CN115838486A - Method for improving long glass fiber-polyolefin composite material interface combination based on non-covalent entanglement - Google Patents
Method for improving long glass fiber-polyolefin composite material interface combination based on non-covalent entanglement Download PDFInfo
- Publication number
- CN115838486A CN115838486A CN202211633209.2A CN202211633209A CN115838486A CN 115838486 A CN115838486 A CN 115838486A CN 202211633209 A CN202211633209 A CN 202211633209A CN 115838486 A CN115838486 A CN 115838486A
- Authority
- CN
- China
- Prior art keywords
- glass fiber
- long glass
- silane coupling
- coupling agent
- polyolefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention belongs to the field of high polymer materials, and discloses a method for improving interface bonding of a long glass fiber-polyolefin composite material based on a non-covalent entanglement effect. The long glass fiber impregnated master batch comprises polyolefin, long glass fiber, a novel silane coupling agent mixture or a novel silane coupling agent mixture, an antioxidant, a lubricant and other various functional auxiliaries. The polyolefin functional master batch contains polyolefin, an antioxidant, a lubricant, a novel silane coupling agent mixture or a novel silane coupling agent mixture and other various functional auxiliaries. The invention improves the interface combination between the long glass fiber and the polyolefin, provides convenience for encapsulation and injection molding in the production process, and greatly improves the mechanical property of the composite material.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a method for improving interface bonding of a long glass fiber-polyolefin composite material based on a non-covalent entanglement effect.
Background
The long glass fiber polyolefin composite material is gradually applied to the fields of automobiles, household appliances and consumer electronics in recent years. While methods for improving the compatibility of glass fibers with the matrix are generally accomplished using conventional silane coupling agent modifications or interfacial compatibilizers. However, the process specificity of the long glass fiber enlarges the effect of the interface action of the glass fiber and the matrix, and also puts higher requirements on interface combination. In fact, since the molecular chain of polyolefin is mainly non-polar, the effect of the common coupling agent system on the polyolefin system is limited, and therefore, it is necessary to research a method for improving the interfacial bonding of the long glass fiber polyolefin system to prepare a long glass fiber-polyolefin product with higher performance and better appearance.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the invention provides a method for improving the interfacial bonding of a long glass fiber-polyolefin composite material based on non-covalent entanglement. The invention utilizes the entanglement among long chain molecules and the interface combination of a long glass fiber polyolefin system to prepare a long glass fiber-polyolefin product with higher performance and better appearance.
The purpose of the invention is realized by the following scheme:
a method for improving long glass fiber-polyolefin composite material interface combination based on non-covalent entanglement, which introduces 0.1-1 wt% of novel silane coupling agent, novel silane coupling agent hydrolysate, novel silane coupling agent oligomer or mixture containing the above substances in the preparation process of the long glass fiber-polyolefin composite material to improve the long glass fiber-polyolefin composite material interface combination;
the long glass fiber-polyolefin composite material is a material with different forms, which is prepared by performing injection molding and other various plastic processing on master batches containing glass fibers with single lengths larger than 3 mm;
the novel silane coupling agent refers to a silane coupling agent with a chemical formula expressed as YSi (X) 3 ) The novel silane coupling agent of (1) is characterized in that Y is a hydrophobic aliphatic functional group containing 5 or more carbon atoms and long chain or long chain branch, X is various oxygen-containing functional groups including hydroxyl, methoxy and ethoxy, chlorine atom or any combination of the above functional groups, and the novel silane coupling agent comprises but is not limited to N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-decyltrimethoxysilane, dodecylmethyldimethoxysilane, dodecyltrimethoxysilane, octadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dodecyltrichlorosilane and the like;
the novel silane coupling agent hydrolysate is a product of the novel silane coupling agent, wherein after water, methanol and ethanol are added, an alcohol exchange reaction is carried out, and a functional group X is replaced by a hydroxyl group;
the novel silane coupling agent oligomer is formed by removing water molecules from hydrolysate of the novel silane coupling agent and contains a Si-O-Si structure;
the introduction mode includes but is not limited to a mode of directly adding the mixture into long glass fiber master batches, functional master batches or mixing before injection molding.
