CN110964258A - Low-shrinkage polypropylene composition and preparation method and application thereof - Google Patents
Low-shrinkage polypropylene composition and preparation method and application thereof Download PDFInfo
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- CN110964258A CN110964258A CN201811145151.0A CN201811145151A CN110964258A CN 110964258 A CN110964258 A CN 110964258A CN 201811145151 A CN201811145151 A CN 201811145151A CN 110964258 A CN110964258 A CN 110964258A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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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Abstract
The invention belongs to the field of polypropylene materials, and discloses a low-shrinkage polypropylene composition, a preparation method and an application thereof, wherein the low-shrinkage polypropylene composition contains 10-30 parts by weight of polypropylene-butadiene copolymer, 1-10 parts by weight of petroleum resin, 10-30 parts by weight of nano inorganic filler and 0.05-4 parts by weight of processing aid, based on 100 parts by weight of polypropylene-butadiene copolymer. The polypropylene material prepared from the polypropylene composition is suitable for preparing 3D printing wires, the wires are uniform in diameter and smooth in surface, the printed product is low in shrinkage rate, and the product is good in appearance.
Description
Technical Field
The invention belongs to the field of polypropylene materials, and particularly relates to a low-shrinkage polypropylene composition, a preparation method thereof and application of the low-shrinkage polypropylene composition in 3D printing.
Background
Polypropylene is a common polymer material, and has wide application in industry and life. Due to the symmetrical regularity of the structure, the polypropylene has high crystallization speed and large shrinkage rate, and in practical application, the appearance of products such as deformation and the like is not perfect and the mechanical property is lost. In order to reduce the shrinkage of polypropylene, a copolymerization component is generally added to destroy the crystallization ability of polypropylene, thereby achieving the purpose of reducing the shrinkage.
Patent document 02144845.0 discloses a novel polypropylene material with ultra-low shrinkage, which comprises polypropylene, polyethylene, ethylene propylene diene monomer, mica powder, an antioxidant, an auxiliary antioxidant, calcium stearate, and a titanate coupling agent CSC. The material is low in price, the cost reduction rate is 91%, and the shrinkage rate can reach 0.4% -0.8%.
Patent document 201510606738.7 discloses a low shrinkage ratio modified polypropylene material, which comprises polypropylene copolymer, four-footed zinc oxide whisker, inorganic powder, α nucleating agent, antioxidant and high density polyethylene, wherein the shrinkage ratio of polypropylene is reduced and the mechanical properties of the material are improved by the synergistic effect of the four-footed zinc oxide whisker, the inorganic powder and the high density polyethylene.
Patent document 201380081112.8 discloses a polypropylene composition with reduced shrinkage and balanced mechanical properties comprising a propylene homopolymer, two heterophasic propylene copolymers, an elastomeric ethylene copolymer and an inorganic filler.
Patent document 201410251238.1 discloses a low shrinkage polypropylene composite material prepared by blending and modifying a mixture of metallocene linear low density polyethylene, a toughening agent and talc powder with low shrinkage polypropylene, which solves the problem of high shrinkage of polypropylene and is easy and convenient to operate.
In summary, the main methods for reducing the shrinkage of polypropylene are: the principle of increasing copolymerization component, inorganic matter or rubber component is to inhibit the crystallization ability of polypropylene.
Disclosure of Invention
In view of the above situation, the present invention aims to provide a low shrinkage polypropylene composition, a preparation method and applications thereof. The polypropylene composition with low shrinkage is obtained by combining the polypropylene, polyethylene, petroleum resin, nano inorganic filler and the like, and can be used as a preparation raw material of 3D printing consumables.
The invention provides a low-shrinkage polypropylene composition, which contains 100 parts by weight of polypropylene-co-polypropylene, 10-30 parts by weight of polyethylene, 1-10 parts by weight of petroleum resin, 10-30 parts by weight of nano inorganic filler and 0.05-4 parts by weight of processing aid.
The second aspect of the invention provides a preparation method of the low-shrinkage polypropylene composition, which comprises the steps of adding the components contained in the low-shrinkage polypropylene composition into a high-speed stirrer according to the content of the components, mixing, adding the mixed materials into a double-screw extruder, drawing yarns through an oral die, cooling through a water tank, and granulating to obtain the low-shrinkage polypropylene composition.
