CN103524935B - A kind of modified PVC CABLE MATERIALS and preparation method thereof - Google Patents
A kind of modified PVC CABLE MATERIALS and preparation method thereof Download PDFInfo
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- CN103524935B CN103524935B CN201310461765.0A CN201310461765A CN103524935B CN 103524935 B CN103524935 B CN 103524935B CN 201310461765 A CN201310461765 A CN 201310461765A CN 103524935 B CN103524935 B CN 103524935B
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- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 8
- 239000000843 powder Substances 0.000 claims abstract description 34
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 20
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 20
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 13
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 8
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 239000010977 jade Substances 0.000 claims abstract description 8
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000019359 magnesium stearate Nutrition 0.000 claims abstract description 8
- PMOWTIHVNWZYFI-UHFFFAOYSA-N o-Coumaric acid Natural products OC(=O)C=CC1=CC=CC=C1O PMOWTIHVNWZYFI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 8
- 229920002545 silicone oil Polymers 0.000 claims abstract description 8
- PMOWTIHVNWZYFI-AATRIKPKSA-N trans-2-coumaric acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1O PMOWTIHVNWZYFI-AATRIKPKSA-N 0.000 claims abstract description 8
- 239000000049 pigment Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000004808 2-ethylhexylester Substances 0.000 claims abstract description 3
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- -1 poly(oxyethylene glycol) Polymers 0.000 claims description 5
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 241000723346 Cinnamomum camphora Species 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229960000846 camphor Drugs 0.000 claims description 3
- 229930008380 camphor Natural products 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000000341 volatile oil Substances 0.000 claims description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 2
- 239000002341 toxic gas Substances 0.000 abstract description 2
- 238000004383 yellowing Methods 0.000 abstract description 2
- 239000003063 flame retardant Substances 0.000 description 4
- 235000019504 cigarettes Nutrition 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 206010023126 Jaundice Diseases 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a kind of modified PVC CABLE MATERIALS, prepared by the component raw material of following weight part and obtain: polyvinyl chloride resin 30-50, polyamide resin 10-20, CPE resin 10-20, powder nitrile rubber 10-15, nano-calcium carbonate calcium powder 10-15, trimellitic acid three monooctyl ester (TOTM) 20-25, dioctyl sebacate 8-10, tribasic lead sulfate 3-4, silicone oil 0.5-0.8, o-hydroxy cinnamic acid 1-2, BDO 0.3-0.5, jade powder 0.2-0.3, Magnesium Stearate 1-3, triphenyl phosphite 1-2, modified filler 15-20, pigment are appropriate.CABLE MATERIALS of the present invention not only has excellent flame retardancy and not flame-retarding power; During burning, the amount of being fuming is considerably less, does not produce toxic gas, does not produce corrosive gases, and simultaneously can meet ROSH instruction and Reach regulation, high temperature resistant, ageing-resistant again, after weathering test material non-yellowing, do not become fragile.This CABLE MATERIALS purposes is comparatively wide, and price is low.
Description
Technical field
The present invention relates to CABLE MATERIALS field, be specifically related to a kind of modified PVC CABLE MATERIALS and preparation method thereof.
Background technology
Electric wire is important materials indispensable in industrial and agricultural production and the modern life, China is that the maximum electric wire in the whole world produces country, wires and cables industry occupies very important status in the national economy of China, but, at present, CABLE MATERIALS on market also exists non-refractory, not ageing-resistant, and after weathering test, material occurs that jaundice becomes fragile phenomenon.Electric wire is aging and fire that is that cause also gets more and more, how to reduce the incidence of fire and presence of fire time mortality ratio, low cigarette, Halogen, the developing direction that fire-retardant, environmental protection also becomes wires and cables industry.Wherein the demand of halide-free low-smoke fireproof cable material is increasing, the production of current halide-free low-smoke fireproof cable material is in polyolefin substrate, add a large amount of Shawinigan blacks or Shawinigan black to reach flame retardant effect mostly, but, adding of a large amount of inorganic materials, have impact on physical and mechanical properties and the processing of CABLE MATERIALS.Fire-retardant, low cigarette, environmental protection, good weatherability, CABLE MATERIALS that cost is low become the direction of CABLE MATERIALS development.
Summary of the invention
The invention provides a kind of modified PVC CABLE MATERIALS and preparation method thereof.The cable be processed into by CABLE MATERIALS of the present invention has good weatherability, low cigarette, ageing-resistant, and flame retardant properties is good.
