CN114350074A - 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, and the influence of an external shearing action on the hollow glass beads in the processing process of the product can be effectively inhibited without pretreatment, so that 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 relieved, and the final product has the advantages of low density and good appearance and can maintain better 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 advance of energy conservation and emission reduction, the light weight of automobiles becomes a research hotspot of various large host factories. There are many methods for reducing the density of the article, and common methods include microfoaming techniques and the addition of low-density fillers such as glass beads. However, the micro-foaming technology has high requirements on equipment, high equipment price and 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, the technical scheme adopts high-crystallization polypropylene copolymer as a base material, silane coupling agent is used for surface treatment of hollow glass microspheres and whiskers, and compatilizer with high maleic anhydride content is added, so that the bonding strength of the hollow glass microspheres, whiskers and polypropylene is enhanced, the finally prepared composite material has high strength, and the density is only 0.88-0.92 g/cm3. CN 108503953A discloses a modified high-crystalline polypropylene composite material, which contains specially-made superfine talcum powder and specially-made hollow glass beads, and the hollow glass beads after surface treatment by an aluminum-titanium coupling agent reduce the density of the material while maintaining the physical properties of the material due to the characteristics of hollows.
However, because pure glass beads have poor compatibility with matrix resin, and 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 subjected to surface treatment by adopting a coupling agent in advance, and the surface treatment of the glass beads undoubtedly increases the working procedures and increases the cost.
In addition, in the extrusion and injection molding processes of the resin composite material, the hollow glass beads in the components are subjected to a strong shearing action, once the hollow glass beads are broken, the effect of reducing the density is greatly reduced, the weight reduction effect cannot be realized, and gas marks are formed on the surface of a sample due to gas escape to influence the appearance.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide a low-density polypropylene composition with good appearance, and the components of the product are matched with the hollow glass beads by using a specific coupling agent and a hyperbranched polymer, and the specific coupling agent, the hyperbranched polymer and the hollow glass beads are subjected to synergistic action, so that the hollow glass beads can be effectively prevented from being 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 purpose, the invention adopts the technical scheme that:
a good-appearance low-density polypropylene composition comprises the following components in parts by weight:
50-80 parts of polypropylene resin, 20-25 parts of hollow glass beads, 0.1-0.5 part of coupling agent, 2-12 parts of filler and 0.5-1.5 parts of hyperbranched polymer;
the hyperbranched polymer is hyperbranched polyester modified by straight-chain fatty acid, 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 good-appearance low-density polypropylene composition, the glycidyl ether oxypropyl silane coupling agent contains a relative amount of epoxy groups, the hyperbranched polyester modified by linear fatty acid (including linear saturated fatty acid and linear unsaturated fatty acid) contains a certain amount of terminal hydroxyl groups, and when the glycidyl ether oxypropyl silane coupling agent and the hyperbranched polyester are mixed with the hollow glass beads, under the condition of a specific proportion, due to the reaction of the hydroxyl groups and the epoxy groups, 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 an optimal thickness, so that the influence of an external shearing action on the hollow glass beads in a processing process can be effectively inhibited without pretreatment, and the appearance of the product is good; on the other hand, the number of long carbon chains in the hyperbranched polyester modified by the straight-chain fatty acid is increased, so that 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 better impact strength.
In addition, the inventor also researches the hydroxyl value of the hyperbranched polymer, and because hydroxyl in the hyperbranched polymer reacts with epoxy in the coupling agent, if the hydroxyl value is low and the content of the hydroxyl is insufficient, more added amount of the hyperbranched polyester needs to be introduced, so that the production cost is improved; if the hydroxyl value is too high and the hydroxyl content is too high, and a large amount of residual unreacted hydroxyl exists when a buffer protective layer with a necessary thickness is formed, the residual unreacted hydroxyl may undergo a degradation reaction with other components such as polypropylene resin 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 straight chain fatty acid is any one of dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, erucic acid and behenic acid.
Preferably, the particle size D50 of the hollow glass bead is 25-40 μm, and the density is 0.5-0.65 g/cm3The compressive strength is more than or equal to 50 MPa.
More preferably, the compressive strength of the hollow glass microspheres is more than or equal to 100 MPa.
The method for testing the compressive strength adopts a gas isostatic pressure method commonly used for quality testing of American 3M company according to a reference method and principle for testing the compressive strength of hollow glass beads, namely novel glass, and tests by using gas as a pressure medium.
