CN115403869A - Low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material and preparation method thereof - Google Patents
Low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material and preparation method thereof Download PDFInfo
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- CN115403869A CN115403869A CN202211136806.4A CN202211136806A CN115403869A CN 115403869 A CN115403869 A CN 115403869A CN 202211136806 A CN202211136806 A CN 202211136806A CN 115403869 A CN115403869 A CN 115403869A
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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
- C08L23/14—Copolymers of propene
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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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention discloses a low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material and a preparation method thereof; the low-shrinkage scratch-resistant high-gloss polypropylene is prepared from the following raw materials in parts by weight: 65-85 parts of polypropylene resin, 8-15 parts of polystyrene, 4-7 parts of styrene-butadiene block copolymer, 5-8 parts of compatilizer, 5-10 parts of high-density polyethylene, 0.3-0.6 part of scratch-resistant agent, 0.4-0.8 part of auxiliary agent and 0.6 part of spraying-free effect powder. The shrinkage rate of the low-shrinkage scratch-resistant high-gloss polypropylene is 0.8-1.2, the surface gloss of the polypropylene is 82-87, the polypropylene can be matched with the size requirement of polypropylene filled minerals, and the polypropylene can endow the material with higher gloss and scratch resistance. The material has wide application prospect in the fields of household appliances, toys and stationery.
Description
Technical Field
The invention belongs to the technical field of polypropylene composite materials, and particularly relates to a low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material and a preparation method thereof.
Background
The polypropylene has wide application in the industries of household appliance shells, stationery, toys and the like due to the characteristics of low density, excellent transparency, glossiness and the like. However, polypropylene has high crystallinity, and the injection molded product has large shrinkage, so that the product has unqualified dimensions in the assembly process. At present, mineral filling is often used for modifying polypropylene to meet the requirements of materials in terms of size, but minerals are scattered on the surface of the materials in a polypropylene system, so that the glossiness of the polypropylene is reduced sharply, and high-gloss materials cannot be obtained.
CN113388207A discloses a high-gloss scratch-resistant easily-sprayed polypropylene composite material and a preparation method and application thereof, wherein a polypropylene filled barium sulfate system is adopted, when mineral filling is excessive, the glossiness of the surface of the material is reduced, and the surface of the material has poor appearances such as pockmarks and the like, so that the appearance requirement of a spraying-free material cannot be met. CN109912884A discloses a high-gloss wear-resistant scratch-resistant polypropylene composite material and a preparation method and application thereof, the composition of the invention is composed of polypropylene and silicon rubber-silane coupling agent-hollow glass bead reactant, however, the preparation process of the invention is more complicated, the material cost is higher, large-scale mass production cannot be carried out on the process, and further the actual requirements of the material cannot be met. Most of the spray-free polypropylene materials on the market are mineral-free or mineral-filled polypropylene materials with a small amount, but the spray-free polypropylene materials cannot be applied to larger parts due to the large shrinkage rate. It is becoming extremely urgent to provide a spray-free polypropylene material having a stable molding size capable of meeting various assembly requirements of a product. Based on the above, the invention provides a low-shrinkage scratch-resistant high-gloss spray-free polypropylene and a preparation method thereof, and the invention is a new way for solving the application range of the spray-free polypropylene material.
Disclosure of Invention
The invention aims to provide a low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material and a preparation method thereof, aiming at the defects of the prior art.
In order to achieve the purpose, the invention is realized by the following scheme:
the invention provides a low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material which comprises the following components in parts by mass:
as an embodiment of the present invention, the polypropylene is a high crystalline co-polypropylene having an angular gloss of 87 at 60 ℃.
As an embodiment of the invention, the polystyrene is a general-purpose polystyrene and has a melt flow rate of 4 to 102/10min at a test condition of 21022 at 220 ℃. The material with too high melt flow has larger surface defects and cannot meet the requirement of spraying-free appearance aesthetic, so the melt flow rate is selected to be 4-102/10min, and the main purpose is to destroy crystallization and improve the shrinkage rate of the polypropylene material.
As an embodiment of the present invention, the styrene-butadiene block copolymer has a number average molecular mass of 1.5210 6 . The number average molecular weight represents the viscosity of the material, and the invention selects the material with the number average molecular weight of 1.5210 6 The high viscosity of the styrene-butadiene block copolymer contributes to the compatibility of the composite material.
As an embodiment of the invention, the compatilizer is polypropylene grafted styrene, and the grafting rate of the styrene is forty percent. The higher grafting rate can increase the interfacial compatibility of polypropylene and polystyrene and better block the continuity of a material crystal region.
As one embodiment of the invention, the scratch resistant agent is a silicone polymer and the effective carrier is polypropylene. Preferably, the scratch resistant agent is an ultra high molecular weight silicone containing fluorine functional groups.
As an embodiment of the invention, the auxiliary agent comprises one or more of an antioxidant, a light stabilizer and a lubricant. The antioxidant may be 168; the secondary antioxidant may be 1010; the light stabilizer may be 2908; the lubricant may be one or more of erucamide and calcium stearate.
