CN111087704A - Polypropylene composition suitable for gas-assisted molding and preparation method thereof - Google Patents
Polypropylene composition suitable for gas-assisted molding and preparation method thereof Download PDFInfo
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- CN111087704A CN111087704A CN201911370453.2A CN201911370453A CN111087704A CN 111087704 A CN111087704 A CN 111087704A CN 201911370453 A CN201911370453 A CN 201911370453A CN 111087704 A CN111087704 A CN 111087704A
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2205/24—Crystallisation aids
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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
- C08L2310/00—Masterbatches
Abstract
The invention discloses a polypropylene composition suitable for gas-assisted molding and a preparation method thereof, wherein the composition comprises the following raw materials in percentage by weight: 63-94% of polypropylene, 0-20% of inorganic filler, 5-15% of nitrile rubber, 0.1-0.3% of nucleating agent, 0.1-1% of antioxidant and 0.1-2% of other additives. The polypropylene composition obtained by the invention has excellent comprehensive performance, can shorten the molding period when being applied in gas-assisted molding, has small possibility of warping and deformation and good surface smoothness, and can be widely applied to gas-assisted molded products such as automobile door handles, window frame trim strips and the like.
Description
Technical Field
The invention belongs to the field of modification and processing of high polymer materials, and particularly relates to a polypropylene composition suitable for gas-assisted molding, and a preparation method and application thereof.
Background
The polypropylene has the characteristics of light weight, high cost performance, easy processing and forming and the like, and is widely applied to the fields of automobile interior and exterior trimming parts. With the advance of light weight of automobiles and the continuous development of injection molding processes, gas-assisted molding is more and more widely applied to the production of automobile plastic products, particularly products with complex structures and thicker wall thickness, such as automobile door handles, window frame decorative strips and the like. The gas-assisted molded product puts higher technical requirements on the resin material, such as the requirement that the material has higher melt strength and proper cooling crystallization speed; meanwhile, the gas-assisted molding has higher requirement on the surface smoothness of the product, and if the material formula is not designed well, the gas-assisted molding product often has the defects of pockmarks, silver wires, wrinkles, warping deformation and the like. Therefore, the development of the polypropylene material suitable for gas-assisted molding has very important practical significance.
In the aspect of gas-assisted forming material technology, Chinese patent CN104448764A discloses an electroplating-grade PC/ABS alloy material for gas-assisted forming, a preparation method and application thereof, and PC/ABS alloy suitable for gas-assisted forming process is prepared by adopting PC, ABS, SAN, heat-resistant agent, antioxidant and lubricant. Patent CN105131589A discloses an air-assisted forming glass fiber reinforced nylon 6 engineering plastic and a preparation method thereof, wherein the air-assisted forming glass fiber reinforced nylon 6 engineering plastic is prepared by adding alkali-free glass fiber, surface-treated carbon fiber and aramid fiber and synergistic action of the three fibers to reinforce resin.
At present, many patents are available on modification of polypropylene materials, but few reports are made on polypropylene compositions suitable for gas-assisted molding and preparation methods thereof.
Disclosure of Invention
The invention provides a polypropylene composition suitable for gas-assisted forming and a preparation method thereof, and the crystallization temperature and the melt strength of the polypropylene composition are improved by the synergistic effect of adding a nucleating agent and adopting nitrile rubber to replace the traditional POE elastomer, so that the composition can be formed more quickly and stably, is particularly suitable for a gas-assisted forming process, and has excellent comprehensive performance.
The purpose of the invention is realized by the following technical scheme:
a polypropylene composition suitable for gas-assisted forming is composed of the following raw materials in percentage by weight:
in the above polypropylene composition suitable for gas-assisted molding:
the polypropylene is copolymerized polypropylene with melt flow rate of 5-50 g/10min under the test condition of 230 ℃ multiplied by 2.16 kg.
The inorganic filler is one or a composition of more than two of talcum powder, barium sulfate and calcium carbonate, and the talcum powder with the particle size range of 1-10 mu m is preferred.
The nitrile rubber is powder nitrile rubber, and the powder particle diameter of the nitrile rubber is 10-50 mu m.
The nucleating agent is one of aliphatic dicarboxylate compounds, phosphate metal salts and aromatic amine nucleating agents, preferably aliphatic dicarboxylate compounds, and specifically bicyclo [2.2.1] heptane dicarboxylate.
The antioxidant is a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is a hindered phenol antioxidant or a thioester antioxidant and is one or a composition of more than two of 3114, 1010 and DSTP; the secondary antioxidant is phosphite or ester antioxidant, and is selected from one or two of 618 and 168.
The other additives are one or a combination of more of various color additives, light stabilizers and various ester or fatty acid lubricants.
The preparation method of the polypropylene composition suitable for gas-assisted forming comprises the following steps:
(1) weighing the raw materials according to the weight ratio;
(2) adding polypropylene, inorganic filler, nitrile rubber, nucleating agent, antioxidant and other additives into a high-speed mixer for dry mixing for 5-15 minutes;
(3) and adding the mixed materials into a double-screw extruder, and cooling and granulating after melt extrusion to obtain the material. Wherein the temperature of the extruder is 190 ℃, 200 ℃, 210 ℃, 220 ℃ and 215 ℃ from the feeding port to the head in sequence.
The polypropylene composition suitable for gas-assisted molding is applied to producing the window frame trim gas-assisted part.
Compared with the prior art, the invention has the following technical effects:
1. by adding the nucleating agent, the crystallization temperature and the crystallization speed of the composition are improved, and the crystallization molding of a product is accelerated; the method effectively improves the problem of warping deformation of the product while shortening the molding period, so that the gas-assisted product has good dimensional stability.
2. According to the invention, the melt strength of the polypropylene composition is improved by adopting a mode of replacing the conventional granular POE elastomer with the powdery nitrile rubber, and the crystallization temperature of the composition is further improved; the product is ensured not to be cracked in the air blowing process, the problems of pockmarks, folds and the like which are easy to appear in the air-assisted forming process are solved, and the surface of the product is endowed with good appearance smoothness.
3. The polypropylene composition obtained by the invention has excellent comprehensive performance and can be widely applied to gas-assisted molded products such as automobile door handles, window frame decorative strips and the like.
4. The method for preparing the polypropylene composition suitable for gas-assisted molding provided by the invention can be realized by adopting the conventional double-screw extruder, is easy for industrial large-scale production and has wide application prospect.
Detailed Description
The present invention will be described in further detail with reference to the following examples:
in the composition formulations of the examples and comparative examples, the polypropylene was a copolymer polypropylene produced by Shanghai petrochemical Co., Ltd, having a melt flow rate of 26g/10min (test conditions: 230 ℃ C.. times.2.16 kg) under the trade name of M2600R. The inorganic filler is HTP2 talcum powder produced by IMIFABI company, and the average grain diameter of the inorganic filler is 5 microns. The nitrile rubber is X146 produced by Langsheng company; POE elastomer is ethylene-butylene copolymer 7487 produced by DOW company; the nucleating agent is HPN-68L produced by Milliken company. The main antioxidant is 1010 from Ciba company and DSTP from ICE company in UK; the secondary antioxidant is 168 available from Ciba company. Black masterbatch, commercially available.
Example 1
Respectively weighing 93.4 parts of polypropylene, 5 parts of nitrile rubber, 0.1 part of nucleating agent, 0.1 part of 1010, 0.2 part of DSTP, 0.2 part of 168 and 1 part of black master batch according to the weight ratio, adding the materials into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, performing melt extrusion, and cooling and granulating to obtain the polypropylene/butadiene-acrylonitrile copolymer. Wherein the temperature of the extruder is 190 ℃, 200 ℃, 210 ℃, 220 ℃ and 215 ℃ from the feeding port to the head in sequence.
Example 2
Respectively weighing 93.3 parts of polypropylene, 5 parts of nitrile rubber, 0.2 part of nucleating agent, 0.1 part of 1010, 0.2 part of DSTP, 0.2 part of 168 and 1 part of black master batch according to the weight ratio, adding the materials into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, performing melt extrusion, and cooling and granulating to obtain the polypropylene/butadiene-acrylonitrile copolymer. Wherein the temperature of the extruder is 190 ℃, 200 ℃, 210 ℃, 220 ℃ and 215 ℃ from the feeding port to the head in sequence.
Example 3
Respectively weighing 93.2 parts of polypropylene, 5 parts of nitrile rubber, 0.3 part of nucleating agent, 0.1 part of 1010, 0.2 part of DSTP, 0.2 part of 168 and 1 part of black master batch according to the weight ratio, adding the materials into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, performing melt extrusion, and cooling and granulating to obtain the polypropylene/butadiene-acrylonitrile copolymer. Wherein the temperature of the extruder is 190 ℃, 200 ℃, 210 ℃, 220 ℃ and 215 ℃ from the feeding port to the head in sequence.
Example 4
Respectively weighing 78.3 parts of polypropylene, 10 parts of talcum powder, 10 parts of nitrile rubber, 0.2 part of nucleating agent, 0.1 part of 1010, 0.2 part of DSTP, 0.2 part of 168 and 1 part of black master batch according to the weight ratio, adding the materials into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, performing melt extrusion, cooling and granulating to obtain the polypropylene/butadiene-acrylonitrile copolymer. Wherein the temperature of the extruder is 190 ℃, 200 ℃, 210 ℃, 220 ℃ and 215 ℃ from the feeding port to the head in sequence.
Example 5
Respectively weighing 63.3 parts of polypropylene, 20 parts of talcum powder, 15 parts of nitrile rubber, 0.2 part of nucleating agent, 0.1 part of 1010, 0.2 part of DSTP, 0.2 part of 168 and 1 part of black master batch according to the weight ratio, adding the materials into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, performing melt extrusion, cooling and granulating to obtain the polypropylene/butadiene-acrylonitrile copolymer. Wherein the temperature of the extruder is 190 ℃, 200 ℃, 210 ℃, 220 ℃ and 215 ℃ from the feeding port to the head in sequence.
Comparative example 1
93.5 parts of polypropylene, 5 parts of nitrile rubber, 0.1 part of 1010, 0.2 part of DSTP, 0.2 part of 168 and 1 part of black master are weighed according to the weight ratio respectively, the materials are added into a high-speed mixer to be mixed uniformly, then are added into a double-screw extruder, and are cooled and granulated after melt extrusion to obtain the polypropylene. Wherein the temperature of the extruder is 190 ℃, 200 ℃, 210 ℃, 220 ℃ and 215 ℃ from the feeding port to the head in sequence.
Comparative example 2
Respectively weighing 78.3 parts of polypropylene, 10 parts of talcum powder, 10 parts of POE, 0.2 part of nucleating agent, 0.1 part of 1010, 0.2 part of DSTP, 0.2 part of 168 and 1 part of black master batch according to the weight ratio, adding the materials into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, performing melt extrusion, cooling and granulating to obtain the polypropylene/polypropylene composite material. Wherein the temperature of the extruder is 190 ℃, 200 ℃, 210 ℃, 220 ℃ and 215 ℃ from the feeding port to the head in sequence.
Comparative example 3
Respectively weighing 63.5 parts of polypropylene, 20 parts of talcum powder, 15 parts of POE, 0.1 part of 1010, 0.2 part of DSTP, 0.2 part of 168 and 1 part of black master batch according to the weight ratio, adding the materials into a high-speed mixer, uniformly mixing, adding into a double-screw extruder, performing melt extrusion, and cooling and granulating to obtain the polypropylene/talcum powder. Wherein the temperature of the extruder is 190 ℃, 200 ℃, 210 ℃, 220 ℃ and 215 ℃ from the feeding port to the head in sequence.
Performance evaluation method and implementation standard:
the particle materials prepared in the examples 1-5 and the comparative examples 1-3 are dried in a blowing oven at 90-100 ℃ for 2-3 hours, and then the dried particles are made into a standard sample strip on an injection molding machine for testing.
And (3) testing tensile strength: according to ISO 527-2 standard, the speed is 50 mm/min; flexural modulus test: according to ISO178 standard, the speed is 2 mm/min; notched impact strength test: according to ISO 179-1 standard; and (3) testing the crystallization temperature: adopting a DSC method; evaluation of product appearance: and preparing the window frame decorative strip gas accessory, and observing defects such as pits, wrinkles, warping deformation and the like on the surface of the product.
The formulations and the results of the various performance tests of the examples and comparative examples are shown in the following tables:
table 1: material formula tables of examples 1 to 5 and comparative examples 1 to 3 (% by weight)
Table 2: performance test results of examples 1 to 5 and comparative examples 1 to 3
As can be seen from the comparison between examples 1-3 and comparative example 1, the crystallization temperature of the polypropylene composition is gradually increased with the increase of the content of the nucleating agent, so that the crystallization molding speed of the product is increased, and the problem of warping deformation of the product is effectively improved. From a comparison of example 4 with comparative example 2, it can be seen that the use of powdered nitrile rubber instead of the conventional particulate POE elastomer further increases the crystallization temperature of the polypropylene composition, while the article does not melt during blowing, giving the article a good surface finish. Comparative example 3 is a conventional PP + EPDM-T20 material, which tends to deform severely and have a poor surface finish when used in the production of gas-assist articles, and is not suitable for gas-assist forming processes. The nucleating agent is added, and the nitrile rubber is adopted to replace the traditional POE elastomer for synergistic effect, so that the material can be molded more quickly and stably, and the method is suitable for a gas-assisted molding process. The method for preparing the polypropylene composition suitable for gas-assisted molding is simple and easy to implement, and can be widely applied to producing gas-assisted products such as automobile door handles, window frame decorative strips and the like.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and the technical solution of the present invention is covered within the scope of the present invention.
Claims (10)
1. A polypropylene composition suitable for gas-assisted molding, characterized in that: the composite material consists of the following raw materials in percentage by weight:
2. the polypropylene composition suitable for gas-assisted forming according to claim 1, wherein: the polypropylene is copolymerized polypropylene with melt flow rate of 5-50 g/10min under the test condition of 230 ℃ multiplied by 2.16 kg.
3. The polypropylene composition suitable for gas-assisted forming according to claim 1, wherein: the inorganic filler is one or a composition of more than two of talcum powder, barium sulfate and calcium carbonate.
4. The polypropylene composition suitable for gas-assisted forming according to claim 3, wherein: the inorganic filler is talcum powder with the particle size range of 1-10 mu m.
5. The polypropylene composition suitable for gas-assisted forming according to claim 1, wherein: the nitrile rubber is powder nitrile rubber, and the powder particle diameter of the nitrile rubber is 10-50 mu m.
6. The polypropylene composition suitable for gas-assisted forming according to claim 1, wherein: the nucleating agent is one of aliphatic dicarboxylic acid salt compounds, phosphate metal salts and aromatic amine nucleating agents.
7. The polypropylene composition suitable for gas-assisted forming according to claim 6, wherein: the nucleating agent is an aliphatic dicarboxylic acid salt compound, in particular bicyclo [2.2.1] heptane dicarboxylate.
8. The polypropylene composition suitable for gas-assisted forming according to claim 1, wherein: the antioxidant is a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is a hindered phenol antioxidant or a thioester antioxidant and is one or a composition of more than two of 3114, 1010 and DSTP; the secondary antioxidant is phosphite or ester antioxidant, and is selected from one or two of 618 and 168.
9. The polypropylene composition suitable for gas-assisted forming according to claim 1, wherein: the other additives are one or a combination of more of various color additives, light stabilizers and various ester or fatty acid lubricants.
10. Process for the preparation of a polypropylene composition suitable for gas-assisted shaping according to any one of claims 1 to 9, wherein: the method comprises the following steps:
(1) weighing the raw materials according to the weight ratio;
(2) adding polypropylene, inorganic filler, nitrile rubber, nucleating agent, antioxidant and other additives into a high-speed mixer for dry mixing for 5-15 minutes;
(3) and adding the mixed materials into a double-screw extruder, and cooling and granulating after melt extrusion to obtain the material. Wherein the temperature of the extruder is 190 ℃, 200 ℃, 210 ℃, 220 ℃ and 215 ℃ from the feeding port to the head in sequence.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111763380A (en) * | 2020-07-22 | 2020-10-13 | 宁波金雨科技实业有限公司 | Thermoplastic elastomer piston material and preparation method thereof |
| CN112552590A (en) * | 2020-12-09 | 2021-03-26 | 上海普利特复合材料股份有限公司 | Talcum powder/glass fiber modified polypropylene composite material for gas-assisted molding and preparation method thereof |
| CN114685891A (en) * | 2022-03-29 | 2022-07-01 | 金发科技股份有限公司 | PP/POE composition for gas-assisted molding and preparation method and application thereof |
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| CN109181118A (en) * | 2018-09-30 | 2019-01-11 | 南京聚隆科技股份有限公司 | One kind exempting from basecoat paint automobile exterior material and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106883512A (en) * | 2017-03-16 | 2017-06-23 | 鑫同吸塑（深圳）有限公司 | A kind of PP composite material that lotus leaf effect is formed to greasy dirt and preparation method thereof |
| CN109181118A (en) * | 2018-09-30 | 2019-01-11 | 南京聚隆科技股份有限公司 | One kind exempting from basecoat paint automobile exterior material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111763380A (en) * | 2020-07-22 | 2020-10-13 | 宁波金雨科技实业有限公司 | Thermoplastic elastomer piston material and preparation method thereof |
| CN112552590A (en) * | 2020-12-09 | 2021-03-26 | 上海普利特复合材料股份有限公司 | Talcum powder/glass fiber modified polypropylene composite material for gas-assisted molding and preparation method thereof |
| CN114685891A (en) * | 2022-03-29 | 2022-07-01 | 金发科技股份有限公司 | PP/POE composition for gas-assisted molding and preparation method and application thereof |
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