CN115960414B - Polypropylene composite material and preparation method and application thereof - Google Patents
Polypropylene composite material and preparation method and application thereof Download PDFInfo
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- -1 Polypropylene Polymers 0.000 title claims abstract description 121
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 104
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 65
- 239000004952 Polyamide Substances 0.000 claims abstract description 28
- 229920002647 polyamide Polymers 0.000 claims abstract description 28
- 239000003365 glass fiber Substances 0.000 claims abstract description 23
- 239000002667 nucleating agent Substances 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000014759 maintenance of location Effects 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000004611 light stabiliser Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 3
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 abstract description 29
- 239000011347 resin Substances 0.000 abstract description 27
- 229920005989 resin Polymers 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 23
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 3
- 230000002787 reinforcement Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 30
- 229930040373 Paraformaldehyde Natural products 0.000 description 20
- 238000000465 moulding Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
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- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- LNKJESSHRFPVPE-UHFFFAOYSA-N 5-(diethylamino)pentyl 3,4,5-trimethoxybenzoate;hydrochloride Chemical compound Cl.CCN(CC)CCCCCOC(=O)C1=CC(OC)=C(OC)C(OC)=C1 LNKJESSHRFPVPE-UHFFFAOYSA-N 0.000 description 1
- 241000218691 Cupressaceae Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 239000010438 granite Substances 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
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- 229920001169 thermoplastic Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polypropylene composite material, a preparation method and application thereof. The polypropylene material comprises the following components in parts by weight: 88 to 95 parts of polypropylene, 2 to 5 parts of resin fiber, 1 to 3 parts of glass fiber, 2 to 5 parts of compatilizer, 0.1 to 0.4 part of alpha nucleating agent and 0 to 1 part of other additives; wherein the resin fiber is polyamide fiber, and the retention length of the polyamide fiber in the polypropylene composite material is more than or equal to 0.4mm. The invention adopts low-flow polypropylene and adds alpha nucleating agent to improve the crystallinity of the material, form stable alpha crystal form, increase the tensile strength of the material and improve the anti-damage capability; glass fiber and resin fiber are added for reinforcement, and under the combined action of the two fibers, the polypropylene has higher strength, toughness and shrinkage rate, and the physical properties can be equivalent to that of polyformaldehyde, and the cost is low.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a polypropylene composite material and a preparation method and application thereof.
Background
Polyoxymethylene (POM) is also known as acetal resin, polyoxymethylene, polyacetal, and is a thermoplastic crystalline high molecular polymer, and is known as "super steel" or "steel racing". The engineering plastic has excellent comprehensive performance, high mechanical performance, such as strength, modulus, wear resistance, toughness, fatigue resistance and creep resistance, excellent electric insulation, solvent resistance and processability, and wide application in the fields of electronic appliances, automobile parts, industrial mechanical devices and the like. However, the existing polyoxymethylene resins are in short supply and expensive, so that an alternative product which is low in cost and has comparable performance to polyoxymethylene is required.
The polypropylene (PP) and the polyformaldehyde belong to five general engineering plastics, and the polypropylene has the advantages of low production finished products, good comprehensive mechanical properties, no toxicity, corrosion resistance, easy recovery and the like, and is widely applied to the fields of chemical industry, building, packaging, automobiles and the like.
Therefore, the polypropylene is modified to have properties (including strength, modulus, toughness, shrinkage performance and the like) equivalent to that of the polyoxymethylene, so that the polypropylene can be used as a substitute of the polyoxymethylene, and the cost is reduced.
Disclosure of Invention
The invention aims to solve the problems of the prior polyformaldehyde that the supply is insufficient and the price is high, and provides a polypropylene composite material with the performance equivalent to that of polyformaldehyde. According to the invention, the reinforced glass fiber and the specific resin fiber are added into the polypropylene matrix, so that the obtained polypropylene composite material is equivalent to the performance of polyoxymethylene in terms of strength, modulus, toughness and shrinkage.
Another object of the present invention is to provide a method for preparing the polypropylene composite material.
Another object of the present invention is to provide the use of the polypropylene composite material for the preparation of electronic appliances, automotive parts or industrial machinery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the polypropylene composite material comprises the following components in parts by weight:
wherein the mass flow rate of the melt of the polypropylene at 230 ℃ under a load of 2.16kg is less than or equal to 11g/10min;
the retention length of the polyamide fiber in the polypropylene composite material is more than or equal to 0.4mm.
