CN113265103A - Low-permeability PPR composition and preparation method and application thereof - Google Patents
Low-permeability PPR composition and preparation method and application thereof Download PDFInfo
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- CN113265103A CN113265103A CN202110297934.6A CN202110297934A CN113265103A CN 113265103 A CN113265103 A CN 113265103A CN 202110297934 A CN202110297934 A CN 202110297934A CN 113265103 A CN113265103 A CN 113265103A
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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
- C08L23/12—Polypropene
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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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
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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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention provides a PPR composition with low air permeability, a preparation method and an application thereof, wherein the PPR composition comprises the following components in parts by weight: 80-100 parts of polypropylene resin; 5-9 parts of nano aluminum particles; 9-22 parts of carbon fiber; 6-13 parts of graphite; 10-18 parts of polyvinyl alcohol; 5-15 parts of a lubricant. The PPR composition has good low air permeability, and the maximum value of the air permeability is 0.932cm3/m2 .24h.0.1MPa。
Description
Technical Field
The invention relates to the technical field of plastic pipes, in particular to a low-permeability PPR composition, and a preparation method and application thereof.
Background
The product of polypropylene random copolymer (PPR) has the characteristics of good toughness, high strength, excellent processing performance, good creep resistance at higher temperature and high transparency. Compared with traditional cast iron pipes, galvanized steel pipes, cement pipes and other products, the PPR pipe has the advantages of energy conservation, material conservation, environmental protection, light weight, high strength, corrosion resistance, smooth inner wall, no scaling, simple and convenient construction and maintenance, long service life and the like, and is widely applied to the fields of buildings, municipal administration, industry, agriculture and the like, such as building water supply and drainage, urban and rural water supply and drainage, urban gas, electric power and optical cable sheaths, industrial fluid delivery, agricultural irrigation and the like.
Along with the rapid development of economy, people have proposed higher requirement to the material performance that uses in the living environment, especially with people's life closely related PPR tubular product, the PPR tubular product is buried in the wall body for a long time, if the air gets into in the tubular product, then the tubular product internal surface can be attached to and breed bacterial microorganism, form some substances similar to mucosa appearance, still can form a large amount of incrustation scale impurity when deriving seriously, it is difficult to wash well through the natural pressure of water, seriously influence quality of water, consequently, prevent that the air from getting into inside just can solving above-mentioned problem of tubular product.
For example, chinese patent (CN101407606A) discloses a novel beta-crystalline polypropylene (beta PP-R) composite material with improved oxygen barrier properties, which is obtained by the synergy of beta nucleating agent, rare earth nanoparticles and sheet-like metallic aluminum multi-component material, but the low air permeability of the composite material is not good.
Disclosure of Invention
The invention provides a low-permeability PPR composition to overcome the defect of poor low permeability.
It is another object of the present invention to provide a process for the preparation of said low permeability PPR composition.
It is another object of the present invention to provide the use of said low permeability PPR composition.
In order to achieve the purpose, the invention adopts the technical scheme that:
a low permeability PPR composition comprising the following components in parts by weight:
according to the invention, the nano aluminum particles, the carbon fibers, the graphite and the polyvinyl alcohol are blended, so that a layer of compact film can be formed in the polypropylene resin, the air permeability of the polypropylene resin can be greatly reduced, and oxygen in the air is prevented from entering the PPR pipe prepared from the composition. The nano aluminum particles, the carbon fibers and the graphite are uniformly dispersed in the polypropylene containing the polyvinyl alcohol to form a cross-linked net structure, the carbon fibers and the graphite can improve the strength of the net structure, and the nano aluminum particles are dispersed and attached in the net structure of the polyvinyl alcohol to improve the low air permeability.
Preferably, the average particle size of the nano aluminum particles is 20-60 nm.
When the average particle size of the nano aluminum particles is between 20nm and 60nm, the dispersing effect of the nano aluminum particles is better, and the low air permeability can be further improved.
Preferably, the diameter of the carbon fiber is 5-7 μm.
When the diameter of the carbon fiber is 5-7 mu m, the carbon fiber can be better distributed in polypropylene, and the mechanical property is better; if the carbon fiber diameter is too long, the toughness of the polypropylene is lowered, and if it is too short, the air permeability of the polypropylene resin is increased.
Preferably, the particle size of the graphite is 2000-5000 meshes.
When the average particle size of the graphite is 2000-5000, the graphite can be better compatible with carbon fibers, and the strength is improved.
Preferably, the molecular weight of the polyvinyl alcohol is 18000-20000.
When the molecular weight of the polyvinyl alcohol is 18000-20000, a good net structure can be formed, the net structure with the excessively low molecular weight is loose, and the air permeability is increased; the polypropylene resin is easily deteriorated due to an excessively high molecular weight.
Preferably, the lubricant is a mixture of calcium stearate and zinc stearate.
Preferably, the composition further comprises an anti-uv agent.
