CN1197088A - 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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- CN1197088A CN1197088A CN 96116145 CN96116145A CN1197088A CN 1197088 A CN1197088 A CN 1197088A CN 96116145 CN96116145 CN 96116145 CN 96116145 A CN96116145 A CN 96116145A CN 1197088 A CN1197088 A CN 1197088A
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Abstract
A high-molecular material composition as thermosensitive resistor material with positive temp coefficient (PTC) is prepared by twin-screw extruding-out technology, and features excellent electric and mechanical performance, high stress cracking and thermal ageing resistance, stable technological condition and good repeatability.
Description
The present invention relates to macromolecular thermosensitive resistor material and preparation technology 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 (87102932A) 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 technology of making the PTC polymer heating material of extruding with twin screw.This process conditions 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: if carbon black must coupling agent treatment the time, earlier carbon black be added in height stirs 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
CB (DPB absorption value 120ml/100g particle diameter 35nm) 35
(through 1% isopropyl tri (dioctylpyrophosphato)titanate coupling agent treatment)
1,1,3-three (2-first cover 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 (DPB 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 (DPB 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 (DPB 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 (DPB 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
| 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 |
* PTC intensity=peak value volume specific resistance/room temperature volume specific resistance;
* 21.6Kg counterweight;
* * through 100 ℃ 1000 hours aging after.
Claims (15)
1. positive temp coefficient high molecular material compositions, it is mainly formed and is:
(a) density of pe 0.910～0.959g/cm
3
Melt flow rate (MFR) (2.16Kg counterweight) 0.05～5.00g/10min
(b) carbon black DBP oil-absorption(number) 100～500ml/100g
Particle diameter 20～100nm
(c) oxidation inhibitor
(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 (a) is a linear polyethylene.
3. composition according to claim 1 is characterized in that selected component (b) is DBP oil-absorption(number) 100～400ml/100g, the carbon black of particle diameter 30～80nm.
4. composition according to claim 1 is characterized in that selected component (b) uses coupling agent treatment, and the coupling agent consumption is 0.5～5.0% of a carbon black weight.
5. as composition as described in the claim 4, it is characterized in that coupling agent is a titante coupling agent, consumption is 1.0～3.0% of a carbon black weight.
6. as composition as described in claim 4 or 5, it is characterized in that used coupling agent is selected from isopropyl tri (dioctylpyrophosphato)titanate, two (dioctylphosphato) metatitanic acid second diester and diisostearoyl ethylene titanate.
7. composition according to claim 1 is characterized in that the antioxidant systems that selected component (c) is made up of in 1: 2～1: 30 ratio phenolic antioxidant and ester kind antioxidant, and the parts by weight of antioxidant systems in composition are 0.5～1.0.
8. as composition as described in the claim 7, it is characterized in that the antioxidant systems that selected component (c) is made up of in 1: 5～1: 15 ratio phenolic antioxidant and ester kind antioxidant.
9. as composition as described in claim 7 or 8, 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.
10. 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 parts by weight of component (d) in composition are 0.5～3.0.
11. composition is characterized in that the mixture of selected component (d) for polyethylene wax and hard ester acid or hard acid ester salt according to claim 1, blending ratio is 1: 0.5～1: 2.0.
12. composition is characterized in that selected component (e) is selected from zinc oxide, talcum powder and titanium dioxide according to claim 1, the parts by weight of component (e) in composition are 3～25.
13. composition is characterized in that also containing in the composition 0～1.0 part anti copper agent dihydroxy-benzene formyl hydrazine according to claim 1.
14. the described preparation of compositions technology of claim 1 may further comprise the steps:
(1) with component (a) and (b), (c), (d) with (e) add height in proportion and stir middle mixing.
(2) mixture that mixes is directly added extruding pelletization in the twin screw extruder, make positive temp coefficient high molecular material compositions.
15. composition as claimed in claim 1 is used for preparation from temperature control sheet material, tubing and sheet material.
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 true CN1197088A (en) | 1998-10-28 |
| CN1068357C 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1068357C (en) |
Cited By (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 |
Family Cites Families (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 |
| CN1007386B (en) * | 1987-04-19 | 1990-03-28 | 中国科学技术大学 | Method for making positive temp. coefficient material and apparatus thereof |
| US5106538A (en) * | 1987-07-21 | 1992-04-21 | Raychem Corporation | Conductive polymer composition |
| JPH0833621B2 (en) * | 1988-02-18 | 1996-03-29 | 富士写真フイルム株式会社 | Packaging material for photosensitive materials |
| 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
Cited By (7)
| 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 |
| WO2003081607A1 (en) * | 2002-03-19 | 2003-10-02 | Therm-O-Disc, Incorporated | Ptc conductive composition containing a low molecular weight polyethylene processing aid |
| CN100343925C (en) * | 2002-03-19 | 2007-10-17 | 热力蒂思科有限公司 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1068357C (en) | 2001-07-11 |
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Owner name: CHINA PETROCHEMICAL CORPORATION Free format text: FORMER OWNER: SINOPEC QILU PETRO-CHEMICAL CORP. Effective date: 20071228 |
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Effective date of registration: 20071228 Address after: Linzi Zibo District, Shandong province Sinopec Qilu Branch of science and technology Patentee after: China Petrochemical Group Corp. Address before: 124 mailbox, Zibo City, Shandong Province Patentee before: Qilu Petrochemical Company of China Petrochemical Corp. |
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Granted publication date: 20010711 Termination date: 20131229 |