A method for improving long glass fiber-polyolefin composite material interface bonding based on non-covalent entanglement specifically comprises the following steps:
(1) Preparing long glass fiber-polyolefin impregnated master batch by using a long glass fiber impregnated coating machine;
the long glass fiber reinforced polyolefin master batch is prepared from the following components in percentage by mass:
polyolefin: 35 to 80 percent of
Long glass fibers: 20 to 60 percent
Novel silane coupling agents or novel silane coupling agent mixtures: 0.1 to 1 percent
Antioxidant: 0.1 to 0.5 percent
Lubricant: 0.1 to 0.5 percent
Other various functional additives: 0 to 30 percent;
(2) Preparing polyolefin functional master batches;
the polyolefin functional master batch is composed of the following components in percentage by mass:
polyolefin: 70 to 97.7 percent
Antioxidant: 0.1 to 0.8 percent
Lubricant: 0.5 to 1.0 percent;
novel silane coupling agents or novel silane coupling agent mixtures: 0.1 to 1 percent;
other various functional additives: 0 to 30 percent;
(3) Mixing the long glass fiber-polyolefin impregnated master batch and the polyolefin functional master batch, and then carrying out various plastic processing such as injection molding and the like to prepare the plastic product.
In the steps (1) and (2), the polyolefin is a polymer with molecular chains mainly composed of aliphatic chains, such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butylene copolymer, ethylene-octene copolymer and the like;
in the step (1), the long glass fiber has a linear density of 2000 to 4000tex and a fiber diameter of 5 to 40 mu m;
in step (1), the novel silane coupling agent mixture is a novel silane coupling agent, a novel silane coupling agent hydrolysate, a novel silane coupling agent oligomer or a mixture comprising the above;
in the steps (1) and (2), the antioxidant is a chemical auxiliary agent which can inhibit or delay the oxidation of the polyolefin and comprises one or at least two of an antioxidant 1010, an antioxidant 3114, an antioxidant 330, an antioxidant 1790, an antioxidant TNPP, an antioxidant DSTDP, an antioxidant 168 and an antioxidant 626;
in the steps (1) and (2), the lubricant is one or at least two of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax and polypropylene wax;
in the steps (1) and (2), the other various functional additives are additives, fillers and toner which can realize various functions of compatibility, toughening, filling, light stabilization, color matching and the like for the composite material;
in the step (3), the two master batches are mixed according to the proportion of 20-99% of the long glass fiber-polyolefin impregnated master batch and 1-80% of the polyolefin functional master batch, and the long glass fiber impregnated master batch and the functional master batch are mixed and adjusted to 10-80% of the long glass fiber.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention introduces the long-chain aliphatic silane coupling agent into the long glass fiber-polyolefin composite material to improve the interface combination of the long glass fiber and the polyolefin, greatly improves the interface combination between the long glass fiber and the polyolefin, provides convenience for encapsulation and injection molding in the production process, and greatly improves the mechanical property of the composite material.
Drawings
FIG. 1 is a schematic view showing the chemical formula and the grafting mechanism of the novel silane coupling agent used and a typical silane coupling agent used in the conventional art.
FIG. 2 shows the fracture micro-topography of example 1 and comparative examples 1 and 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
In the embodiment, the long glass fiber impregnated master batch is prepared from the following components in percentage by mass: 53.1% of MN90B type polypropylene, 40% of ER4305 type long glass fiber, 0.2% of novel silane coupling agent, 4.6% of compatilizer 5701, and 1010% of antioxidant: 0.1%, antioxidant DSTDP, antioxidant 168, TAF lubricant: 2 percent. The materials are mixed and added into a hopper of a special long glass fiber dipping and coating machine, then the mixture is coated to a glass fiber bundle drawn by a tractor after being preheated, and then the long glass fibers are cut to 12mm by a granulator at a linkage rotating speed after being cooled by water and dried by air.