6-17 parts of the anti-ultraviolet agent; the ultraviolet resistant agent is 2- (2H-benzotriazol-2-yl) -4, 6-di (1-methyl-1-phenylethyl) phenol.
The preparation method of the low-permeability PPR composition comprises the following steps:
s1, weighing polypropylene, nano aluminum particles, carbon fibers, graphite, polyvinyl alcohol, an ultraviolet-proof agent and a lubricant according to a proportion, and uniformly mixing to obtain a premix;
s2, extruding and molding the premix obtained in the step S1 in an extruder to obtain the low-permeability PPR composition.
Preferably, the temperature of the extruder is 180-220 ℃.
A PPR pipe is prepared from the low-permeability PPR composition.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a low-permeability PPR composition, wherein a pipe is prepared by blending polypropylene resin, nano aluminum particles, carbon fibers and graphite, wherein the nano aluminum particles, the carbon fibers and the graphite are uniformly dispersed in polypropylene containing polyvinyl alcohol to form a cross-linked net-shaped structure, the carbon fibers and the graphite can improve the strength of the net-shaped structure, and the nano aluminum particles are dispersed in the net-shaped structure to improve the low permeability. The maximum value of the air permeability of the PPR composition is 0.932cm3/m2 .24h.0.1MPa。
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention in any way. The reagents, methods and apparatus employed in the present invention are conventional in the art, unless otherwise specified.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Polypropylene resin: atactic polypropylene;
nano aluminum particles a: the average grain diameter is 10 nm;
nano aluminum particles B: the average grain diameter is 20 nm;
nano aluminum particles C: the average grain diameter is 40 nm;
nano aluminum particles D: the average grain diameter is 70 nm;
nano aluminum particles E: the average particle size is 90 nm;
flake nano aluminum: is commercially available
Carbon fiber A: the diameter is 2 mu m;
carbon fiber B: diameter 5 μm;
carbon fiber C: diameter 6 μm;
carbon fiber D: diameter 7 μm;
carbon fiber E: diameter 9 μm;
graphite: the grain size is 2000 meshes;
polyvinyl alcohol A: molecular weight 15000;
polyvinyl alcohol B: a molecular weight of 18000;
polyvinyl alcohol C: a molecular weight of 19000;
polyvinyl alcohol D: molecular weight 20000;
polyvinyl alcohol E: a molecular weight of 22000;
anti-ultraviolet agent: exxelor PO 1020;
lubricant: a mixture of calcium stearate and zinc stearate.
The above reagents are all commercially available.
The PPR pipe is prepared by the following method in the following examples and comparative examples, and the components are weighed according to the weight ratio shown in the table 1-2; the method comprises the following specific steps:
s1, weighing polypropylene resin, nano aluminum particles, carbon fibers, graphite, polyvinyl alcohol, an ultraviolet-proof agent and a lubricant according to a proportion, adding the mixture into a high-speed mixer, uniformly mixing at a mixing speed of 700r/min for 20min to obtain a premix;
s2, extruding and molding the premix obtained in the step S1 in an extruder to obtain a PPR pipe with low air permeability; the temperature of the extruder is 180-220 ℃.
Examples 1 to 5
Examples 1-5 provide a series of low permeability PPR compositions, the specific formulation of which is shown in Table 1, and the effect of the average particle size of the nano-aluminum particles on the air permeability is mainly explored.
TABLE 1 formulations (parts) of examples 1 to 5
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Polypropylene resin | 90 | 90 | 90 | 90 | 90 |
| Nano aluminum particles A | 6 | — | — | — | — |
| Nano aluminum particles B | — | 6 | — | — | — |
| Nano aluminum particles C | — | — | 6 | — | — |
| Nano aluminum particles D | — | — | — | 6 | — |
| Nano-aluminum particles E | — | — | — | — | 6 |
| Carbon fiber C | 10 | 10 | 10 | 10 | 10 |
| Graphite | 8 | 8 | 8 | 8 | 8 |
| Polyvinyl alcohol B | 12 | 12 | 12 | 12 | 12 |
| Lubricant agent | 8 | 8 | 8 | 8 | 8 |
Examples 6 to 11
Examples 6-9 provide a series of low permeability PPR compositions, the specific formulations of which are shown in Table 2, with the effect of carbon fiber diameter on air permeability being primarily explored.