As an embodiment of the invention, the spraying-free effect powder is aluminum silver powder 8980.
As an embodiment of the invention, the shrinkage rate of the low-shrinkage scratch-resistant high-gloss polypropylene is 0.8-1.2, and the surface gloss is 80-87.
The invention also provides a preparation method of the low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material, which comprises the following steps: the polypropylene, the polystyrene, the styrene-butadiene block copolymer, the compatilizer, the high-density polyethylene, the scratch-resistant agent, the auxiliary agent and the spraying-free effect powder are fully mixed in a stirrer according to the weight parts, added into a double-screw extruder and subjected to melt mixing granulation at the temperature of 200-230 ℃ to prepare the low-shrinkage scratch-resistant high-gloss polypropylene.
The principle of the invention is as follows:
the high crystallinity of polypropylene is the underlying cause for high shrinkage of polypropylene materials. Polystyrene and high-density polyethylene are introduced into a polypropylene material to destroy the crystallization performance of the polypropylene, the polystyrene is an amorphous polymer and can occupy the space of a polypropylene molecular chain in the crystallization stage of the polypropylene composite material to disturb the regular arrangement of the polypropylene molecular chain so as to reduce the crystallinity of the polypropylene material, and a polar group graft is introduced into a styrene-butadiene block copolymer and a polypropylene grafted styrene compatilizer to improve the interfacial compatibility of the two polymers so as to cut off the continuity of the internal crystallization of the material. And the molecular chain of the high-density polyethylene is penetrated into the crystal lattice of the polypropylene in the blending process to destroy the regularity of the molecular chain. The shrinkage of the polypropylene composite material is increased through the destruction of molecular chain arrangement and the destruction of lattice regularity. The basis of the material selection is that the glossiness and the modulus of the surface of the material cannot be damaged, so that the material has low shrinkage, scratch resistance and high gloss, and the application field of the spraying-free material is enriched.
Compared with the prior art, the invention has the following beneficial effects:
1) The preparation method of the low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material is simple and feasible and has low cost.
2) The invention can meet the size of mineral filled polypropylene material by improving the shrinkage rate of the polypropylene composite material, thereby enabling the spraying-free material to be applied to products such as automobiles, refrigerators, washing machines and the like. Therefore, the use of spray paint is reduced, the environmental pollution is reduced, the product cost is reduced, and the individual pursuit of people for bright appearance is enriched.
3) The lattice in the polypropylene composite material is damaged, so that the scratch-resistant agent can be easily and low transferred to the surface of the material to improve the scratch-resistant performance of the material, and the application prospect of the material can be expanded.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
The scratch-resistant agent used in the embodiment of the invention is HG-600, the auxiliary agent comprises antioxidant 168, auxiliary antioxidant 1010, light stabilizer 2908, lubricant erucamide or calcium stearate, and the mass ratio of the antioxidant to the auxiliary agent is 1.
Example 1
A preparation method of a low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material adopts the following formula:
fully mixing polypropylene, polystyrene, styrene-butadiene block copolymer, compatilizer, high-density polyethylene, scratch-resistant agent, auxiliary agent and spraying-free effect powder in a stirrer according to a mass ratio, adding the mixture into a double-screw extruder, and controlling the processing temperature within the range of 200-230 ℃.
The prepared low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material has the glossiness of 85, the dimensional shrinkage rate of 1.0 and the cross scratch Delta L (10N) of 1.2.
Comparative example 1
The preparation method of the low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material is basically the same as that in example 1, the difference is that the formula does not contain high-density polyethylene, 75 parts of polypropylene resin is used, the glossiness of the finally prepared low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material reaches 83, the dimensional shrinkage rate is 1.3, and the cross scratch delta L is 1.8.
Comparative example 2
A preparation method of a low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material is basically the same as that in example 1, the difference is that a formula does not contain polystyrene, 79 parts of polypropylene resin are used, the glossiness of the finally prepared low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material reaches 83, the dimensional shrinkage rate is 1.6, and the cross scratch delta L is 2.1.
Comparative example 3
The preparation method of the low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material is basically the same as that in example 1, except that the formula does not contain a compatilizer, 74 parts of polypropylene resin are used, the glossiness of the finally prepared low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material reaches 68, the dimensional shrinkage rate is 1.4, and the cross scratch delta L is 2.6.
Comparative example 4
A preparation method of a low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material is basically the same as that in example 1, the difference is that a formula does not contain a styrene-butadiene block copolymer, 73 parts of polypropylene resin are used, the glossiness of the finally prepared low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material reaches 72, the dimensional shrinkage rate is 1.5, and the cross scratch delta L is 2.4.
Comparative example 5
A preparation method of a low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material is basically the same as that in example 1, except that polystyrene is replaced by impact-resistant polystyrene in a formula, and the finally prepared low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material has the glossiness of 62, the dimensional shrinkage of 1.5 and the cross scratch delta L of 2.3.