The technical solution used in the present invention is:
A kind of modified PVC CABLE MATERIALS, is characterized in that, is prepared and obtain by the component raw material of following weight part:
Polyvinyl chloride resin 30-50, polyamide resin 10-20, CPE resin 10-20, powder nitrile rubber 10-15, nano-calcium carbonate calcium powder 10-15, trimellitic acid three monooctyl ester (TOTM) 20-25, dioctyl sebacate 8-10, tribasic lead sulfate 3-4, silicone oil 0.5-0.8, o-hydroxy cinnamic acid 1-2, BDO 0.3-0.5, jade powder 0.2-0.3, Magnesium Stearate 1-3, triphenyl phosphite 1-2, modified filler 15-20, pigment are appropriate.
Described modified PVC CABLE MATERIALS, is characterized in that, is prepared and obtain by the component raw material of following weight part:
Polyvinyl chloride resin 40, polyamide resin 18, CPE resin 15, powder nitrile rubber 12, nano-calcium carbonate calcium powder 13, trimellitic acid three monooctyl ester 24, dioctyl sebacate 9, tribasic lead sulfate 3, silicone oil 0.7, o-hydroxy cinnamic acid 1, BDO 0.4, jade powder 0.2, Magnesium Stearate 2, triphenyl phosphite 1, modified filler 20, pigment are appropriate.
Described modified PVC CABLE MATERIALS, is characterized in that, described modified filler is obtained by following method preparation preparation:
Diatomite is calcined 3-4 hour at 500-550 DEG C, after taking-up, add in the sodium hydroxide solution of 3-4% and grind 1-2 hour, then, add the hydrochloric acid soln of 12-15%, adjustment pH value is 4-5, ageing 10-15 hour, repeated hydrogenation sodium hydroxide solution regulates lapping liquid pH to be neutral, filter, oven dry obtains filler powder, then, the camphor essential oil being equivalent to powder weight 1-2% is added in gained powder, the nano-sized carbon of 1-2%, 2-3% hypo-aluminum orthophosphate, after co-ground 1-2 hour, add the 3-aminopropyl trimethoxysilane being equivalent to powder weight 2-3% again, 4-5% poly(oxyethylene glycol) 400, the morpholine of 2-3%, the high speed dispersion of 12000-15000 rev/min is even, obtain.
The preparation method of modified PVC CABLE MATERIALS of the present invention:
Each component is taken by formula rate, then first stop the polyvinyl chloride resin taken, polyamide resin, CPE resin, powder nitrile rubber, nano-calcium carbonate calcium powder, trimellitic acid three monooctyl ester, dioctyl sebacate high-speed mixer after high-speed mixer high speed mixing 5-10min, tribasic lead sulfate, silicone oil, o-hydroxy cinnamic acid, 1 is added again in mixing machine, all the other compositions such as 4-butyleneglycol, jade powder, Magnesium Stearate, then after high-speed mixing 15-20min, material is released for subsequent use; The material mixed is sent in the loading hopper of tablets press; open tablets press; the rotating speed controlling tablets press is 300-400r/min; control feed cylinder of granulator front portion, middle part, rear portion and head temperature be respectively: 150-165 DEG C, 160-175 DEG C, 175-185 DEG C, 185-190 DEG C, the material extruded from tablets press through water-cooled, pelletizing, sieve, dry, pack after be finished cable material.
Beneficial effect
CABLE MATERIALS of the present invention not only has excellent flame retardancy and not flame-retarding power; During burning, the amount of being fuming is considerably less, does not produce toxic gas, does not produce corrosive gases, and simultaneously can meet ROSH instruction and Reach regulation, high temperature resistant, ageing-resistant again, after weathering test material non-yellowing, do not become fragile.This CABLE MATERIALS purposes is comparatively wide, and price is low.
Embodiment
A kind of modified PVC CABLE MATERIALS, prepared by the component raw material of following weight (kg) and obtain:
Polyvinyl chloride resin 40, polyamide resin 18, CPE resin 15, powder nitrile rubber 12, nano-calcium carbonate calcium powder 13, trimellitic acid three monooctyl ester 24, dioctyl sebacate 9, tribasic lead sulfate 3, silicone oil 0.7, o-hydroxy cinnamic acid 1, BDO 0.4, jade powder 0.2, Magnesium Stearate 2, triphenyl phosphite 1, modified filler 20, pigment are appropriate.