TABLE 2 formulations (parts) of examples 6 to 11
| Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | |
| Polypropylene resin | 90 | 90 | 90 | 90 | 80 | 100 |
| Nano aluminum particles C | 6 | 6 | 6 | 6 | 9 | 5 |
| Carbon fiber C | — | — | — | — | 22 | 9 |
| Carbon fiber A | 10 | — | — | — | — | — |
| Carbon fiber B | — | 10 | — | — | — | — |
| Carbon fiber D | — | — | 10 | — | — | — |
| Carbon fiber E | — | — | — | 10 | — | — |
| Graphite | 8 | 8 | 8 | 8 | 6 | 13 |
| Polyvinyl alcohol B | 12 | 12 | 12 | 12 | 18 | 10 |
| Anti-ultraviolet agent | — | — | — | — | 6 | 17 |
| Lubricant agent | 8 | 8 | 8 | 8 | 15 | 5 |
Examples 12 to 15 and comparative examples 1 to 3
Examples 12-15 provide a series of low permeability PPR compositions, primarily investigating the effect of the molecular weight of polyvinyl alcohol on air permeability; comparative examples 1-3 provide a series of PPR compositions, the specific formulations are shown in Table 3.
TABLE 3 formulations (parts) of examples 12 to 15 and comparative examples 1 to 3
The PPR pipes with low gas permeability prepared in the above examples and comparative examples were subjected to the following performance tests, according to the following standards and methods:
1. permeability was tested according to ASTM E2178-2001 with oxygen as the test gas;
2. impact strength: tested according to GB/T14152-2001.
TABLE 4 data for examples and comparative examples
| Air permeability/cm3/m2.24h.0.1MPa | Impact strength | |
| Example 1 | 0.916 | 50/50 has no damage |
| Example 2 | 0.865 | 50/50 has no damage |
| Example 3 | 0.856 | 50/50 has no damage |
| Example 4 | 0.877 | 50/50 has no damage |
| Example 5 | 0.923 | 50/50 has no damage |
| Example 6 | 0.870 | 50/50 has no damage |
| Example 7 | 0.860 | 50/50 has no damage |
| Example 8 | 0.873 | 50/50 has no damage |
| Example 9 | 0.875 | 49/50 has no damage |
| Example 10 | 0.932 | 50/50 has no damage |
| Example 11 | 0.924 | 50/50 has no damage |
| Example 12 | 0.875 | 50/50 has no damage |
| Example 13 | 0.870 | 50/50 has no damage |
| Example 14 | 0.855 | 50/50 has no damage |
| Example 15 | 0.850 | 49/50 has no damage |
| Comparative example 1 | 1.963 | 50/50 has no damage |
| Comparative example 2 | 1.625 | 50/50 has no damage |
| Comparative example 3 | 1.453 | 50/50 has no damage |
From examples 1 to 5, the average particle size of the nano aluminum particles has an influence on the air permeability, and the air permeability is most excellent when the average particle size is 20 to 70 nm. From examples 6 to 9, the carbon fibers with the diameter of 5 to 7 μm can be better distributed in polypropylene, and have good mechanical properties and good air permeability; if the carbon fiber diameter is too long, the toughness of the polypropylene is lowered, and if it is too short, the air permeability of the polypropylene resin is increased. From examples 12 to 15, when the molecular weight of the polyvinyl alcohol is 18000 to 20000, a good network structure can be formed, and when the molecular weight is too low, the network structure is loose, and the air permeability is increased; the polypropylene resin is easily deteriorated due to an excessively high molecular weight.
From comparative examples 1 to 3, when no nano aluminum particles or polyvinyl alcohol are added, the air permeability effect is poor, which indicates that the air permeability can be reduced only by the combined action of the nano aluminum particles and the polyvinyl alcohol. When flake aluminum is added, the low air permeation effect is also poor.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. It will be apparent to those skilled in the art that other variations and modifications can be made on the basis of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A PPR composition with low air permeability is characterized by comprising the following components in parts by weight:
2. the low permeability PPR composition of claim 1, wherein the nano-aluminum particles have an average particle size of 20-60 nm.
3. The low permeability PPR composition of claim 1, wherein said carbon fibers have a diameter of 5 to 7 μm.
4. The low permeability PPR composition of claim 1, wherein said graphite particles have a particle size of 2000-5000 mesh.
5. The low permeability PPR composition of claim 1, wherein the molecular weight of the polyvinyl alcohol is 18000-20000.
6. The low permeability PPR composition of claim 1, wherein said lubricant is a mixture of calcium stearate and zinc stearate.
7. The low permeability PPR composition of claim 1, further comprising said uv resistant agent.
8. A method of making a low permeability PPR composition according to any of claims 1 to 7, comprising the steps of:
s1, weighing polypropylene, nano aluminum particles, carbon fibers, graphite, polyvinyl alcohol, an ultraviolet-proof agent and a lubricant according to a proportion, and uniformly mixing to obtain a premix;
s2, extruding and molding the premix obtained in the step S1 in an extruder to obtain the low-permeability PPR composition.
9. The method for preparing a low permeability PPR composition according to claim 8, wherein the temperature of said extruder is 180-220 ℃.
10. A PPR pipe, characterized by being prepared from the low-permeability PPR composition of any one of claims 1-7.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116120664A (en) * | 2022-12-30 | 2023-05-16 | 河南联塑实业有限公司 | Temperature-resistant PPR water supply pipe and preparation method and application thereof |
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