CN1258692A - Crosslinked halide-free fireproof composite polyolefine material and its preparation - Google Patents
Crosslinked halide-free fireproof composite polyolefine material and its preparation Download PDFInfo
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- CN1258692A CN1258692A CN 98126595 CN98126595A CN1258692A CN 1258692 A CN1258692 A CN 1258692A CN 98126595 CN98126595 CN 98126595 CN 98126595 A CN98126595 A CN 98126595A CN 1258692 A CN1258692 A CN 1258692A
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- crosslinked
- halide
- antioxidant
- fireproof composite
- composite polyolefine
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Abstract
The material is prepared by using low density polyethylene and/or copolymer of ethylene and ethyl acetate as base material and adding antioxidant, cross linking agent, modified inorganic stuffing and other assistant, and through the modification of inorganic stuffing, mixing of the base material, antioxidant and other assistant, mixing of the inorganic stuffing and the mixture while adding cross linking agent for irradiation or chemical cross linking. The material of the present invention has high limited oxygen index, high tensile strength at room temperature, high elongation at rupture and excellent machining fluidity. The present invention changes the surface performance of inorganic stuffing with proper surfactant to raise its affinity to polyolefine and to inhibit the drcrease of cohesion energy density and strengthens the cohesional state of polymer material through cross linking.
Description
The present invention relates to a kind of polymer novel material, especially a kind of crosslinked halide-free fireproof composite polyolefine material and preparation method thereof.
The low-smoke non-halogen flame-retardant technology is up-to-date flame retarded polymeric material technology, and it is fire-retardant with PVC, have halogen polyolefine low smoke and low halogen technology to compare, and has the nontoxic characteristics of low cigarette (smokelessly), thereby becomes a focus of the nineties high polymer material technology.The combustioncharacteristics and the terminological interpretation of relevant halogen-free low-smoke flame retardant material for example in Britain's periodical " Plastics, Rubber and CompositesProcessing and Application " [24 (5), 271 (1995)], have been reported.China's " specialty elastomer goods " 1997 the 13rd volumes the 4th phase page 4 has been reported the exploitation and the application of used in nuclear power station halogen-free fireproof rubber, and China's " polymer material science and engineering " introduced by electron beam irradiation and improved HDPE and Mg (OH) 1997 the 13rd the 1st phases of volume
2The technology of the halogen-free low-smoke flame retardant material mechanical property of blend; This area research is very active over nearly 5 years.But, in halide-free fireproof composite polyolefine material, a large amount of Mg (OH)
2, Al (OH)
3,, the adding of red phosphorus and other crystal form mineral filler, changed the aggregated structure of polyolefin substrate, reduced high molecular cohesive energy density(CED), thereby made its mechanical properties decrease, show as the decline of tensile strength and the loss of elongation; With ethylene vinyl acetate copolymer (EVA) is example, and the anti-intensity of pure EVA reaches 18MPa, elongation at break reaches 800%, adds the Mg (OH) of 50 parts of 20 μ M
2After drop to 4.5MPa and 70% respectively.Therefore, do not have the halogen-free low-smoke flame retardant material that is suitable for industrial application to put goods on the market so far as yet, existing like product is at mechanical strength, and all there is deficiency aspects such as anti-aging, resistance toheat.
The objective of the invention is for improve a kind of limiting oxygen index(LOI) height, the room temperature tensile strength is good, elongation at break is high, and has the crosslinked halide-free fireproof composite polyolefine material of good processing flowability and anti ageing property.
Another object of the present invention is for a kind of surface property that utilizes suitable tensio-active agent to change mineral filler is provided, improve itself and polyolefinic affinity, suppress the decline of blend system cohesive energy density(CED), and adopt cross-linking method to strengthen the preparation method of the crosslinked halide-free fireproof composite polyolefine material of high molecular interior poly-state.
Purpose of the present invention can realize by following measure:
A kind of crosslinked halide-free fireproof composite polyolefine material is to be base-material with new LDPE (film grade) and/or ethylene vinyl acetate copolymer, adds antioxidant, linking agent, mineral filler and other auxiliary agent therein and makes; This matrix material is made by the raw material that comprises following weight parts: 100 parts of new LDPE (film grade) and/or ethylene vinyl acetate copolymers, at least a antioxidant 3-11 part, mineral filler 70-110 part, resol encapsulated red phosphorus 5-12 part, carbon black 0-8 part, linking agent 2-5 part.Another object of the present invention also can realize by following measure:
1. a kind of preparation method of crosslinked halide-free fireproof composite polyolefine material comprises the steps: earlier to add Al (OH) in being heated to 60-80 ℃ high speed kneader
3And/or Mg (OH)
2, add Zinc Stearate and two iso stearate base isopropyl titanates then and mediate at a high speed and get final product discharging; 2. in 150-180 ℃ of two roller mills, add the plasticizing of new LDPE (film grade) and/or ethylene vinyl acetate copolymer evenly, add the antioxidant mixing then, add 1. middle mineral filler of handling of step and resol encapsulated red phosphorus, carbon black again, the mixing discharging; 3. with step 2. in the mixture of preparation add the high speed kneader, add cross-linking radiation agent or chemical cross-linking agent again crosslinked getting final product under the cross-linking radiation condition or under the chemically crosslinked condition.
The present invention has following advantage compared to existing technology:
1, utilize surfactant-modified mineral filler and polyolefin base material blend in the prescription of the present invention, add synergistic antioxidant and other auxiliary agents simultaneously, and utilize cross-linking method to strengthen poly-state in the polymer, a large amount of mineral fillers have been overcome in the prior art to the damage of polyolefine material mechanical property, use high flame retardant and excellent mechanical property, processing characteristics and anti ageing property integrally combine, make the limiting oxygen index(LOI) of matrix material of the present invention can reach 41, the room temperature tensile strength reaches 11MPa, elongation at break reaches 450%, and have good processing flowability and anti ageing property, be applicable to that the matrix material of public place is decorated, electric wire and annex etc. thereof.
2, the suitable tensio-active agent that is to use of method of the present invention carries out surface modification to mineral filler, thereby mineral filler and polyolefinic affinity have been improved, suppress the decline of blend system cohesive energy density(CED), adopted cross-linking method to strengthen poly-state in the polymer simultaneously; Thereby the matrix material that utilizes the inventive method preparation has high flame retardant and excellent mechanical property, process industrial art performance and anti ageing property.
The present invention also will be described in further detail in conjunction with the embodiments:
Embodiment one:
A kind of crosslinked halide-free fireproof composite polyolefine material is to be base-material with new LDPE (film grade) and ethylene vinyl acetate copolymer, adds antioxidant, linking agent, mineral filler and other auxiliary agent therein and makes; This matrix material is made by the raw material that comprises following weight parts: 70 parts of new LDPE (film grade)s, 30 parts of ethylene vinyl acetate copolymers, 3-(3,5-di-t-butyl-hydroxy phenyl) 4 parts of propionic acid octadecyl esters, 1,1,3 parts of butane of 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl), 105 parts of mineral fillers, 12 parts of resol encapsulated red phosphorus, 0 part of carbon black, 4 parts of triallyl isocyanates.
Described mineral filler is made by the raw material that comprises following weight parts: Zinc Stearate 3%, two iso stearate base isopropyl titanates 0.5%, its surplus is Al (OH)
3And Mg (OH)
2, Al (OH) wherein
3And Mg (OH)
2Ratio be 3: 1.
1. a kind of preparation method of crosslinked halide-free fireproof composite polyolefine material comprises the steps: earlier to add Al (OH) in being heated to 70 ℃ high speed kneader
3And Mg (OH)
2, add Zinc Stearate and two iso stearate base isopropyl titanates then and mediate at a high speed and get final product discharging; 2. in 165 ℃ of two roller mills, add the plasticizing of new LDPE (film grade) and ethylene vinyl acetate copolymer evenly, add the antioxidant mixing then, add 1. middle mineral filler and the resol encapsulated red phosphorus of handling of step again, the mixing discharging; 3. the 2. middle mixture for preparing of step is added the high speed kneader, add triallyl isocyanate again; Cross-linking radiation gets final product under the cross-linking radiation condition.
Embodiment two:
A kind of crosslinked halide-free fireproof composite polyolefine material is to be base-material with the new LDPE (film grade), adds antioxidant, linking agent, mineral filler and other auxiliary agent therein and makes; This matrix material is made by the raw material that comprises following weight parts: 100 parts of new LDPE (film grade)s, 3-(3,5-di-t-butyl-hydroxy phenyl) 5 parts of propionic acid octadecyl esters, 2,2,4-trimethylammonium-1,5 parts in the dicumyl peroxide mixture of 5 parts of 2-dihyaroquinolines, 95 parts of mineral fillers, 8 parts of resol encapsulated red phosphorus, 3 parts of carbon blacks, talcum powder and dilution.
Described mineral filler is made by the raw material that comprises following weight parts: Zinc Stearate 3%, two iso stearate base isopropyl titanates 2%, its surplus is Al (OH)
3
Its preparation method and example are together only changed the raw material in raw material and the present embodiment, and to change cross-linking radiation be chemically crosslinked.
Embodiment two:
A kind of crosslinked halide-free fireproof composite polyolefine material is to be base-material with its polymers of ethylene vinyl acetate, adds antioxidant, linking agent, mineral filler and other auxiliary agent therein and makes; This matrix material is made by the raw material that comprises following weight parts: 100 parts of ethylene vinyl acetate copolymers, 2 parts of propionic acid octadecyl esters of 3-(3,5-di-t-butyl-hydroxy phenyl), 3 parts of Tyox Bs, 100 parts of mineral fillers, 6 parts of polyphosphoric acid purulence, 6 parts of carbon blacks, 3 parts of triallyl isocyanates.
Described mineral filler is made by the raw material that comprises following weight parts: Zinc Stearate 6%, two iso stearate base isopropyl titanates 1%, its surplus is Mg (OH)
2
Its preparation method and example are together only changed the raw material in raw material and the present embodiment.
Embodiment three:
A kind of crosslinked halide-free fireproof composite polyolefine material is to be base-material with new LDPE (film grade) and its polymers of ethylene vinyl acetate, adds antioxidant, linking agent, mineral filler and other auxiliary agent therein and makes; This matrix material is made by the raw material that comprises following weight parts: 40 parts of 60 parts of new LDPE (film grade)s, ethylene vinyl acetate copolymer, 2,2,4-trimethylammonium-1,2 parts of 2-dihyaroquinolines, 2 parts of Tyox Bs, 70 parts of mineral fillers, 11 parts of polyphosphoric acid amine, 8 parts of carbon blacks, 2 parts of triallyl isocyanates.
Described mineral filler is made by the raw material that comprises following weight parts: Zinc Stearate 5%, two iso stearate base isopropyl titanates 1.5%, its surplus is Al (OH)
3And Mg (OH)
2, Al (OH)
3And Mg (OH)
2Ratio be 2: 1.
Its preparation method and example are together only changed the raw material in raw material and the present embodiment.
Embodiment four:
A kind of crosslinked halide-free fireproof composite polyolefine material is to be base-material with new LDPE (film grade) and its polymers of ethylene vinyl acetate, adds antioxidant, linking agent, mineral filler and other auxiliary agent therein and makes; This matrix material is made by the raw material that comprises following weight parts: 20 parts of 80 parts of new LDPE (film grade)s, ethylene vinyl acetate copolymer, 1,1,2 parts of the dicumyl peroxides of 9 parts of butane of 3-three (2-methyl-4-hydroxyl-power butyl phenyl), 85 parts of mineral fillers, 7 parts of resol encapsulated red phosphorus, 0 part of carbon black, talcum powder and dilution.
Described mineral filler is made by the raw material that comprises following weight parts: Zinc Stearate 4%, two iso stearate base isopropyl titanates 1%, its surplus is Al (OH)
3And Mg (OH)
2, Al (OH)
3And Mg (OH)
2Ratio be 1: 1.
Its preparation method and example are together only changed the raw material in raw material and the present embodiment, and changing cross-linking radiation is chemically crosslinked.
Claims (8)
1, a kind of crosslinked halide-free fireproof composite polyolefine material is to be base-material with new LDPE (film grade) and/or ethylene vinyl acetate copolymer (EVA), adds antioxidant, linking agent, mineral filler and other auxiliary agent therein and makes; It is characterized in that this matrix material made by the raw material that comprises following weight parts:
100 parts of new LDPE (film grade) and/or ethylene vinyl acetate copolymers (EVA)
At least a antioxidant 3-11 part mineral filler 70-110 part
Resol encapsulated red phosphorus 5-12 part carbon black 0-8 part linking agent 2-5 part.
2, crosslinked halide-free fireproof composite polyolefine material as claimed in claim 1 is characterized in that described antioxidant can be hindered phenol, hindered amines antioxidant; Hindered phenol anti-oxidants is 3-(3,5-di-t-butyl-hydroxy phenyl) propionic acid octadecyl ester preferably; The hindered amines antioxidant can be preferred 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane.
3, crosslinked halide-free fireproof composite polyolefine material as claimed in claim 1, it is characterized in that described antioxidant also can be hindered phenol and the mixture that contains thioesters class antioxidant, wherein contains preferably Tyox B of thioesters class antioxidant.
4, crosslinked halide-free fireproof composite polyolefine material as claimed in claim 1, it is characterized in that mineral filler made by the raw material that comprises following weight parts: Zinc Stearate 3-8%, two iso stearate base isopropyl titanate 0.5-2%, its surplus is Al (OH)
3And/or Mg (OH)
2
5, crosslinked halide-free fireproof composite polyolefine material as claimed in claim 1 is characterized in that described resol encapsulated red phosphorus can replace with polyphosphoric acid amine, and weight part is constant in its prescription.
6, crosslinked halide-free fireproof composite polyolefine material as claimed in claim 1 is characterized in that described linking agent can be radiation crosslinker, preferably triallyl isocyanate.
7, crosslinked halide-free fireproof composite polyolefine material as claimed in claim 1, but it is characterized in that described linking agent chemical cross-linking agent, can be preferably mix with the dicumyl peroxide of talcum powder and dilution.
8,1. a kind of method for preparing the described crosslinked halide-free fireproof composite polyolefine material of claim 1 is characterized in that comprising the steps: earlier adding Al (OH) in being heated to 60-80 ℃ high speed kneader
3And/or Mg (OH)
2, add Zinc Stearate and two iso stearate base isopropyl titanates then and mediate at a high speed and get final product discharging; 2. in 150-180 ℃ of two roller mills, add the plasticizing of new LDPE (film grade) and/or ethylene vinyl acetate copolymer evenly, add the antioxidant mixing then, add 1. middle mineral filler of handling of step and resol encapsulated red phosphorus, carbon black again, the mixing discharging; 3. with step 2. in the mixture of preparation add the high speed kneader, add cross-linking radiation agent or chemical cross-linking agent again crosslinked getting final product under the cross-linking radiation condition or under the chemically crosslinked condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98126595 CN1258692A (en) | 1998-12-31 | 1998-12-31 | Crosslinked halide-free fireproof composite polyolefine material and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98126595 CN1258692A (en) | 1998-12-31 | 1998-12-31 | Crosslinked halide-free fireproof composite polyolefine material and its preparation |
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|---|---|
| CN1258692A true CN1258692A (en) | 2000-07-05 |
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|---|---|---|---|
| CN 98126595 Pending CN1258692A (en) | 1998-12-31 | 1998-12-31 | Crosslinked halide-free fireproof composite polyolefine material and its preparation |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005096852A1 (en) * | 2004-04-06 | 2005-10-20 | Jiangchun Lin | A portable pocket-type ashtray |
| CN100448926C (en) * | 2005-09-28 | 2009-01-07 | 中国石油化工股份有限公司 | Polyolefine toughening modifier and its production |
| CN102408604A (en) * | 2011-08-29 | 2012-04-11 | 洪惠泉 | Application of high-pressure polyethylene material |
| CN102436872A (en) * | 2011-09-13 | 2012-05-02 | 江苏达胜热缩材料有限公司 | Thermal-shrinkage-type insulation anode exhaust sealing cap and preparation method thereof |
| CN102731896A (en) * | 2012-07-16 | 2012-10-17 | 江苏达胜高聚物有限公司 | Highly oil-resistant, low-smoke, halogen-free and radiation cross-linked sheath material and preparation method thereof |
| CN102807699A (en) * | 2012-07-27 | 2012-12-05 | 苏州市兴吴工程塑胶有限公司 | Formula of flame-retardant polyethylene plastic |
| CN103772784A (en) * | 2013-12-19 | 2014-05-07 | 安徽特力电缆有限公司 | Halogen-free flame-retardant modified polyethylene cable sheath material |
| CN103865156A (en) * | 2014-03-26 | 2014-06-18 | 马鞍山市佳源环保科技有限公司 | Flexible cross-linked polyethylene insulated cable material and preparation method of cable material |
| CN103865146A (en) * | 2014-02-12 | 2014-06-18 | 合肥安聚达新材料科技有限公司 | Peroxide pre-crosslinked low smoke zero halogen flame retarding irradiation crosslinking polyolefin composite and preparation method thereof |
| CN105295185A (en) * | 2015-08-31 | 2016-02-03 | 无锡市嘉邦电力管道厂 | Heat-conducting and anti-static halogen-free inflaming retarding type composite material as well as preparation method and application thereof |
| CN105623044A (en) * | 2016-02-04 | 2016-06-01 | 爱普高分子技术宜兴有限公司 | GE locomotive cable insulating sheath material |
-
1998
- 1998-12-31 CN CN 98126595 patent/CN1258692A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005096852A1 (en) * | 2004-04-06 | 2005-10-20 | Jiangchun Lin | A portable pocket-type ashtray |
| CN100448926C (en) * | 2005-09-28 | 2009-01-07 | 中国石油化工股份有限公司 | Polyolefine toughening modifier and its production |
| CN102408604A (en) * | 2011-08-29 | 2012-04-11 | 洪惠泉 | Application of high-pressure polyethylene material |
| CN102436872B (en) * | 2011-09-13 | 2013-04-17 | 江苏达胜热缩材料有限公司 | Thermal-shrinkage-type insulation anode exhaust sealing cap and preparation method thereof |
| CN102436872A (en) * | 2011-09-13 | 2012-05-02 | 江苏达胜热缩材料有限公司 | Thermal-shrinkage-type insulation anode exhaust sealing cap and preparation method thereof |
| CN102731896A (en) * | 2012-07-16 | 2012-10-17 | 江苏达胜高聚物有限公司 | Highly oil-resistant, low-smoke, halogen-free and radiation cross-linked sheath material and preparation method thereof |
| CN102807699A (en) * | 2012-07-27 | 2012-12-05 | 苏州市兴吴工程塑胶有限公司 | Formula of flame-retardant polyethylene plastic |
| CN102807699B (en) * | 2012-07-27 | 2014-05-14 | 太仓市天丝利塑化有限公司 | Formula of flame-retardant polyethylene plastic |
| CN103772784A (en) * | 2013-12-19 | 2014-05-07 | 安徽特力电缆有限公司 | Halogen-free flame-retardant modified polyethylene cable sheath material |
| CN103865146A (en) * | 2014-02-12 | 2014-06-18 | 合肥安聚达新材料科技有限公司 | Peroxide pre-crosslinked low smoke zero halogen flame retarding irradiation crosslinking polyolefin composite and preparation method thereof |
| CN103865146B (en) * | 2014-02-12 | 2016-03-30 | 安徽合聚阻燃新材料股份有限公司 | A kind of superoxide precrosslink low-smoke non-halogen flame-retardant cross-linking radiation composite polyolefine material and preparation method thereof |
| CN103865156A (en) * | 2014-03-26 | 2014-06-18 | 马鞍山市佳源环保科技有限公司 | Flexible cross-linked polyethylene insulated cable material and preparation method of cable material |
| CN103865156B (en) * | 2014-03-26 | 2016-03-16 | 马鞍山市佳源环保科技有限公司 | A kind of soft cross-linked polyethylene insulating CABLE MATERIALS and preparation method thereof |
| CN105295185A (en) * | 2015-08-31 | 2016-02-03 | 无锡市嘉邦电力管道厂 | Heat-conducting and anti-static halogen-free inflaming retarding type composite material as well as preparation method and application thereof |
| CN105623044A (en) * | 2016-02-04 | 2016-06-01 | 爱普高分子技术宜兴有限公司 | GE locomotive cable insulating sheath material |
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