CN102532668B - Flame-retarding polyethylene prepared by grafting low-polymerization-degree polyvinyl chloride and preparation method thereof - Google Patents

Flame-retarding polyethylene prepared by grafting low-polymerization-degree polyvinyl chloride and preparation method thereof Download PDF

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Publication number
CN102532668B
CN102532668B CN201210007373.2A CN201210007373A CN102532668B CN 102532668 B CN102532668 B CN 102532668B CN 201210007373 A CN201210007373 A CN 201210007373A CN 102532668 B CN102532668 B CN 102532668B
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district
flame
low
polyethylene
chloride
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CN102532668A (en
Inventor
左林君
戴志龙
戴岳明
陆斌
刘卫清
蒋辉
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JIANGSU NAYA CABLE GROUP CO Ltd
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JIANGSU NAYA CABLE GROUP CO Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

Abstract

The invention discloses flame-retarding polyethylene prepared by grafting low-polymerization-degree polyvinyl chloride, which is characterized by comprising the following components in part by weight: 100 parts of low-density polyethylene (LDPE), 15 to 25 parts of low-polymerization-degree polyvinyl chloride (PVC), 0.2 to 0.6 part of initiator dicumyl peroxide (DCP), 1 to 3 parts of divinylbenzene, 6 to 10 parts of antimonous oxide, 0.1 to 0.3 parts of antioxygen and 0.5 to 1.5 parts of lubricating agent. According to the flame-retarding polyethylene disclosed by the invention, low-polymerization-degree PVC is grafted onto a polyethylene macro molecular chain in an extrusion process to form a grafted copolymer; the macro molecule contains a chlorine molecule, so the formula does not contain flame-retarding synergist; and thus, the physical and mechanical properties of the flame-retarding polyethylene are improved greatly and the flame-retarding polyethylene has high process extrusion performance. The preparation method is simple.

Description

Flame-proof polyethylene prepared by the grafting polyvinyl-chloride of low-polymerization degree and preparation method thereof
Technical field
The invention belongs to chemical field, be specifically related to flame-proof polyethylene prepared by a kind of grafting polyvinyl-chloride of low-polymerization degree and preparation method thereof.
Background technology
Polyethylene has good comprehensive mechanical performance, and wires and cables industry has been used a large amount of polythene materials.Along with the continuous increase of social demand is also more and more higher to the requirement of performance, particularly flame retardant properties has been proposed to very high requirement.
Flame-proof polyethylene was to add fire retardant antimonous oxide (Sb in polyethylene in the past 2o 3) and flame retardancy synergists chlorinated paraffin-70 (the clorafin P-Cl 70 of chlorinity 70%) flame retardant effect better, but that physical and mechanical properties, processing performance descend is a lot.Therefore need to provide a kind of novel flame-proof polyethylene and preparation method thereof.
Summary of the invention
The flame-proof polyethylene that the object of the present invention is to provide a kind of grafting polyvinyl-chloride of low-polymerization degree to prepare.
The preparation method of the flame-proof polyethylene that another object of the present invention is to provide a kind of grafting polyvinyl-chloride of low-polymerization degree to prepare.
Purpose of the present invention can be achieved through the following technical solutions:
Flame-proof polyethylene prepared by a kind of grafting polyvinyl-chloride of low-polymerization degree, it is characterized in that by weight, comprise following component: 0.5～1.5 part of 100 parts of polyethylene LDPE, 15～25 parts of PVC resin with low degree of polymerizations, 0.2～0.6 part of initiator DCP, 1～3 part of Vinylstyrene, 6～10 parts of antimonous oxides, 0.1～0.3 part, oxidation inhibitor and lubricant.
Be preferably: 1 part of 100 parts of polyethylene LDPE, 20 parts of PVC resin with low degree of polymerizations, 0.4 part of initiator DCP, 2 parts of Vinylstyrenes, 8 parts of antimonous oxides, 0.2 part, oxidation inhibitor and lubricant.
Flame-proof polyethylene prepared by above-mentioned grafting polyvinyl-chloride of low-polymerization degree, it is that described lubricant is polyethylene wax.Described oxidation inhibitor is 1010 or antioxidant 1076.
Flame-proof polyethylene prepared by above-mentioned grafting polyvinyl-chloride of low-polymerization degree, it is that the density of described polyethylene LDPE is 0.921～0.925g/m 3, the polymerization degree of PVC resin with low degree of polymerization is 700～800.
Flame-proof polyethylene prepared by above-mentioned grafting polyvinyl-chloride of low-polymerization degree, it is that described flame-proof polyethylene adopts the following methods preparation: after first LDPE, PVC, oxidation inhibitor, antimonous oxide being mixed, add lubricant, initiator, Vinylstyrene to mix, extruding pelletization in twin screw extruder; Technological temperature: district to four district is that 120～150 ℃， five district to eight districts are 170～180 ℃, head 165-175 ℃.The selection process temperature is: a district: 120 ℃， 2nd district: 120 ℃， 3rd district: 130 ℃， 4th district: 150 ℃， 5th district: 180 ℃， 6th district: 180 ℃， 7th district: 180 ℃， 8th district: 170 ℃, and head: 170 ℃.
The preparation method of flame-proof polyethylene prepared by above-mentioned grafting polyvinyl-chloride of low-polymerization degree, comprise the following steps: after first LDPE, PVC, oxidation inhibitor, antimonous oxide being mixed in proportion, add lubricant, initiator, Vinylstyrene to mix, extruding pelletization in twin screw extruder; Technological temperature: district to four district is that 120～150 ℃， five district to eight districts are 170～180 ℃, head 165-175 ℃.The selection process temperature is: a district: 120 ℃， 2nd district: 120 ℃， 3rd district: 130 ℃， 4th district: 150 ℃， 5th district: 180 ℃， 6th district: 180 ℃， 7th district: 180 ℃， 8th district: 170 ℃, and head: 170 ℃.
The preparation method of flame-proof polyethylene prepared by above-mentioned grafting polyvinyl-chloride of low-polymerization degree, it is that described lubricant is polyethylene wax.Described oxidation inhibitor is 1010 or antioxidant 1076.LDPE is Low Density Polyethylene degree polyethylene.PVC is polyvinyl chloride.
The present invention is grafted on PVC resin with low degree of polymerization on the polyethylene macromolecular chain in extrusion, make it become graft copolymer, owing to having contained the chlorine molecule in macromole, therefore do not use flame retardancy synergists in formula, therefore greatly improved the physical and mechanical properties of product, and good technique extrusion performance has been arranged.
Beneficial effect of the present invention:
Flame-proof polyethylene of the present invention is PVC resin with low degree of polymerization to be grafted on the polyethylene macromolecular chain in extrusion, make it become graft copolymer, owing to having contained the chlorine molecule in macromole, therefore do not use flame retardancy synergists in formula, therefore greatly improved the physical and mechanical properties of product, and good technique extrusion performance has been arranged.And the preparation method is simple.
Embodiment
Embodiment 1
Figure BDA0000128483620000021
First by LDPE (commercially available, the Shanghai industry plastic cement company limited of shaking, density: 0.921～0.925g/m 3), PVC (model S-700, the polymerization degree: 700, SINOPEC Qilu Petro-Chemical Corp), antioxidant 1010 is (commercially available, Yixing City angel chemical industry company limited), antimonous oxide is (commercially available, chemical industry company limited is controlled in Shanghai together) mix after, add polyethylene wax (commercially available, Ninghai County praises and chemical industry company limited, model: PEW-6), initiator DCP (dicumyl peroxide, No. CAS: 80-43-3, commercially available, Nanjing East Germany Chemical Industry Science Co., Ltd), Vinylstyrene (commercially available, Qingdao letter Feng Huagong company limited) mixes; Extruding pelletization in co-rotating twin screw extruder; Technological temperature is: a district: 120 ℃， 2nd district: 120 ℃， 3rd district: 130 ℃， 4th district: 150 ℃， 5th district: 180 ℃， 6th district: 180 ℃， 7th district: 180 ℃， 8th district: 170 ℃, and head: 170 ℃.
Embodiment 2
Figure BDA0000128483620000031
First by LDPE (commercially available, the Shanghai industry plastic cement company limited of shaking, density: 0.921～0.925g/m 3), PVC (model S-700, the polymerization degree: 700, SINOPEC Qilu Petro-Chemical Corp), antioxidant 1076 is (commercially available, Yixing City angel chemical industry company limited), antimonous oxide is (commercially available, chemical industry company limited is controlled in Shanghai together) mix after, add polyethylene wax (commercially available, Ninghai County praises and chemical industry company limited, model: PEW-6), initiator DCP (dicumyl peroxide, No. CAS: 80-43-3, commercially available, Nanjing East Germany Chemical Industry Science Co., Ltd), Vinylstyrene (commercially available, Qingdao letter Feng Huagong company limited) mixes; Extruding pelletization in co-rotating twin screw extruder; Technological temperature is: a district: 120 ℃， 2nd district: 120 ℃， 3rd district: 130 ℃， 4th district: 150 ℃， 5th district: 180 ℃， 6th district: 180 ℃， 7th district: 180 ℃， 8th district: 170 ℃, and head: 170 ℃.
Embodiment 3
Figure BDA0000128483620000032
First by LDPE (commercially available, the Shanghai industry plastic cement company limited of shaking, density: 0.921～0.925g/m 3), PVC (model S-700, the polymerization degree: 700, SINOPEC Qilu Petro-Chemical Corp), antioxidant 1010 is (commercially available, Yixing City angel chemical industry company limited), antimonous oxide is (commercially available, chemical industry company limited is controlled in Shanghai together) mix after, add polyethylene wax (commercially available, Ninghai County praises and chemical industry company limited, model: PEW-6), initiator DCP (dicumyl peroxide, No. CAS: 80-43-3, commercially available, Nanjing East Germany Chemical Industry Science Co., Ltd), Vinylstyrene (commercially available, Qingdao letter Feng Huagong company limited) mixes; Extruding pelletization in co-rotating twin screw extruder; Technological temperature is: a district: 120 ℃， 2nd district: 120 ℃， 3rd district: 130 ℃， 4th district: 150 ℃， 5th district: 180 ℃， 6th district: 180 ℃， 7th district: 180 ℃， 8th district: 170 ℃, and head: 170 ℃.
The quality examination result of flame-proof polyethylene prepared by table 1 embodiment 1-3
Test item Embodiment 1 Embodiment 2 Embodiment 3
Tensile strength MPa 13.4 13.3 13.2
Elongation at break % 360 359 358
Oxygen index OI 32 31 32
Melting index g/10min 3.2 3.1 3.3

Claims (9)

1. a flame-proof polyethylene prepared by the grafting polyvinyl-chloride of low-polymerization degree, is characterized in that by weight, comprises following component:
2. the flame-proof polyethylene that prepared by grafting polyvinyl-chloride of low-polymerization degree according to claim 1 is characterized in that comprising following component:
Figure FDA0000128483610000012
3. the flame-proof polyethylene that prepared by grafting polyvinyl-chloride of low-polymerization degree according to claim 1, is characterized in that described lubricant is polyethylene wax, and described oxidation inhibitor is 1010 or antioxidant 1076.
4. the flame-proof polyethylene that prepared by grafting polyvinyl-chloride of low-polymerization degree according to claim 1, the density that it is characterized in that described polyethylene LDPE is 0.921～0.925g/m 3, the polymerization degree of PVC resin with low degree of polymerization is 700～800.
5. the flame-proof polyethylene that prepared by grafting polyvinyl-chloride of low-polymerization degree according to claim 1, it is characterized in that described flame-proof polyethylene adopts the following methods preparation: after first LDPE, PVC, oxidation inhibitor, antimonous oxide being mixed, add lubricant, initiator, Vinylstyrene to mix, extruding pelletization in twin screw extruder; Technological temperature: district to four district is that 120～150 ℃， five district to eight districts are 170～180 ℃, head 165-175 ℃.
6. the flame-proof polyethylene that prepared by grafting polyvinyl-chloride of low-polymerization degree according to claim 5, it is characterized in that described technological temperature is: a district: 120 ℃, 2nd district: 120 ℃, 3rd district: 130 ℃， 4th district: 150 ℃， 5th district: 180 ℃, 6th district: 180 ℃, 7th district: 180 ℃， 8th district: 170 ℃, head: 170 ℃.
7. the preparation method of the flame-proof polyethylene that prepared by grafting polyvinyl-chloride of low-polymerization degree claimed in claim 1, it is characterized in that comprising the following steps: after first LDPE, PVC, oxidation inhibitor, antimonous oxide being mixed in proportion, add lubricant, initiator, Vinylstyrene to mix, extruding pelletization in twin screw extruder; Technological temperature: district to four district is that 120～150 ℃， five district to eight districts are 170～180 ℃, head 165-175 ℃.
8. the preparation method of the flame-proof polyethylene that prepared by grafting polyvinyl-chloride of low-polymerization degree claimed in claim 7, it is characterized in that described technological temperature is: a district: 120 ℃, 2nd district: 120 ℃, 3rd district: 130 ℃， 4th district: 150 ℃， 5th district: 180 ℃, 6th district: 180 ℃, 7th district: 180 ℃， 8th district: 170 ℃, head: 170 ℃.
9. the preparation method of the flame-proof polyethylene that prepared by grafting polyvinyl-chloride of low-polymerization degree according to claim 7, is characterized in that described lubricant is polyethylene wax, and described oxidation inhibitor is 1010 or antioxidant 1076.
CN201210007373.2A 2012-01-03 2012-01-03 Flame-retarding polyethylene prepared by grafting low-polymerization-degree polyvinyl chloride and preparation method thereof Expired - Fee Related CN102532668B (en)

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CN103772616A (en) * 2014-01-22 2014-05-07 南通市海鸥救生防护用品有限公司 Polyethylene-polyvinyl chloride foam and preparation method thereof
CN104861389A (en) * 2015-04-28 2015-08-26 安徽顺驰电缆有限公司 Environmental-friendly flame-retardant cable material

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Publication number Priority date Publication date Assignee Title
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CN102020814A (en) * 2009-09-10 2011-04-20 湖南五强产业集团股份有限公司 Recycled polypropylene modified polrvinyl chloride sectional material and preparation method thereof

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许承威 等.PVC/PE共混体系中增容-交联协同效应的研究.《中国塑料》.1991,第5卷(第2期),

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