rate of 0.5g/10min at 230℃under 2.16kg test according to ASTM D1238-2013; its density was 0.899g/cm according to ASTM D792-2013 3 The method comprises the steps of carrying out a first treatment on the surface of the Taiwan region of China;
toughening agent: POE elastomer, POE engage 8137, melt mass flow rate of 13g/10min at 190℃under 2.16kg test according to ASTM D1238-2013; a dow chemical;
filler 1: commercial magnesium sulfate whiskers;
filler 2: commercial 3000 mesh talc;
hollow glass bead 1: HL60-18000; particle diameter D50 is 30 mu m, density is 0.58-0.63 g/cm 3 The compressive strength is 125MPa; zhengzhou holly;
hollow glass bead 2: HL60-12000; particle diameter D50 is 35 mu m, density is 0.58-0.62 g/cm 3 Compressive strength is 83MPa; zhengzhou holly;
hollow glass bead 3: HL60S; particle diameter D50 is 25 mu m, density is 0.58-0.62 g/cm 3 The compressive strength is 55MPa; zhengzhou holly;
hollow glass beads 4: HL42; particle diameter D50 is 35 mu m, density is 0.38-0.42 g/cm 3 Compressive strength 41MPa; zhengzhou holly;
coupling agent 1: glycidyl ether oxypropyl silane coupling agent; KH-560A, nanjing dawn;
coupling agent 2: vinyl tris (2-methoxyethoxy) silane; SG-Si 172, nanjing dawn;
hyperbranched polymer 1: linear stearic acid (octadecanoic acid) modified hyperbranched polyester with 18 carbon atoms and hydroxyl value of 40-70 mgKOH/g; brand CYD-P218; a morning source;
hyperbranched polymer 2: hyperbranched modified polyester is generated by directly reacting polyhydroxy carboxyl compound and polyol compound, linear fatty acid is not introduced in the reaction process for modification, CYD-T010 is not introduced, and the hydroxyl value is 190-250 mgKOH/g; a morning source;
hyperbranched polymer 3: linear stearic acid (octadecanoic acid) modified hyperbranched polyester with 18 carbon atoms and hydroxyl value of 75-110 mgKOH/g; brand CYD-T1050; a morning source;
maleic anhydride grafted polypropylene resin: CA 100, france academy;
an antioxidant: a mixture of a commercially available hindered phenol antioxidant and a commercially available phosphite antioxidant in a mass ratio of 1:1;
toner: black master is commercially available.
The commercial materials used in each example and comparative example were all of the same variety.
Examples 1 to 10
Examples of good appearance low density polypropylene compositions of the present invention having the component ingredients shown in table 1.
TABLE 1
The preparation method of the polypropylene composition comprises the following steps:
(1) Uniformly mixing polypropylene resin, a toughening agent, a filler, a coupling agent and a hyperbranched polymer by a high-speed mixer to obtain a premix; the stirring speed of the mixing is 1000-2000 r/min, and the time is 1-3 min;
(2) The premix is sent into a main feeding port of a double-screw extruder, hollow glass beads are added into a side feeding port and mixed uniformly, and the temperature of each area of the screw is 190-230 ℃; and (3) granulating through vacuum melting extrusion to obtain the low-density polypropylene composition with good appearance.
Comparative examples 1 to 8
The comparative examples differ from example 2 only in the raw materials used or the proportions, and the composition of the comparative example products is shown in Table 2.
TABLE 2
Effect example 1
The products obtained in examples 1 to 10 and comparative examples 1 to 8 were subjected to performance tests, and the test items and methods were as follows:
(1) Flexural modulus: the test was performed according to ISO 178-2010, with a bending speed of 2mm/min.
(2) Cantilever impact strength: the cantilever beam notch impact strength, A-type notch and impact pendulum weight capability of 5.5J of the material are tested by adopting ISO180-2000 standard.
(3) Density: tests were performed using the ISO 1183-1-2012 standard.
(4) Air mark evaluation grade: the square plate with 100mm x 2mm of each product is molded at 200 ℃, and the degree classification is very obvious because the gas marks of the polypropylene solid product are split needles, and the square plate can be basically and directly divided into three different gas mark degrees (1 grade: obvious gas marks; 2 grade: no obvious gas marks; 3 grade: no gas marks) in the figure 1, so that the gas marks on the surface of the sample plate can be directly observed by visual observation, and the surface is rated according to the gas mark degrees.
