CN1054387C - Polyvinyl composition of cladding metal pipe and preparing technology - Google Patents
Polyvinyl composition of cladding metal pipe and preparing technology Download PDFInfo
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- CN1054387C CN1054387C CN96116144A CN96116144A CN1054387C CN 1054387 C CN1054387 C CN 1054387C CN 96116144 A CN96116144 A CN 96116144A CN 96116144 A CN96116144 A CN 96116144A CN 1054387 C CN1054387 C CN 1054387C
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Abstract
The present invention discloses a polyethylene composite for wrapping pipes and a manufacture method for the polyethylene composite, which belongs to the technical field of polymer composites and pipeline corrosion prevention. The present invention is characterized in that a composite antioxygen system is formed by using an ethylene-alpha olefin copolymer as a base resin, using low-density polyethylene or linear low-density polyethylene as a modification component and using an amine antioxidant as a main antioxidant. The composite of the present invention is prepared by a two-step technique. The composite has good physical and mechanical properties, a low-temperature impact resistant property and a favorable forming machining property, and an environmental stress cracking resistant property and a heat oxygen aging resistant property are obvious; the present invention can be widely used for corrosion prevention inside and outside various metal pipes, and the extrusion of pipes and plates.
Description
The invention belongs to the polymeric composition field, specifically the present invention relates to have the polyethylene composition of heat oxygen aging resistance and resisting environmental stress and cracking, be used for the inside and outside anticorrosive coating of metallic conduit and container and extruding pipe material, sheet material with polyethylene, oxidation inhibitor and pigment prepared.
The corrosion of metal tube is one of the key factor in restriction pipeline work-ing life, pipeline corrosion protection material and Study on anticorrosion technique are paid much attention to always, polyethylene is as a kind of novel impregnating material, compare with traditional impregnating material, have excellent mechanical intensity, electrical insulation capability and easy construction property, required for using in addition, such material also should possess good environmental stress cracking resistance, high and low temperature resistance and ageing-resistant performance.The Japanese Patent spy opens clear 58-210947 and discloses a kind of polyethylene composition that is used for the low-temperature impact resistance of steel pipe corrosion-proof, and said composition comprises polyethylene and ethylene-alpha-olefin copolymer.It is to adopt density greater than 0.950g/cm
3, melt flow rate (MFR) (2.16kg counterweight) is polyethylene (A) 30～60 weight parts of (5～2000) g/10min, with density be (0.890～0.940) g/cm
3, melt flow rate (MFR) (2.16kg counterweight) is that ethylene-alpha-olefin copolymer (B) 40～70 weight parts of (0.005～0.1) g/10min mix, and adds oxidation inhibitor, UV light absorber, stablizer composition.This composition has good low-temperature resistance impact property and stress crack resistance performance, but this invention and fail to solve the heat oxygen aging resistance problem of material.
The object of the present invention is to provide a kind of both had good physical mechanical property, low-temperature impact-resistant performance, stress crack resistance performance, have the polyethylene composition of good heatproof air aging performance again concurrently.
The present invention also aims to provide the preparation technology and the purposes of the present composition.
