CN1341681A - Flexible polyvinyl chloride plastics for making wire and cable - Google Patents
Flexible polyvinyl chloride plastics for making wire and cable Download PDFInfo
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- CN1341681A CN1341681A CN 00112518 CN00112518A CN1341681A CN 1341681 A CN1341681 A CN 1341681A CN 00112518 CN00112518 CN 00112518 CN 00112518 A CN00112518 A CN 00112518A CN 1341681 A CN1341681 A CN 1341681A
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Abstract
The flexible polyvinylchloride plastics for electric wire and cable are characterized by that its raw material composition includes (by weight portion) 100 portions of polyvinyl chloride, 30-90 portions of main plasticizer, 3-10 portions of calcium zinc composite stabilizing agent, 2-15 portions of auxiliary plasticizer and 5-50 portions of filler. Its thermally stable time can be up to 100-120 min. under the condition of 200 deg.C, and it has the advantages of no lead and no pollution.
Description
The present invention relates to a kind of soft polyvinyl chloride plastic material, belong to industrial polymeric material field.
In the prior art, the polarity of the molecule of polyvinyl chloride is very strong, and it mainly is the linear macromolecule that is formed by the monomer chloroethylene polymerization, because intermolecular active force is large, thereby its softening temperature and melt temperature are high, vitrification point high (Tg=80～82 ℃). Therefore, generally need be heated to and just can make its plasticizing processing more than 150～160 ℃, so common processing temperature is between 150～210 ℃. But general commercially available Corvic is extremely unstable under heating condition, temperature just begins to decompose above 90 ℃ when it is heated, temperature is higher than 120 ℃ and just obviously decomposes, the result emits a large amount of hydrogen chloride (HCL) gas, with the increase of effusion hydrogen chloride (HCL) amount, the igelite color deepens gradually. Therefore the pure Corvic that does not add stabilizing agent can't be processed and use. Along with to the going deep into of polyvinyl chloride research, in plastics, add lead salt stabilizer after, polyvinyl chloride just is sure to occupy the prostatitis of each large plastics by feat of good physical property and fire resistance. In not crosslinked situation, common soft polyvinyl chloride plastic hot strength can reach about 20Mpa, and elongation at break is about 300%, and it can also be combined well with common fillers, and heatproof can reach 105 ℃, and the oxygen index (OI) of pure polyvinyl chloride can reach 41%. In addition, it also has excellent electrical apparatus insulation performance, thereby leading at wires and cables industry, particularly aspect the low tension wire cable, occupies great advantage. But these soft polyvinyl chloride plastics all contain heavy metal lead salt or other heavy metal. Although lead salt stabilizer has splendid stability, it directly has influence on human life along with the aging or alternate manner of flexible PVC enters human life, has also caused serious negative effect to environment. For the unleaded research of soft polyvinyl chloride plastic, a large amount of work has been done by scientific research institution both at home and abroad, has also found some approach. Wherein a kind ofly be: the polyvinyl chloride that contains organotin. It is good that organic tin stabilizer has a stablizing effect, and the advantage that consumption is few is mainly used in the high transparent hard and flexible plastic products, but organotin has toxicity mostly, and most of also have off-odor, though processing initial stage form and aspect are good, but blackspot appears in the very fast variable color of later stage meeting. Another then is to use: calcium stearate and zinc stearate cooperate chelating agent, China Patent Publication No. CN1032014C discloses " Novel blood or transfusion soft polyvinyl chloride plastic composite ", adopt exactly this system, but losing what shake is that its heat-stable time is too short, and heat endurance can't satisfy the requirement of wires and cables industry.
The object of the present invention is to provide a kind of soft polyvinyl chloride plastic that is used for electric wire unleaded, Heat stability is good that has.
Technical scheme of the present invention is: a kind of soft polyvinyl chloride plastic for electric wire, its weight proportion comprises
100 parts of polyvinyl chloride;
30～90 parts of primary plasticizers;
3～10 parts of calcium-zinc composite stabilizing agents;
2～15 parts of co-plasticizer;
5～50 parts of fillers.
After described calcium-zinc composite stabilizing agent carries out saponification by the mixture of calcium hydroxide and zinc hydroxide and higher fatty acids (as: stearic acid (also claiming stearic acid), along Octadec-9-enoic Acid etc.), concentrated through purifying again, then cooperate other auxiliary agent, such as antioxidant, filler, lubricant etc. and its Main Ingredients and Appearance of high effect nontoxic stabilizing agent of a kind of soft polyvinyl chloride plastic for wires and cables industry of making is organic calcium salt and organic zinc salt, in whole calcium-zinc composite stabilizing agent, calcium content accounts for 0.05～0.5%, and zinc content accounts for 8～10%.
The present invention compared with prior art has following advantages:
Properties of the present invention after tested, it meets the requirement of soft PVC plastic for electric wire and cable fully, and its heat endurance and weather resisteant all significantly improve. According to the GB8815-88 standard testing, the heat-stable time of old unleaded flexible PVC is 30 minutes, and heat-stable time of the present invention is 100-120 minute. Test condition is temperature: 200 ℃, and medium: glycerine, test paper: Congo red. And in the GB8815-88 standard, the heat-stable time of the highest a kind of flexible PVC (H-90) is: 80 minutes.
Can be found out that by above result the present invention can satisfy the heat-staple requirement of GB8815-88 fully, thereby break through the bottleneck of unleaded flexible PVC heat endurance. Simultaneously, this product has odorlessness, the characteristics such as easy processing. Described odorlessness refers to all free from extraneous odour generations in processing and secondary processing process of this product, has so greatly improved workman's working environment. Described easy processing refers to that this product processing T skill is simple, easy to operate, in granulation process through batching → high-speed kneading → heat extrude → pelletizing packs. Extruding processing temperature exists: 150 ℃～160 ℃. Need not special special screw rod when backguy, temperature is controlled at about 170 ℃.
Embodiment: a kind of soft polyvinyl chloride plastic for electric wire, its weight proportion comprises
100 parts of polyvinyl chloride;
30～90 parts of primary plasticizers;
3～10 parts of calcium-zinc composite stabilizing agents;
2～15 parts of co-plasticizer;
5～50 parts of fillers.
0～2.5 part of lubricant.
After described calcium-zinc composite stabilizing agent carries out saponification by the mixture of calcium hydroxide and zinc hydroxide and higher fatty acids (as: stearic acid (also claiming stearic acid), along Octadec-9-enoic Acid etc.), concentrated through purifying again, then cooperate other auxiliary agent, such as antioxidant, filler, lubricant etc. and the high effect nontoxic stabilizing agent of a kind of soft polyvinyl chloride plastic for wires and cables industry of making. Its Main Ingredients and Appearance is organic calcium salt and organic zinc salt, and in whole calcium-zinc composite stabilizing agent, calcium content accounts for 0.05～0.5%, and zinc content accounts for 8～10%.
Operating temperature depending on plastics is different, can select different primary plasticizers, when described soft polyvinyl chloride plastic was the nominal operation temperature of 70 degree Celsius, described primary plasticizer adopted O-phthalic acids plasticizer or terephthaldehyde's acids plasticizer or trimellitic acid class plasticizer or its mixture; When described soft polyvinyl chloride plastic was the nominal operation temperature of 80 degree Celsius, described primary plasticizer adopted diisooctyl phthalate or terephthaldehyde's acids plasticizer or its mixture in trimellitic acid class plasticizer or the O-phthalic acids plasticizer; When described soft polyvinyl chloride plastic was the nominal operation temperature of 90 degree Celsius, described primary plasticizer adopted diisooctyl phthalate or trimellitic acid class plasticizer or its mixture in terephthaldehyde's acids plasticizer or the O-phthalic acids plasticizer; When described soft polyvinyl chloride plastic was the nominal operation temperature of 105 degree Celsius, described primary plasticizer adopted trimellitic acid class plasticizer or its mixture.
Described O-phthalic acids plasticizer can be ester or dibutyl phthalate (DHP) or diisooctyl phthalate etc. of phthalic acid two (2-ethyl); Described terephthaldehyde's acids plasticizer can be the own ester of terephthalic acid (TPA) two (2-ethyl) etc.; Described trimellitic acid class plasticizer can be trioctyl trimellitate (TOTM) etc. Described co-plasticizer is epoxidised soybean oil or epoxidized oil acid butyl ester or its mixture. Described filler is calcium carbonate or potter's clay or its mixture. Described lubricant is stearic acid or paraffin or Tissuemat E or its mixture.
Instantiation 1:
70 ℃ 80 ℃ 90 ℃ 105 ℃ of temperature resistant grades
(1) polyvinyl chloride 100 100 100 100
(2) the own ester 30～40 of phthalic acid one or two (2-7 yl)
(3) diisooctyl phthalate 30～80 30～80
(4) the own ester 30 of terephthalic acid (TPA) two (2-ethyl)～40 10～20 10～20
(5) trioctyl trimellitate (TOTM) 30～90
(6) calcium-zinc composite stabilizing agent 3～10 3～10 3～10 3～10
(7) co-plasticizer 2～15 2～15 2～15 2～15
(8) filler 5～50 5～50 5～50 5～50
(9) lubricant 0～2.5 0～2.5 0～2.5 0～2.5
Above umber is parts by weight, and primary plasticizer is also only enumerated commonly used several.
Instantiation 2, concrete prescription is as follows as an example of 70 ℃ of materials example:
70 ℃ of protective cover materials of 70 ℃ of Insulation Material
(1) 100 parts of polyvinyl chloride (weight) 100 parts (weight)
(2) 30～90 parts of primary plasticizers (weight) 30～90 parts (weight)
(3) 3～10 parts of calcium-zinc composite stabilizing agents (weight) 3～10 parts (weight)
(4) 2～15 parts of co-plasticizer (weight) 2～15 parts (weight)
(5) 5～40 parts in calcium carbonate (weight) 5～50 parts (weight)
(6) 5～15 parts in potter's clay (weight)---
(7) 0～2.5 part of lubricant (weight) 0～2.5 part (weight)
Instantiation 3:
60～75 100 parts of values of polyvinyl chloride loose type K (weight)
10～40 parts of trimellitate classes (weight)
10～40 parts of two isodecyl esters of O-phthalic (weight)
2～10 parts of epoxidized soybean oils (weight)
5～50 parts in calcium carbonate (weight)
0～30 part in potter's clay (weight)
0.3～0.5 part of Tissuemat E (weight)
0.2～0.5 part of titanium dioxide (pigment) (weight)
Processing method of the present invention is: batching → high-speed kneading → twin-screw extrusion → pelletizing packing. Mediate the temperature of powder about 100 ℃, the kneading time is: about 6 minutes; Extrude processing temperature: twin-screw is controlled at 150 ℃～160 ℃. After the granulation, through 170 ℃ of left and right sides screw rod backguys, the thin-walled line of making can satisfy J1128 standard and JASO D611-94 standard to the requirement of insulating materials.
Main physical performance test of the present invention is as follows:
| Performance | Unit | Index | Representative value | Test method |
| Hot strength | Mpa | ≥19.5 | 23.88 | GB1040 |
| Elongation at break | ％ | ≥250 | 327.56 | GB1040 |
| The thermal ageing test condition | 121℃×168h GB8815-88 | |||
| The residual rate of hot strength | ％ | ≥80 | 98.4 | GB1040 |
| The residual rate of elongation at break | ％ | ≥75 | 88.4 | GB1040 |
| 20 ℃ of specific volume resistances | Ω.M | ≥1.0×10 12 | 2.0×10 12 | GB1410 |
| Specific volume resistance in the time of 80 ℃ | Ω.M | ≥1.0×10 10 | 5.0×10 11 | GB1410 |
| 200 ℃ of heat-stable times | Min | ≥90 | 120.5 | GB/T2917-89 |
| Impact brittle temperature | ℃ | ≥-20 | By | GB5470 |
| Thermal deformation | ％ | ≤30 | 15 | |
| Dielectric strength | MV/m | ≥20 | 25 | GB1408 |
| Proportion | g/cm 3 | 1.27-1.33 | 1.31 | GB1033-1034-86 |
| Hardness (shore D) | 43-51 | 49 | ||
| Outward appearance | Plasticizing is good, and color and luster is without obviously mechanical admixture is even. |
Claims (8)
1, a kind of soft polyvinyl chloride plastic for electric wire, it is characterized in that: its weight proportion comprises
100 parts of polyvinyl chloride;
30～90 parts of primary plasticizers;
3～10 parts of calcium-zinc composite stabilizing agents;
2～15 parts of co-plasticizer;
5～50 parts of fillers.
Described calcium-zinc composite stabilizing agent is mainly the product after the mixture of calcium hydroxide and zinc hydroxide and higher fatty acids carry out saponification, its Main Ingredients and Appearance is organic calcium salt and organic zinc salt, in whole calcium-zinc composite stabilizing agent, calcium content accounts for 0.05～0.5%, and zinc content accounts for 8～10%.
2, the soft polyvinyl chloride plastic for electric wire according to claim 1 is characterized in that: it also comprises and is less than or equals 2.5 parts lubricant.
3, the soft polyvinyl chloride plastic for electric wire according to claim 1, it is characterized in that: when described soft polyvinyl chloride plastic was the nominal operation temperature of 70 degree Celsius, described primary plasticizer adopted O-phthalic acids plasticizer or terephthaldehyde's acids plasticizer or trimellitic acid class plasticizer or its mixture; When described soft polyvinyl chloride plastic was the nominal operation temperature of 80 degree Celsius, described primary plasticizer adopted diisooctyl phthalate or terephthaldehyde's acids plasticizer or its mixture in trimellitic acid class plasticizer or the O-phthalic acids plasticizer; When described soft polyvinyl chloride plastic was the nominal operation temperature of 90 degree Celsius, described primary plasticizer adopted diisooctyl phthalate or trimellitic acid class plasticizer or its mixture in terephthaldehyde's acids plasticizer or the O-phthalic acids plasticizer; When described soft polyvinyl chloride plastic was the nominal operation temperature of 105 degree Celsius, described primary plasticizer adopted trimellitic acid class plasticizer or its mixture.
4, the soft polyvinyl chloride plastic for electric wire according to claim 3 is characterized in that: described O-phthalic acids plasticizer is ester or dibutyl phthalate (DHP) or diisooctyl phthalate of phthalic acid two (2-ethyl); Described terephthaldehyde's acids plasticizer is ester of terephthalic acid (TPA) two (2-ethyl); Described trimellitic acid class plasticizer is trioctyl trimellitate (TOTM).
5, the soft polyvinyl chloride plastic for electric wire according to claim 1 is characterized in that: described co-plasticizer is epoxidised soybean oil or epoxidized oil acid butyl ester or its mixture.
6, the soft polyvinyl chloride plastic for electric wire according to claim 1 is characterized in that: described filler is calcium carbonate or potter's clay or its mixture.
7, the soft polyvinyl chloride plastic for electric wire according to claim 2 is characterized in that: described lubricant is stearic acid or paraffin or Tissuemat E or its mixture.
8, the soft polyvinyl chloride plastic for electric wire according to claim 1, it is characterized in that: described higher fatty acids comprises: stearic acid or suitable Octadec-9-enoic Acid or its composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00112518 CN1341681A (en) | 2000-09-07 | 2000-09-07 | Flexible polyvinyl chloride plastics for making wire and cable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00112518 CN1341681A (en) | 2000-09-07 | 2000-09-07 | Flexible polyvinyl chloride plastics for making wire and cable |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1341681A true CN1341681A (en) | 2002-03-27 |
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|---|---|---|---|
| CN 00112518 Pending CN1341681A (en) | 2000-09-07 | 2000-09-07 | Flexible polyvinyl chloride plastics for making wire and cable |
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| CN100356483C (en) * | 2001-05-29 | 2007-12-19 | 东京毅力科创株式会社 | Electric wire and cable with coating/covering of polyvinyl chloride family resin composition |
| CN100516131C (en) * | 2005-09-16 | 2009-07-22 | 无锡江南电缆有限公司 | Soft PVC plastic for electric wire and cable |
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