The invention adopts low-flow polypropylene and adds alpha nucleating agent to improve the crystallinity of the material, form stable alpha crystal form, increase the tensile strength of the material and improve the anti-damage capability. The invention further increases the tensile strength of the polypropylene material by adding the glass fiber, but the increase of the content of the glass fiber also leads to the decrease of the toughness of the material, the decrease of the shrinkage rate and the failure of the strength and the shrinkage rate of the polyoxymethylene. Therefore, the invention also adds specific resin fiber and glass fiber to act together, and can improve the strength and toughness of polypropylene at the same time under the condition of small fiber addition amount, and the addition of small fiber can ensure that the polypropylene maintains higher crystallinity and shrinkage rate equivalent to that of polyoxymethylene. The addition of the resin fiber has good compatibility with polypropylene, and is beneficial to maintaining and even further improving the toughness of the polypropylene; on the other hand, the resin fiber with a certain length is uniformly dispersed in the polypropylene, presents isotropy, improves the tensile strength of the polypropylene together with the glass fiber, and has very good toughness deformability compared with the glass fiber, so that the shrinkage rate of the polypropylene material is little influenced, and the shrinkage rate of the material is not obviously reduced while the strength of the material is improved.
The compatibility of the resin fiber and the PP can be improved by controlling the melt mass flow rate of the polypropylene, so that the adhesion force between the surface of the resin fiber and the PP base material is stronger, and the reinforcing effect of the resin fiber is exerted. Preferably, the polypropylene has a melt mass flow rate of 0.25 to 10g/10min at 230℃under a load of 2.16 kg. Further preferably, the polypropylene has a melt mass flow rate of 0.3 to 0.4g/10min at 230℃under a load of 2.16 kg. However, when the melt mass flow rate of polypropylene is too small, the mechanical strength of the resulting polypropylene composite is poor.
Preferably, the polyamide fibers have a retention length in the polypropylene composite of 0.4 to 3.5mm. Further preferably, the polyamide fibers have a retention length in the polypropylene composite of 1.4 to 3mm. The length of the polyamide fiber is too short to play a role in common reinforcement; the length of the polyamide fiber is too long, the polyamide fiber is unevenly dispersed in the matrix, aggregation is easy to occur, the polyamide fiber also easily extends to the surface of the composite material, and the appearance of the material is affected.
Conventional polyamide resins can be prepared into polyamide fibers for use in the present invention. Optionally, the polyamide resin in the polyamide fiber includes, but is not limited to, at least one of PA6, PA66, or PA 610. According to the invention, the performance of the polypropylene material modified by adding the PA6 fiber is closer to that of polyoxymethylene, and the modification effect is better.
Preferably, the glass fibers have a diameter of 13 μm or less, for example, 4 to 8 μm,8 to 10 μm,10 to 13 μm. Glass fibers in this diameter range have good dispersibility in polypropylene matrix.
Conventional alpha nucleating agents may be used in the present invention, including but not limited to aryl phosphate salt nucleating agents. Compared with the beta nucleating agent, the alpha nucleating agent is more stable, so that the crystallization performance of the obtained polypropylene is also more stable. The aryl phosphate salt nucleating agent comprises at least one of MP-6, NA-11 (sodium 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate) and NA-21.
In the invention, other additives are functional additives, and can be optionally added or not added according to the needs. The other additives include, but are not limited to, at least one of antioxidants, light stabilizers, or lubricants.
Optionally, the antioxidant is a hindered phenol antioxidant and/or a phosphite antioxidant.
Optionally, the light stabilizer includes, but is not limited to, at least one of a hindered amine light stabilizer or a benzotriazole light stabilizer.
The lubricant is stearate lubricant.
The preparation method of the polypropylene composite material comprises the following steps:
according to the formula, polypropylene, polyamide fiber, glass fiber, compatilizer, alpha nucleating agent and other additives are mixed and then are melt extruded at 180-230 ℃ to obtain the polypropylene composite material.
Preferably, the mixing is performed in a high speed mixer.
Preferably, the melt extrusion is performed in a twin screw extruder having a screw aspect ratio of (48-56): 1 and a screw speed of 350-450 rpm.
