CN1312209C - Flexible vinyl dedicated to wire and cable - Google Patents
Flexible vinyl dedicated to wire and cable Download PDFInfo
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- CN1312209C CN1312209C CNB200510095273XA CN200510095273A CN1312209C CN 1312209 C CN1312209 C CN 1312209C CN B200510095273X A CNB200510095273X A CN B200510095273XA CN 200510095273 A CN200510095273 A CN 200510095273A CN 1312209 C CN1312209 C CN 1312209C
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Abstract
The present invention relates to a special heat resistant flexible polyvinyl chloride plastic, which belongs to electric wire and cable insulating material in industrial macromolecular material. The present invention is composed of raw materials with the following weight proportion of 100 portions of polyvinyl chloride resin, 40-100 portions of heat resistant plasticizer, 8-12 portions of stabilizing agent, 0.5-1.5 portions of anti-oxidant, 5-60 portions of filling agent and 0-3 portions of lubricator. The flexible polyvinyl chloride plastic provided by the present invention has the heat resistant class of 120 DEG C and the thermal ageing condition of 150 DEG C * 312h or 150 DEG C * 168h, when the aging of the flexible polyvinyl chloride plastic is accelerated under the condition of 150 DEG C * 312h, the retention rate of the tensile strength and the elongation of the flexible polyvinyl chloride plastic is over 70 percent, and the weight loss is lower than 4 percent; the thermostable duration of the flexible polyvinyl chloride plastic is over 300 minutes, and the heat-resisting property is good; in addition, the present invention also has the advantages of small volatility at high temperature, no odor, easy manufacture, etc.
Description
Technical field
The invention belongs to the wire cable insulating material in the industrial macromolecular material, more specifically say it is a kind of special heat-resisting soft polyvinyl chloride plastic that is used for electric wire.
Background technology
The copper conductor of electric wire needs transmission of electric energy, a certain amount of electric current of load, and copper cash produces higher temperature when operation simultaneously.When one timing of copper conductor sectional area, the electric current of conveying is big more, and then the temperature of Chan Shenging is also high more, and therefore the insulating material to electric wire has stable on heating requirement; Size according to carrying electric current produces different temperature, therefore insulating material is had different heat-resisting requirements, so that it keeps the favorable mechanical physicals to satisfy service requirements under long term high temperature.
Soft polyvinyl chloride plastic has comprehensive good physical mechanical electric property, is suitable for insulating material and the sheath material of making the low tension wire cable.By different service requirementss, its temperature classification roughly is divided into several grades such as 70 ℃, 80 ℃, 90 ℃ and 105 ℃, accelerated deterioration performance assessment criteria to these temperature classifications is divided into 100 ℃ * 168h (promptly wearing out 168 hours) in 100 ℃ of thermal ageing casees, 113 ℃ * 168h, 121 ℃ * 168h and 135 ℃ * 168h.The highest temperature classification of the soft polyvinyl chloride plastic in the prior art is 105 ℃, and the instant heating aging temperature is 135 ℃.
China's national standard of the soft polyvinyl chloride plastic of using at electric wire is GB/T8815, the highest heat ageing test condition is 135 ℃ * 240h in this standard, the highest temperature classification of PVC Insulation Material is 105 ℃ in the U.S. UL standard, test conditions is 136 ℃ * 168h, and the highest test conditions of listing national standard at present in the world in is that the test conditions among the VD0207 is 140 ℃ * 336h.
Chinese patent publication number CN1341681A has introduced the soft polyvinyl chloride plastic that a kind of electric wire is used, and its disclosed weight proportion is:
100 parts of polyvinyl chloride (PVC) RESINS
Primary plasticizer 30-90 part
Calcium-zinc composite stabilizing agent 3-10 part
Extender plasticizer 2-15 part
Filler 5-50 part
Its heat-stable time is 100-120 minute, and the temperature classification of using on electric wire is 70-105 ℃.The described the upper limit temperature of heat tolerance of this patent is 105 ℃.The shortcoming that exists is: the thermotolerance of its softening agent can not satisfy higher temperature classification service requirements, and its stabilising system and antioxidant system are not enough to satisfy the stable and anti-oxidant requirement under the high temperature.When higher temperature classification is used, can not stand the heat ageing test of 150 ℃ * 312h, material has turned brown or dark brown with this understanding.
Japanese Patent JP2001-266649A and JP10-306185A and JP9-132689A all disclose the polychloroethylene composition of electric wire, in the composition of three pieces of documents, as if oxidation inhibitor attached undue importance to one thing to the neglect of the other to some extent, but, the applicant thinks as the polychloroethylene composition of electric wire, whether containing oxidation inhibitor is correlated with to the quality of the resistance toheat of product, particularly, to aging back draft strength retention ratio, aging back reserved elongation at break, heat-stable times etc. all can bring influence, especially, also can directly influence aforesaid mechanical and physical performance for whether proper the concrete selection of oxidation inhibitor kind is.
The highest temperature classification of the soft polyvinyl chloride plastic that the electric wire in the prior art is used only is 105 ℃, and temperature classification is unsatisfactory.Therefore,, can improve it and keep the favorable mechanical physicalies, use and avoid premature aging and the work-ing life of extending wire cable at 120 ℃ of following life-time service by improving the resistance toheat of the soft polyvinyl chloride plastic that electric wire uses.
Summary of the invention
Task of the present invention is the soft polyvinyl chloride plastic that will provide a kind of electric wire with superior heat resistance performance to use.
Task of the present invention is finished like this, the soft polyvinyl chloride plastic that a kind of electric wire is used, and it is to be made of following raw materials in weight portion:
100 parts of polyvinyl chloride (PVC) RESINS;
Heat-resisting softening agent 40-100 part;
Stablizer lead cyanurate 8-12 part;
Oxidation inhibitor B225 0.5-0.8 part;
Anti-oxidant DLTP 0.1-0.2 part;
Weighting agent 5-60 part;
Lubricant 0-3 part.
Polyvinyl chloride (PVC) RESINS of the present invention be in SG2 type resin, the SG3 type resin any one or appoint from SG2 type resin, SG3 type resin that to select one and the polymerization degree be 2500 resin blended mixture mutually.
Heat-resisting softening agent of the present invention is the mixture of pyromellitic acid ester plasticizer or pyromellitic acid ester plasticizer and bis(pentaerythritolester) class softening agent and trimellitic acid ester plasticizer.
Weighting agent of the present invention is any one or more than one the mixture in lime carbonate, the calcinated argil.
Lubricant of the present invention is any one or more than one the mixture in stearic acid, stearates, polyethylene wax, the paraffin.
Pyromellitic acid ester plasticizer of the present invention is any one or more than one the mixture in tetraoctyl 1,2,4,5-benzenetetra-carboxylate, pyromellitic acid ester in four ninth of the ten Heavenly Stems, the pyromellitic acid four isodecyl esters; Described bis(pentaerythritolester) is any one or more than one the mixture in dipentaerythritol monooctyl ester, the dipentaerythritol mixed ester; And described trimellitic acid ester plasticizer is any one or more than one the above mixture in trioctyl trimellitate, tri trimellitate ester in the ninth of the ten Heavenly Stems, the triisodecyl trimellitate.
By the temperature classification of soft polyvinyl chloride plastic provided by the present invention is that 120 ℃, thermal ageing condition are 150 ℃ * 312h or 150 ℃ * 168h, accelerated deterioration back draft intensity, elongation retention rate are more than 70% under 150 ℃ * 312h condition, and weight loss is below 4%; Heat-stable time is greater than 300min, Good Heat-resistance; Have in addition that volatility under the high temperature is little, odorlessness, the easy advantage of processing.
Description of drawings
Figure 1 shows that with raw material disclosed in this invention and be processed into the process flow sheet that is extruded the particle that goes on the electric wire.
Embodiment
Following applicant is described in detail the present invention, to help the understanding of the present invention.
In the polyvinyl chloride (PVC) RESINS that the applicant recommended, SG2 type resin and SG3 type resin are meant SG2 type resin described in the GB/T5761 and SG3 type resin in the CNS, and wherein: the trade mark that the former chemical inc in SG2 type resin such as Chinese Shanghai sky is produced and sold is a SG2 type resin; The so-called polymerization degree is that the resin of 1300-2500 is meant with vinylchlorid to the monomer polymerization degree to be the resin of 1300-2500, and the polymerization degree is that the trade mark that 1300 polyvinyl chloride (PVC) RESINS such as Chinese Shanghai chemical industry for making chlorine and alkali limited-liability company produce and sell is S-PVC WS-1300S; The polymerization degree is that the trade mark that the former chemical inc in 2500 polyvinyl chloride (PVC) RESINS such as Chinese Shanghai sky is produced and sold is SH200.In whole proportioning raw materials, both can independently use SG2 type resin or SG3 type resin, also can be with SG2 type resin or SG3 type resin and the use of high-polymerization degree mixed with resin.From the above, to be the polymerization degree of polyvinyl chloride resin be 1300 to PVC1300; The polymerization degree that PVC SH200 is polyvinyl chloride resin is 2500.
In the described heat-resisting softening agent of applicant, as the pyromellitic ester class, though enumerated tetraoctyl 1,2,4,5-benzenetetra-carboxylate (TOPM), pyromellitic acid ester in four ninth of the ten Heavenly Stems, pyromellitic acid four isodecyl esters, do not got rid of and do not lift the not raw material that belongs to the pyromellitic ester class in list that reaches; With example, as the trimellitate class, reached trioctyl trimellitate (TOTM), tri trimellitate ester in the ninth of the ten Heavenly Stems, triisodecyl trimellitate though only lift, as long as belong to trimellitate class category, all should think row at list; Equally, as bis(pentaerythritolester), also be not restricted to described dipentaerythritol monooctyl ester, dipentaerythritol mixed ester.These heat-resisting softening agent can be a kind of, also can be more than one mixtures, and for example tetraoctyl 1,2,4,5-benzenetetra-carboxylate and bis(pentaerythritolester) are shared in whole prescription.
The stablizer that the applicant mentions is by lead salt stabilizer, rare-earth stabilizer, calcium-zinc composite stabilizing agent, wherein: be preferably lead cyanurate for lead salt stabilizer; Be not subjected to the restriction that compiled a name list equally as the phenolic antioxidant of oxidation inhibitor, weighting agent and lubricant are also right, so all can not limit the present invention therefrom.
Foregoing rare-earth stabilizer adopts as Chinese Guangdong is economized the trade mark REC-259E of wide foreign high-tech share company limited producing and selling or the rare-earth stabilizer of any one trade mark among REC-459 or the REC-409; It is the BAEROPANR8890 calcium-zinc composite stabilizing agent that described calcium-zinc composite stabilizing agent both can adopt the goods number of being produced and being sold in Chinese Shanghai by German bear board company, also can adopt by German Kening Co.,Ltd and produce and be Stabiol cz 3046 calcium-zinc composite stabilizing agents at the Chinese Shanghai product sold trade mark; Described stearic acid such as stearic acid etc.; Described stearates such as barium stearate, calcium stearate, stearate lead etc.; Described oxidation inhibitor B225 is the composite antioxidant that comprises antioxidant 1010 and phosphorous acid ester, and the goods number of being produced and sold by Switzerland vapour Bagong department is Irganox B225; The chemical name of antioxidant CA is 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, and trade name is an antioxidant CA, is produced by Lik-Sang chemical plant, Chinese Tianjin; Antioxidant 1010 is four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, and the goods number of being produced and sold by Switzerland vapour Bagong department is Irganox1010; The chemical name of anti-oxidant DLTP is a Tyox B, as the LOWINOX DLTDP by U.S. big lake chemical company.
Embodiment:
The following examples will help to understand the present invention more, but not limit content of the present invention.
Embodiment 1:
The polymerization degree is 100 parts of 1300PVC resins;
50 parts of tetraoctyl 1,2,4,5-benzenetetra-carboxylates (TOPM);
10 parts of lead cyanurate;
0.8 part of oxidation inhibitor B225;
0.2 part of anti-oxidant DLTP;
30 parts in lime carbonate;
1 part of barium stearate.
Embodiment 2:
The polymerization degree is 30 parts of 1300PVC resins;
The polymerization degree is 70 parts of 2500PVC resins;
90 parts of tetraoctyl 1,2,4,5-benzenetetra-carboxylates (TOPM);
10 parts of lead cyanurate;
0.8 part of oxidation inhibitor B225;
0.2 part of anti-oxidant DLTP;
30 parts in lime carbonate;
1 part of barium stearate.
Embodiment 3:
0.5 part of oxidation inhibitor B225;
0.1 part of anti-oxidant DLTP;
All the other amounts of getting are with embodiment 1.
Embodiment 4:
The polymerization degree is 100 parts of 1300PVC resins;
65 parts of tetraoctyl 1,2,4,5-benzenetetra-carboxylates (TOPM);
10 parts of lead cyanurate;
0.8 part of oxidation inhibitor B225;
0.2 part of anti-oxidant DLTP;
30 parts in lime carbonate;
1 part of barium stearate.
Embodiment 5:
55 parts of tetraoctyl 1,2,4,5-benzenetetra-carboxylates (TOPM);
10 parts of trioctyl trimellitates (TOTM);
All the other amounts of getting are with embodiment 4.
Comparative example 1:
The polymerization degree is 100 parts of 1300PVC resins;
50 parts of tetraoctyl 1,2,4,5-benzenetetra-carboxylates (TOPM);
10 parts of lead cyanurate;
30 parts in lime carbonate;
1 part of barium stearate.
Comparative example 2:
The polymerization degree is 100 parts of 1300PVC resins;
50 parts of tetraoctyl 1,2,4,5-benzenetetra-carboxylates (TOPM);
10 parts of lead cyanurate;
0.5 part of oxidation inhibitor dihydroxyphenyl propane;
30 parts in lime carbonate;
1 part of barium stearate.
Comparative example 3:
The polymerization degree is 100 parts of 1300PVC resins;
65 parts of trioctyl trimellitates (TOTM);
10 parts of lead cyanurate;
0.8 part of oxidation inhibitor B225;
0.2 part of anti-oxidant DLTP;
30 parts in lime carbonate;
1 part of barium stearate.
Embodiment 1,2 and 3 under 150 ℃ * 312h thermal ageing tensile strength and the retention rate of elongation at break all more than 70%, aging back specimen surface is yellow.
Comparative example 1 is compared with embodiment 1, does not add oxidation inhibitor B225 and DLTP, and the elongation retention rate after the thermal ageing is 37%, is starkly lower than 70%, and aging back weightlessness is also big, and aging back specimen surface is brown; Comparative example 2 is compared with embodiment 1, and interpolation oxidation inhibitor is dihydroxyphenyl propane, and the elongation after wearing out is lower than 70%, but is better than not adding the comparative example 1 of oxidation inhibitor, and concrete test performance sees the following form:
| 150 ℃ * 312h of thermal ageing | Embodiments of the invention | Comparative example | |||
| 1 | 2 | 3 | 1 | 2 | |
| 200 ℃ of heat-stable time min of weightless % after the reserved elongation at break % thermal ageing of the aging back of aging back draft strength retention ratio % | 89 80 1.8 ＞300 | 86 87 2.3 ＞300 | 88 76 2.6 - | 80 37 4.4 - | 81 62 4.0 210 |
Embodiment 4 and 5 is behind 150 ℃ of following thermal ageing 312h, and the retention rate of sample tensile strength and elongation is all greater than 70%.
Comparative example 3 is compared with 5 with embodiment 4, and softening agent adopts trioctyl trimellitate, and the elongation retention rate of sample is lower than 70%, and concrete test performance sees the following form:
| 150 ℃ * 312h of thermal ageing | Embodiments of the invention | Comparative example | |
| 4 | 5 | 3 | |
| The aging back of aging back draft strength retention ratio % elongation retention rate % | 104 91 | 91 81 | 97 67 |
Embodiment and comparative example are at 150 ℃ of following thermal ageing 312h, measure thermal ageing back draft strength retention ratio and elongation retention rate, tensile strength or the elongation of the retention rate of tensile strength and elongation after with thermal ageing calculates and gets divided by tensile strength before aging or elongation.Require retention rate more than 70%.Weightless behind the heat aging, deduct aging back test piece weight with test piece weight before aging and calculate and get divided by test piece weight before aging again.Heat-stable time refers to material is tested under 200 ℃, becomes blue with congo-red test paper, and the time that promptly begins to discharge hydrogenchloride (HCL) is heat-stable time.
Embodiment and comparative example mix the back with polyvinyl chloride resin and each component and roll 160 ℃ two that mixing plasticizing pulls into sheet in the mill, then 170 ℃ depress to 1mm after, be cut into test piece and test.
By the disclosed raw material of the foregoing description 1-5 through processing process figure shown in Figure 1, the polyvinyl chloride (PVC) RESINS of soon being recommended, heat-resisting softening agent, stablizer, oxidation inhibitor, bulking agent, lubricant are weighed by the weight part ratio of being recommended after the preparation, plastic particle processing technology with routine is about 100 ℃ to mediate temperature, the kneading time is to carry out high speed in 5-8 minute to mediate, more successively preface through twin screw extrusion plasticizing, granulation, be packaged to be have a special resistance toheat and softish igelite particle.Wherein, the temperature of extrusion plasticizing and prilling temperature are controlled to be 130～150 ℃ respectively.This plastic pellet supply lines cable production firm can directly extrude outside the electric wire core with extruding machine with the electric wire of routine.Has the mechanical and physical performance shown in the following table after tested.
| Performance | Unit | Test value | Test method |
| Tensile strength | Mpa | 18.8 | GB1040 |
| Elongation at break | ％ | 280 | GB1040 |
| Thermal ageing condition 150 ℃ * 312 | GB8815 | ||
| Aging back draft strength retention ratio | ％ | 91 | |
| Aging back extension at break retention rate | ％ | 83 | |
| The thermal ageing mass loss | ％ | 2.9 | |
| 200 ℃ of heat-stable times | min | ＞300 | GB8815 |
| Impact embrittlement temperature | -20℃ | By | GB5470 |
| Thermal distortion | ％ | 20 | GB8815 |
| Dielectric strength | MV/m | 26 | GB1408 |
| 20 ℃ of volume specific resistances | Ω·m | 2×10 12 | GB1410 |
Claims (6)
1, the soft polyvinyl chloride plastic used of a kind of electric wire is characterized in that it is to be made of following raw materials in weight portion:
100 parts of polyvinyl chloride (PVC) RESINS;
Heat-resisting softening agent 40-100 part;
Stablizer lead cyanurate 8-12 part;
Oxidation inhibitor B225 0.5-0.8 part;
Anti-oxidant DLTP 0.1-0.2 part;
Weighting agent 5-60 part;
Lubricant 0-3 part.
2, the soft polyvinyl chloride plastic used of electric wire according to claim 1, it is characterized in that described polyvinyl chloride (PVC) RESINS be in SG2 type resin, the SG3 type resin any one or appoint from SG2 type resin, SG3 type resin that to select one and the polymerization degree be 2500 resin blended mixture mutually.
3, the soft polyvinyl chloride plastic used of electric wire according to claim 1 is characterized in that described heat-resisting softening agent is the mixture of pyromellitic acid ester plasticizer or pyromellitic acid ester plasticizer and bis(pentaerythritolester) class softening agent and trimellitic acid ester plasticizer.
4, the soft polyvinyl chloride plastic used of electric wire according to claim 1 is characterized in that described weighting agent is any one or more than one the mixture in lime carbonate, the calcinated argil.
5, the soft polyvinyl chloride plastic used of electric wire according to claim 1 is characterized in that described lubricant is any one or more than one the mixture in stearic acid, stearates, polyethylene wax, the paraffin.
6, the soft polyvinyl chloride plastic used of electric wire according to claim 3 is characterized in that described pyromellitic acid ester plasticizer is any one or more than one the mixture in tetraoctyl 1,2,4,5-benzenetetra-carboxylate, pyromellitic acid ester in four ninth of the ten Heavenly Stems, the pyromellitic acid four isodecyl esters; Described bis(pentaerythritolester) is any one or more than one the mixture in dipentaerythritol monooctyl ester, the dipentaerythritol mixed ester; And described trimellitic acid ester plasticizer is any one or more than one the mixture in trioctyl trimellitate, tri trimellitate ester in the ninth of the ten Heavenly Stems, the triisodecyl trimellitate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510095273XA CN1312209C (en) | 2005-11-04 | 2005-11-04 | Flexible vinyl dedicated to wire and cable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510095273XA CN1312209C (en) | 2005-11-04 | 2005-11-04 | Flexible vinyl dedicated to wire and cable |
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| CN1760258A CN1760258A (en) | 2006-04-19 |
| CN1312209C true CN1312209C (en) | 2007-04-25 |
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| CNB200510095273XA Active CN1312209C (en) | 2005-11-04 | 2005-11-04 | Flexible vinyl dedicated to wire and cable |
Country Status (1)
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| KR101721802B1 (en) * | 2016-05-17 | 2017-03-30 | 주식회사 호만테크 | Pvc compound composition and preparing method thereof |
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