The particle size and the density of the hollow glass beads influence the surface coating effect of the combination of the hyperbranched polymer and the coupling agent, and further influence the dispersibility of the hyperbranched polymer in a polypropylene resin matrix, so that the product shows different flexural moduli and impact strengths; in addition, the higher the intrinsic compressive strength of the hollow glass microspheres, the better the resistance to damage during processing and injection molding. Preferably, the hollow glass microspheres with the particle size and the density within the range and the compressive strength of more than or equal to 50MPa (preferably more than or equal to 100MPa, but the higher the compressive strength of the hollow glass microspheres in the prior art, the higher the production difficulty and the cost, and the compressive strength of the prepared product is basically not more than 200MPa) are used as components, so that the product has 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 0.894-0.914 g/cm as measured according to ASTM D792-2013 standard3The melt mass flow rate of the polypropylene resin is 0.5-100 g/10min at 230 ℃ under the 2.16kg test condition according to ASTM D1238-2013.
By selecting different polypropylene resins as the matrix within the above range, products meeting different actual performance requirements can be obtained.
Preferably, the good-appearance low-density polypropylene composition further comprises 0-6 parts of a toughening agent.
The introduction of the toughening agent and the filler can effectively improve the toughness and the rigidity of the product, and different addition ratios can enable the prepared product to better meet the requirements of practical application.
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 is 0.1-30 g/10min at 190 ℃ under the test condition of 2.16kg according to ASTM D1238-2013;
preferably, the other filler is at least one of talc powder and whisker.
Preferably, the components of the good-appearance low-density polypropylene composition further comprise a processing aid;
more preferably, the processing aid is 0.1-0.5 part of antioxidant, 0-0.5 part of nucleating agent, 0-2 parts of toner and 0-0.5 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 the 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 from a side feeding port, uniformly mixing, and performing vacuum melting extrusion granulation 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 to carry out any surface pretreatment on the hollow glass beads, and can realize industrial mass production.
Preferably, the mixing in the step (1) is carried out by a high-speed mixer, the mixing stirring speed is 1000-2000 r/min, and the mixing time is 1-3 min;
preferably, the temperature of the vacuum melting extrusion granulation in the step (2) is 190-230 ℃.
It is a further object of the present invention to provide the use of the good looking low density polypropylene composition for the preparation of low density articles including automotive trim parts or smart wear products.
According to the low-density polypropylene composition with good appearance, the hollow glass beads are used as a main filler system, so that the density of the polypropylene composition is remarkably reduced compared with that of the existing polypropylene products of the same type, and due to the introduction of the special coupling agent and the matching of the hyperbranched polymer and the hollow glass beads, the compatibility of the hollow glass beads and the polypropylene resin matrix is improved, and meanwhile, the condition that the hollow glass beads are damaged due to external shearing force in the product processing process is remarkably relieved, and the obtained product not only has good impact strength and bending modulus, but also has 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, and the hyperbranched polymer, the coupling agent and the hollow glass beads are compounded in the components of the product, so that a protective buffer layer is formed on the surfaces of the hollow glass beads, and the influence of the external shearing action on the hollow glass beads in the processing process of the product can be effectively inhibited without pre-treatment, so that 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 relieved, and the final product has the advantages of low density and good appearance and can maintain better impact strength. The invention also provides a preparation method and application of the low-density polypropylene composition with good appearance.
Drawings
FIG. 1 shows the classification criteria of the good appearance low density polypropylene composition of the present invention in judging gas mark grade.
Detailed Description
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples and comparative examples, which are intended to be understood in detail, but not intended to limit the invention. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention. The experimental reagents and instruments designed for implementing the invention are common reagents and instruments unless otherwise specified.