The application of the polypropylene composite material in the preparation of electronic appliances, automobile parts or industrial mechanical devices is also within the protection scope of the invention. Specifically, the polypropylene composite material is used for preparing automobile door panels, bumper supports, automobile uprights, air inlet pipes, air pipe valves, drawer sliding rails and the like.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts low-flow polypropylene and adds alpha nucleating agent to improve the crystallinity of the material, form stable alpha crystal form, increase the tensile strength of the material and improve the anti-damage capability; glass fiber and resin fiber are added for reinforcement, and under the combined action of the two fibers, the polypropylene has higher strength, toughness and shrinkage rate, and the physical properties can be equivalent to that of polyformaldehyde, and the cost is low.
The tensile strength of the polypropylene composite material can be kept at 50-57 MPa, the impact strength is kept at 4.2-5.9 MPa, and the molding shrinkage is kept at 0.17-0.20%, which is equivalent to the performance of polyoxymethylene.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples, which are not intended to limit the present invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The reagents and materials used in the present invention are commercially available unless otherwise specified.
The following raw materials are selected in the embodiment of the invention:
polypropylene:
PP-1: PP B8101, available from Yanshan petrochemical industry, has a melt mass flow rate of 0.3g/10min at 230℃under a load of 2.16 kg;
PP-2: PPB-1801, available from Yanshan petrochemical industry, having a melt mass flow rate of 0.4g/10min at 230℃under a 2.16kg load;
PP-3: k9010, melt mass flow rate 10g/10min at 230℃under a 2.16kg load, purchased from bench top;
PP-4: PPR-4220S, available from Yanshan petrochemical industry, having a melt mass flow rate of 0.25g/10min at 230℃under a 2.16kg load;
PP-5: PPH-MM20-S, melt mass flow rate of 22g/10min at 230℃under a load of 2.16kg, purchased from Zhongxiao;
the melt mass flow rate of polypropylene was tested according to the method in the standard ISO 1133-2-2011.
Resin fiber:
PA6 fiber: 840D-96F, purchased from Shenzhen TELI New material;
PA66 fiber: 15D-3MM from Shenzhen Teli new material;
polyester fiber: FX105, available from GRANITE;
carbon fiber: ST 600, purchased from guangzhou sendan specialty new material;
glass fiber:
glass fiber-1: e7CS10-03-508A, the diameter of the fiber is 10 mu m, purchased from China stone-like glass fiber;
glass fiber-2: 249AF-10C 4MM with a diameter of 10 μm, available from Eurasian;
maleic anhydride grafted polypropylene (MAH-g-PP): PC-1, purchased from Buddha south China sea cypress morning polymer new material;
aryl phosphate salt nucleating agents, NA-11, available from Ai Dike;
other additives:
antioxidant 1010: are commercially available;
antioxidant 168: are commercially available;
and (3) a lubricant: calcium stearate, commercially available;
in the present invention, the other additives (such as an antioxidant and a lubricant) are the same in the parallel test.
Examples 1 to 12
The embodiment of the invention provides a series of polypropylene composite materials, which are prepared by a preparation method comprising the following steps:
according to the formula shown in tables 1-2, polypropylene, resin fiber, glass fiber, compatilizer, alpha nucleating agent and other additives are added into a high-speed mixer, after being mixed uniformly, the mixture is fed into a double-screw extruder (the length-diameter ratio of the screw is 48:1), the screw speed is 350-450 rpm, and the mixture is subjected to melt extrusion at 180-230 ℃, wherein the temperature of each region from a machine head to a discharge hole in the double-screw extruder is 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ and 230 ℃ from a feeding section to ten regions of the machine head, so that the polypropylene composite material can be obtained.
Table 1 raw material formulations (parts by weight) of polypropylene composite materials of examples 1 to 4
Table 2 raw material formulations (parts by weight) of Polypropylene composite materials of examples 5 to 12
In the present invention, the resin fiber is purchased as long fiber, and is cut into a predetermined length when used and then added into the composite material, but the fiber length is reduced during processing under the shearing of the screw of the twin-screw extruder, so that the retention length of the resin fiber in the composite material is obtained by observing the product under a microscope and calculating the average retention length.