Wherein, modified filler is prepared by following method and obtains:
Diatomite is calcined 3.5 hours at 540 DEG C, after taking-up, add in the sodium hydroxide solution of 3% and grind 1.5 hours, then, add the hydrochloric acid soln of 13%, adjustment pH value is 4-5, ageing 12 hours, repeated hydrogenation sodium hydroxide solution regulates lapping liquid pH to be neutral, filter, oven dry obtains filler powder, then, the camphor essential oil being equivalent to powder weight 1% is added in gained powder, the nano-sized carbon of 1%, 2% hypo-aluminum orthophosphate, co-ground is after 1.5 hours, add the 3-aminopropyl trimethoxysilane being equivalent to powder weight 2% again, 4.5% poly(oxyethylene glycol) 400, the morpholine of 2%, the high speed dispersion of 13000 revs/min is even, obtain.
The preparation method of modified PVC CABLE MATERIALS:
First modified filler is prepared, then each component is taken by formula rate, first stop the polyvinyl chloride resin taken, polyamide resin, CPE resin, powder nitrile rubber, nano-calcium carbonate calcium powder, trimellitic acid three monooctyl ester, dioctyl sebacate high-speed mixer after high-speed mixer high speed mixing 5-10min, tribasic lead sulfate, silicone oil, o-hydroxy cinnamic acid, 1 is added again in mixing machine, all the other compositions such as 4-butyleneglycol, jade powder, Magnesium Stearate, then after high-speed mixing 15-20min, material is released for subsequent use; The material mixed is sent in the loading hopper of tablets press; open tablets press; the rotating speed controlling tablets press is 300-400r/min; control feed cylinder of granulator front portion, middle part, rear portion and head temperature be respectively: 150-165 DEG C, 160-175 DEG C, 175-185 DEG C, 185-190 DEG C, the material extruded from tablets press through water-cooled, pelletizing, sieve, dry, pack after be finished cable material.
The performance test results of the CABLE MATERIALS that the present embodiment obtains is as following table:
Claims (2)
1. a modified PVC CABLE MATERIALS, is characterized in that, is prepared and obtain by the component raw material of following weight part:
Polyvinyl chloride resin 30-50, polyamide resin 10-20, CPE resin 10-20, Powdered acrylonitrile-butadiene rubber 10-15, nano-calcium carbonate calcium powder 10-15, trimellitic acid three monooctyl ester (TOTM) 20-25, dioctyl sebacate 8-10, tribasic lead sulfate 3-4, silicone oil 0.5-0.8, o-hydroxy cinnamic acid 1-2, BDO 0.3-0.5, jade powder 0.2-0.3, Magnesium Stearate 1-3, triphenyl phosphite 1-2, modified filler 15-20, pigment are appropriate;
Described modified filler is prepared by following method and obtains: diatomite is calcined at 500-550 DEG C 3-4 hour, after taking-up, add in the sodium hydroxide solution of 3-4% and grind 1-2 hour, then, add the hydrochloric acid soln of 12-15%, adjust ph is 4-5, ageing 10-15 hour, repeated hydrogenation sodium hydroxide solution regulates lapping liquid pH to be neutral, filter, oven dry obtains filler powder, then, the camphor essential oil being equivalent to powder weight 1-2% is added in gained powder, the nano-sized carbon of 1-2%, 2-3% hypo-aluminum orthophosphate, after co-ground 1-2 hour, add the 3-aminopropyl trimethoxysilane being equivalent to powder weight 2-3% again, 4-5% poly(oxyethylene glycol) 400, the morpholine of 2-3%, the high speed dispersion of 12000-15000 rev/min is even, obtain.
2. modified PVC CABLE MATERIALS according to claim 1, it is characterized in that, prepared by the component raw material of following weight part and obtain: polyvinyl chloride resin 40, polyamide resin 18, CPE resin 15, Powdered acrylonitrile-butadiene rubber 12, nano-calcium carbonate calcium powder 13, trimellitic acid three monooctyl ester 24, dioctyl sebacate 9, tribasic lead sulfate 3, silicone oil 0.7, o-hydroxy cinnamic acid 1, BDO 0.4, jade powder 0.2, Magnesium Stearate 2, triphenyl phosphite 1, modified filler 20, pigment are appropriate.
