CN1280054A - Method for producing foamed polyolefine plastic pipe - Google Patents
Method for producing foamed polyolefine plastic pipe Download PDFInfo
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- CN1280054A CN1280054A CN 99110249 CN99110249A CN1280054A CN 1280054 A CN1280054 A CN 1280054A CN 99110249 CN99110249 CN 99110249 CN 99110249 A CN99110249 A CN 99110249A CN 1280054 A CN1280054 A CN 1280054A
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Abstract
A radiation crosslinking process to produce foamed polyolefine plastics pipe uses polyolefine as basic raw material and includes the steps of heating to mix while adding foaming agent, foaming activator, nucleating agent, radiation crosslinking sensitizer, antioxidant, pigment and processing, assistant, then pelletizing and pipe extrusion in meanwhile strictly controlling working temp., and then irradiation and final heating to foam. During the process, the working temperature is controlled to be not lower than the melting temperature of resin and not higher than the thermal decomposition temperature of the foaming agent.
Description
The invention belongs to the manufacture method of foamed polyolefine plastic pipe.
Make the more existing patents of polyethylene foams (PEF), for example U.S. Pat P3067147 discloses the technology of the direct extrusion molding manufacturing PEF of DOW chemical company; P.899389, BP British discloses the technology of the chemical crosslinking manufactured PEF of BXL Plastics Company; Japan Patent 41-6278,42-18832 etc. disclose ponding chemistry and Dong Li company crosslinking with radiation technology.Directly the advantage of extruding technology is that production technology is simple, cost is low, and shortcoming is the PEF that is difficult to make high-power foaming, and the product combination property is relatively poor.The advantage of chemical crosslink technique is that equipment is simple, small investment, can make the PEF of high-power foaming, and shortcoming is that cross-linking process is difficult to control.Still imperfect tense begin to have decomposed in cross-linking reaction often, and production process is discontinuous, can not produces the sheet material of continuous length with regard to some blowing agent.Japan is used to make PEF to the crosslinking with radiation technology, and the advantage of this technology is accurately to control the degree of cross linking, and cross-linking reaction is at room temperature carried out.Radiation processing technology does not produce the three wastes, free from environmental pollution.The shortcoming of this technology is the equipment more complicated, and it is big to one-time fix assets investment.The present invention is new results of having introduced radiation chemistry and foaming process dynamics research on above-mentioned patent basis again.
The manufacture method that the purpose of this invention is to provide a kind of polyolefin foamed plastics tubing.This method is raw material with the polyolefin, adopt radiosensitization crosslinked with reduction irradiation expense, employing compound foaming agent adjustment foaming agent decomposition temperature and reaction heat balance, the present invention is without fused salt, hot blast, but infrared directly-heated type heating has improved efficient, has simplified the foaming furnace structure.
The realization of the object of the invention is by following means:
Because the polymer moieties macromolecule after crosslinked changes network structure into from linear molecule, thereby its melt viscosity and melt strength have improved more than fusing point, and this selection and the stable of foaming process that helps thermal decomposition type blowing agent carries out.Adopt suitable blowing promotor can adjust the thermal balance of blowing temperature and reaction within the specific limits.Use with in the time of two classes heat absorptions and heat release type blowing agent and can prevent the side reaction that causes because of reaction heat is too high.The polyolefin that the present invention adopts comprises the blend of polyethylene, polypropylene, ethylene propylene copolymer, ethylene vinyl acetate copolymer (EVA) and these resins.Polyethylene is divided into the polyethylene that high density polyethylene (HDPE), low density polyethylene (LDPE) and metallocene catalyst are produced again.Blend can be adjusted the performance of processing characteristics and final products in sizable scope.The sensitization crosslinking agent mainly is to adopt organic polyfunctional monomer, just in same molecule, contain two or more pairs of keys, for example GDMA, trimethyl acrylic acid glyceride, itaconic acid two propylene esters, aconitic acid three propylene esters, cyanuric acid three propylene esters, talan etc.The consumption of these sensitizers both had been decided by and will be decided by the activity of sensitizer itself again by the resin of sensitization that general consumption was 0.5～10phr.What the present invention was used is thermal decomposition type CBA, and different blowing agents is with different activators, and activator has zinc oxide, zinc stearate, triethanolamine, citric acid, benzoic acid, hexanedioic acid etc.N-nitroso compound blowing agent urea, carbamide derivative, organic acid etc.The advantage of heat absorption/heat release type composite foamable agent is to have overcome the shortcoming of bringing because of single heat absorption or single heat release, and what help reacting steadily carries out.Acid carbonate, nitrite and special silicate belong to endothermic decomposition formula blowing agent.