Comparative example 1
This comparative example provides a polypropylene composite, prepared according to the method of example 1, which differs from example 1 in that polypropylene is replaced with PP-5 having a greater melt mass flow rate.
Comparative example 2
This comparative example provides a polypropylene composite material prepared according to the preparation method of example 1, which differs from example 1 in that 3 parts of glass fiber are replaced with 3 parts of polyamide fiber PA6, and the other raw materials are unchanged, i.e. only polyamide fiber is added, and no glass fiber is added.
Comparative example 3
This comparative example provides a polypropylene composite material prepared according to the preparation method of example 1, which differs from example 1 in that 4 parts of polyamide fiber PA6 are replaced with 4 parts of glass fiber-1, and the other raw materials are unchanged, i.e. only glass fiber is added, and no resin fiber is added.
Comparative example 4
This comparative example provides a polypropylene composite material prepared according to the preparation method of example 1, which differs from example 1 in that polyamide fiber PA6 is replaced with polyester fiber in equal amounts.
Comparative example 5
This comparative example provides a polypropylene composite material prepared according to the preparation method of example 1, which differs from example 1 in that polyamide fiber PA6 is replaced with carbon fiber in equal amounts.
Comparative example 6
This comparative example provides a polypropylene composite material prepared according to the preparation method of example 1, which is different from example 1 in that the retention length of the resin fiber in the composite material is 0.3mm.
Comparative example 7
This comparative example provides a polypropylene composite, prepared according to the method of example 1, which differs from example 1 in that the alpha nucleating agent is replaced with a beta nucleating agent (TMB-5, available from Shanxi chemical institute).
Comparative example 8
This comparative example provides a polypropylene composite, prepared according to the method of example 1, except that the PA6 fiber was replaced with PA6 resin (PA 6 VOLGAMID28, available from gulbyshev).
Performance testing
The properties of the polypropylene composites and polyoxymethylene (M90-44, from Bao Lian Plastic) obtained in the examples and comparative examples above were characterized, and specific test items and test methods and results were as follows:
1. tensile strength (MPa): the above composite material was injection molded into a tensile bar (type IB), tested by reference to the method in Standard ISO527-1-2010, and stretched at 50mm/min at room temperature (25 ℃ C.), the test results being shown in Table 3;
2. bending properties: the composite material is molded into impact splines, and the flexural modulus (MPa) is tested by referring to the method in the standard ISO178-2011, and the test results are shown in Table 3;
3. toughness: the composite material is molded into impact splines, and is tested by referring to the method in the standard ISO179-2010, the type of the notch of the spline is A type, and the Zwick HIT5.5P electronic display impact instrument is adopted to test the notch impact strength (kJ/m) of the composite material 2 ) The test results are shown in Table 3;
4. molding shrinkage rate: after the composite material is injection molded in a square plate mold of 80 x 220 x 2mm, standing and molding for 48 hours at 23 ℃ and 50% relative humidity, measuring the difference between the size of the molded square plate and the size of the mold, and calculating the molding shrinkage (%), wherein the molding shrinkage is the average value of the transverse shrinkage and the longitudinal shrinkage, and the transverse shrinkage is calculated according to the following formula: transverse shrinkage (%) = |a t -a 0 ∣/a 0 *100, wherein a t To the length after molding, a 0 Is the length of the mould; the longitudinal shrinkage is the shrinkage in the width direction, and the calculation formula thereof is similar to that of the transverse shrinkage.
The test results are shown in Table 3.
