CN111100348A - Polyolefin composition and preparation method and application thereof - Google Patents
Polyolefin composition and preparation method and application thereof Download PDFInfo
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- CN111100348A CN111100348A CN201811250959.5A CN201811250959A CN111100348A CN 111100348 A CN111100348 A CN 111100348A CN 201811250959 A CN201811250959 A CN 201811250959A CN 111100348 A CN111100348 A CN 111100348A
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
The invention belongs to the technical field of water supply pipes, and discloses a polyolefin composition, and a preparation method and application thereof. The polyolefin composition comprises a polyolefin resin, an antioxidant and a chlorine-resistant additive, wherein the chlorine-resistant additive is at least one compound selected from the group consisting of compounds represented by the formula (I) wherein R is1And R2Each independently selected from substituted or unsubstituted C1‑C6Alkyl, and R1And R2Not simultaneously being substituted C1‑C6And the substituted substituent is halogen, and n is an integer of 20-200. The chlorine-resistant polyolefin composition has good aging resistance and chlorine resistance, and is favorable for improving the continuous contact with drinking water containing chlorine disinfectantThe polyolefin water pipe has the advantages of long service life and environmental protection.
Description
Technical Field
The invention belongs to the technical field of water supply pipes, and particularly relates to a polyolefin composition, a preparation method thereof and application of the polyolefin composition in preparation of a water pipe material.
Background
At present, the problems of water resource shortage and water environment pollution in China are increasingly serious, design, construction and maintenance of a building water supply and drainage system are well done, and the method is an urgent need for realizing energy conservation, emission reduction and environmental protection. The water pipe and the pipe fitting used in the municipal drinking water distribution pipeline system require that the pipeline has the requirements of no toxicity, no radiation, no containing of harmful substances such as heavy metal and the like, good corrosion resistance, long service life and the like. Compared with the traditional cast iron pipe, galvanized steel pipe, cement pipe and other pipes, the plastic pipe has the advantages of energy conservation, material saving, 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 favored by the pipeline engineering industry. However, the plastic polymer compound is easily aged under the influence of oxidizing agents, light and heat. It is well known in the art to add various types of additives to polymers to protect them during processing and to achieve desired end-use properties. Conventional and commonly used antioxidants include sterically hindered phenols, aromatic amines, hindered amine stabilizers, organic phosphites/phosphonites. However, the appropriate combination of stabilizers must be carefully selected depending on the desired final properties that the polymer article should have.
There is still a need for more effective antioxidants to ensure good quality of drinking water, such as often removing, inactivating or killing pathogenic microorganisms with chlorine-containing disinfectants such as chlorine water or chlorine dioxide. However, polyolefin pipes are easy to age in chlorine water, and high-concentration chlorine can cause early brittle fracture of polyolefin pipes and reduce the service life of the water pipes. From pressure tests in the laboratory and from field experience, it has been shown that high concentrations of chlorine in water can lead to early brittle fracture of polyolefin pipes. In addition, it is more important for the various antioxidants added to avoid ageing of the polyolefin pipes to avoid contamination of the medium conveyed in the pipes made of the polyolefin composition. In general, in order to reduce the amount of antioxidant which may be leached out by the water transported in the pipe, it is preferred to use as low a concentration of antioxidant as possible. In this connection, it is desirable, in terms of improved optimization of the water supply pipe polymer material, that the antioxidants used have a lower tendency to be extracted by the water transported in the pipe.
Therefore, the need to develop and improve polyolefin compositions suitable for water pipes, particularly polyolefin compositions with improved resistance to aqueous contact with chlorine-containing disinfectants, is of great importance for energy saving and environmental protection.
Disclosure of Invention
In view of the above situation, the present invention provides a polyolefin composition, a preparation method thereof, and an application of the polyolefin composition in the preparation of water pipe. The polyolefin composition has high tolerance to drinking water containing chlorine or chlorine dioxide disinfectants.
The first aspect of the present invention provides a polyolefin composition comprising a polyolefin resin, an antioxidant and a chlorine-resistant additive selected from at least one compound represented by the formula (I);
in the formula (I), R1And R2Each independently selected from substituted or unsubstituted C1-C6Alkyl, and R1And R2Not simultaneously being substituted C1-C6And the substituted substituent is halogen, and n is an integer of 20-200.