Mixing, the granulation of raw material, extrude on special equipment and carry out, strict control processing temperature, processing temperature can not be lower than the fusing point of resin, must not be higher than the heat decomposition temperature of used blowing agent.Irradiation will be considered the influence of nitrogen with X-ray, gamma-radiation and electron beam when radiation dose rate is smaller, the energy of electronics will enough penetrate sample and can guarantee that product is by evenly crosslinked during with accelerator irradiation.
The present invention adopts polyethylene, polyethylene is divided into high density polyethylene (HDPE) again, the polyethylene that low density polyethylene (LDPE) and metallocene catalyst are produced, polypropylene, ethylene propylene copolymer, 100 parts of any two kinds of blends in ethylene vinyl acetate copolymer (EVA) a kind of and these resins wherein, press the product coefficient of foaming and add compound foaming agent N, N '-dinitroso five methine tetramines (DPT), 4,4-diphenyl ether sulfohydrazide (OBSH), Celogen Az (AC), azoformic acid barium, 5～20 parts of any two kinds of blends in p-toluene sulfonylsemicarbazide a kind of and these blowing agents wherein, add activator zinc oxide, zinc stearate, triethanolamine, citric acid, benzoic acid, 1～10 part in any two kinds of mixtures in adipic acid a kind of and these activators wherein; Add antioxidant 2,6-di-t-butyl-4-cresols, four [(3-3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 1,1,3-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 2,2 '-0.1～1 part in any two kinds of mixtures in di-2-ethylhexylphosphine oxide (4-methyl-6-t-butyl phenol) a kind of and these antioxidant wherein; Nucleator zinc oxide, calcium carbonate, brium carbonate, chromium carbonate, 1～15 part in any two kinds of mixtures in silica a kind of and these nucleators wherein, sensitization crosslinking agent GDMA, trimethyl acrylic acid glyceride, itaconic acid two propylene esters, aconitic acid three propylene esters, cyanuric acid three propylene esters, 1～5 part of talan a kind of 0.5～15 part and processing aid barium stearate wherein, mixing in homogenizer, again with driving refining or banbury, mixing granulator under the temperature that is higher than 10～20 ℃ of melting point resin temperature is again with being lower than extruding pipe material under the foaming agent decomposition temperature on the extruder; With tubing irradiation in cobalt source or electron accelerator, irradiation dose is 0.5～10Mrad, and the tubing that irradiation is good foams in vertical foaming furnace, blowing temperature be 180 ℃ to 210 ℃, make foamed polyolefine plastic pipe.
In order to improve the temperature resistant grade of polyethylene pipe, can the polyethylene pipe of sending out good bubble again secluding air replenish irradiation 10～20Mrad,, abscess little by the foamed pipe density of this manufactured evenly, cortex construction is arranged, chemically stable is ageing-resistant, water absorption rate is low, good heat insulating.Mainly be used in the adiabatic field of insulation.
Embodiment provided by the invention is as follows:
Embodiment 1: 100 parts of polyethylene from high pressure processes, 20 parts of organic chemistry blowing agent Celogen Azs, 1 part in blowing agent activator zinc oxide, 5 parts in nucleator calcium carbonate, processing aid barium stearate, antioxidant 2,0.5 part of 6-di-t-butyl-4-cresols.150 ℃ of mixing, granulations of following temperature, 170 ℃ of following temperature are squeezed pipe.Use electron accelerator irradiation, irradiation dose is 5Mrad.In the foamable stove, foam under 200 ℃ of temperature.
Embodiment 2: 100 parts of the polyethylene that metallocene catalyst is produced add blowing agent N, 20 parts of N-dinitroso five methine tetramines (DPT), 5 parts of foaming activator zinc stearates, 120 ℃ mixing, and 140 ℃ are squeezed pipe, use electron accelerator irradiation 5Mrad, 190 ℃ of foaming.
Embodiment 3: with the polyethylene foams pipe of gained among the embodiment 1 again secluding air replenish irradiation, use Co
60-gamma-rays, irradiation dose 20Mrad has improved about 10 ℃ of polyethylene pipe serviceability temperatures.
Embodiment 4: ethylene propylene copolymer, 85%100 parts of therein ethylene content 15% propylene contents, add 15 parts of blowing agent azoformic acid barium, add 1 part of radiosensitization crosslinking agent GDMA, 5 parts in nucleator calcium carbonate, mixing at melting temperature, squeeze pipe, use electron accelerator irradiation 0.5Mrad, being heated to must the polypropylene foam pipe after the foaming agent decomposition temperature foaming.
Embodiment 5: 100 parts of acrylic resins, 20 parts of blowing agent azoformic acid barium, 2 parts of sensitization crosslinking agent cyanuric acid three propyl ester, 5 parts of nucleator brium carbonates, 2 parts of Lip river agent zinc stearates are 190 ℃ of batch mixing granulations, squeeze pipe, irradiation 1Mrad, 240 ℃ of foaming under 220 ℃ of temperature.
Embodiment 6: 50 parts of polyethylene from high pressure processes, 50 parts of ethylene-vinyl acetate copolymers, N, 10 parts of N '-dinitroso five methine tetramines, 4,4 '-10 parts of diphenyl ether sulfohydrazides, 2 parts of zinc stearate and triethanolamine blends, 5 parts of chromium carbonate and silica blends, press embodiment 1 condition machine-shaping, blowing temperature is 200 ℃.
Embodiment 7: 50 parts of low density polyethylene (LDPE)s, and 50 parts of high density polyethylene (HDPE)s add 4,20 parts of 4 '-two benzene sulfonyl hydrazides, protect oxygen agent 2,20 parts of 6-di-t-butyls-4-cresols 0.5 p-toluene sulfonylsemicarbazide, antioxidant four [(3-3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 0.5 part of pentaerythritol ester, 5 parts of nucleator silica 1s, 150 ℃ of mixing, granulations, 180 ℃ are squeezed pipe, irradiation 10Mrad foams under 200 ℃ of temperature.
Embodiment 8: 20 parts of high density polyethylene (HDPE)s, and 80 parts of low density polyethylene (LDPE)s, 10 parts of Celogen Azs, 15 parts of p-toluene sulfonylsemicarbazides are pressed embodiment 7 condition moulding, and irradiation 3Mrad foams under 190 ℃ of conditions.
Embodiment 9: 90 parts of low density polyethylene (LDPE)s, and 10 parts of ethylene-vinyl acetate copolymers add 20 parts of azodicarbonamide foaming agents, 3 parts of activator triethanolamine and benzoic acid blends, 15 parts in nucleator zinc oxide, 145 ℃ of mixing, granulations, 175 ℃ are squeezed pipe, and irradiation 7Mrad is 180 ℃ of foaming.
Embodiment 10: ethylene propylene copolymer, 65%100 parts of therein ethylene content 35% propylene contents, add 20 parts of blowing agent azoformic acid barium Celogen Az blends, 2 parts of nucleator calcium carbonate and zinc oxide blends, 5 parts of sensitization crosslinking agent trimethyl acrylic acid glyceride, 180 ℃ of batch mixings, granulation, 195 ℃ are squeezed pipe, irradiation 3Mrad, 210 ℃ of foaming.
Embodiment 11: 100 parts of ethylene-vinyl acetate copolymers, add 4,4 '-20 parts of diphenyl ether sulfohydrazides, 5 parts of activator ethanedioic acid and benzoic acid blends, 1-1,3-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 2,2 '-0.5 part of the blend of di-2-ethylhexylphosphine oxide (4-methyl-6-t-butyl phenol), 10 parts in nucleator zinc oxide.150 ℃ of mixing, granulations, 170 ℃ are squeezed pipe, and irradiation 7Mrad is 180 ℃ of foaming.
Claims (3)
1. the manufacture method of a foamed polyolefine plastic pipe, it is characterized in that adopting the polyethylene of polyethylene and metallocene catalyst production, polypropylene, ethylene propylene copolymer, 100 parts of any two kinds of blends in ethylene vinyl acetate copolymer (EVA) a kind of and these resins wherein, press the product coefficient of foaming and add compound foaming agent N, N '-dinitroso five methine tetramines (DPT), 4,4 '-diphenyl ether sulfohydrazide (OBSH), Celogen Az (AC), azoformic acid barium, 5～20 parts of any two kinds of blends in p-toluene sulfonylsemicarbazide a kind of and these blowing agents wherein, add activator zinc oxide, zinc stearate, triethanolamine, citric acid, benzoic acid, 1～10 part in any two kinds of mixtures in adipic acid a kind of and these activators wherein; Add antioxidant 2,6-di-t-butyl-4-cresols, four [(3-3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 1,1,3-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 2,2 '-0.1～1 part in any two kinds of mixtures in di-2-ethylhexylphosphine oxide (4-methyl-6-t-butyl phenol) a kind of and these antioxidant wherein; Nucleator zinc oxide, calcium carbonate, brium carbonate, chromium carbonate, 1～15 part in any two kinds of mixtures in silica a kind of and these nucleators wherein, sensitization crosslinking agent GDMA, trimethyl acrylic acid glyceride, itaconic acid two propylene esters, aconitic acid three propylene esters, cyanuric acid three propylene esters, 1～5 part of talan a kind of 0.5～15 part and processing aid barium stearate wherein, mixing in homogenizer, again with driving refining or banbury, mixing granulator under the temperature that is higher than 10～20 ℃ of melting point resin temperature is again with being lower than extruding pipe material under the foaming agent decomposition temperature on the extruder; With tubing irradiation in cobalt source or electron accelerator, irradiation dose is 0.5～10Mrad, and the tubing that irradiation is good foams in vertical foaming furnace, blowing temperature be 180 ℃ to 210 ℃, make foamed polyolefine plastic pipe.
2. the manufacture method of foamed polyolefine plastic pipe as claimed in claim 1 is characterized in that described polyethylene is a high density polyethylene (HDPE).
3. the manufacture method of foamed polyolefine plastic pipe as claimed in claim 1 is characterized in that described polyethylene is a low density polyethylene (LDPE).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99110249A CN1103346C (en) | 1999-07-07 | 1999-07-07 | Method for producing foamed polyolefine plastic pipe |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99110249A CN1103346C (en) | 1999-07-07 | 1999-07-07 | Method for producing foamed polyolefine plastic pipe |
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| CN1280054A true CN1280054A (en) | 2001-01-17 |
| CN1103346C CN1103346C (en) | 2003-03-19 |
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| CN99110249A Expired - Fee Related CN1103346C (en) | 1999-07-07 | 1999-07-07 | Method for producing foamed polyolefine plastic pipe |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824198A (en) * | 2010-04-29 | 2010-09-08 | 中国科学院长春应用化学研究所 | Polyethylene-polystyrene foam and preparation method thereof |
| CN101437595B (en) * | 2006-03-28 | 2011-05-04 | 巴斯夫欧洲公司 | Tube filled with an open-cell melamine/formaldehyde resin foam and use as a filter or static mixer |
| CN101255250B (en) * | 2008-04-14 | 2011-08-31 | 常州天晟新材料股份有限公司 | Ethane-vinyl acetate copolymer hole-opening foaming profile and method for manufacturing same |
| CN102295799A (en) * | 2010-06-25 | 2011-12-28 | 中国石油天然气股份有限公司 | Polyethylene resin composition for pipes |
| CN102358794A (en) * | 2011-08-31 | 2012-02-22 | 佛山佛塑科技集团股份有限公司 | Cross-linked polyvinyl chloride (PVC) foaming material and preparation method thereof |
| CN101448884B (en) * | 2006-05-26 | 2012-05-09 | 株式会社Jsp | Expandable polyethylene resin particle and method for production thereof |
| CN102816363A (en) * | 2011-06-07 | 2012-12-12 | 东莞市宏恩塑胶制品有限公司 | High-resilience flame-retarding antistatic foamed polyethylene material |
| CN102109070B (en) * | 2009-12-24 | 2013-03-27 | 黑龙江省科学院技术物理研究所 | Radiation cross-linked polyethylene thermal expansion pipe and manufacturing method |
| CN103205011A (en) * | 2013-03-04 | 2013-07-17 | 鲁奎 | Melamine-formaldehyde foamed plastic foaming agent |
| CN103374167A (en) * | 2012-04-27 | 2013-10-30 | 东北林业大学 | High-filling calcium carbonate/polyethylene bacteriostatic foam material and preparation method thereof |
| CN104558780A (en) * | 2015-01-21 | 2015-04-29 | 浙江伟星新型建材股份有限公司 | High-density polyethylene microporous foamed tube and preparation method thereof |
| CN105175647A (en) * | 2015-08-03 | 2015-12-23 | 苏州云舒新材料科技有限公司 | Polyethylene foam material and preparation method therefor |
| CN108841067A (en) * | 2018-06-06 | 2018-11-20 | 嘉兴中易碳素科技有限公司 | Low density polyethylene (LDPE) foaming coiled and preparation method thereof |
| CN109337119A (en) * | 2018-09-25 | 2019-02-15 | 广东省稀有金属研究所 | A kind of vulcanizing activator and preparation method thereof |
| CN113527790A (en) * | 2021-07-19 | 2021-10-22 | 中广核高新核材科技（苏州）有限公司 | Anti-static irradiation crosslinked polyethylene foam material and preparation method thereof |
| CN113831646A (en) * | 2021-09-08 | 2021-12-24 | 南京雷泰克材料科技有限公司 | Preparation method of polypropylene foam |
| CN113915424A (en) * | 2021-10-25 | 2022-01-11 | 福建赛维特水管科技有限公司 | Electronic radiation foaming thermal insulation pipe and processing technology thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5056456A (en) * | 1973-09-21 | 1975-05-17 | ||
| JPS58151226A (en) * | 1983-02-14 | 1983-09-08 | Sekisui Plastics Co Ltd | Molded product of thermoplastic resin foam |
| JP2918412B2 (en) * | 1993-04-01 | 1999-07-12 | 積水化学工業株式会社 | Polyolefin resin foam |
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- 1999-07-07 CN CN99110249A patent/CN1103346C/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101437595B (en) * | 2006-03-28 | 2011-05-04 | 巴斯夫欧洲公司 | Tube filled with an open-cell melamine/formaldehyde resin foam and use as a filter or static mixer |
| CN101448884B (en) * | 2006-05-26 | 2012-05-09 | 株式会社Jsp | Expandable polyethylene resin particle and method for production thereof |
| CN101255250B (en) * | 2008-04-14 | 2011-08-31 | 常州天晟新材料股份有限公司 | Ethane-vinyl acetate copolymer hole-opening foaming profile and method for manufacturing same |
| CN102109070B (en) * | 2009-12-24 | 2013-03-27 | 黑龙江省科学院技术物理研究所 | Radiation cross-linked polyethylene thermal expansion pipe and manufacturing method |
| CN101824198A (en) * | 2010-04-29 | 2010-09-08 | 中国科学院长春应用化学研究所 | Polyethylene-polystyrene foam and preparation method thereof |
| CN101824198B (en) * | 2010-04-29 | 2011-11-02 | 中国科学院长春应用化学研究所 | Polyethylene-polystyrene foam and preparation method thereof |
| CN102295799A (en) * | 2010-06-25 | 2011-12-28 | 中国石油天然气股份有限公司 | Polyethylene resin composition for pipes |
| CN102295799B (en) * | 2010-06-25 | 2012-11-14 | 中国石油天然气股份有限公司 | Polyethylene resin composition for pipes |
| CN102816363A (en) * | 2011-06-07 | 2012-12-12 | 东莞市宏恩塑胶制品有限公司 | High-resilience flame-retarding antistatic foamed polyethylene material |
| CN102358794A (en) * | 2011-08-31 | 2012-02-22 | 佛山佛塑科技集团股份有限公司 | Cross-linked polyvinyl chloride (PVC) foaming material and preparation method thereof |
| CN103374167A (en) * | 2012-04-27 | 2013-10-30 | 东北林业大学 | High-filling calcium carbonate/polyethylene bacteriostatic foam material and preparation method thereof |
| CN103205011A (en) * | 2013-03-04 | 2013-07-17 | 鲁奎 | Melamine-formaldehyde foamed plastic foaming agent |
| CN104558780A (en) * | 2015-01-21 | 2015-04-29 | 浙江伟星新型建材股份有限公司 | High-density polyethylene microporous foamed tube and preparation method thereof |
| CN105175647A (en) * | 2015-08-03 | 2015-12-23 | 苏州云舒新材料科技有限公司 | Polyethylene foam material and preparation method therefor |
| CN108841067A (en) * | 2018-06-06 | 2018-11-20 | 嘉兴中易碳素科技有限公司 | Low density polyethylene (LDPE) foaming coiled and preparation method thereof |
| CN109337119A (en) * | 2018-09-25 | 2019-02-15 | 广东省稀有金属研究所 | A kind of vulcanizing activator and preparation method thereof |
| CN113527790A (en) * | 2021-07-19 | 2021-10-22 | 中广核高新核材科技（苏州）有限公司 | Anti-static irradiation crosslinked polyethylene foam material and preparation method thereof |
| CN113831646A (en) * | 2021-09-08 | 2021-12-24 | 南京雷泰克材料科技有限公司 | Preparation method of polypropylene foam |
| CN113915424A (en) * | 2021-10-25 | 2022-01-11 | 福建赛维特水管科技有限公司 | Electronic radiation foaming thermal insulation pipe and processing technology thereof |
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