The functional master batch is prepared from the following components in percentage by mass: 22% of MN90B type polypropylene, 75.7% of 8842 type ethylene-octene copolymer, 1010% of antioxidant: 0.1%, antioxidant DSTDP, compatilizer CMG5701, antioxidant 168, TAF lubricant: total 2%, novel silane coupling agent: 0.2 percent. The materials are extruded by a double-screw extruder, cooled by water, dried by air and cut into granules to obtain the material.
Mixing the long glass fiber impregnated master batch and the functional master batch until the content of the long glass fiber is 30%, and then adding the mixture into an injection molding machine for injection molding to obtain a corresponding plastic product.
Example 2
In the embodiment, the long glass fiber impregnated master batch is prepared from the following components in percentage by mass: 43.1% of MN70 type polypropylene, 50% of ER4305 type long glass fiber, 0.2% of novel silane coupling agent, 4.6% of compatilizer CMG5701, and 1010% of antioxidant: 0.1%, antioxidant DSTDP, antioxidant 168, TAF lubricant: and 2 percent in total. The materials are mixed and then added into a hopper of a special impregnation coating machine for long glass fibers, then the mixture is coated to a glass fiber bundle drawn by a tractor after being preheated, and then the long glass fibers are cut to 12mm by a granulator at a linkage rotating speed after being cooled by water and dried by air.
The functional master batch is prepared from the following components in percentage by mass: 51.1% of MN70 type polypropylene, 46.4% of ethylene-butylene copolymer, 1010% of antioxidant: 0.1%, antioxidant DSTDP, antioxidant 168, TAF lubricant: 2%, novel silane coupling agent: 0.4 percent. The materials are extruded by a double-screw extruder, cooled by water, dried by air and cut into granules to obtain the product.
And mixing the long glass fiber impregnated master batch and the functional master batch until the content of the long glass fiber is 30%, and adding the mixture into an injection molding machine for injection molding to obtain a corresponding plastic product.
Example 3
In the embodiment, the long glass fiber impregnated master batch is prepared from the following components in percentage by mass: 43.3% of MN70 type polypropylene, 50% of ER4305 type long glass fiber, 0.2% of novel silane coupling agent, 4.6% of compatilizer CMG5701, and 1010% of antioxidant: 0.1%, antioxidant DSTDP, antioxidant 168, TAF lubricant: and 2 percent in total. The materials are mixed and then added into a hopper of a special impregnation coating machine for long glass fibers, then the mixture is coated to a glass fiber bundle drawn by a tractor after being preheated, and then the long glass fibers are cut to 12mm by a granulator at a linkage rotating speed after being cooled by water and dried by air.
The functional master batch is prepared from the following components in percentage by mass: 55% of MN70 type polypropylene, 42.3% of ethylene-butylene copolymer, and 1010% of antioxidant: 0.1%, antioxidant DSTDP, antioxidant 168, TAF lubricant: 2%, novel silane coupling agent: 0.6 percent. The materials are extruded by a double-screw extruder, cooled by water, dried by air and cut into granules to obtain the material.
Mixing the long glass fiber impregnated master batch and the functional master batch until the content of the long glass fiber is 30%, and then adding the mixture into an injection molding machine for injection molding to obtain a corresponding plastic product.
Comparative example 1
In the embodiment, the long glass fiber impregnated master batch is prepared from the following components in percentage by mass: 63.3% of MN90B type polypropylene, 40% of ER4305 type long glass fiber, 4.6% of compatilizer, 1010% of antioxidant: 0.1%, antioxidant DSTDP, compatilizer CMG5701, antioxidant 168, TAF lubricant: 2 percent. The materials are mixed and then added into a hopper of a special impregnation coating machine for long glass fibers, then the mixture is coated to a glass fiber bundle drawn by a tractor after being preheated, and then the long glass fibers are cut to 12mm by a granulator at a linkage rotating speed after being cooled by water and dried by air.