The reagent raw materials used in the examples and comparative examples are as follows:
polypropylene resin 1: a copolypropylene, BX3900 having a melt mass flow rate of 55.5g/10min at 230 ℃ under 2.16kg test conditions according to ASTM D1238-2013; the density was 0.905g/cm as measured according to ASTM D792-20133(ii) a Korea SK;
polypropylene resin 2: a copolypropylene, B8101, having a melt mass flow rate of 0.5g/10min at 230 ℃ under 2.16kg test conditions according to ASTM D1238-2013; the density was 0.899g/cm as measured according to ASTM D792-20133(ii) a Taiwan area of China;
a toughening agent: POE elastomer, POEEngage 8137, with a melt mass flow rate of 13g/10min at 190 ℃ under 2.16kg test conditions according to ASTM D1238-2013; (ii) the chemistry of the dow;
packing 1: commercially available magnesium sulfate whiskers;
and (3) filler 2: commercially available 3000 mesh talc;
hollow glass beads 1: HL 60-18000; the particle diameter D50 is 30 μm, and the density is 0.58-0.63 g/cm3The compressive strength is 125 MPa; zhengzhou saint laite;
hollow glass beads 2: HL 60-12000; the particle diameter D50 is 35 μm, and the density is 0.58-0.62 g/cm3The compressive strength is 83 MPa; zhengzhou saint laite;
hollow glass beads 3: HL 60S; a particle diameter D50 of 25 μm and a density of 0.58-0.62 g/cm3The compressive strength is 55 MPa; zhengzhou saint laite;
hollow glass beads 4: HL 42; the particle diameter D50 is 35 μm, and the density is 0.38-0.42 g/cm3The compressive strength is 41 MPa; zhengzhou saint laite;
coupling agent 1: a glycidyl ether oxypropylsilane coupling agent; KH-560A, Nanjing eosin;
coupling agent 2: vinyltris (2-methoxyethoxy) silane; SG-Si 172, Nanjing eosin;
hyperbranched polymer 1: c18 straight chain stearic acid (octadecanoic acid) modified hyperbranched polyester, wherein the hydroxyl value is 40-70 mgKOH/g; the designation CYD-P218; a Weihaichen source;
hyperbranched polymer 2: the hyperbranched modified polyester is generated by directly reacting a polyhydroxy carboxyl compound with a polyol compound, and linear fatty acid is not introduced for modification in the reaction process, wherein the CYD-T010 has a hydroxyl value of 190-250 mgKOH/g; a Weihaichen source;
hyperbranched polymer 3: c18 straight chain stearic acid (octadecanoic acid) modified hyperbranched polyester, wherein the hydroxyl value is 75-110 mgKOH/g; brand CYD-T1050; a Weihaichen source;
maleic anhydride-grafted polypropylene resin: CA 100, arkema, france;
antioxidant: a mixture of a commercially available hindered phenol antioxidant and a commercially available phosphite antioxidant, wherein the mass ratio of the hindered phenol antioxidant to the commercially available phosphite antioxidant is 1: 1;
toner: commercially available black color masterbatch.
The commercially available raw materials used in the examples and comparative examples were the same species.
Examples 1 to 10
Examples of good appearance low density polypropylene compositions according to the present invention, the components of which are shown in table 1.
TABLE 1
The preparation method of the polypropylene composition comprises the following steps:
(1) uniformly mixing the polypropylene resin, the toughening agent, the filler, the coupling agent and the hyperbranched polymer by using 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) feeding the premix into a main feeding port of a double-screw extruder, adding hollow glass beads from a side feeding port, and uniformly mixing, wherein the temperature of each zone of a screw is 190-230 ℃; and (3) performing vacuum melting extrusion granulation 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 or ratios used, and the composition of the products of the comparative examples is shown in table 2.
TABLE 2
Effect example 1
The products obtained in examples 1-10 and comparative examples 1-8 were subjected to performance tests, and the test items and methods were as follows:
(1) flexural modulus: the test was carried out according to ISO 178-2010 standard, with a bending speed of 2 mm/min.
(2) Cantilever beam impact strength: the notched Izod impact strength of the material is tested by adopting ISO180-2000 standard, and the impact pendulum capacity of the A-type notch is 5.5J.
(3) Density: the test was carried out using the ISO 1183-1-2012 standard.
(4) Evaluation grade of gas mark: the air marks of each product are injected into a square plate with the thickness of 100mm x 2mm at the temperature of 200 ℃, the degree grading is very obvious because the air marks of the polypropylene entity products are in split needle shapes, and the polypropylene entity products can be basically directly divided into three different air mark degrees (1 grade: obvious air marks; 2 grade: unobvious air marks; 3 grade: no air marks) in the graph 1, so the air marks on the surface of the sample plate can be directly observed by visual observation, and the surface can be graded according to the air mark degrees.
The test results are shown in tables 3 and 4.