The test results are shown in tables 3 and 4.
TABLE 3 Table 3
TABLE 4 Table 4
As can be seen from tables 3 and 4, the products obtained in the examples of the present invention have good basic mechanical properties (flexural modulus not less than 1800MPa, izod impact strength not less than 4 KJ/m) 2 ) The product of the invention has low density and excellent appearance grade (more than or equal to 2 grade), which fully shows that the product has excellent comprehensive performance after the cavity glass beads are added as filling materials due to the specific hyperbranched polymer and the coupling agent. In contrast, the product of comparative example 1 does not contain coupling agent and hyperbranched polymer, has poorer appearance performance and relatively high density; although the product obtained in the comparative example 2 uses a common filler protection modifier, the product is difficult to play a role in improving the compatibility of the hollow glass beads and the polypropylene resin all the time, the impact strength of the product is always poorer, and if the modifier and the hyperbranched polymer are compounded, the impact resistance of the product obtained in the comparative example 8 is not improved, and the appearance of the product is weakened; as can be seen from the properties of the products of comparative examples 3-7, the hyperbranched polymer and the coupling agent in the product of the invention are mutually matched, and the ideal effect is difficult to achieve even if the types of the hyperbranched polymer and the coupling agent are improperly selected. As is clear from the comparison of the products of example 2 and examples 9-10, the particle size and density of the hollow glass beads in the product have a certain influence on the product performance, the D50 is 25-40 μm, the density is 0.5-0.65 g/cm 3 And the product has better mechanical property when the compressive strength is more than or equal to 50MPa.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (11)
1. The low-density polypropylene composition with good appearance is characterized by comprising the following components in parts by weight:
50 to 80 parts of polypropylene resin, 20 to 25 parts of hollow glass beads, 0.1 to 0.5 part of coupling agent, 2 to 12 parts of other fillers and 0.5 to 1.5 parts of hyperbranched polymer;
the hyperbranched polymer is linear fatty acid modified hyperbranched polyester, the hydroxyl value is 40-70 mgKOH/g, and the number of carbon atoms of the linear fatty acid is 12-22; the coupling agent is glycidyl ether oxypropyl silane coupling agent.
2. The low density polypropylene composition of claim 1, wherein said hollow glass microspheres have a particle size D50 of 25 to 40 μm and a density of 0.5 to 0.65g/cm 3 The compressive strength is more than or equal to 50MPa.
3. The low density polypropylene composition of claim 1, wherein the polypropylene resin is at least one of a homo-polypropylene and a co-polypropylene.
4. The low-density polypropylene composition according to claim 3, wherein said polypropylene resin has a density of 0.894 to 0.914g/cm 3 The mass flow rate of the melt of the polypropylene resin under the test condition of 2.16kg at 230 ℃ is 0.5-100 g/10min.
5. The low density, good appearance polypropylene composition according to claim 1, wherein the low density, good appearance polypropylene composition further comprises 0 to 6 parts of a toughening agent.
6. The low density polypropylene composition of claim 1, wherein said other filler is at least one of talc and whisker.
7. The low density good appearance polypropylene composition according to claim 1, wherein said low density good appearance polypropylene composition further comprises a processing aid in the components thereof.
8. The low density polypropylene composition according to claim 7, wherein said processing aid is selected from the group consisting of 0.1 to 0.5 part of antioxidant, 0 to 0.5 part of nucleating agent, 0 to 2 parts of toner and 0 to 0.5 part of lubricant.
9. The method for producing a low-density polypropylene composition having a good appearance according to any one of claims 1 to 8, comprising the steps of:
(1) Uniformly mixing other components except the hollow glass beads to obtain a premix;
(2) And (3) feeding the premix into a main feeding port of a double-screw extruder, adding hollow glass beads into a side feeding port, uniformly mixing, and granulating by vacuum melting extrusion to obtain the low-density polypropylene composition with good appearance.
10. The method for producing a low-density polypropylene composition having a good appearance according to claim 9, wherein said mixing in step (1) is carried out by a high-speed mixer, and the stirring rate of said mixing is 1000 to 2000r/min for 1 to 3min; the temperature of the vacuum melting extrusion granulation in the step (2) is 190-230 ℃.
11. Use of the low density polypropylene composition of good appearance according to any of claims 1 to 8 for the preparation of low density articles comprising automotive trim parts or smart wear products.
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