CN1760015A - Technique for steel-plastic composite tube enhanced by antistatic flame retardant Nano fibers - Google Patents
Technique for steel-plastic composite tube enhanced by antistatic flame retardant Nano fibers Download PDFInfo
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- CN1760015A CN1760015A CN 200510012953 CN200510012953A CN1760015A CN 1760015 A CN1760015 A CN 1760015A CN 200510012953 CN200510012953 CN 200510012953 CN 200510012953 A CN200510012953 A CN 200510012953A CN 1760015 A CN1760015 A CN 1760015A
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Abstract
A nanofiber reinforced steel-plastic pipe with antistatic and flame-retarding functions is composed of liner layer, reinforcing layer and surface layer. Its preparing process includes such steps as mixing thermosetting resin with flame-retarding agent, antistatic agent, solidifying agent and filler, winding the fibers or fiber fabric on a tubular mould while coating said mixture, adding spiral steel wire mesh skeleton, and solidifying.
Description
Technical field
The present invention relates to improvement, be specially adapted to the explosion-proof engineering under the mine inflammable gas, liquid or fluidized solids transfer tube structural design.
Background technology
Much inflammable, explosive occasion needs large-scale pipeline to carry gas, liquid even fluidized solids.The gas that a lot of pipelines are carried, liquid or liquid stateization solid itself are exactly explosives, inflammable items, as the various transfer pipelines under the mine, the underground air high, blast furnace gas, flyash as firedamp drainage content.Under this occasion, transfer conduit there is higher requirement, as anti-combustion, prevent electrostatic phenomenon, wear-resisting, anti-leakage etc.So traditional engineering discipline can only use cast iron pipe, or large-diameter steel pipe.Its weight is big, and corrosion is too fast, if it is too high to consider that the friction loss meeting is directed at use cost.So the occasion in the needs construction is often invested greatly.In the last few years along with the raising of material technology, technology, owing to solved fire-retardant and antistatic problem well in pvc pipe road and the composite glass steel pipe.The plastic composite pipe of PVC and fiberglass and so on also has been widely used under the mine and similar occasion.Be base-material by fiber or fabric in the composite plastic pipe manufacture craft, with the thermosetting resin adhesive is adhesive, add and join fire retardant, antistatic additive, curing agent and inserts are formed the adhering and solidifying agent, twine the agent of base-material limit coating adhering and solidifying in tubular mould top, the final pipeline that solidifies back formation and the combination of prefabricated ring flange accessory, the structure of pipeline comprises three layers: on tubular mould, twine fiber or its fabric simultaneously evenly coating have that the thermosetting resin adhesive of conduction and flame-retarding characteristic is formed to have impervious and inner liner anti-wear performance, on the basis that ring flange mould and inner liner form, twine enhanced fiber or its fabric simultaneously evenly coating have the formed strength layer of thermosetting resin adhesive of conduction and flame-retarding characteristic, on the surface of strength layer, twine fine and close fiber or its fabric and evenly apply thermosetting resin adhesive simultaneously and form the surface conductance layer with strong conduction and flame-retarding characteristic., corrosion resistance low owing to its cost is strong, reach 50 years and be subjected to great welcome service life.But along with application, significant disadvantages in having exposed, too low as flexural strength, difficulty of construction is bigger.Then except that above weakness, also have capacity of resisting impact load relatively poor, quality is crisp, poor toughness causes comminuted breakage easily under adverse circumstances, easily reveal and do not possess excellent safety, its anti-wear performance is also relatively poor, then show hidden danger on tangible deficiency and the safety for the conveying of big gas of dustiness and fluidized solids.
Summary of the invention
The present invention seeks to the technology and the structure of the multiple tube of this plastics and fiber-like are done further improvement design.It is being realized outside good fire-retardant and antistatic, the corrosion resistant performance energy, improving the plastics microstructure and to set up intensity and the resistant to bending elastic modelling quantity of the technical scheme of rigid backbone, thereby produce a brand-new enhancing composite metal plastic pipe product with further raising anti-wear performance, anti-shock loading.
Basic design of the present invention is to take three big measures in design.At first be in having the conduction and the thermosetting resin adhesive of flame-retarding characteristic, to add to have joined the nano-calcium carbonate that improves each layer of multiple tube microstructure and do filler, thereby improve the affinity between plastics and the fiber, increase the fine and closely woven degree of molecule between the plastics, can also improve its structural strength, pliability and elastic modelling quantity, and then improve anti-wear performance, add the nano-calcium carbonate of filling out 3-36 part according to the resin glue of the per 100 parts of weight of the needs of each layer 26S Proteasome Structure and Function; Moreover be in having the conduction and the thermosetting resin adhesive of flame-retarding characteristic, to add to have joined the nanometer carbon black that improves each layer of multiple tube electric conductivity and do modifier, can also further reduce frosting frictional resistance, require the resin glue of per 100 parts of weight to add the nanometer carbon black of filling out 0.5-3 part to the difference of electric conductivity according to each layer; Be the enhancing skeleton of forming by the helical form steel wire being provided with at last at strength layer, and by the affinity interaction of calcium carbonate superfine powder, itself and base fiber and thermosetting material are combined closely, produce the stronger anti-crack ability and the excellent elasticity of anti-shock loading, make pipeline have better bending resistance.