The second aspect of the present invention provides a method for preparing the above polyolefin composition, wherein the polyolefin resin, the antioxidant and the chlorine-resistant additive are stirred, mixed, extruded and granulated to obtain the polyolefin composition.
In a third aspect the present invention provides the use of the above polyolefin composition in the manufacture of water pipe tubing.
The compound shown in the formula (I) is used as the chlorine-resistant additive to be mixed with the polyolefin resin to prepare the polyolefin composition, and the polyolefin composition is used for preparing the water pipe.
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, there is provided a polyolefin composition comprising a polyolefin resin, an antioxidant and a chlorine-resistant additive selected from at least one compound represented by the formula (I);
in the formula (I), R1And R2Each independently selected from substituted or unsubstituted C1-C6Alkyl, and R1And R2Not simultaneously being substituted C1-C6And the substituted substituent is halogen, and n is an integer of 20-200.
Preferably, in formula (I), R1And R2Each independently selected from the group consisting ofOr unsubstituted C1-C3Alkyl, said substituted substituent is halogen, and R1And R2Not simultaneously being substituted C1-C3Alkyl, n is an integer of 20 to 100.
Further preferably, in the formula (I), R1And R2Each independently is CH3Or CH2X is not simultaneously CH2X and X are halogen, and n is an integer of 20-100.
The source of the chlorine-resistant additive is not particularly limited in the present invention, and the chlorine-resistant additive can be obtained commercially or prepared by a conventional method in the field of organic synthesis.
In the present invention, the polyolefin resin is high density polyethylene. High density polyethylene is a well-known meaning in the art, namely an ethylene polymer having a density of from 0.941 to 0.960, which may be a homopolymer or copolymer of ethylene.
According to the present invention, preferably, the antioxidant comprises antioxidant a and antioxidant B.
Wherein the antioxidant A can be selected from one or more of pentaerythritol tetrakis (3- (3 ', 5 ' -di-tert-butyl-4-hydroxyphenyl) propionate) (Irganox 1010), octadecyl 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate (Irganox 1076), 1, 2-bis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazide (Irganox MD1024) and N, N ' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (Irganox 1098).
The antioxidant B may be selected from one or more of tris (2, 4-di-tert-butyl) phenyl phosphite (Irgafos 168), pentaerythritol bis (2, 4-tert-butylphenyl) diphosphite (Ultranox 626) and distearylpentaerythritol phosphite (Weston 618).
In the antioxidant, the weight ratio of antioxidant A to antioxidant B can be 1: 0.5-2.
According to a preferred embodiment of the present invention, the antioxidant is a mixture of pentaerythritol tetrakis (3- (3 ', 5' -di-tert-butyl-4-hydroxyphenyl) propionate) and phenyl tris (2, 4-di-tert-butyl) phosphite in a weight ratio of 1: 0.8 to 1.5, more preferably 1: 1.
In the present invention, the antioxidant may be present in an amount of 0.1 to 5 parts by weight and the chlorine-resistant additive may be present in an amount of 0.02 to 1 part by weight, based on 100 parts by weight of the polyolefin resin.
Preferably, the antioxidant is contained in an amount of 0.1 to 2 parts by weight, based on 100 parts by weight of the polyolefin resin; the content of the chlorine-resistant additive is 0.02-0.5 weight part.
The second aspect of the present invention provides a method for preparing the above polyolefin composition, wherein the polyolefin resin, the antioxidant and the chlorine-resistant additive are stirred, mixed, extruded and granulated to obtain the polyolefin composition. Specifically, the polyolefin resin, the antioxidant and the chlorine-resistant additive are stirred and mixed at a high speed in a mixer, and the mixed materials are extruded and granulated by a double screw to obtain the polyolefin composition.
In the invention, the mixing time of the materials in the mixer is preferably 10-15min, and the rest parameters which are not limited belong to the conventional technical means in the field.
In a third aspect the present invention provides the use of the above polyolefin composition in the manufacture of water pipe tubing.
According to one embodiment, the pelletized polyolefin composition is fed to a single screw extruder for extrusion and formed in a die to provide a water pipe.
Compared with a water pipe sample prepared without the chlorine-resistant additive composition, the water pipe sample prepared from the polyolefin composition has longer oxidation induction time, and the comparison of the oxidation induction time is more obvious after the water pipe sample is soaked for a longer time. Meanwhile, the water pipe sample prepared from the polyolefin composition has more excellent physical properties. Therefore, the water pipe prepared from the polyolefin composition has good chlorine resistance and good aging resistance, and can prolong the service life of the polyolefin pipe which is continuously contacted with chlorine-containing tap water.
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:
polyolefin resin: high density polyethylene, No. 6380M, available from china petrochemical Yanshan petrochemical company;
antioxidant: antioxidant Irganox 1010, antioxidant Irgafos 168;
chlorine-resistant additive: compound (I) wherein R1Is CH3，R2Is CH2Br, n is 78.
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 water pipe sample comprises the following steps: stirring and mixing the high-density polyethylene, the antioxidant and the chlorine-resistant additive in a mixer at high speed for 10-15min, and extruding and granulating by using a double screw; and then sending the granular mixture material to a single-screw extruder for extrusion, and forming in a die to obtain the water pipe sample.
TABLE 1
| Raw materials | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| High density polyethylene | 100 | 100 | 100 | 100 | 100 | 100 |
| Antioxidant Irganox 1010 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Antioxidant Irgafos 168 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Chlorine resistant additive | 0.02 | 0.25 | 0.5 | 0.75 | 1 | 0 |
The following performance tests were performed on the samples obtained in examples and comparative examples, and the specific results are shown in tables 2 to 4.
1. Chlorine resistance:
10cm long samples prepared according to the above examples and comparative examples were taken, soaked in an aqueous solution of chlorine having a chlorine content of 10ppm (the chlorine concentration was monitored and adjusted to be constant during the test), kept at a pH of 6.6. + -. 0.1 and soaked at 80 ℃ for various times, and then removed for stability.
2. Oxidative Induction Time (OIT):
the measurement is carried out by adopting a differential scanning calorimeter of a DSC 8000 model of Perkinelmer company in the United states according to the GB/T19466.6-2009 standard. A round sample material of 5mm diameter and about 10mg weight to be measured was introduced into the DSC cell at room temperature. Firstly introducing nitrogen for 5min, then heating from 50 ℃ to 200 ℃ at a speed of 20 ℃/min in the nitrogen atmosphere, keeping the temperature for 3min, then switching the gas into oxygen, and continuing to keep the temperature until 5min after the point of obvious change of heat release appears. And obtaining the isothermal OIT time according to a map. 3 samples were run in parallel under each condition and the average was calculated.
3. Elongation at break:
the elongation at break is tested by adopting the GB/T8804.3-2003 standard, a pipe sample is prepared by mechanical processing and is tested under the conditions of 23 +/-2 ℃ and the testing speed of 100 mm/min.
4. Hydrostatic strength:
the hydrostatic strength is tested by adopting GB/T6111-2003 standard, the test temperature is 80 ℃, the test time is 165h, and the hydrostatic stress is 5.5 MPa.
TABLE 2
TABLE 3
TABLE 4
As can be seen from the data in tables 2 to 4, the water pipe samples prepared according to the composition of the polyolefin composition of the present invention have a longer oxidation induction time than the water pipe samples prepared without adding the chlorine-resistant additive, and the comparison of the oxidation induction time is more obvious after the soaking time is longer. Meanwhile, the physical properties of the polyolefin water pipe sample prepared by the method are more excellent. Therefore, the water pipe material obtained by the polyolefin composition has good chlorine resistance and good aging resistance, and is beneficial to prolonging the service life of the polyolefin pipe material which is continuously contacted with chlorine-containing tap water.
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 (10)
1. A polyolefin composition comprising a polyolefin resin, an antioxidant and a chlorine-resistant additive, wherein the chlorine-resistant additive is at least one compound selected from the group consisting of compounds represented by the formula (I);
in the formula (I), R1And R2Each independently selected from substituted or unsubstituted C1-C6Alkyl, and R1And R2Not simultaneously being substituted C1-C6And the substituted substituent is halogen, and n is an integer of 20-200.