The functional master batch is prepared from the following components in percentage by mass: 21.9% of MN90B type polypropylene, 75.7% of 8842 type ethylene-octene copolymer, and 1010% of antioxidant: 0.1%, antioxidant DSTDP, compatilizer CMG5701, antioxidant 168, TAF lubricant: 2%, silane coupling agent KH560:0.2 percent. The materials are extruded by a double-screw extruder, cooled by water, dried by air and cut into granules to obtain the material.
Mixing the long glass fiber impregnated master batch and the functional master batch until the content of the long glass fiber is 30%, and then adding the mixture into an injection molding machine for injection molding to obtain a corresponding plastic product.
Comparative example 2
In the embodiment, the long glass fiber impregnated master batch is prepared from the following components in percentage by mass: 63.3% of MN90B type polypropylene, 40% of ER4305 type long glass fiber, 4.6% of compatilizer, 1010% of antioxidant: 0.1%, antioxidant DSTDP, compatilizer CMG5701, antioxidant 168, TAF lubricant: 2 percent. The materials are mixed and then added into a hopper of a special impregnation coating machine for long glass fibers, then the mixture is coated to a glass fiber bundle drawn by a tractor after being preheated, and then the long glass fibers are cut to 12mm by a granulator at a linkage rotating speed after being cooled by water and dried by air.
The functional master batch is prepared from the following components in percentage by mass: 96.6% of MN90B type polypropylene, 40% of ER4305 type long glass fiber, 4.6% of compatilizer, 1010% of antioxidant: 0.1%, antioxidant DSTDP, compatilizer CMG5701, antioxidant 168, TAF lubricant: 2 percent. The materials are extruded by a double-screw extruder, cooled by water, dried by air and cut into granules to obtain the material.
Mixing the long glass fiber impregnated master batch and the functional master batch until the content of the long glass fiber is 30%, and then adding the mixture into an injection molding machine for injection molding to obtain a corresponding plastic product.
The products obtained in the examples and comparative examples 1 to 3 were subjected to izod notched impact test, drop weight impact test, and low temperature drop weight impact test to obtain the results shown in the following table, and the surface topography of the product and the notched surface were observed by an optical microscope (fig. 2). Comparative example 1 compared with comparative example 2, the cantilever beam notched impact strength of the product is improved by 1kJ/m 2 At the expense of the sample being directly broken when dealing with more complex drop hammer impact tests. It is clear from the combination of FIG. 2 that the glass fibers in comparative example 2 have smooth surfaces, indicating that there is hardly any interfacial interaction, although toThe glass fiber surface of the comparative example 1 is more complicated than that of the comparative example 2, but the surface has much floating fiber and much exposure, which indicates that KH560 only interacts with the compatilizer in the system, but does not have obvious interface action with the matrix. The use of the novel silane coupling agent in the backsight embodiment not only greatly improves the notch impact strength of the cantilever beam, but also keeps the unburst level in the drop hammer impact test, and the surface appearance has no floating fiber and no poor interface combination. The long-chain aliphatic molecules and the polypropylene matrix generate interface entanglement, and non-covalent effects such as dispersion, van der waals force and the like exist at the same time, so that the reinforcing efficiency of the glass fiber is greatly improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for improving long glass fiber-polyolefin composite material interface combination based on non-covalent entanglement is characterized in that a novel silane coupling agent, a novel silane coupling agent hydrolysate, a novel silane coupling agent oligomer or a mixture containing the silane coupling agent oligomer are introduced in the preparation process of a long glass fiber-polyolefin composite material to improve the long glass fiber-polyolefin composite material interface combination.
2. The method for improving the interfacial bonding of the long glass fiber-polyolefin composite material based on the non-covalent entanglement as recited in claim 1, wherein the method comprises the following steps:
the long glass fiber-polyolefin composite material is a material with different forms, which is prepared by carrying out injection molding and other various plastic processing on master batches containing glass fibers with the length of more than 3 mm;
the novel silane coupling agent, novel silane coupling agent hydrolysate, novel silane coupling agent oligomer or mixture containing the same is used in an amount of 0.1 to 1wt%.