Good effect of the present invention is: three layers of compo multiple tube that existing two ends are provided with the ring flange of fixing or sleeve type improve and become three layers of enhanced type steel plastic composite.Improve the back body and between fiber, steel skeleton and thermosetting plastics, be filled with nano level calcium carbonate and nano level carbon black, strengthened the ability of its bending strength and anti-shock loading when having changed the fine structure of each layer, anti-wear performance and conductive capability are significantly improved.
How further specify goal of the invention of the present utility model below in conjunction with accompanying drawing realizes.
Description of drawings:
Fig. 1 is a structural representation of the present utility model.
Wherein, 1 represents the surface conductance layer of multiple tube, and 2 representatives strengthen stress layer, and 2A represents the helical form steel wire, and 2B represents axial ribs, and 3 represent inner liner, and 4 represent ring flange, and 4A is the through hole on the ring flange.5 represent mould.
The specific embodiment
Each structure sheaf of steel-plastics composite pipe of the present invention adds the man-hour concrete used thermosetting resin adhesive embodiment with conduction and flame-retarding characteristic and forms than preparing by following composition by weight:
1. barrier properties inner liner 1 usefulness
| Embodiment | Resin glue | Fire retardant | Curing agent | Promoter | Nano-calcium carbonate | Nanometer carbon black |
| 1 2 3 4 5 | 100 100 100 100 100 | 100 20 30 50 10 | 0.5 1 2 3 4 | 4 3 2 1 0.5 | 3 10 15 20 30 | 0.5 3 1 2 1.5 |
2. wearability inner liner 1 usefulness
| Embodiment | Resin glue | Fire retardant | Curing agent | Promoter | Nano-calcium carbonate | Nanometer carbon black | Silica |
| 6 | 100 | 30 | 0.5 | 4 | 25 | 1.2 | 80 |
| 7 8 9 10 | 100 100 100 100 | 20 30 30 26 | 1 2 3 4 | 3 2 1 0.5 | 10 20 26 24 | 1.2 1.2 1.2 1.2 | 60 50 30 10 |
3. strength layer 2 usefulness
| Embodiment | Resin glue | Fire retardant | Curing agent | Promoter | Nano-calcium carbonate | Nanometer carbon black | Silica flour |
| 11 12 13 14 15 | 100 100 100 100 100 | 40 30 18 15 20 | 0.5 1 2 3 4 | 4 3 2 1 0.5 | 3 10 15 20 30 | 2 1.5 1.5 1 1 | 10 20 20 25 25 |
(4) superficial layer 3 usefulness
| Embodiment | Resin glue | Fire retardant | Curing agent | Promoter | Nano-calcium carbonate | Nanometer carbon black | Antistatic additive |
| 16 17 18 19 20 | 100 100 100 100 100 | 20 40 60 80 150 | 0.5 1 2 3 4 | 4 3 2 1 0.5 | 10 15 20 25 30 | 1.5 1.7 1 3 0.5 | 30 20 15 5 1 |
More than among each embodiment used resin glue be meant commercial resin glue, can adopt unsaturated polyester resin, phenolic resins, epoxy resin all can.Antistatic additive specifically can adopt the commodity of Jinan, Shandong chemical institute public offering, and trade name is " a glass fibre highly effective antistatic agent ", or adopts other similar market commodity.Promoter specifically can be adopted cobalt naphthenate or methylaniline.Curing agent specifically can adopt in peroxidating ketone, ethyl ketone, peroxidating formyl, the cycloethanone peroxide any.Fire retardant specifically can adopt in algeldrate, antimony cream, the lithium bromide any.Other raw material can adopt the commodity of selling on the market.The particle mean size of nano-calcium carbonate should guarantee below 200 nanometers, to guarantee good modified effect.
The technical performance of this multiple tube depends on the quality and the structure of prescription He the composite fibre that participates in of heat-curing plastic.Among the present invention selecting for use with structure of fiber done following improvement:
Wear-resisting inner liner 1 add man-hour concrete used fiber or fabric be that glass fibre and two kinds of alternatively layereds of nylon fibre nonwoven twine, it is that glass fabric and PVC film tape mixed and alternate twine that the inner liner 1 of antiseepage adds man-hour concrete used fiber or fabric.