2. The polyolefin composition according to claim 1, wherein in the formula (I), R is1And R2Each independently selected from substituted or unsubstituted C1-C3Alkyl, and R1And R2Not simultaneously being substituted C1-C3And the substituted substituent is halogen, and n is an integer of 20-100.
3. The polyolefin composition according to claim 2, wherein in the formula (I), R is1And R2Each independently is CH3Or CH2X is not simultaneously CH2X and X are halogen, and n is an integer of 20-100.
4. The polyolefin composition of claim 1, wherein the polyolefin resin is a high density polyethylene.
5. The polyolefin composition of claim 1, wherein the antioxidant comprises antioxidant a and antioxidant B; the antioxidant A is selected from one or more of pentaerythritol tetrakis (3- (3 ', 5 ' -di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate, 1, 2-bis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazide and N, N ' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine; the antioxidant B is selected from one or more of tri (2, 4-di-tert-butyl) phenyl phosphite, pentaerythritol bis (2, 4-tert-butylphenyl) diphosphite and distearyl pentaerythritol phosphite; the weight ratio of antioxidant A to antioxidant B is 1: 0.5-2.
6. The polyolefin composition according to claim 5, wherein the antioxidant is a mixture of pentaerythritol tetrakis (3- (3 ', 5' -di-tert-butyl-4-hydroxyphenyl) propionate) and phenyl tris (2, 4-di-tert-butyl) phosphite in a weight ratio of 1: 0.8-1.5.
7. The polyolefin composition according to any one of claims 1 to 6, wherein the antioxidant is contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyolefin resin; the content of the chlorine-resistant additive is 0.02-1 part by weight.
8. The polyolefin composition according to claim 7, wherein the antioxidant is contained in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the polyolefin resin; the content of the chlorine-resistant additive is 0.02-0.5 weight part.
9. The process for producing a polyolefin composition according to any one of claims 1 to 8, wherein the polyolefin resin, the antioxidant and the chlorine-resistant additive are mixed under stirring and extruded to produce pellets, thereby obtaining the polyolefin composition.
10. Use of a polyolefin composition according to any of claims 1 to 8 in the production of a water pipe.
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| CN201811250959.5A CN111100348B (en) | 2018-10-25 | 2018-10-25 | Polyolefin composition and preparation method and application thereof |
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| CN201811250959.5A CN111100348B (en) | 2018-10-25 | 2018-10-25 | Polyolefin composition and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041814A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Chlorine-resistant polyethylene composition and preparation method and application thereof |
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| CN102108120A (en) * | 2011-01-19 | 2011-06-29 | 吉林大学 | Allyl-group-containing cross-linked poly(aryl ether sulfone) polymer and preparation method thereof |
| CN105435644A (en) * | 2014-09-29 | 2016-03-30 | 中国石油化工股份有限公司 | Nanofiltration membrane and preparation method thereof |
| CN106458883A (en) * | 2014-06-11 | 2017-02-22 | 弗纳技术股份有限公司 | Chlorine-resistant polyethylene compound and articles made therefrom |
| CN107254171A (en) * | 2017-06-15 | 2017-10-17 | 金发科技股份有限公司 | A kind of sulfone polymer composition and its application |
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- 2018-10-25 CN CN201811250959.5A patent/CN111100348B/en active Active
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| EP1080777A1 (en) * | 1999-08-31 | 2001-03-07 | Nitto Denko Corporation | Ultrafiltration membrane and method for producing the same, dope composition used for the same |
| JP2010082573A (en) * | 2008-10-01 | 2010-04-15 | Nitto Denko Corp | Porous film and method for manufacturing the same |
| CN102108120A (en) * | 2011-01-19 | 2011-06-29 | 吉林大学 | Allyl-group-containing cross-linked poly(aryl ether sulfone) polymer and preparation method thereof |
| CN106458883A (en) * | 2014-06-11 | 2017-02-22 | 弗纳技术股份有限公司 | Chlorine-resistant polyethylene compound and articles made therefrom |
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| CN116041814A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Chlorine-resistant polyethylene composition and preparation method and application thereof |
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