3. The method for improving the interfacial bonding of the long glass fiber-polyolefin composite material based on the non-covalent entanglement as recited in claim 1, wherein the method comprises the following steps:
the novel silane coupling agent refers to a silane coupling agent represented by the chemical formula YSi (X) 3 ) The novel silane coupling agent is characterized in that Y is a long-chain or long-chain branched hydrophobic aliphatic functional group containing 5 or more carbon atoms, X is various oxygen-containing functional groups including hydroxyl, methoxy and ethoxy, chlorine atoms or any combination of the above functional groups, and the novel silane coupling agent comprises but is not limited to N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-decyltrimethoxysilane, dodecylmethyldimethoxysilane, dodecyltrimethoxysilane, octadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane and dodecyltrichlorosilane.
4. The method for improving the interfacial bonding of the long glass fiber-polyolefin composite material based on the non-covalent entanglement as recited in claim 1, wherein the method comprises the following steps: the novel silane coupling agent hydrolysate is a product of the novel silane coupling agent, wherein after water, methanol and ethanol are added, an alcohol exchange reaction is carried out, and a functional group X is replaced by a hydroxyl group.
5. The method for improving the interfacial bonding of the long glass fiber-polyolefin composite material based on the non-covalent entanglement as recited in claim 1, wherein the method comprises the following steps: the novel silane coupling agent oligomer refers to an oligomer containing a Si-O-Si structure formed after water molecules are removed from a hydrolysate of the novel silane coupling agent.
6. The method for improving the interfacial bonding of the long glass fiber-polyolefin composite material based on the non-covalent entanglement as recited in claim 1, wherein the method comprises the following steps: the introduction mode includes but is not limited to direct addition to the long glass fiber master batch, the functional master batch or mixing before injection molding.
7. A method for improving long glass fiber-polyolefin composite material interface bonding based on non-covalent entanglement is characterized by comprising the following steps:
(1) Preparing long glass fiber-polyolefin impregnated master batch by using a long glass fiber impregnated coating machine;
the long glass fiber reinforced polyolefin master batch is prepared from the following components in percentage by mass:
polyolefin: 35 to 80 percent of
Long glass fibers: 20 to 60 percent
Novel silane coupling agents or novel silane coupling agent mixtures: 0.1 to 1 percent
Antioxidant: 0.1 to 0.5 percent
Lubricant: 0.1 to 0.5 percent
Other various functional additives: 0 to 30 percent;
(2) Preparing polyolefin functional master batches;
polyolefin: 70 to 97.7 percent
Antioxidant: 0.1 to 0.8 percent
Lubricant: 0.5 to 1.0 percent;
novel silane coupling agents or novel silane coupling agent mixtures: 0.1 to 1 percent;
other various functional additives: 0 to 30 percent;
(3) Mixing the long glass fiber-polyolefin impregnated master batch and the polyolefin functional master batch, and then carrying out plastic processing to prepare the plastic product.
8. The method for improving the interfacial bonding of the long glass fiber-polyolefin composite material based on the non-covalent entanglement as recited in claim 7, wherein:
in the step (1), the polyolefin is at least one of polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butylene copolymer and ethylene-octene copolymer;
in the step (1), the long glass fiber has a linear density of 2000 to 4000tex and a fiber diameter of 5 to 40 mu m;
in step (1), the novel silane coupling agent mixture is a novel silane coupling agent, a novel silane coupling agent hydrolysate, a novel silane coupling agent oligomer, or a mixture comprising the above.
9. The method for improving the interfacial bonding of long glass fiber-polyolefin composite based on non-covalent entanglement, as claimed in claim 7, wherein:
in the steps (1) and (2), the antioxidant is at least one of an antioxidant 1010, an antioxidant 3114, an antioxidant 330, an antioxidant 1790, an antioxidant TNPP, an antioxidant DSTDP, an antioxidant 168 and an antioxidant 626;
in the steps (1) and (2), the lubricant is at least one of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax and polypropylene wax;
in the step (2), the other various functional additives are at least one of additives, fillers and toner for realizing compatibility, toughening, filling, light stabilization and color matching functions of the composite material.
