CN100532441C - Silane crosslinked polyethylene plastic for low shrinkage anti-crack tube and its preparation method - Google Patents
Silane crosslinked polyethylene plastic for low shrinkage anti-crack tube and its preparation method Download PDFInfo
- Publication number
- CN100532441C CN100532441C CNB2005100266383A CN200510026638A CN100532441C CN 100532441 C CN100532441 C CN 100532441C CN B2005100266383 A CNB2005100266383 A CN B2005100266383A CN 200510026638 A CN200510026638 A CN 200510026638A CN 100532441 C CN100532441 C CN 100532441C
- Authority
- CN
- China
- Prior art keywords
- silane
- preparation
- tert
- butyl
- crosslinked polyethylene
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates the silicon alky cross-linking low-middle-high density vinyon. The components comprises 0.8-3.0wt% silicon alky cross linking agent, 0.02-2.0wt% cross linking initiating agent, 0.02-1.0wt% cross linking catalyst, 0.01-3.0wt% anti-oxidant and 0.05-3.0wt% modified auxiliary agent. The method comprises the following steps: preparing silicon alky grafting material A, mixing A and B materials, handing with extrusion machine to get tubing product, keeping it in water bath at 85Deg.C or vaporium for 8 hours, and getting the product. The invention overcomes the defects of big contraction percentage and degelatinizing phenomena between polythene layer and metal layer; the invention has the advantages of short production circle, stable technology and high rate of finished products.
Description
Technical field
The present invention relates to a kind of low middle-high density polythene material that overall plastic pipe, aluminum-plastic laminated tube and steel are moulded pipe tubing ectonexine that is used for.Relate in particular to a kind of low-shrinkage, resist various environmental crackings, improve the material of vinyon mechanical property, resistance toheat by the crosslinked with silicane mode.
Background technology
Traditional drinking-water pipe, industrial gas transmission, oil pipeline generally all are to adopt galvanized steel pipe, and galvanized steel pipe usually because get rusty fouling, cause the secondary pollution of tap water, and the liquid flow resistance is big in decades, and work-ing life is short relatively.So people seek a kind of novel material and substitute original galvanized steel pipe.PPR, crosslinked polyethylene become active material.
Intensity is low under the hot condition of PPR, uses in the occasion of fluid temperature (F.T.) below 70 ℃.The hot-fluid of carrying higher temperature adopts crosslinked polyethylene.General crosslinked polyethylene has overcome the defective of galvanized steel pipe, has excellent physical strength, and ratio of damping has certain elasticity for a short time, can effectively weaken water hammer and fluid impact and noise.Anticorrosive, anti-various acid, alkali, salt.Can be around reducing joint from line bend.Its temperature use range-40 ℃～90 ℃.But the tubing environmental stress crack resistance that common crosslinked polyethylene is made can be not ideal enough, and particularly tubing easily ftractures in abominable relatively environment for use, directly influences the work-ing life of pipe; The tubing shrinking percentage that common in addition crosslinked polyethylene material is made is relatively large, and the user reflects that generally being used for aluminum-plastic laminated tube and steel moulds pipe, copper and mould pipe ectonexine production and cause the hoop hot melt adhesive can't be with metal and crosslinked polyethylene bonding firmly because of the contraction of crosslinked polyethylene; Shelf life of products is short; Stable processing technique is poor; The continuous production cycle is short, frequent parking cleaning, and the tubing yield rate is low.
Summary of the invention
Purpose of the present invention is improved the shortcoming of big, the anti-environmental stress cracking difference of its shrinking percentage when keeping all advantages of common crosslinked polyethylene.Modification by material makes crosslinked polyethylene layer and metal level well bond by hot melt adhesive, and the phenomenon that the release of crosslinked polyethylene ply stress is shunk and metal level separates does not take place.The splitting resistance of material also is greatly improved.Enlarge the use occasion of cross-linked polyethylene pipe material, prolonged the work-ing life of tubing.
The present invention is achieved in that this silane crosslinked polyethylene plastic for low shrinkage anti-crack tube is formed and comprises: following component is in parts by weight,
Polyvinyl resin 100
Silane crosslinker 0.8～3.0
Crosslinking catalyst 0.001～2.0
Cross-linked evocating agent 0.02～3.0
Oxidation inhibitor 0.02～4.0
Modified additive 0.05～2.5.