TABLE 3 Performance test results
| Performance of | Tensile Strength | Flexural modulus | Notched impact Strength | Shrinkage/% |
| Example 1 | 53 | 2715 | 4.9 | 0.2 |
| Example 2 | 56 | 2688 | 4.5 | 0.18 |
| Example 3 | 51 | 2523 | 5.1 | 0.2 |
| Example 4 | 50 | 2510 | 5.7 | 0.2 |
| Example 5 | 54 | 2762 | 5 | 0.17 |
| Example 6 | 50 | 2522 | 5.9 | 0.17 |
| Example 7 | 51 | 2656 | 4.8 | 0.18 |
| Example 8 | 57 | 2776 | 5.2 | 0.18 |
| Example 9 | 53 | 2630 | 4.2 | 0.19 |
| Example 10 | 50 | 2552 | 4.6 | 0.19 |
| Example 11 | 51 | 2681 | 5 | 0.19 |
| Example 12 | 50 | 2643 | 4.8 | 0.2 |
| Comparative example 1 | 48 | 2480 | 4.3 | 0.13 |
| Comparative example 2 | 42 | 2250 | 4.5 | 0.21 |
| Comparative example 3 | 57 | 2920 | 4.6 | 0.1 |
| Comparative example 4 | 41 | 2289 | 4.3 | 0.19 |
| Comparative example 5 | 50 | 2589 | 4.3 | 0.14 |
| Comparative example 6 | 44 | 2320 | 4.5 | 0.19 |
| Comparative example 7 | 45 | 2358 | 4.4 | 0.22 |
| Comparative example 8 | 42 | 2253 | 4.6 | 0.14 |
| Polyoxymethylene | 60 | 2600 | 6 | 0.21 |
From the above results, it can be seen that:
the physical properties of the polypropylene composite material prepared by the embodiments of the invention are equivalent to those of polyformaldehyde, and the polypropylene composite material can be used as a substitute of polyformaldehyde in the related application fields, so that the production cost is reduced.
The results of examples 1 to 4 show that the mechanical properties and molding shrinkage of the polypropylene composite material obtained are closer to those of polyoxymethylene in the above-mentioned amount range of the present invention.
The results of examples 1, 5 to 6, example 12 and comparative example 1 show that the effect of impregnating the polypropylene molecular chains around the resin fibers and the effect of adhering the resin fibers to the PP molecules can be improved by controlling the melt mass flow rate of the polypropylene, so that the adhesion between the surface of the resin fibers and the PP base material is stronger, and the reinforcing effect of the resin fibers can be exerted. If the flow rate of polypropylene is too high (as in comparative example 1), the filling saturation of the polypropylene with the same volume in the filler is higher, and the shrinkage of the obtained polypropylene composite material product is obviously reduced, and the shrinkage of the polypropylene composite material product is greatly different from that of polyoxymethylene, so that the polypropylene composite material product cannot be applied to the product instead of polyoxymethylene.
The results of example 1, examples 7 to 9, and comparative example 6 show that the mechanical strength (e.g., tensile strength) of the prepared polypropylene composite material tends to be increased and then decreased as the retention length of the resin fibers (in the resin matrix) is increased. The polyamide fibers are too short in length (as in comparative example 6) to provide co-reinforcement; the length of the polyamide fiber is too long, the dispersion in the matrix becomes poor gradually, agglomeration is easy to occur, and the strength of the prepared polypropylene composite material tends to be reduced; and also easily extends to the surface of the composite material, affecting the appearance of the material.
The results of examples 1 and 10 to 11 show that polypropylene composite materials having properties similar to those of polyoxymethylene can be obtained within the selection range of suitable polyamide fibers and glass fibers of the present invention; in particular, the performance of the polypropylene material obtained by using the PA6 fiber is more similar to that of polyoxymethylene, and the modification effect is better.
The results of comparative examples 2 to 7 and example 1 show that the polyamide resin fibers and the glass fibers can jointly enhance the mechanical strength of polypropylene and have proper molding shrinkage, for example, the polyamide fibers are replaced by other types of resin fibers, and only the polyamide fibers are added or not added, so that the mechanical strength and the molding shrinkage of the obtained polypropylene composite material cannot reach the level equivalent to that of the polyoxymethylene resin at the same time.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The polypropylene composite material is characterized by comprising the following components in parts by weight:
88-95 parts of polypropylene;
2-5 parts of polyamide fiber;
1-3 parts of glass fiber;
2-5 parts of a compatilizer;
0.1-0.4 part of alpha nucleating agent;
0-1 part of other additives;
wherein the mass flow rate of the melt of the polypropylene at 230 ℃ under a load of 2.16kg is less than or equal to 11g/10min;
the retention length of the polyamide fiber in the polypropylene composite material is 0.4-3.5 mm.
2. The polypropylene composite material according to claim 1, wherein the polypropylene has a melt mass flow rate of 0.3 to 0.4g/10min at 230 ℃ under a load of 2.16 kg.
3. The polypropylene composite material according to claim 1, wherein the polyamide fibers have a retention length of 1.4 to 3mm in the polypropylene composite material.