A third aspect of the invention provides the use of the low shrinkage polypropylene composition described above in 3D printing.
The invention can reduce the crystallinity of polypropylene by adding a small amount of polyethylene and petroleum resin, can reduce the shrinkage rate by adding nano inorganic filler, improves the toughness and tensile property, and in addition, the addition of processing aids such as slipping agents is mainly used for improving the surface smoothness of wires, and limits the dosage of each component according to the application of the polypropylene composition. The polypropylene material prepared by the polypropylene composition and the method is suitable for preparing 3D printing wires, the wires are uniform in diameter, smooth in surface, low in shrinkage rate of printed products and good in appearance of the printed products, and can be widely applied to the field of fused deposition rapid forming.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, the present invention provides a low shrinkage polypropylene composition, which comprises, based on 100 parts by weight of a polypropylene-co-polypropylene, 10 to 30 parts by weight of polyethylene, 1 to 10 parts by weight of petroleum resin, 10 to 30 parts by weight of a nano inorganic filler, and 0.05 to 4 parts by weight of a processing aid.
In order to be more suitable for preparing 3D printing wire materials, preferably, the content of the polyethylene is 10-25 parts by weight, the content of the petroleum resin is 5-10 parts by weight, the content of the nano inorganic filler is 10-20 parts by weight, and the content of the processing aid is 0.1-1 part by weight, based on 100 parts by weight of the polypropylene-butadiene copolymer.
Preferably, the melt index of the propane-butadiene copolymerized polypropylene at 230 ℃ under a load of 2.16kg is 10-30 g/10 min.
Preferably, the polyethylene is linear low density polyethylene, and the number average molecular weight is 50000-300000.
In the invention, petroleum resin is added into polypropylene, so that the crystallinity of the polypropylene can be obviously reduced. The petroleum resin is a thermoplastic resin produced by the processes of pretreatment, polymerization, distillation and the like, and is not a high polymer but an oligomer, wherein the petroleum resin is a C5-C9 fraction which is a byproduct in petroleum cracking. The petroleum resin has good cohesiveness, good intersolubility with rubber and resin, good fluidity, good viscosity, and outstanding initial viscosity, and can improve the wettability of the main material. Preferably, the petroleum resin is C5-C9 petroleum resin which is an oligomer with the molecular weight of 300-3000.
In addition, since petroleum resin is a low-melting organic substance, and is easily precipitated when the content is high, and is easily broken when the 3D printing material is prepared and drawn, the content is limited to 1 to 10 parts by weight, preferably 5 to 10 parts by weight.
In the invention, the nano inorganic filler is mainly added to reduce the shrinkage rate of polypropylene, improve the melt strength and facilitate the preparation of wires, and can be selected from nano inorganic fillers conventionally used in the field. Preferably, the nano inorganic filler is selected from one or more of nano calcium carbonate, talcum powder, nano silica, carbon nano tube and carbon black.
In addition, when the content of the nano inorganic filler is too high, the toughness is reduced, and the wire is easy to break in the winding process of preparing the wire material; the content is too low and does not play a role, so the content of the nano inorganic filler is limited to 10 to 30 parts by weight, preferably 10 to 20 parts by weight.
In the invention, the processing aid can be added according to specific application requirements, and the type and the adding amount of the processing aid are conventional in the field.
Preferably, the processing aid is a slipping agent and/or an antioxidant, the slipping agent is 0.05-0.5 part by weight, more preferably 0.1-0.2 part by weight, and the antioxidant is 0.1-3 parts by weight, more preferably 0.2-0.8 part by weight, based on 100 parts by weight of the polypropylene-co-polypropylene.
In order to improve the surface roughness of the 3D printing wire, the processing aid slipping agent is added. Preferably, the slip agent is one or more of oleamide, erucamide and ethylene bis stearamide.
According to the invention, the antioxidant is selected from one or two of antioxidant 1010, antioxidant 1076, antioxidant 2246, antioxidant CA, antioxidant 1098, antioxidant 168, antioxidant 626 and antioxidant 636.
Preferably, the antioxidant is an antioxidant 1098 and an antioxidant 168, and the mass ratio of the antioxidant 1098 to the antioxidant 168 is 1: 0.8-1.2, and more preferably 1: 1.