Comparative example 6
The preparation method of the low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material is basically the same as that in example 1, except that a compatilizer polypropylene grafted polystyrene is replaced by polypropylene grafted maleic anhydride, 67 parts of polypropylene resin is used, and the finally prepared low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material has the gloss of 60, the dimensional shrinkage of 1.7 and the cross scratch DeltaL of 2.8.
Example 2
A preparation method of a low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material adopts the following formula:
fully mixing polypropylene, polystyrene, styrene-butadiene block copolymer, compatilizer, high-density polyethylene, scratch-resistant agent, auxiliary agent and spraying-free effect powder in a stirrer according to a mass ratio, adding the mixture into a double-screw extruder, and controlling the processing temperature to be within the temperature range of 200-230 ℃.
The prepared low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material has the glossiness of 87, the size shrinkage rate of 0.8 and the cross scratch delta L of 0.6.
Example 3
A preparation method of a low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material adopts the following formula:
fully mixing polypropylene, polystyrene, styrene-butadiene block copolymer, compatilizer, high-density polyethylene, scratch-resistant agent, auxiliary agent and spraying-free effect powder in a stirrer according to a mass ratio, adding the mixture into a double-screw extruder, and controlling the processing temperature within the range of 200-230 ℃.
The prepared low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material has the glossiness of 84, the dimensional shrinkage rate of 1.2 and the cross scratch Delta L of 1.4.
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. The low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material is characterized by comprising the following components in parts by weight:
2. the low shrinkage, scratch resistant, high gloss spray free polypropylene composite of claim 1 wherein the polypropylene resin is a high crystalline co-polypropylene with a 60 ° angle gloss of 87.
3. The low shrinkage, scratch resistant, high gloss spray free polypropylene composite of claim 1 wherein the polystyrene is a general purpose grade polystyrene having a melt flow rate of 4 to 102/10min at 220 ℃ 21022 test conditions.
4. The low shrinkage, scratch resistant, high gloss spray free polypropylene composite of claim 1, wherein the styrene-butadiene block copolymer has a relative molecular mass of 1.5210 6 。
5. The low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material according to claim 1, wherein the compatilizer is polypropylene grafted styrene, and the grafting ratio of styrene is 40%.
6. The low shrinkage, scratch resistant, high gloss spray free polypropylene composite of claim 1 wherein the scratch resistant agent is an ultra high molecular weight silicone containing a fluorine functional group.
7. The low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material according to claim 1, wherein the auxiliary additive comprises one or more of an antioxidant, a light stabilizer and a lubricant.
8. The low-shrinkage, scratch-resistant and high-gloss spray-free polypropylene composite material according to claim 1, wherein the spray-free effect powder is aluminum silver powder.
9. The low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material according to claim 1, wherein the shrinkage rate of the low-shrinkage scratch-resistant high-gloss polypropylene is 0.8-1.2, and the surface gloss is 82-87.
10. The preparation method of the low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material according to any one of claims 1 to 9, characterized in that the polypropylene resin, the polystyrene, the styrene-butadiene block copolymer, the compatilizer, the high-density polyethylene, the scratch-resistant agent, the auxiliary agent and the spray-free effect powder are mixed according to the weight parts, added into a double-screw extruder, and subjected to melt mixing and granulation at the temperature of 200-230 ℃.
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| CN202211136806.4A CN115403869A (en) | 2022-09-19 | 2022-09-19 | Low-shrinkage scratch-resistant high-gloss spray-free polypropylene composite material and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5106696A (en) * | 1988-11-15 | 1992-04-21 | Ferro Corporation | Polyolefins compatibilized with styrene copolymers and/or polymer blends and articles produced therefrom |
| KR19990038126A (en) * | 1997-11-03 | 1999-06-05 | 유현식 | Polypropylene resin composition excellent in heat resistance and strength |
| CN101659766A (en) * | 2008-08-26 | 2010-03-03 | 金发科技股份有限公司 | Low-shrinkage sprayable PP/PS blend alloy and preparation method thereof |
| CN102250413A (en) * | 2011-05-18 | 2011-11-23 | 合肥会通新材料有限公司 | Modified polypropylene composite material of high gloss and low shrinkage 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 |
-
2022
- 2022-09-19 CN CN202211136806.4A patent/CN115403869A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5106696A (en) * | 1988-11-15 | 1992-04-21 | Ferro Corporation | Polyolefins compatibilized with styrene copolymers and/or polymer blends and articles produced therefrom |
| KR19990038126A (en) * | 1997-11-03 | 1999-06-05 | 유현식 | Polypropylene resin composition excellent in heat resistance and strength |
| CN101659766A (en) * | 2008-08-26 | 2010-03-03 | 金发科技股份有限公司 | Low-shrinkage sprayable PP/PS blend alloy and preparation method thereof |
| CN102250413A (en) * | 2011-05-18 | 2011-11-23 | 合肥会通新材料有限公司 | Modified polypropylene composite material of high gloss and low shrinkage 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 |
Non-Patent Citations (3)
| Title |
|---|
| 刘瑞雪: "简明精细化工大辞典", 辽宁科学技术出版社, pages: 724 * |
| 家电科技, no. 7, pages 79 * |
| 现代塑料, no. 1, pages 52 * |
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