Density of pe among the present invention is 0.900～0.970, and melting index is≤15 grams/10 minutes, can be one or more.
Silane crosslinker among the present invention is to choose any one kind of them in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl-three-(2-methoxy ethoxy) silane, vinyl methyl dimethoxysilane, methyltrimethoxy silane, octyltri-ethoxysilane, Union carbide A-162, γ-(methacryloxy) propyl trimethoxy silicane or the γ-An Bingjisanyiyangjiguiwan or several.Its effect is grafted onto and forms cross-linked structure on the polyethylene, improves poly physical strength, temperature classification.
Crosslinking catalyst of the present invention is to choose any one kind of them in dibutyl tin laurate, Bis(lauroyloxy)dioctyltin or the lauric acid toxilic acid dibutyl tin or several.Its effect is the hydrolysis rate that quickens silane crosslinker, and the assurance product is finished cross-linking process fast under the certain hour certain temperature.
Cross-linked evocating agent of the present invention is a ditertiary butyl peroxide, 2,5-dimethyl-2, two (tert-butyl peroxy base) hexanes of 5-, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, 2,5-dimethyl-2, two (tert-butyl peroxy base) hexins-3 of 5-, α, α-two (tert-butyl peroxy base) diisopropylbenzene(DIPB) or 1,4 is chosen any one kind of them in-two (tert-butyl peroxy base) diisopropylbenzene(DIPB) or several.Its effect is a snap-out release free radical at a certain temperature, and the hydrogen on the free radical picked-up Polyethylene Chain makes polyethylene become the living chain of band free radical, with the silane crosslinker grafting.
Oxidation inhibitor of the present invention is that four [3-(3 ', 5 ',-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 4,4 '-thiobis (6-tertiary butyl meta-cresol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane 2,6-DI-tert-butylphenol compounds, 2, choose any one kind of them in 6-di-tert-butyl-4-methy phenol or the 4-methylol-2,6 di t butyl phenol or several.Its effect protection polyethylene is avoided under the effect of oxygen oxidation taking place and polyethylene is degraded, the heat resistance of raising goods.
Modified additive of the present invention is the organosilicon oligopolymer
Wherein R and R ' are CH
3,-(CH
2)-
nCH
3,-CH
2=CH
2-, NH
2, Cl or
Its effect is lubricated to offer convenience to processing, and the self-cleaning of screw rod is improved, and reduces course of processing precrosslink particulate and produces, and the goods of producing are apparent smooth, and good hand touch changes the material crystalline state simultaneously except that lubricated, reduce the contraction of material.
The preparation method of the silane crosslinked polyethylene plastic for low shrinkage anti-crack tube among the present invention is a two step method, comprise that the each component consumption proportion by aforementioned these plastics prepares A material and B material, and the mixing of A material and B material, A material silane grafted material, the B material is catalyst masterbatch.
Preparation process is:
The preparation of a, A material: the polyvinyl resin pre-treatment is dried to moisture content less than 500ppm, properties-correcting agent mixes according to a certain ratio with polyethylene, make modified master in the granulation of 125 ℃～160 ℃ process Banbury mixer kneading extruders, polyethylene, silane crosslinker, cross-linked evocating agent, modified master are 120 ℃～220 ℃ forcing machine grafting granulations, the later finished product of granulation is dried to moisture content and is lower than 200ppm, is stored in the vacuum packaging bag.
The preparation of b, B material: polyvinyl resin, oxidation inhibitor, crosslinking catalyst thorough mixing enter 120 ℃～200 ℃ forcing machine granulations, and the moisture content of finished products after the granulation is controlled at below the 200ppm, is stored in the vacuum packaging bag.
Among step a and the b, polyvinyl resin is used for the A material and is the 90-98 weight % of its total amount, is used for the B material and is the 2-10 weight % of its total amount.
C, A, B material thorough mixing when using enter forcing machine and extrude and make pipe material product, and product is finished cross-linking process in water-bath more than 85 ℃.
Compared with prior art, the present invention has following advantage:
A, the present invention have possessed all advantages of cross-linked polyethylene pipe material.