10. The method for improving the interfacial bonding of the long glass fiber-polyolefin composite material based on the non-covalent entanglement as recited in claim 7, wherein:
in the step (3), the two master batches are mixed according to the proportion of 20-99% of the long glass fiber-polyolefin impregnated master batch and 1-80% of the polyolefin functional master batch, and the long glass fiber impregnated master batch and the functional master batch are mixed until the length of the long glass fiber is 10-80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211633209.2A CN115838486A (en) | 2022-12-19 | 2022-12-19 | Method for improving long glass fiber-polyolefin composite material interface combination based on non-covalent entanglement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211633209.2A CN115838486A (en) | 2022-12-19 | 2022-12-19 | Method for improving long glass fiber-polyolefin composite material interface combination based on non-covalent entanglement |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115838486A true CN115838486A (en) | 2023-03-24 |
Family
ID=85578828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211633209.2A Pending CN115838486A (en) | 2022-12-19 | 2022-12-19 | Method for improving long glass fiber-polyolefin composite material interface combination based on non-covalent entanglement |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115838486A (en) |
-
2022
- 2022-12-19 CN CN202211633209.2A patent/CN115838486A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114196115B (en) | Polypropylene material and preparation method thereof | |
| CN112608553A (en) | Plant fiber reinforced polypropylene composite material and preparation method thereof | |
| Bettini et al. | Effect of sawdust surface treatment and compatibilizer addition on mechanical behavior, morphology, and moisture uptake of polypropylene/sawdust composites | |
| CN101880432B (en) | Polyhydric graft ethylene-octene copolymer and preparation method thereof | |
| CN1415661A (en) | Cross blend material based on polycarbonate and its prepn. method | |
| CN114230953B (en) | Dimensionally stable mechanically reinforced transparent resin composition, and preparation method and application thereof | |
| CN1847316A (en) | Resin/hollow glass bead composite material and its prepn process | |
| CN115838486A (en) | Method for improving long glass fiber-polyolefin composite material interface combination based on non-covalent entanglement | |
| CN101215410A (en) | Polybutylene terephthalate modified resin | |
| CN116875009A (en) | Reinforced and toughened polylactic acid composite material and preparation method and application thereof | |
| CN115353687B (en) | Cellulose reinforced polypropylene composition and preparation method and application thereof | |
| JP6373727B2 (en) | Resin molded body | |
| CN115353722A (en) | Glass fiber reinforced PET material and preparation method thereof | |
| Gatenholm et al. | Cellulose-polymer composites with improved properties | |
| GB2030160A (en) | Mouldable compositions based on a thermoplastic polymer glass fibres and a bis-maleimide | |
| CN1158348C (en) | Thermoplastic composition capable of being used as fan material | |
| HOSSEN et al. | IMPROVED MECHANICAL PROPERTIES OF SILANE TREATED JUTE/POLYETHYLENE/CLAY NANOCOMPOSITES. | |
| CN114213792A (en) | PMMA alloy material with high scratch resistance and preparation method thereof | |
| CN110760124B (en) | Glass fiber waste silk reinforced polypropylene composite material and preparation method thereof | |
| CN114437538A (en) | Long glass fiber reinforced nylon composite material and preparation method and application thereof | |
| EP1362079A1 (en) | Polypropylene resin composition with improved surface hardness and scratch resistance properties | |
| CN115260709B (en) | Low-temperature-resistant impact-resistant PET modified material and preparation method thereof | |
| CN111087696A (en) | Lightweight, low-cost, low-odor and degradable natural fiber reinforced polypropylene reclaimed material and preparation method thereof | |
| CN109504028A (en) | Resin combination and resin-formed body | |
| CN112300441B (en) | Polypropylene compound with high surface polarity and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |