CN111978637A - Scratch-resistant polypropylene composite material with shallow sink marks - Google Patents
Scratch-resistant polypropylene composite material with shallow sink marks Download PDFInfo
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- CN111978637A CN111978637A CN202010849599.1A CN202010849599A CN111978637A CN 111978637 A CN111978637 A CN 111978637A CN 202010849599 A CN202010849599 A CN 202010849599A CN 111978637 A CN111978637 A CN 111978637A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a scratch-resistant polypropylene composite material with shallow sink marks, which is characterized in that: the material is prepared by a raw material melt extrusion mode; the raw materials at least comprise polypropylene resin, expanded and vitrified micro bubbles, silica lime, SEBS and auxiliary agents; the addition amount of the expanded and vitrified micro bubbles is at least 10wt% of the polypropylene; the amount of the silica lime added is at least 12wt% of the polypropylene. The invention adds the expanded and vitrified micro-bead and the silica fume; the former can migrate to the surface of the polypropylene substrate during melting, thereby increasing the surface strength of the polypropylene material and the injection molding product thereof, improving the scratch resistance of the surface and reducing the sink marks of the product; the polypropylene material has the advantages of improving the crystallinity of the surface of the polypropylene material, and playing a positive role in improving scratch resistance and reducing sink marks on the surface of the material.
Description
Technical Field
The invention relates to the field of polypropylene materials, in particular to a scratch-resistant polypropylene composite material with shallow sink marks.
Background
Polypropylene (PP) is one of five general-purpose plastics, has the excellent characteristics of low density, fatigue resistance, no toxicity, excellent chemical stability, easy processing and forming and the like, and is widely applied to the fields of automobile products, living goods, household appliances and the like.
However, polypropylene also has a number of problems; for example, the polypropylene material is slow in cooling and solidifying speed after injection molding, and a position with a variable thickness exists in a manufactured part, so that a sink mark phenomenon is easy to occur; sink marks are localized depressions in the surface of the part, which are often found in areas of localized wall thickness, behind ribs or protrusions, caused by the fact that the thick-walled parts of the part are not adequately compensated for when cooled. Such surface defects seriously affect the aesthetic appearance of the article and remain visible after spraying, greatly limiting the use of polypropylene materials in the appearance of parts. In addition, polypropylene materials have low surface hardness and are easily scratched by hard objects, and scratches caused by scratching seriously reduce the appearance of the product.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides the polypropylene composite material with scratch resistance and shallow sink marks.
In order to achieve the purpose, the invention adopts the technical scheme that: the provided polypropylene composite material with scratch resistance and shallow sink mark is characterized in that: the material is prepared by a raw material melt extrusion mode; the raw materials at least comprise polypropylene resin, expanded and vitrified micro bubbles, silica lime, SEBS and auxiliary agents; the addition amount of the expanded and vitrified micro bubbles is at least 10wt% of the polypropylene; the amount of the silica lime added is at least 12wt% of the polypropylene.
Preferably, the composite material further comprises maleic anhydride grafted POE, K resin and glass fiber.
More preferably, the auxiliary agent comprises a compatibilizer and an antioxidant.
As a more preferable scheme, the flame-retardant polypropylene composite material comprises 100 parts by mass of polypropylene, 15-25 parts by mass of expanded and vitrified micro bubbles, 18-25 parts by mass of silicon lime, 3-7 parts by mass of SEBS, 4-10 parts by mass of maleic anhydride grafted POE, 3-8 parts by mass of K resin, 8-18 parts by mass of glass fiber, 1-2.5 parts by mass of compatilizer and 1-3 parts by mass of antioxidant.
Preferably, the density of the expanded and vitrified micro bubbles is lower than 80kg/m, and the grain diameter is controlled to be 0.3-0.8 mm.
As a preferable scheme, the particle size of the silicon lime is 1000-2000 meshes.
As a preferable mode, the flow rate of the polypropylene resin under the load of 2.16kg at the temperature of 230 ℃ is 35-50 g/min; the total styrene content of the SEBS is 25-40 wt%.
The invention has the beneficial technical effects that: provides a polypropylene composite material with scratch resistance and shallow sink mark. The invention adds the expanded and vitrified micro-bead and the silica fume; the former can migrate to the surface of the polypropylene substrate during melting, thereby increasing the surface strength of the polypropylene material and the injection molding product thereof, improving the scratch resistance of the surface and reducing the sink marks of the product; the polypropylene material has the advantages of improving the crystallinity of the surface of the polypropylene material, and playing a positive role in improving scratch resistance and reducing sink marks on the surface of the material.