B, the invention solves the excessive defective of tubing shrinking percentage that general crosslinked polyethylene material is extruded, overcome inner plastic and shrink and produce the phenomenon of coming unstuck and can't ensure because of the fixed length size of shrinking product.
C, the present invention have improved common cross-linking tube material environmental stress cracking resistance, and prolong the work-ing life of material.
D, the present invention have improved common cross-linking tube YIELD STRENGTH, make tubing can bear bigger burstpressures.
E, the present invention solve short defective of tubing continuous production cycle, the continuous production cleaning of need not stopping in 30 days, the yield rate of raising tubing.
F, stability of material height of the present invention bring advantage to the user.
Embodiment
In conjunction with the embodiments content of the present invention is described further.
Silane crosslinker is a vinyltriethoxysilane; Crosslinking catalyst is a Bis(lauroyloxy)dioctyltin; Cross-linked evocating agent A is a dicumyl peroxide, and cross-linked evocating agent B is 2,5-dimethyl-2, two (tert-butyl peroxy base) hexanes of 5-; Oxidation inhibitor A is β-positive octadecanol ester of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid, and oxidation inhibitor B is 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol); Modified additive is a methyl vinyl silicone rubber, more than the product performance of two examples as follows:
| Project | Embodiment 1 | Embodiment 2 |
| 1. tensile strength MPa | 25.6 | 28.2 |
| 2. tensile yield strength MPa | 20 | 22 |
| 3. elongation at break % | 546 | 600 |
| 4. environmental stress cracking F 5050℃h | 5000 | 5000 |
| 5. impact embrittlement temperature-76 ℃ | By | By |
| 6. heat ageing test test temperature: 150 ℃ ± 3 ℃ maximum velocity of variation % of the maximum velocity of variation % of the aging back draft intensity of test period: 168h aging back elongation at break | 9.6 8.2 | 2.8 3.6 |
| 7. degree of crosslinking % | 80.1 | 75.4 |
| 8. shrinking percentage % | 0.95 | 1.10 |
Embodiment 1, is used for the occasion that degree of crosslinking is had relatively high expectations.
Embodiment 2, are used for the apparent occasion of having relatively high expectations of tubing.
Claims (6)
1, a kind of preparation method of silane crosslinked polyethylene plastic for low shrinkage anti-crack tube is characterized in that: following component is in parts by weight, and this silane crosslinked polyethylene plastic is formed and comprised:
Polyvinyl resin 100
Silane crosslinker 0.8～3.0
Crosslinking catalyst 0.001～2.0
Cross-linked evocating agent 0.02～1.0
Oxidation inhibitor 0.02～3.0
Modified additive 0.05～2.5
Described modified additive is a methyl vinyl silicone rubber;
The preparation method is a two step method, comprises by silane crosslinked polyethylene plastic each component consumption proportion preparing A material and B material, and the mixing of A material and B material, the A material is the silane grafted material, the B material is catalyst masterbatch;
The preparation of a, A material
The polyvinyl resin pre-treatment is dried to below the moisture content 500ppm, and modified additive mixes according to a certain ratio with polyethylene, makes modified master in the granulation of 125 ℃～160 ℃ process Banbury mixer kneading extruders; Polyethylene, silane crosslinker, cross-linked evocating agent, modified master thorough mixing, extruding pelletization, extruding pelletization temperature are at 120 ℃～220 ℃ in forcing machine, finished product after the granulation carries out drying treatment, and moisture content is controlled at below the 200ppm, is stored in the aluminium foil bag to vacuumize;
The preparation of b, B material
Polyvinyl resin, oxidation inhibitor, crosslinking catalyst thorough mixing in high-speed mixer, the rotating speed of high-speed mixer is controlled at 100～200 rev/mins, compound drops into the forcing machine granulation, 100 ℃～200 ℃ of forcing machine prilling temperatures, the later finished product of granulation carries out drying treatment, moisture content is controlled at below the 200ppm, is stored in the aluminium foil bag to vacuumize;
What polyvinyl resin was used for A material among step a and the step b be 90～98 weight % of its total amount, be used for B and expect to be 2～10 weight % of its total amount,
Enter forcing machine behind A, the B material thorough mixing when c, use and make all kinds of pipe material products, water-bath or steam room placement that the pipe material product of making immerses more than 85 ℃ were finished cross-linking process more than 8 hours.