Strength layer 2 add man-hour concrete used fiber or fabric be that glass fibre and polypropylene short fiber or two kinds of alternatively layereds of nonwoven twine.
Superficial layer 3 add man-hour concrete used fiber or fabric two kinds of alternatively layereds of pre-oxidized fibers of being glass fibre and pre-oxidation polyacrylonitrile twine.
Steel wire spiral in the set enhancing skeleton 2A of strength layer 2 is left-handed or dextrorotation, or left-handed with dextrorotation be provided with simultaneously and intersect even distribution and with three to six road linearity axial ribs 2B axially be set form netted enhancing skeleton.The netted enhancing skeleton of being made up of steel wire is when being worked into certain thickness along with strength layer 2, steel wire is integral by road winding processing and by heat-curing plastic and fiber combinations, thereby the intensity index of strong nexine is significantly improved, form unique steel-plastics composite pipe structure.
More than collocation between each layer fiber fully taken into account functional parameter and price factor that each layer born.Because the adding of nanoscale high-tech material make the physical and chemical index of steel-plastics composite pipe have increased significantly, thereby the increase of intensity can suitably reduce the thickness of each layer, and the weight of improving the back product is significantly decreased.Ratio between each layer thickness after the improvement is: the ratio of the thickness of surface conductance layer 1 and inner liner 3 and strength layer 2 is 1: 5-10: 25-50.
Existing multiple tube is by wear-resistant antiseepage inner liner 3, middle stress layer 2, the composite bushing structure that surface conductance layer 1 is formed, the sleeve pipe two ends are provided with ring flange 4 fixing or sleeve type, and every layer of structure adds fire retardant by fiber, resin, composite curing moulding behind the antistatic additive, between fiber and resin, be filled with nano level calcium carbonate and nano level carbon black now,, added spiral enhancing steel-wire carcass 2A at stress layer 2.
The spiral that strengthens steel-wire carcass 2A is left-handed or dextrorotation, or left-handedly is provided with simultaneously with dextrorotation and intersects in the stress layer 2 that is evenly distributed on enhancing.
Strengthen in the helical structure of steel-wire carcass 2A left-handed to dextrorotation to corresponding settings of spiral, respectively evenly distribute formation cross network enhancing skeleton for the 2-6 head.
What cross network strengthened skeleton axially is provided with three to six road linearity axial ribs 2B, by linearity axial ribs 2B and cross network strengthen skeleton form in the middle of casing play in the stress layer.This linearity axial ribs 2B adds that the enhancing steel-wire carcass of the enhancing steel-wire carcass 2A of 2-6 left-hand screw and 2-4 right-hand screw evenly distributes and combines, and forms cross network and strengthens skeleton, thereby form stronger impact resistance.
Because the increase of intensity can suitably reduce the thickness of each layer, thereby the weight of improving the back product is significantly decreased.Ratio between each layer thickness after the improvement is: the ratio of the thickness of surface conductance layer 1 and inner liner 3 and enhancing stress layer 2 is 1: 5-10: 25-50.
Anti-electrostatic fire retardant nanofiber according to above process structure manufacturing strengthens steel-plastics composite pipe, by wear-resistant antiseepage inner liner 3, middle stress layer 2, surface conductance layer 3 is formed, the sleeve pipe two ends are provided with ring flange 4 fixing or sleeve type, and every layer of structure be by fiber, resin, add composite curing moulding behind fire retardant, the antistatic additive, but this steel-plastics composite pipe has adopted said technology to make, and has just formed a kind of new steel-plastics composite pipe.
Claims (10)
1, a kind of anti-electrostatic fire retardant nanofiber strengthens the steel-plastics composite pipe manufacture craft, by fiber or fabric is base-material, with the thermosetting resin adhesive is adhesive, add and join fire retardant, antistatic additive, curing agent and inserts are formed the adhering and solidifying agent, twine the agent of base-material limit coating adhering and solidifying in tubular mould top, the final pipeline that solidifies back formation and the combination of prefabricated ring flange accessory, the structure of pipeline comprises three layers: twine fiber or the even simultaneously formed inner liner (1) with impervious or anti-wear performance of thermosetting resin adhesive with conduction and flame-retarding characteristic that applies of its fabric at tubular mould (5), on the basis that ring flange mould and inner liner (1) form, twine enhanced fiber or its fabric simultaneously evenly coating have the formed strength layer of thermosetting resin adhesive (2) of conduction and flame-retarding characteristic, on the surface of strength layer (2), twine fine and close fiber or its fabric and evenly apply conductive surface layer that thermosetting resin adhesive forms (3) simultaneously, it is characterized in that the manufacture craft of this multiple tube has been taked following technological improvement with strong conduction and flame-retarding characteristic:
1. have to add in the conduction and the thermosetting resin adhesive of flame-retarding characteristic and joined the nano-calcium carbonate that improves each layer of multiple tube microstructure and do filler, the resin glue of per 100 parts of weight adds the nano-calcium carbonate of filling out 3-36 part,
2. have to add in the conduction and the thermosetting resin adhesive of flame-retarding characteristic and joined the nanometer carbon black that improves each layer of multiple tube electric conductivity and do modifier, the resin glue of per 100 parts of weight adds the nanometer carbon black of filling out 0.5-3 part,
3. be provided with the enhancing skeleton of forming by the helical form steel wire (2A) at strength layer (2).