TABLE 3
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 is not less than 1800MPa, and cantilever beam impact strength is not less than 4 KJ/m)2) The product of the invention has excellent comprehensive performance after being added with the cavity glass beads as filling materials due to the introduction of the specific hyperbranched polymer and the coupling agent. Compared with the product of the comparative example 1 which does not contain the coupling agent and the hyperbranched polymer, the appearance performance is poor and the density is relatively high; although the product obtained in the comparative example 2 uses the 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, the impact strength of the product is poor all the time, and if the modifier and the hyperbranched polymer are adopted for compounding, the obtained comparative example8 the product has no improvement on the impact resistance, and the appearance of the product is weakened; as can be seen from the performance of the comparative examples 3-7, the hyperbranched polymer and the coupling agent in the product are matched with each other, but the product is not suitable for all, and the ideal effect is difficult to achieve due to improper selection of the type of the hyperbranched polymer. As can be seen from comparison between the products in the examples 2 and 9-10, the particle size and density of the hollow glass beads in the product have certain influence on the product performance, the D50 is 25-40 mu m, and the density is 0.5-0.65 g/cm3And the product has better mechanical property when the compressive strength is more than or equal to 50 MPa.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The low-density polypropylene composition with good appearance is characterized by comprising the following components in parts by weight:
50-80 parts of polypropylene resin, 20-25 parts of hollow glass beads, 0.1-0.5 part of coupling agent, 2-12 parts of other fillers and 0.5-1.5 parts of hyperbranched polymer;
the hyperbranched polymer is hyperbranched polyester modified by straight-chain fatty acid, and the hydroxyl value is 40-70 mgKOH/g; the coupling agent is glycidyl ether oxypropyl silane coupling agent.
2. The good-appearance low-density polypropylene composition according to claim 1, wherein the hollow glass beads have a particle size D50 of 25 to 40 μm and a density of 0.5 to 0.65g/cm3The compressive strength is more than or equal to 50 MPa.
3. The good-appearance low-density polypropylene composition according to claim 1, wherein the number of carbon atoms of the linear fatty acid is 12 to 22.
4. As in claimThe good appearance low density polypropylene composition according to claim 1, wherein the polypropylene resin is at least one of homo-polypropylene and co-polypropylene; preferably, the density of the polypropylene resin is 0.894-0.914 g/cm3The melt mass flow rate of the polypropylene resin at 230 ℃ under the test condition of 2.16kg is 0.5-100 g/10 min.
5. The good appearance low density polypropylene composition of claim 1, wherein the good appearance low density polypropylene composition further comprises 0 to 6 parts of a toughening agent.
6. The good looking low density polypropylene composition of claim 1, wherein said other filler is at least one of talc and whiskers.
7. The good appearance low density polypropylene composition of claim 1 further comprising processing aids; preferably, the processing aid is 0.1-0.5 part of antioxidant, 0-0.5 part of nucleating agent, 0-2 parts of toner and 0-0.5 part of lubricant.
8. The method for preparing a good appearance low density polypropylene composition according to any one of claims 1 to 7, comprising the steps of:
(1) uniformly mixing the 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 from a side feeding port, uniformly mixing, and performing vacuum melting extrusion granulation to obtain the low-density polypropylene composition with good appearance.
9. The method for preparing the good-appearance low-density polypropylene composition according to claim 8, wherein the mixing in the step (1) is performed by a high-speed mixer, the mixing stirring speed is 1000-2000 r/min, and the mixing time is 1-3 min; and (3) the temperature of the vacuum melting extrusion granulation in the step (2) is 190-230 ℃.
10. Use of the good looking low density polypropylene composition of any one of claims 1 to 7 in the preparation of a low density article comprising an automotive trim part or a smart wear product.
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| CN109456538A (en) * | 2018-10-12 | 2019-03-12 | 万华化学集团股份有限公司 | A kind of low-density, low-shrinkage, PP composite material of argentine texture and preparation method thereof |
| CN112759833A (en) * | 2020-12-29 | 2021-05-07 | 金发科技股份有限公司 | High-rigidity high-toughness polypropylene composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109456538A (en) * | 2018-10-12 | 2019-03-12 | 万华化学集团股份有限公司 | A kind of low-density, low-shrinkage, PP composite material of argentine texture and preparation method thereof |
| CN112759833A (en) * | 2020-12-29 | 2021-05-07 | 金发科技股份有限公司 | High-rigidity high-toughness polypropylene composite material and preparation method and application thereof |
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