2, the preparation method of silane crosslinked polyethylene plastic according to claim 1 is characterized in that: the density of described polyvinyl resin is 0.900～0.970, and melting index is≤15 grams/10 minutes.
3, the preparation method of silane crosslinked polyethylene plastic according to claim 1 is characterized in that: described silane crosslinker is to choose any one kind of them in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl-three-(2-methoxy ethoxy) silane, vinyl methyl dimethoxysilane, methyltrimethoxy silane, octyltri-ethoxysilane, Union carbide A-162, γ-(methacryloxy) propyl trimethoxy silicane and the γ-An Bingjisanyiyangjiguiwan or several.
4, the preparation method of silane crosslinked polyethylene plastic method according to claim 1 is characterized in that: described crosslinking catalyst is to choose any one kind of them in dibutyl tin laurate, Bis(lauroyloxy)dioctyltin and the lauric acid toxilic acid dibutyl tin or several.
5, the preparation method of silane crosslinked polyethylene plastic according to claim 1, it is characterized in that: described cross-linked evocating agent is a ditertiary butyl peroxide, 2,5-dimethyl-2, two (tert-butyl peroxy base) hexanes of 5-, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, 2,5-dimethyl-2, two (tert-butyl peroxy base) hexins-3 of 5-, α, α-two (tert-butyl peroxy base) diisopropylbenzene(DIPB) and 1,4 ,-two (tert-butyl peroxy base) diisopropylbenzene(DIPB) is chosen any one kind of them or is several.
6, the preparation method of silane crosslinked polyethylene plastic according to claim 1, it is characterized in that: described oxidation inhibitor is four [3-(3 ' 5 '-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 4,4 '-thiobis (6-tertiary butyl meta-cresol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 2, the 6-DI-tert-butylphenol compounds, choose any one kind of them in 2,6 di tert butyl 4 methyl phenol and the 4-hydroxymethyl-2,6 di t butyl phenol or several.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100266383A CN100532441C (en) | 2005-06-10 | 2005-06-10 | Silane crosslinked polyethylene plastic for low shrinkage anti-crack tube and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100266383A CN100532441C (en) | 2005-06-10 | 2005-06-10 | Silane crosslinked polyethylene plastic for low shrinkage anti-crack tube and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1876706A CN1876706A (en) | 2006-12-13 |
| CN100532441C true CN100532441C (en) | 2009-08-26 |
Family
ID=37509279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100266383A Active CN100532441C (en) | 2005-06-10 | 2005-06-10 | Silane crosslinked polyethylene plastic for low shrinkage anti-crack tube and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100532441C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585323A (en) * | 2011-01-17 | 2012-07-18 | 高玉森 | Super wear resistant high-adhesion composite tube and manufacturing method thereof |
| CN103808754A (en) * | 2012-11-05 | 2014-05-21 | 上海凯波特种电缆料厂有限公司 | Method for detecting thermal shrinkage property of silane crosslinking polyethylene insulation material |
| CN103012931B (en) * | 2012-12-20 | 2015-04-15 | 浙江伟星新型建材股份有限公司 | Functional master-batch for organosilane crosslinked polyethylene pipe, and preparation method and application of functional master-batch |
| CN103642356A (en) * | 2013-12-07 | 2014-03-19 | 天津市华鑫达投资有限公司 | Crosslinked polypropylene viscoelastic composite coating and preparation method thereof |
| CN106117701A (en) * | 2016-06-23 | 2016-11-16 | 郁世超 | A kind of high-density polyethylene material being prone to welding |
| CN106188745A (en) * | 2016-07-14 | 2016-12-07 | 安庆师范大学 | A kind of anti-electromagnetic-radiation cable tubing |
| CN107987353B (en) * | 2017-12-11 | 2020-04-17 | 济南热力工程有限公司 | Floor heating pipe with low linear expansion coefficient and preparation method thereof |
| CN108395611A (en) * | 2018-03-06 | 2018-08-14 | 上海高分子功能材料研究所 | A kind of silane crosslinked polyethylene plastic and its preparation method and application that lubricity is good |
| CN110239123A (en) * | 2019-06-24 | 2019-09-17 | 倍适（北京）科技有限公司 | The preparation method and application of the hot winding structure pipe of heavy caliber high density crosslinked polyethylene |
| CN112223854A (en) * | 2020-09-18 | 2021-01-15 | 威海联桥新材料科技股份有限公司 | Three-layer composite PVC/PEX water delivery pipe and preparation method thereof |
| CN114276625A (en) * | 2020-09-27 | 2022-04-05 | 日丰企业集团有限公司 | Polymer alloy and preparation method and application thereof |
| CN113074283A (en) * | 2021-03-15 | 2021-07-06 | 广东联塑科技实业有限公司 | Heat-resistant steel wire mesh framework PE composite pipe and preparation method and application thereof |
| CN115746433A (en) * | 2022-11-16 | 2023-03-07 | 河北旺源管业有限公司 | Special silane crosslinked polyethylene pipe, application thereof and crosslinked polyethylene pipeline system for middle-deep geothermal energy utilization |
-
2005
- 2005-06-10 CN CNB2005100266383A patent/CN100532441C/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 聚硅氧烷在高密度聚乙烯中的分布及对高密度聚乙烯性能的影响. 李骥安，周持兴，穆肖斌.上海塑料，第总第121期. 2003 |
| 聚硅氧烷在高密度聚乙烯中的分布及对高密度聚乙烯性能的影响. 李骥安，周持兴，穆肖斌.上海塑料，第总第121期. 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1876706A (en) | 2006-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100532441C (en) | Silane crosslinked polyethylene plastic for low shrinkage anti-crack tube and its preparation method | |
| CN101531783B (en) | Delayed cross-linked type silicane cross-linked polyethylene plastic | |
| FI86876B (en) | MED SILAN TV BUMPER MACHINERY AND FOUND FARING FOR FOUNDATION. | |
| CN101902101B (en) | EPDM cold shrinking power cable accessory and preparation method thereof | |
| CN101580612B (en) | PP/PET alloy material and preparation process thereof | |
| CN110194879B (en) | High-strength MPP material, preparation method thereof and prepared cable protection tube | |
| KR910005572B1 (en) | Thermo plastic resin composition | |
| CN110183784A (en) | A kind of cold-resistant EPDM composite material and preparation method | |
| CN104672613A (en) | High-temperature-resistant thermoplastic elastomer material and preparation method thereof | |
| CN103571059A (en) | Polypropylene composite material as well as preparation method and use thereof | |
| CN113861587A (en) | Special pipe for rainwater drainage of high-rise building and preparation method and application thereof | |
| CN103172937B (en) | A kind of Silane Grafted PPR pipe PP Pipe Compound and preparation method thereof | |
| CN107936441A (en) | A kind of method of two-step method silane natural-crosslinked polyethylene | |
| CN102241864A (en) | Silane-grafted high-density polyethylene room-temperature cross-linking special material and preparation method thereof | |
| CN114292364A (en) | Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof | |
| CN106543625A (en) | A kind of natural fibre reinforced polylactic acid composite material and preparation method thereof | |
| CN103275274B (en) | The method of single screw extrusion machine One-step production organosilane crosslinked polyethylene hot water hose | |
| CN102532772A (en) | Method for improving performances of regenerated PE mulching film by using graft copolymerization | |
| CN106947165A (en) | A kind of high strength heat resistant polypropylene plastics tubing and preparation method thereof | |
| CN115785582A (en) | Environment-friendly efficient silane crosslinked polypropylene material and preparation method thereof | |
| CN104311982B (en) | A kind of room temperature silane self-crosslinking POE flexible pipe and preparation method thereof | |
| CN114933878A (en) | Strong plastic-lined metal pipe rapid bonding adhesive and preparation method thereof | |
| JP3817993B2 (en) | Methyl methacrylate resin composition | |
| JP2006265364A (en) | Polyethylene-based resin composition and crosslinked polyethylene pipe | |
| CN1139608C (en) | Mechanochemical method for fusion-grafting vinyl monomer by using polyolefine plastics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |