CN1068357C - Positive temp coefficient high molecular material compsns. and prepn. process thereof - Google Patents
Positive temp coefficient high molecular material compsns. and prepn. process thereof Download PDFInfo
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- CN1068357C CN1068357C CN96116145A CN96116145A CN1068357C CN 1068357 C CN1068357 C CN 1068357C CN 96116145 A CN96116145 A CN 96116145A CN 96116145 A CN96116145 A CN 96116145A CN 1068357 C CN1068357 C CN 1068357C
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Abstract
The present invention relates to a high molecular thermosensitive resistor material and a preparation process thereof. The present invention provides a PTC high molecular material composition. Compared with the existing composition, the PTC high molecular material composition has good electric performance, mechanical performance, environmental stress cracking resistance and thermal aging resistance. In the present invention, the process for manufacturing the composition by extruding a double-screw rod is used, and the defect of the poor repeatability of a product caused by small mixing refinement amount at each time and multiple human factors of process control among batches in the preparation of the composition by a seal refining or double-roller process is overcome. The present invention has the advantages of stable process operation condition and easy control and is convenient for mass production. The high molecular composition with the positive temperature coefficient (PTC) characteristic, which is prepared by the process can be used as an automatic temperature control electrical heating material.
Description
The present invention relates to macromolecular thermosensitive resistor material and preparation method thereof.Specifically, the present invention relates to macromolecular material, conductive filler material and auxiliary agent, the polymeric composition that preparation has positive temperature coefficient (PTC) characteristic is used as from the temperature control electric heating material.
Polymeric composition with ptc characteristics is a kind of functional composite material, can be widely used in from fields such as temperature control heating, autocontrol switch.United States Patent (USP) (U.S.5,106,538), with high density polyethylene(HDPE) (HDPE), carbon black and oxidation inhibitor consolute material in Banbury mixer, extrusion moulding makes the temperature controllable temperature again behind radiation crosslinking be 120 ℃ exothermic material.Replace above-mentioned HDPE with EVA, make 75 ℃ exothermic material in the same way.Chinese patent (87 1 02932A) is dosed the HDPE of 0-5% (weight) and carbon black and auxiliary agent with new LDPE (film grade) (LDPE) and is adopted two rollers to open smelting method makes 85 ± 5 ℃ through radiation crosslinking exothermic material.Report from present open source literature, this based composition all adopts banburying or two roller or the first banburying technology of two rollers again, and the each mixing amount of this type of technology is little, makes the product performance poor repeatability between batch the technology controlling and process human factor more.
The object of the present invention is to provide a kind of method of making the PTC polymer heating material of extruding with twin screw.This method operational condition is stable, is easy to control, is convenient to produce in enormous quantities.Regulate processing condition and can prepare this based composition easily.
The present invention also aims to provide a kind of PTC high molecular material compositions, it is compared with existing this based composition, has excellent mechanical property, environmental stress crack resistance energy, heat aging performance and electric aging resistance.
Composition provided by the invention mainly consists of: polyethylene (density 0.910～0.959g/cm
3Melt flow rate (MFR) (2.16Kg counterweight) 0.05～5.00g/10min), carbon black (dibutyl phthalate (DBP) absorption value 100～500ml/100g, particle diameter 20～100nm), oxidation inhibitor, lubricant and mineral filler, each parts by weight of forming is: (a) 100 (b) 20～50 (c), 0.2～3.0 (d) 0.5～5.0 (e) 0～35.
Composition provided by the invention can also contain 0～1.5 part anti copper agent, is preferably the dihydroxy-benzene formyl hydrazine.
Base resin polyethylene in the composition provided by the invention can LLDPE (LLDPE), HDPE, LDPE or the blend between them, for guaranteeing the mechanical property of composition, is preferably linear polyethylene, i.e. LLDPE or HDPE.No matter adopt a kind of polyethylene or two or more poly blend to do base resin, its density range is 0.910～0.959g/cm
3, melt flow rate (MFR) (2.16Kg counterweight) scope is 0.05～5.00g/10min, is beneficial to extrude processing.
High structure during carbon black in the composition provided by the invention has, its best DBP absorption value scope is 100～400ml/100g, the optimum grain-diameter scope is 30～80nm.For the mechanical property and the electrical property carbon black that improve composition can be through coupling agent treatment; preferable coupling agent is titanate coupling agent, particularly isopropyl tri (dioctylpyrophosphato)titanate, two (dioctylphosphato) metatitanic acid second diester and diisostearoyl ethylene titanate.The coupling agent consumption is 0.5～5.0% of a carbon black weight, is preferably 1.0～3.0%.
Oxidation inhibitor in the composition provided by the invention is for having the antioxidant systems that the ester kind antioxidant of synergistic effect is formed by phenolic antioxidant with phenolic antioxidant.For guaranteeing good synergy, the ratio of two kinds of oxidation inhibitor is 1: 2～1: 30, is preferably 1: 5～1: 15.The parts by weight of antioxidant systems in composition are preferably 0.5～1.0.The selected phenolic antioxidant of the present invention is selected from 1,1, [3-(3 ' for butane, four for 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl), 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester and β-positive 18 phosphorus alcohol esters of (4-hydroxyl-3-5-di-tert-butyl-phenyl) propionic acid, selected ester kind antioxidant is preferably thio-2 acid 2 stearyl ester, thio-2 acid bay octadecyl ester, Tyox B and thio-2 acid two (13) ester for containing the thioesters kind antioxidant.
Lubricant in the composition provided by the invention can be polyethylene wax and (or) stearic acid and its esters.Can use a kind of lubricant, also can use polyethylene wax and stearic acid or stearate lubricant system in 1: 0.5～1: 2.0 ratio composition.The parts by weight of lubricant total amount in composition are preferably 0.5～3.0.
Can add mineral filler in the composition provided by the invention, mineral filler can be chosen from talcum powder, zinc oxide or titanium dioxide.But add mineral filler stable composition PTC effect, improve product size stability, but add too much mineral filler meeting material mechanical performance is descended significantly, so the parts by weight of mineral filler in composition are preferably 3～25.For guaranteeing the good distribution of filler, packing material size is selected between 800～2500 orders.
Preparation technology: during as if carbon black palpus coupling agent treatment, earlier carbon black is added during height stirs, add again take out behind coupling agent treatment 2～10min of 0.5～5.0% of carbon black weight standby, carbon black, base resin (powdery), auxiliary agent and filler etc. are added during height stirs in proportion discharging after 5～15min high-speed mixing.To mix confected materials and add extruding pelletization in the twin screw extruder, temperature range is 160～250 ℃ (selected according to different base resins), make the PTC composition, with said composition can be by molding, technology such as extrude and make sheet material, sheet material, band, obtain the PTC macromolecule material product through radiation crosslinking again.
Composition provided by the invention also can utilize such at present general material banburying or the preparation of two roller working method.Composition provided by the invention has excellent mechanical property, environmental stress crack resistance.The antioxidant systems that the elite major-minor oxidation inhibitor with synergistic effect constitutes obviously improves the material heatproof air aging performance.Adopt powder directly to add the preparation method of mixing granulation in the twin screw, technical process is simplified, the operational condition easy-regulating, the PTC composition surface of extruding is smooth, and has improved production efficiency.With embodiment effect of the present invention is described below.
Embodiment 1: prescription (parts by weight):
LLDPE(MI=2.0g/10min d=0.92g/cm
3) 100
Carbon black (CB) (DBP absorption value 120ml/100g particle diameter 35nm) 35
(through 1% isopropyl tri (dioctylpyrophosphato)titanate coupling agent treatment)
1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane 0.15
Tyox B 0.75
Polyethylene wax 0.8
Zinc oxide 15
Dihydroxy-benzene formyl hydrazine 0.5
Embodiment 2: prescription (parts by weight):
HDPE(MI=0.1g/10min d=0.95g/cm
3) 95
LLDPE(MI=2.0g/10min d=0.92g/cm
3) 5
CB (DBP absorption value 120ml/100g particle diameter 35nm) 29
(through 3% 2 (dioctylphosphato) metatitanic acid second diester coupling agent treatment)
1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane 0.07
Tyox B 0.7
Polyethylene wax 2
Embodiment 3: prescription (parts by weight):
HDPE(MI=0.1g/10min d=0.95g/cm
3) 92
LLDPE(MI=2.0g/10min d=0.92g/cm
3) 8
CB (DBP absorption value 120ml/100g particle diameter 35nm) 31
1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane 0.15
Thio-2 acid 2 stearyl ester 0.75
Stearic acid 0.8
Polyethylene wax 0.7
Talcum powder 7
Embodiment 4: prescription (parts by weight):
HDPE(MI=0.1g/10min d=0.95g/cm
3) 70
LLDPE(MI=2.0g/10min d=0.92g/cm
3) 30
CB (DBP absorption value 120ml/100g particle diameter 35nm) 33
Four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester
0.3
Thio-2 acid 2 stearyl ester 0.6
Polyethylene wax 0.9
Barium stearate 0.8
Embodiment 5: prescription (parts by weight):
HDPE(MI=0.1g/10min d=0.95g/cm
3) 83
LLDPE(MI=2.0g/10min d=0.92g/cm
3) 17
CB (DBP absorption value 400ml/100g particle diameter 42nm) 29
Four [3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester 0.3
Thio-2 acid 2 stearyl ester 0.6
Barium stearate 1.6
Titanium dioxide 5 embodiment effects are as shown in table 1.The effect of table 1. embodiment
*PTC intensity=peak value volume specific resistance/room temperature volume specific resistance;
*21.6Kg counterweight;
* *Through 100 ℃ 1000 hours aging after.
| Project | Unit | Standard | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| The temperature controllable temperature | ℃ | 70±5 | 95±5 | 90±5 | 85±5 | 88±5 | |
| PTC intensity * | 4.0 | 5.2 | 6.0 | 5.1 | 6.7 | ||
| The room temperature volume specific resistance | Ω·cm | GB3048.3 | 1.2×10 3 | 4.7×10 2 | 2.5×10 2 | 9.3×10 2 | 7.2×10 2 |
| Melt flow rate (MFR) ** | g/10min | GB3682 | 25.8 | 6.1 | 6.0 | 10.1 | 7.2 |
| Stretching yield stress | MPa | GB1040 | 11.4 | 23.4 | 25.2 | 18.1 | 20.2 |
| Elongation at break | ％ | GB1040 | 650 | 530 | 444 | 520 | 480 |
| Resisting environmental stress and cracking (50 ℃) | Hour | ASTM D1693 | ＞2000 | ＞1500 | ＞2000 | ＞1500 | ＞1500 |
| Oxidation induction period (210 ℃) | min | ASTM D3895 | 110 | 131 | 122 | 118 | 131 |
| Oxidation induction period ***(210℃) | min | ASTM D3895 | 81 | 82 | 89 | 103 | 94 |
Claims (12)
1. positive temp coefficient high molecular material compositions, it is mainly formed and is:
(a) linear polyethylene density 0.910～0.959g/cm
32.16Kg the melt flow rate (MFR) 0.05～5.00g/10min under the counterweight condition
(b) carbon black dibutyl phthalate oil-absorption(number) 100～400ml/100g particle diameter 30～80nm
Carbon black is handled through titanate coupling agent, and the coupling agent consumption is 0.5～5.0% of a carbon black weight
(c) antioxidant systems of forming by 1: 2～1: 30 part by weight by phenolic antioxidant and ester kind antioxidant
(d) lubricant
(e) mineral filler
Each parts by weight of forming is: (a) 100 (b) 20～50 (c), 0.2～2.0 (d) 0.5～5.0 (e) 0～35.
2. composition according to claim 1 is characterized in that selected component (b) is dibutyl phthalate oil-absorption(number) 100～120ml/100g, the carbon black of particle diameter 30～80nm.
3. composition according to claim 1 is characterized in that selected component (b) is dibutyl phthalate oil-absorption(number) 120ml/100g, the carbon black of particle diameter 35nm.
4. composition according to claim 1 is characterized in that the titanate coupling agent consumption is 1.0～3.0% of a carbon black weight in the selected component (b).
5. as composition as described in claim 1 or 4, it is characterized in that titanate coupling agent is selected from isopropyl tri (dioctylpyrophosphato)titanate, two (dioctylphosphato) metatitanic acid second diester and diisostearoyl ethylene titanate in the selected component (b).
6. composition according to claim 1 is characterized in that the antioxidant systems that selected component (c) is made up of by 1: 5～1: 15 part by weight phenolic antioxidant and ester kind antioxidant.
7. as composition as described in claim 1 or 6, it is characterized in that selected phenolic antioxidant is selected from 1,1, [3-(3 ' for butane, four for 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl), 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester and β-positive 18 phosphorus alcohol esters of (4-hydroxyl-3-5-di-tert-butyl-phenyl) propionic acid, selected ester kind antioxidant is for containing the thioesters kind antioxidant.
8. composition according to claim 1 is characterized in that selected component (d) is selected from a kind of in polyethylene wax, stearic acid and the stearate, and the content of component (d) in composition is 0.8～3.0 parts by weight.
9. composition according to claim 1 is characterized in that the mixture of selected component (d) for polyethylene wax and stearic acid or stearate, and the blended part by weight is 1: 0.5～1: 2.0.
10. composition according to claim 1 is characterized in that also containing in the composition anti copper agent dihydroxy-benzene formyl hydrazine of 0.5～1.5 weight part.
11. the described arbitrary preparation of compositions method of claim 1 to 10 may further comprise the steps:
(1) with component (a) and (b), (c), (d) and (e) powder add during height stirs discharging after 5～15min high-speed mixing in proportion;
(2) will mix confected materials and add extruding pelletization in the twin screw extruder, temperature range is 160～250 ℃, makes positive temp coefficient high molecular material compositions.
12. the described preparation method of claim 11 is characterized in that wherein said component (b) earlier through coupling agent treatment, treatment process is earlier carbon black to be added during height stirs, add again take out behind coupling agent treatment 2～10min standby.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116145A CN1068357C (en) | 1996-12-29 | 1996-12-29 | Positive temp coefficient high molecular material compsns. and prepn. process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116145A CN1068357C (en) | 1996-12-29 | 1996-12-29 | Positive temp coefficient high molecular material compsns. and prepn. process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1197088A CN1197088A (en) | 1998-10-28 |
| CN1068357C true CN1068357C (en) | 2001-07-11 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96116145A Expired - Fee Related CN1068357C (en) | 1996-12-29 | 1996-12-29 | Positive temp coefficient high molecular material compsns. and prepn. process thereof |
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|---|---|
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072243C (en) * | 1998-01-14 | 2001-10-03 | 中山大学 | Manufacture of positive temperature coefficient type conductive high polymer composite material using modified conductive filler |
| US6620343B1 (en) * | 2002-03-19 | 2003-09-16 | Therm-O-Disc Incorporated | PTC conductive composition containing a low molecular weight polyethylene processing aid |
| CN100409375C (en) * | 2003-12-23 | 2008-08-06 | 上海长园维安电子线路保护股份有限公司 | Thermistor and its producing method |
| CN100416709C (en) * | 2004-12-23 | 2008-09-03 | 比亚迪股份有限公司 | Carbon oil in use for making carbon resistance element, preparation method, and prepared element of carbon resistance |
| CN112094449A (en) * | 2020-09-16 | 2020-12-18 | 东莞市竞沃电子科技有限公司 | Curie point adjustable PTC polymer conductive composite material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2459815A1 (en) * | 1979-06-26 | 1981-01-16 | Comp Generale Electricite | High strength polyolefin material with good thermal conductivity - comprising high-density polyethylene, ethylene!-propylene! copolymer and carbon black |
| JPS60202138A (en) * | 1984-03-26 | 1985-10-12 | Sumitomo Electric Ind Ltd | Resin composition |
| CN87102932A (en) * | 1987-04-19 | 1988-11-02 | 中国科学技术大学 | Positive temperature coefficient (PTC) material manufacturing method and equipment thereof |
| JPH01209134A (en) * | 1988-02-18 | 1989-08-22 | Fuji Photo Film Co Ltd | Packing material for photosensitive substance |
| US5106538A (en) * | 1987-07-21 | 1992-04-21 | Raychem Corporation | Conductive polymer composition |
| US5382622A (en) * | 1993-06-29 | 1995-01-17 | Metagal Industria E Comercio Ltda. | Semiconductor polymeric compound based on lampblack, polymeric semiconductor body, and methods of making the semiconductor polymeric compound and the polymeric semiconductor body |
-
1996
- 1996-12-29 CN CN96116145A patent/CN1068357C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2459815A1 (en) * | 1979-06-26 | 1981-01-16 | Comp Generale Electricite | High strength polyolefin material with good thermal conductivity - comprising high-density polyethylene, ethylene!-propylene! copolymer and carbon black |
| JPS60202138A (en) * | 1984-03-26 | 1985-10-12 | Sumitomo Electric Ind Ltd | Resin composition |
| CN87102932A (en) * | 1987-04-19 | 1988-11-02 | 中国科学技术大学 | Positive temperature coefficient (PTC) material manufacturing method and equipment thereof |
| US5106538A (en) * | 1987-07-21 | 1992-04-21 | Raychem Corporation | Conductive polymer composition |
| JPH01209134A (en) * | 1988-02-18 | 1989-08-22 | Fuji Photo Film Co Ltd | Packing material for photosensitive substance |
| US5382622A (en) * | 1993-06-29 | 1995-01-17 | Metagal Industria E Comercio Ltda. | Semiconductor polymeric compound based on lampblack, polymeric semiconductor body, and methods of making the semiconductor polymeric compound and the polymeric semiconductor body |
Non-Patent Citations (1)
| Title |
|---|
| 《塑料橡胶助剂手册》 1995.9.1 吕世光编中国轻工业出版社 * |
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|---|---|
| CN1197088A (en) | 1998-10-28 |
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