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| CN103524935B true CN103524935B (en) | 2016-04-13 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861388A (en) * | 2015-04-28 | 2015-08-26 | 安徽顺驰电缆有限公司 | PVC (Polyvinyl Chloride) insulated wire and cable |
| CN105968636A (en) * | 2016-06-02 | 2016-09-28 | 陈昌 | Environmentally friendly material for cable jacket and preparation method thereof |
| CN108017916A (en) * | 2017-11-28 | 2018-05-11 | 安徽华源电缆集团有限公司 | A kind of wrapped layer material of electricity cable |
| CN108192227A (en) * | 2017-11-28 | 2018-06-22 | 安徽华源电缆集团有限公司 | A kind of cable insulation layer material |
| CN109942925A (en) * | 2019-03-13 | 2019-06-28 | 张现春 | One kind is exempted to vulcanize wire cable insulating rubber grain and preparation method thereof |
| CN113603986B (en) * | 2021-09-01 | 2022-10-21 | 湖南惟楚线缆高分子材料有限公司 | Preparation method of high-strength weather-resistant PVC cable material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4154892A (en) * | 1974-04-09 | 1979-05-15 | Montedison S.P.A. | Electric cables having a sheathing comprising a plasticized vinylchloride polymer |
| EP0751535A2 (en) * | 1995-06-30 | 1997-01-02 | AT&T IPM Corp. | Cable having superior resistance to flame spread and smoke evolution |
| CN102382392A (en) * | 2011-09-29 | 2012-03-21 | 芜湖海杉型材有限公司 | PVC plastic pipe and its preparation method |
| CN102492191A (en) * | 2011-12-01 | 2012-06-13 | 江苏德威新材料股份有限公司 | Environmentally friendly, high and low temperature resistant, oil resistant, wear resistant and fire retardant rubber plastic composition |
| CN103214774A (en) * | 2013-03-26 | 2013-07-24 | 安徽华峰电缆集团有限公司 | Polyvinylchloride insulating electric power cable material and preparation method thereof |
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2013
- 2013-09-30 CN CN201310461765.0A patent/CN103524935B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4154892A (en) * | 1974-04-09 | 1979-05-15 | Montedison S.P.A. | Electric cables having a sheathing comprising a plasticized vinylchloride polymer |
| EP0751535A2 (en) * | 1995-06-30 | 1997-01-02 | AT&T IPM Corp. | Cable having superior resistance to flame spread and smoke evolution |
| CN102382392A (en) * | 2011-09-29 | 2012-03-21 | 芜湖海杉型材有限公司 | PVC plastic pipe and its preparation method |
| CN102492191A (en) * | 2011-12-01 | 2012-06-13 | 江苏德威新材料股份有限公司 | Environmentally friendly, high and low temperature resistant, oil resistant, wear resistant and fire retardant rubber plastic composition |
| CN103214774A (en) * | 2013-03-26 | 2013-07-24 | 安徽华峰电缆集团有限公司 | Polyvinylchloride insulating electric power cable material and preparation method thereof |
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Effective date of registration: 20190225 Address after: 311200 No. 59 Kenhui Sixth Road, Hongken Farm, Xiaoshan Economic and Technological Development Zone, Hangzhou City, Zhejiang Province Patentee after: HANGZHOU DACHENG PIPES CO., LTD. Address before: 236800 3 building 207, Hai Jing building, Qiaocheng District, Bozhou, Anhui Patentee before: Bozhou Woye Intellectual Property Service Co. Ltd. |
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| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 310000 No.59, kenhui 6th Road, hongken farm, Xiaoshan Economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee after: Hangzhou Dacheng pipe industry Intelligent Manufacturing Co., Ltd Address before: 311200 No. 59 Kenhui Sixth Road, Hongken Farm, Xiaoshan Economic and Technological Development Zone, Hangzhou City, Zhejiang Province Patentee before: HANGZHOU DACHENG PIPES Co.,Ltd. |
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| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 310000 No.59, kenhui 6th Road, hongken farm, Xiaoshan Economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee after: Zhejiang Dacheng pipe industry Intelligent Manufacturing Co., Ltd Address before: 310000 No.59, kenhui 6th Road, hongken farm, Xiaoshan Economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee before: Hangzhou Dacheng pipe industry Intelligent Manufacturing Co.,Ltd. |