Detailed Description
The invention is further described with reference to specific examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
The scratch-resistant and light-sink-mark-resistant polypropylene composite material is prepared from 100 parts by mass of polypropylene, 15 parts by mass of expanded and vitrified micro-beads, 25 parts by mass of silica lime, 6 parts by mass of SEBS, 10 parts by mass of maleic anhydride grafted POE, 3 parts by mass of K resin, 8 parts by mass of glass fiber, 1 part by mass of compatilizer and 3 parts by mass of antioxidant.
Wherein: the flow rate of the polypropylene resin at a temperature of 230 ℃ under a load of 2.16kg is 35 to 50 g/min.
Carrying out high-speed transformation on the expanded and vitrified micro bubbles, wherein the density of the expanded and vitrified micro bubbles is less than 80kg/m, the micro bubbles have the characteristic of light weight, the surface of the micro bubbles is vitrified, and the micro bubbles have larger particle strength; the polypropylene material can migrate to the surface of the polypropylene substrate during melting, thereby increasing the surface strength of the polypropylene material and injection molding products thereof, improving the surface scratch resistance and reducing the sink marks of the products; the grain diameter of the vitrified micro bubbles is controlled to be 0.3-0.8mm, and the influence on the appearance of the final polypropylene product is not large.
The particle size of the silicon lime is 1000-2000 meshes, the silicon lime can play a role of a filler when added, can also improve the crystallinity of the surface of the polypropylene material, and plays a positive role in improving the scratch resistance; meanwhile, the material can also improve the shrinkage rate of the polypropylene composite material and injection molding products thereof, and reduce the shrinkage marks on the surface of the material.
SEBS is a linear triblock copolymer which takes polystyrene as a terminal segment and takes an ethylene-butylene copolymer obtained by hydrogenation of polybutadiene as a middle elastic block, namely hydrogenated SEBS; the total styrene content is 25-40 wt%; the substance plays a role of a silver streak expanding agent and can disperse silver streaks generated on the surface of a material, so that the surface color difference caused by the silver streaks is reduced, and the influence of scratches and sink marks on the appearance of a polypropylene material and an injection molding product thereof is reduced.
Maleic anhydride grafted POE is a thermoplastic elastomer with narrow relative molecular mass distribution and uniform short chain branch distribution; the elastomer has the advantages of small density, good toughness, good flexibility, high impact resistance, good forming capability, reusability and the like; meanwhile, maleic anhydride is adopted for grafting, so that the compatibility of the polypropylene base material with the maleic anhydride can be improved; the K resin is a butylbenzene transparent impact-resistant resin, is a block copolymer formed by polymerizing styrene and butadiene serving as monomers and alkyl lithium serving as an initiator by adopting an anionic solution, and has good impact resistance and processability. The two materials are both beneficial to improving the shrinkage rate of the polypropylene material, reducing the shrinkage marks on the surface of the material and reducing the warpage.
The glass fiber is used for enhancing the mechanical property of the composite material, the cross section of the glass fiber is oval, and the density of the glass fiber is2.2-2.66g/cm3(ii) a Compared with the conventional circular cross section, the elliptical cross section reduces the orientation of the glass fibers, reduces the anisotropy of the glass fibers and can improve the physical and mechanical properties of the polypropylene composite material.
The compatilizer is maleic anhydride grafted polypropylene (PP-g-MAH); the antioxidant is hindered phenol antioxidant.
The preparation process of the material comprises the following steps: firstly, mixing the raw materials, and then extruding the mixture by using a double-screw extruder at the temperature of 220 ℃ and 240 ℃, wherein the length-diameter ratio of the double-screw extruder is 30-40: 1; and then cooling and granulating to obtain a finished product.
Example 2
This embodiment is substantially the same as embodiment 1 except that: the polypropylene composite material is prepared from 100 parts by mass of polypropylene, 25 parts by mass of expanded and vitrified micro-beads, 20 parts by mass of silicon lime, 3 parts by mass of SEBS, 6 parts by mass of maleic anhydride grafted POE, 6 parts by mass of K resin, 15 parts by mass of glass fiber, 2.5 parts by mass of compatilizer and 1 part by mass of antioxidant.
Example 3
This embodiment is substantially the same as embodiment 1 except that: the polypropylene resin is prepared from 100 parts by mass of polypropylene, 20 parts by mass of expanded and vitrified micro bubbles, 18 parts by mass of silicon lime, 7 parts by mass of SEBS, 4 parts by mass of maleic anhydride grafted POE, 8 parts by mass of K resin, 18 parts by mass of glass fiber, 1.5 parts by mass of compatilizer and 2 parts by mass of antioxidant.
Comparative example 1
This comparative example differs from example 1 in that: the composition does not contain the expanded and vitrified micro-bead.
The concrete raw materials comprise: 100 parts by mass of polypropylene, 25 parts by mass of silica fume, 6 parts by mass of SEBS, 10 parts by mass of maleic anhydride grafted POE, 3 parts by mass of K resin, 8 parts by mass of glass fiber, 1 part by mass of a compatibilizer, and 3 parts by mass of an antioxidant.
Comparative example 2
This comparative example differs from example 1 in that: the composition does not contain the silicon lime, but contains the talcum powder as a filler.
The concrete raw materials comprise: 100 parts by mass of polypropylene, 15 parts by mass of expanded and vitrified micro bubbles, 25 parts by mass of talcum powder, 6 parts by mass of SEBS, 10 parts by mass of maleic anhydride grafted POE, 3 parts by mass of K resin, 8 parts by mass of glass fiber, 1 part by mass of compatilizer and 3 parts by mass of antioxidant.
And (3) performance testing:
the polypropylene composites provided in examples 1-3 and comparative examples 1-2 were injection molded on an injection molding machine to prepare specimens and tested for properties.
And (3) testing tensile strength: reference standard: ISO 527-2; and (3) testing conditions are as follows: the clamping distance is 50mm, and the speed is 50 mm/min.
And (3) testing the bending strength: reference standard: ISO 178; and (3) testing conditions are as follows: span 64mm, speed 14 mm/min.
Flexural modulus test: reference standard: ISO 178; and (3) testing conditions are as follows: span 64mm, speed 2 mm/min.
Unnotched impact strength test: reference standard: ISO 179; and (3) testing conditions are as follows: the span is 62 mm.
Notched impact strength test: reference standard: ISO 179; and (3) testing conditions are as follows: span 62mm, notch depth 1/3D.
And (3) shrinkage testing: reference standard: ISO 2577-2007.
And (3) sink mark testing: and measuring the depth of the sample by using a step profiler for characterization.
Scratch resistance test: the method comprises the following steps: scraping a line segment graph on the prepared plastic surface by using a mechanically driven scraper; and respectively measuring the surface light scattering values of the sample before and after scratching by using a spectrocolorimeter, measuring the scratch resistance of the polypropylene by using the light scattering difference delta E before and after scratching, wherein the smaller the delta E value is, the better the scratch resistance of the product is.
The detection results are as follows:
example 1:
tensile strength: 65MPa, bending strength: 80MPa, flexural modulus: 3500MPa, unnotched impact strength: 35 J.m-2Notched impact strength: 5KJ · m-2Shrinkage rate: 0.8%, sink mark: 1.2 μm,. DELTA.E: 1.35.
example 2:
tensile strength: 68Mpa, flexural strength: 82MPa, flexural modulus: 3500MPa, unnotched impact strength: 38 J.m-2Notched impact strength: 7KJ · m-2Shrinkage rate: 0.7%, sink mark: 1.0 μm,. DELTA.E: 1.12.
example 3:
tensile strength: 70MPa, bending strength: 83MPa, flexural modulus: 4000Mpa, unnotched impact strength: 38 J.m-2Notched impact strength: 8KJ · m-2Shrinkage rate: 0.7%, sink mark: 1.2 μm,. DELTA.E: 1.48.
comparative example 1:
tensile strength: 66MPa, bending strength: 78MPa, flexural modulus: 3500MPa, unnotched impact strength: 34 J.m-2Notched impact strength: 5 KJ.m-2Shrinkage rate: 1.0%, sink mark: 5.2 μm,. DELTA.E: 7.35.
comparative example 2:
tensile strength: 65MPa, bending strength: 81Mpa, flexural modulus: 3800MPa, unnotched impact strength: 34 J.m-2Notched impact strength: 6KJ · m-2Shrinkage rate: 1.0%, sink mark: 6.3 μm,. DELTA.E: 4.35.
according to the detection result, the following can be found: the polypropylene materials obtained in examples 1-3 were injection molded to produce samples having lower sink marks and Δ E than the samples of comparative examples 1 and 2; the addition of the expanded and vitrified micro bubbles and the silicon lime is shown to have positive significance for improving the scratch resistance of the polypropylene composite material and the injection molding product thereof and improving the surface sink marks of the polypropylene composite material and the injection molding product thereof.