4. The polypropylene composite of claim 1, wherein the polyamide in the polyamide fiber is at least one of PA6, PA66, or PA 610.
5. The polypropylene composite according to claim 1, wherein the glass fibers have a diameter of 13 μm or less.
6. The polypropylene composite of claim 1, wherein the alpha nucleating agent is an aryl phosphate salt nucleating agent.
7. The polypropylene composite material of claim 1, wherein the compatibilizer is a maleic anhydride grafted polypropylene.
8. The polypropylene composite of claim 1, wherein the other additives comprise at least one of antioxidants, light stabilizers, or lubricants.
9. The method for preparing the polypropylene composite material according to any one of claims 1 to 8, comprising the steps of:
and mixing polypropylene, polyamide fiber, glass fiber, compatilizer, alpha nucleating agent and other additives according to the formula, and then carrying out melt extrusion at 180-230 ℃ to obtain the polypropylene composite material.
10. Use of the polypropylene composite according to any one of claims 1 to 8 for the preparation of electronic appliances, automotive parts or industrial machinery.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810872A (en) * | 2006-02-23 | 2006-08-02 | 广州金发科技股份有限公司 | Continuous long fiber reinforced composite nylon/polyolefin material and its prepn |
| JP2007091792A (en) * | 2005-09-27 | 2007-04-12 | Toyobo Co Ltd | Organic fiber-reinforced polypropylene resin composition |
| CN106916447A (en) * | 2017-03-02 | 2017-07-04 | 山东道恩高分子材料股份有限公司 | A kind of preparation method of the modified long glass fibres reinforced thermoplastics of aramid fiber |
| CN107345026A (en) * | 2016-05-07 | 2017-11-14 | 秦皇岛天秦装备制造股份有限公司 | A kind of -55 DEG C of impact resistances of low temperature, 70 DEG C of resistance to deformation PP composite materials of high temperature and preparation method thereof |
| CN107903509A (en) * | 2017-11-09 | 2018-04-13 | 南京聚隆科技股份有限公司 | Outer plate material of a kind of overall plastic tail-gate of automobile and preparation method thereof |
| WO2018206815A1 (en) * | 2017-05-12 | 2018-11-15 | École Polytechnique Fédérale De Lausanne (Epfl) | Polyamide material |
| CN109705543A (en) * | 2018-11-14 | 2019-05-03 | 上海长伟锦磁工程塑料有限公司 | Modified long glass fiber reinforced PET/PPO alloy of a kind of aramid fiber and preparation method thereof |
-
2022
- 2022-12-30 CN CN202211726273.5A patent/CN115960414B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007091792A (en) * | 2005-09-27 | 2007-04-12 | Toyobo Co Ltd | Organic fiber-reinforced polypropylene resin composition |
| CN1810872A (en) * | 2006-02-23 | 2006-08-02 | 广州金发科技股份有限公司 | Continuous long fiber reinforced composite nylon/polyolefin material and its prepn |
| CN107345026A (en) * | 2016-05-07 | 2017-11-14 | 秦皇岛天秦装备制造股份有限公司 | A kind of -55 DEG C of impact resistances of low temperature, 70 DEG C of resistance to deformation PP composite materials of high temperature and preparation method thereof |
| CN106916447A (en) * | 2017-03-02 | 2017-07-04 | 山东道恩高分子材料股份有限公司 | A kind of preparation method of the modified long glass fibres reinforced thermoplastics of aramid fiber |
| WO2018206815A1 (en) * | 2017-05-12 | 2018-11-15 | École Polytechnique Fédérale De Lausanne (Epfl) | Polyamide material |
| CN107903509A (en) * | 2017-11-09 | 2018-04-13 | 南京聚隆科技股份有限公司 | Outer plate material of a kind of overall plastic tail-gate of automobile and preparation method thereof |
| CN109705543A (en) * | 2018-11-14 | 2019-05-03 | 上海长伟锦磁工程塑料有限公司 | Modified long glass fiber reinforced PET/PPO alloy of a kind of aramid fiber and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 纤维增强聚丙烯复合材料研究进展;李智鑫，张才前;纺织科技进展(第6期);6-9，52 * |
| 聚丙烯增强改性的研究概况;王丹 等;当代化工;第43卷(第11期);2403-2405 * |
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