Preferably, the low-shrinkage polypropylene composition contains 10 to 30 parts by weight of nano-powder rubber, more preferably 20 to 30 parts by weight of nano-powder rubber, based on 100 parts by weight of the polypropylene-co-polypropylene.
Preferably, the nano-powder rubber is one or more of fully vulcanized styrene-butadiene rubber, fully vulcanized carboxylated styrene-butadiene rubber, fully vulcanized nitrile-butadiene rubber, fully vulcanized carboxylated nitrile-butadiene rubber, fully vulcanized acrylate rubber, fully vulcanized ethylene-vinyl acetate rubber, fully vulcanized silicone rubber and fully vulcanized butadiene-styrene-pyridine rubber which are subjected to radiation crosslinking.
According to a second aspect of the present invention, the present invention provides a preparation method of the above low shrinkage polypropylene composition, wherein the components contained in the low shrinkage polypropylene composition are added into a high speed mixer according to the content of the components to be mixed, the mixed materials are added into a double screw extruder, and after drawing through an oral die, the raw materials are cooled in a water tank and granulated to obtain the low shrinkage polypropylene composition.
In the invention, the melting temperature of the low-shrinkage polypropylene composition in a double-screw extruder is 190-210 ℃, and the other parameters which are not limited belong to the conventional technical means in the field.
According to a third aspect of the present invention, the present invention provides the use of the low shrinkage polypropylene composition as described above in 3D printing.
The polypropylene material prepared by the polypropylene composition and the method is used for preparing 3D printing wires, the wires are uniform in diameter and smooth in surface, the printed product is low in shrinkage rate, and the product is good in appearance.
Specific embodiments of the present invention will be described in more detail below.
The raw materials used in the following examples and comparative examples are as follows:
polypropylene-co-polypropylene, MT18S, manufactured by Zhenhai refining Co;
polyethylene, LD605, manufactured by yanshan petrochemical company;
styrene-butadiene latex (fully vulcanized styrene-butadiene rubber) provided by Beijing chemical research institute;
petroleum resin, OPPERA, EXXON MOBILE;
nano calcium carbonate, produced by ruicheng xintai nanomaterials ltd;
erucamide, produced by Haomi chemical Co., Ltd, Guangzhou;
antioxidant 1098, antioxidant 168, produced by basf bus, germany.
The specific formulations of the examples and comparative examples are shown in table 1, wherein the materials are in parts by weight.
The preparation method of the polypropylene composition sample comprises the following steps: mixing the polypropylene-butadiene copolymer, polyethylene, nano powder rubber, petroleum resin, nano inorganic filler, slipping agent and antioxidant in an amount shown in Table 1 in a high-speed stirrer, adding into a double-screw extruder, melting at 190-210 ℃, drawing yarns through an oral die, cooling by a water tank, and granulating.
TABLE 1
After the pellets obtained in examples 1 to 8 and comparative examples 1 to 2 were charged into an injection molding machine and injection-molded (the temperature of each stage of the injection molding machine was 180 ℃, 190 ℃, 210 ℃, 210 ℃, 200 ℃, the holding pressure was 50MPa, the holding time was 60s, and the cooling time was 10s), injection-molded samples were prepared and tested, and the specific test results are shown in table 2.
The physical property test of the injection molding sample is carried out according to the national standard respectively: the tensile strength is tested according to GB/T1040-2006; the impact strength of the notch of the simply supported beam is tested according to GB/T1043 + 1993; shrinkage was measured according to GB/T17037.4-2003.
TABLE 2
As can be seen from Table 2, the unmodified polypropylene has a higher shrinkage and a lower impact strength; after modification, the shrinkage rate of polypropylene is greatly reduced, the toughness is improved, and the tensile strength is not obviously reduced; the effect is better when the ingredient composition of the application is adopted for modification; and the formulations in the preferred range of the present application have better properties than the formulations in the non-preferred range.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (12)
1. The low-shrinkage polypropylene composition is characterized by comprising 100 parts by weight of polypropylene-co-polypropylene, 10-30 parts by weight of polyethylene, 1-10 parts by weight of petroleum resin, 10-30 parts by weight of nano inorganic filler and 0.05-4 parts by weight of processing aid.