The consisting of of composition provided by the invention (weight): ethene polymers A density (0.930～0.949) g/cm
3, 70～95 parts of melt flow rate (MFR) (2.16kg counterweight) (0.05～1.0) g/10min, polyethylene B density (0.890～0.930) g/cm
3, 5～30 parts of melt flow rate (MFR) (2.16kg counterweight) (1.0～10.0) g/10min, 0.1～1.0 part in oxidation inhibitor, 0～3.0 part of pigment.Preferably a kind of ethylene-alpha-olefin copolymer of ethene polymers A, its density optimum range are (0.935～0.945) g/cm
3Melt flow rate (MFR) preferred aspect scope (2.16kg counterweight) is (0.1～0.5) g/10min, polyethylene B is selected from a kind of in low density or the linear low density polyethylene, the purpose of adding this component mainly is to make things convenient for preparation of compositions, because can adding to earlier, pigment, oxidation inhibitor makes concentrated masterbatch among the polyethylene B, so just can guarantee that low dose of pigment and oxidation inhibitor are evenly distributed in composition, simultaneously, add the moulding processability that polyethylene B has also improved composition.The density optimum range of polyethylene B is (0.900～0.920) g/cm
3, the melt flow rate (MFR) optimum range is (2.16kg counterweight) (2.0～5.0) g/10min.Oxidation inhibitor can only contain oxidation inhibitor A, also can be formed antioxidant systems or be formed antioxidant systems by oxidation inhibitor A, oxidation inhibitor B and oxidation inhibitor C by oxidation inhibitor A and oxidation inhibitor B.Oxidation inhibitor A is an amine antioxidants, oxidation inhibitor B and oxidation inhibitor C are selected from a kind of in thioesters kind antioxidant, phenolic antioxidant, the phosphite ester kind antioxidant respectively, when forming antioxidant systems by oxidation inhibitor A and oxidation inhibitor B, its weight ratio is A: B=(1～5): 1.When forming antioxidant systems by oxidation inhibitor A, oxidation inhibitor B and oxidation inhibitor C, its weight ratio is A: B: C=(1～10): (1～5): 1.Oxidation inhibitor A preferably has
Structure to aniline type oxidation inhibitor, wherein R, R ' are respectively alkyl or phenyl.This antioxidant systems has good antioxygen efficient, is particularly suitable for dark material, especially black material.The oxidation inhibitor consumption is 0.1～1.0 part in composition, and the too low heatproof air aging performance that can't guarantee composition has too highly not only increased cost, and the heatproof air aging performance of composition descends on the contrary.The present invention does not add pigment also can reach the invention effect, but the photostabilization of composition is poor, and the pigment optimization among the present invention is a carbon black.
Preparation of compositions technology provided by the invention is " two-step approach " technology, at first pigment, oxidation inhibitor are mixed with polyethylene B, through the mixing masterbatch that is kneaded into of closed plastics processing mill, two roll plastic mixing mill and screw extrusion press, then masterbatch and ethene polymers A are mixed with composition.
Possess good physical and mechanical properties, low-temperature impact-resistant performance and stress crack resistance performance, the adding of composite antioxidant system, improved the heatproof air aging performance of composition significantly, adopt " two-step approach " prepared composition, can guarantee various component uniform distribution and dispersion in the composition, improve composition properties stability and reliability, so composition possesses excellent comprehensive performances.
Polyethylene composition provided by the invention is used to prepare the external anti-corrosion layer of metallic conduit, container and corrosion-proof lining layer and extruding pipe material, sheet material.
Following examples illustrate effect of the present invention, and the embodiment performance measurement the results are shown in Table 1.
Embodiment 1:
Ethene polymers A density 0.945g/cm
3, melt flow rate (MFR) (2.16kg counterweight) 0.15g/10min:85 part, polyethylene B density 0.920g/cm
3, melt flow rate (MFR) (2.16kg counterweight) 2.5g/10min:15 part, 0.2 part of oxidation inhibitor N.N '-two (1-ethyl-3-methyl amyl) Ursol D.
Embodiment 2:
Ethene polymers A density 0.945g/cm
3, melt flow rate (MFR) (2.16kg counterweight) 0.15g/10min:85 part, polyethylene B density 0.920g/cm
3, melt flow rate (MFR) (2.16kg counterweight) 2.5g/10min:15 part, 0.3 part of oxidation inhibitor N.N '-two (1-ethyl-3-methyl amyl) Ursol D.2.0 parts of carbon blacks.
Embodiment 3:
Ethene polymers A density 0.945g/cm
3, melt flow rate (MFR) (2.16kg counterweight) 0.15g/10min:85 part, polyethylene B density 0.920g/cm
3, melt flow rate (MFR) (2.16kg counterweight) 2.5g/10min:15 part, 0.3 part of oxidation inhibitor N.N '-two (1-ethyl-3-methyl amyl) Ursol D.0.1 part of oxidation inhibitor triphenyl phosphite, 2.0 parts of carbon blacks.
Embodiment 4
Ethene polymers A density 0.940g/cm
3, melt flow rate (MFR) (2.16kg counterweight) 0.15g/10min:90 part, polyethylene B density 0.920g/cm
3, melt flow rate (MFR) (2.16kg counterweight) 2.5g/10min:10 part, 0.2 part of oxidation inhibitor N.N '-two (1-ethyl-3-methyl amyl) Ursol D.0.1 part of oxidation inhibitor Tyox B, 2.0 parts of carbon blacks.
Embodiment 5:
Ethene polymers A density 0.935g/cm
3, melt flow rate (MFR) (2.16kg counterweight) 0.10g/10min:80 part, polyethylene B density 0.920g/cm
3, melt flow rate (MFR) (2.16kg counterweight) 2.5g/10min:20 part, 0.3 part of oxidation inhibitor N.N '-2-dimethyl-p-phenylenediamine, 0.1 part of oxidation inhibitor triphenyl phosphite, 0.1 part of oxidation inhibitor four (3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid) pentaerythritol ester, 2.0 parts of carbon blacks.
Embodiment 6:
Ethene polymers A density 0.935g/cm
3, melt flow rate (MFR) (2.16kg counterweight) 0.10g/10min:95 part, polyethylene B density 0.920g/cm
3, melt flow rate (MFR) (2.16kg counterweight) 2.5g/10min:5 part, 0.2 part of oxidation inhibitor N.N '-2-dimethyl-p-phenylenediamine, 0.1 part of oxidation inhibitor triphenyl phosphite, 0.1 part of oxidation inhibitor Tyox B, 2.0 parts of carbon blacks.
Table 1 embodiment The performance test results
| Project | Testing method | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Density (g/cm 3) | ASTM D1505 | 0.940 | 0.950 | 0.947 | 0.947 | 0.941 | 0.942 |
| Melt flow rate (MFR) (21.6kg) (g/10min) | ASTM D1238 | 0.20 | 0.20 | 0.18 | 0.17 | 0.25 | 0.12 |
| Tensile strength (MPa) | ASTM D638 | 31.0 | 30.8 | 30.9 | 29.7 | 32.2 | 31.8 |
| Elongation at break (%) | ASTM D638 | 850 | 950 | 870 | 900 | 880 | 910 |
| Resisting environmental stress and cracking (h) | ASTM D1693 | ＞1000 | ＞1000 | ＞1000 | ＞1000 | ＞1000 | ＞1000 |
| The impact embrittlement temperature (℃) | ASTM D746 | ＜-100 | ＜-100 | ＜-100 | ＜-100 | ＜-100 | ＜-100 |
| The oxidation inducing temperature (℃) | ASTM D3350 | 255 | 257 | 275 | 270 | 275 | 281 |
Claims (11)
1, a kind of polyvinyl composition of cladding metal pipe, it consists of:
(a) ethene polymers A density 0.930g/cm
3～0.949g/cm
3, melt flow rate (MFR) is 0.05g/10min～1.0g/10min;
(b) polyethylene B density 0.890g/cm
3～0.930g/cm
3, melt flow rate (MFR) is 1.0g/10min～10.0g/10min;
(c) oxidation inhibitor;
(d) pigment;
The weight content of each component is 70～95 parts of ethene polymers A, 5～30 parts of polyethylene B, 0.1～1.0 part in oxidation inhibitor, 0～3.0 part of pigment.
2, composition as claimed in claim 1 is characterized in that ethene polymers A is an ethylene-alpha-olefin copolymer, and density range is 0.935g/cm
3～0.945g/cm
3, the melt flow rate (MFR) scope is 0.1g/10min～0.5g/10min.
3, composition as claimed in claim 1 is characterized in that polyethylene B is selected from a kind of in new LDPE (film grade) and the linear low density polyethylene, and density range is 0.900g/cm
3～0.920g/cm
3, the melt flow rate (MFR) scope is 2.0g/10min～5.0g/10min.
4, composition as claimed in claim 1 is characterized in that oxidation inhibitor is to select oxidation inhibitor A amine antioxidants.
5, composition as claimed in claim 1, it is characterized in that oxidation inhibitor by oxidation inhibitor A and oxidation inhibitor B by weight (1～5): 1 forms, and oxidation inhibitor A is an amine antioxidants, and oxidation inhibitor B is selected from phenols, phosphorous acid esters, thioesters kind antioxidant.
6, composition as claimed in claim 1, it is characterized in that oxidation inhibitor by oxidation inhibitor A, oxidation inhibitor B and oxidation inhibitor C by weight (1～10): (1～5): 1 forms, oxidation inhibitor A is an amine antioxidants, and oxidation inhibitor B and oxidation inhibitor C are selected from phenols, phosphorous acid esters, thioesters kind antioxidant respectively.
7, be meant as the oxidation inhibitor A one of as described in the claim 4 to 6 and contain
Structure to aniline type oxidation inhibitor, R, R ' are respectively alkyl or phenyls.
8, composition as claimed in claim 1 is characterized in that pigment is carbon black.
9, a kind of technology of preparation of compositions according to claim 1 may further comprise the steps: oxidation inhibitor, carbon black and polyethylene B are mixed and made into masterbatch, then masterbatch and ethene polymers A are mixed and made into polyvinyl composition of cladding metal pipe.
10, composition as claimed in claim 1 is used for extruding pipe material, sheet material.
11, composition as claimed in claim 1 is used to prepare the external anti-corrosion layer and the corrosion-proof lining layer of metallic conduit, container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116144A CN1054387C (en) | 1996-12-29 | 1996-12-29 | Polyvinyl composition of cladding metal pipe and preparing technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116144A CN1054387C (en) | 1996-12-29 | 1996-12-29 | Polyvinyl composition of cladding metal pipe and preparing technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1186821A CN1186821A (en) | 1998-07-08 |
| CN1054387C true CN1054387C (en) | 2000-07-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96116144A Expired - Fee Related CN1054387C (en) | 1996-12-29 | 1996-12-29 | Polyvinyl composition of cladding metal pipe and preparing technology |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079104C (en) * | 1999-04-28 | 2002-02-13 | 中美合资宁波安达胶带制品有限公司 | Composite polyethylene antiseptic adhesive tape and production method thereof |
| BRPI0707025A2 (en) * | 2006-02-23 | 2011-04-19 | Basell Poliolefine Srl | propylene polymers for injection molding applications |
| CN103509220B (en) * | 2012-06-26 | 2016-05-25 | 深圳市联嘉祥科技股份有限公司 | Cold-resistant waterproof material manufacture method |
| JP5771254B2 (en) | 2013-09-26 | 2015-08-26 | 住友電気工業株式会社 | Multi-layer heat recovery article, wire splice and wire harness |
| CN106566051A (en) * | 2016-11-03 | 2017-04-19 | 苏州圣鑫莱新材料有限公司 | Shock-resistant and corrosion-resistant PE plastic pipe |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59240A (en) * | 1982-06-25 | 1984-01-05 | Meguro Denpa Sokki Kk | Amplitude limiting device |
| CN1038661A (en) * | 1988-05-19 | 1990-01-10 | 斯塔米卡本公司 | The manufacture method of polyethylene composition and goods thereof and its foam article |
| CN1117508A (en) * | 1994-04-27 | 1996-02-28 | 住友化学工业株式会社 | A method of coating a steel with a resin composition and a laminated article obtained by said method |
-
1996
- 1996-12-29 CN CN96116144A patent/CN1054387C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59240A (en) * | 1982-06-25 | 1984-01-05 | Meguro Denpa Sokki Kk | Amplitude limiting device |
| CN1038661A (en) * | 1988-05-19 | 1990-01-10 | 斯塔米卡本公司 | The manufacture method of polyethylene composition and goods thereof and its foam article |
| CN1117508A (en) * | 1994-04-27 | 1996-02-28 | 住友化学工业株式会社 | A method of coating a steel with a resin composition and a laminated article obtained by said method |
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| Publication number | Publication date |
|---|---|
| CN1186821A (en) | 1998-07-08 |
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Owner name: CHINA PETROCHEMICAL CORPORATION Free format text: FORMER OWNER: SINOPEC QILU PETRO-CHEMICAL CORP. Effective date: 20071228 |
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Effective date of registration: 20071228 Address after: Linzi Zibo District, Shandong province Sinopec Qilu Branch of science and technology Patentee after: China Petrochemical Group Corp. Address before: 124 mailbox, Zibo City, Shandong Province Patentee before: Qilu Petrochemical Company of China Petrochemical Corp. |
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Granted publication date: 20000712 Termination date: 20131229 |