In light of the foregoing description of the preferred embodiment of the present invention, it is to be understood that various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (7)
1. The scratch-resistant polypropylene composite material with the shallow sink marks is characterized in that: the material is prepared by a raw material melt extrusion mode; the raw materials at least comprise polypropylene resin, expanded and vitrified micro bubbles, silica lime, SEBS and auxiliary agents; the addition amount of the expanded and vitrified micro bubbles is at least 10wt% of the polypropylene; the amount of the silica lime added is at least 12wt% of the polypropylene.
2. The scratch resistant, light sink mark polypropylene composite of claim 1, wherein: also comprises maleic anhydride grafted POE, K resin and glass fiber.
3. The polypropylene composite of claim 2, wherein the polypropylene composite is characterized by: the auxiliary agent comprises a compatilizer and an antioxidant.
4. The scratch resistant, light sink mark polypropylene composite of claim 3, wherein: the flame-retardant polypropylene composite material comprises, by mass, 100 parts of polypropylene, 15-25 parts of expanded and vitrified micro-beads, 18-25 parts of silicon lime, 3-7 parts of SEBS, 4-10 parts of maleic anhydride grafted POE, 3-8 parts of K resin, 8-18 parts of glass fibers, 1-2.5 parts of a compatilizer and 1-3 parts of an antioxidant.
5. The polypropylene composite material with scratch resistance and shallow sink mark as claimed in any one of claims 1 to 4, wherein: and (3) carrying out high-speed transformation on the expanded and vitrified micro bubbles, wherein the density of the expanded and vitrified micro bubbles is less than 80kg/m, and the grain diameter is controlled to be 0.3-0.8 mm.
6. The polypropylene composite material with scratch resistance and shallow sink mark as claimed in any one of claims 1 to 4, wherein: the particle size of the silicon lime is 1000-2000 meshes.
7. The polypropylene composite material with scratch resistance and shallow sink mark as claimed in any one of claims 1 to 4, wherein: the flow rate of the polypropylene resin is 35-50g/min under the load of 2.16kg at the temperature of 230 ℃; the total styrene content of the SEBS is 25-40 wt%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010849599.1A CN111978637A (en) | 2020-08-21 | 2020-08-21 | Scratch-resistant polypropylene composite material with shallow sink marks |
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| CN202010849599.1A CN111978637A (en) | 2020-08-21 | 2020-08-21 | Scratch-resistant polypropylene composite material with shallow sink marks |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113662A (en) * | 2011-11-17 | 2013-05-22 | 上海金发科技发展有限公司 | Low-odor ultrahigh-toughness polypropylene compound and preparation method thereof |
| CN110358193A (en) * | 2019-08-22 | 2019-10-22 | 苏州润佳工程塑料股份有限公司 | A kind of polypropylene material of surface good attachment |
| CN111117058A (en) * | 2018-11-01 | 2020-05-08 | 中国石油化工股份有限公司 | High-gloss scratch-resistant polypropylene material and preparation method thereof |
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2020
- 2020-08-21 CN CN202010849599.1A patent/CN111978637A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113662A (en) * | 2011-11-17 | 2013-05-22 | 上海金发科技发展有限公司 | Low-odor ultrahigh-toughness polypropylene compound and preparation method thereof |
| CN111117058A (en) * | 2018-11-01 | 2020-05-08 | 中国石油化工股份有限公司 | High-gloss scratch-resistant polypropylene material and preparation method thereof |
| CN110358193A (en) * | 2019-08-22 | 2019-10-22 | 苏州润佳工程塑料股份有限公司 | A kind of polypropylene material of surface good attachment |
Non-Patent Citations (1)
| Title |
|---|
| 俞飞 等: "低收缩、低线性膨胀系数聚丙烯材料研究", 《工程塑料应用》 * |
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