2. The low shrinkage polypropylene composition according to claim 1, wherein the polyethylene is contained in an amount of 10 to 25 parts by weight, the petroleum resin is contained in an amount of 5 to 10 parts by weight, the nano inorganic filler is contained in an amount of 10 to 20 parts by weight, and the processing aid is contained in an amount of 0.1 to 1 part by weight, based on 100 parts by weight of the polypropylene copolymer.
3. The low shrinkage polypropylene composition of claim 1, wherein the polypropylene copolymer has a melt index of 10 to 30g/10min at 230 ℃ under a 2.16kg load; the polyethylene is linear low-density polyethylene, and the number average molecular weight is 50000-300000.
4. The low shrinkage polypropylene composition according to claim 1, wherein the petroleum resin is a C5-C9 petroleum resin.
5. The low shrinkage polypropylene composition of claim 1, wherein the nano inorganic filler is selected from one or more of nano calcium carbonate, talc, nano silica, carbon nanotubes, and carbon black.
6. The low-shrinkage polypropylene composition according to claim 1, wherein the processing aid is a slipping agent and/or an antioxidant, the slipping agent is 0.05 to 0.5 part by weight, preferably 0.1 to 0.2 part by weight, and the antioxidant is 0.1 to 3 parts by weight, preferably 0.2 to 0.8 part by weight, based on 100 parts by weight of the propylene-butylene copolymer polypropylene.
7. The low shrinkage polypropylene composition of claim 6, wherein the slip agent is one or more of oleamide, erucamide, and ethylene bis stearamide.
8. The low shrinkage polypropylene composition of claim 6, wherein the antioxidant is selected from one or two of antioxidant 1010, antioxidant 1076, antioxidant 2246, antioxidant CA, antioxidant 1098, antioxidant 168, antioxidant 626 and antioxidant 636; preferably an antioxidant 1098 and an antioxidant 168, wherein the mass ratio of the antioxidant 1098 to the antioxidant 168 is 1: 0.8-1.2.
9. The low shrinkage polypropylene composition according to any one of claims 1 to 8, wherein the low shrinkage polypropylene composition comprises 10 to 30 parts by weight, preferably 20 to 30 parts by weight of nano-powder rubber based on 100 parts by weight of the trimethylene co-polypropylene.
10. The low shrinkage polypropylene composition of claim 9, wherein the nano-powder rubber is one or more of radiation crosslinked fully vulcanized styrene-butadiene rubber, fully vulcanized carboxylated styrene-butadiene rubber, fully vulcanized nitrile rubber, fully vulcanized carboxylated nitrile rubber, fully vulcanized acrylate rubber, fully vulcanized ethylene vinyl acetate rubber, fully vulcanized silicone rubber, and fully vulcanized vinylpyridine butadiene rubber.
11. The method for preparing a low shrinkage polypropylene composition as claimed in any one of claims 1 to 10, wherein the components contained in the low shrinkage polypropylene composition are added into a high speed mixer according to the content thereof for mixing, the mixed material is added into a double screw extruder, and after drawing yarns through an oral die, the polypropylene composition is cooled by a water tank and granulated to obtain the low shrinkage polypropylene composition.
12. Use of the low shrinkage polypropylene composition according to any one of claims 1 to 10 for 3D printing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114621517A (en) * | 2020-12-08 | 2022-06-14 | 中国石油天然气股份有限公司 | Polypropylene composition for fused deposition 3D printing and preparation method thereof |
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| CN102002186A (en) * | 2010-11-02 | 2011-04-06 | 苏州旭光聚合物有限公司 | Mineral filled low-shrinkage modified polypropylene composite material and preparation method thereof |
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| CN102002186A (en) * | 2010-11-02 | 2011-04-06 | 苏州旭光聚合物有限公司 | Mineral filled low-shrinkage modified polypropylene composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621517A (en) * | 2020-12-08 | 2022-06-14 | 中国石油天然气股份有限公司 | Polypropylene composition for fused deposition 3D printing and preparation method thereof |
| CN114621517B (en) * | 2020-12-08 | 2023-06-30 | 中国石油天然气股份有限公司 | Polypropylene composition for fused deposition 3D printing and preparation method thereof |
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