2, strengthen the steel-plastics composite pipe manufacture craft according to the said anti-electrostatic fire retardant nanofiber of claim 1, the inner liner (1) that it is characterized in that antiseepage adds the man-hour concrete used thermosetting resin adhesive with conduction and flame-retarding characteristic and forms than preparing by following composition by weight:
Resin glue: 100 parts,
Fire retardant: 10--100 part,
Curing agent: 0.5-4 part,
Promoter: 0.5-4 part,
Nano-calcium carbonate: 3-30 part,
Nanometer carbon black: 0.5-3 part.
3, strengthen the steel-plastics composite pipe manufacture craft according to the said anti-electrostatic fire retardant nanofiber of claim 1, it is characterized in that wear-resisting inner liner (1) adds the man-hour concrete used thermosetting resin adhesive with conduction and flame-retarding characteristic and forms than preparing by following composition by weight:
Resin glue: 100 parts,
Fire retardant: 20-36 part,
Curing agent: 0.5-4 part,
Promoter: 0.5-4 part,
Nano-calcium carbonate: 10-26 part,
Nanometer carbon black: 1-1.5 part.
Silica: 10-80 part.
4, strengthen the steel-plastics composite pipe manufacture craft according to the said anti-electrostatic fire retardant nanofiber of claim 1, it is characterized in that strength layer (2) adds the man-hour concrete used thermosetting resin adhesive with conduction and flame-retarding characteristic and forms than preparing by following composition by weight:
Resin glue: 100 parts,
Fire retardant: 15-40 part,
Curing agent: 0.5-4 part,
Promoter: 0.5-4 part,
Nano-calcium carbonate: 3-30 part,
Nanometer carbon black: 1-2 part.
Silica flour: 10-25 part.
5, strengthen the steel-plastics composite pipe manufacture craft according to the said anti-electrostatic fire retardant nanofiber of claim 1, it is characterized in that superficial layer (3) adds the man-hour concrete used thermosetting resin adhesive with conduction and flame-retarding characteristic and forms than preparing by following composition by weight
Resin glue: 100 parts,
Fire retardant: 20-150 part,
Curing agent: 0.5-4 part,
Promoter: 0.5-4 part,
Nano-calcium carbonate: 3-30 part,
Nanometer carbon black: 1-3 part.
Antistatic additive: 1--30 part.
6, strengthen the steel-plastics composite pipe manufacture craft according to the said anti-electrostatic fire retardant nanofiber of claim 1, it is characterized in that wear-resisting inner liner (1) add man-hour concrete used fiber or fabric be that glass fibre and two kinds of alternatively layereds of nylon fibre nonwoven twine, it is that glass fabric and PVC film tape mixed and alternate twine that the inner liner of antiseepage (1) adds man-hour concrete used fiber or fabric.
7, strengthen the steel-plastics composite pipe manufacture craft according to the said anti-electrostatic fire retardant nanofiber of claim 1, it is characterized in that strength layer (2) add man-hour concrete used fiber or fabric be that glass fibre and polypropylene short fiber or two kinds of alternatively layereds of nonwoven twine.
8, strengthen the steel-plastics composite pipe manufacture craft according to the said anti-electrostatic fire retardant nanofiber of claim 1, it is characterized in that it is that glass fibre and two kinds of alternatively layereds of pre-oxidation polyacrylonitrile twine that superficial layer (3) adds man-hour concrete used fiber or fabric.
9, strengthen the steel-plastics composite pipe manufacture craft according to the said anti-electrostatic fire retardant nanofiber of claim 1, it is characterized in that the steel wire spiral in the set enhancing skeleton (2A) of strength layer (2) is left-handed or dextrorotation, or left-handedly be provided with simultaneously and intersect even distribution and form netted enhancing skeleton with three to six roads linearity axial ribs (2B) of axial setting with dextrorotation.
10, a kind of anti-electrostatic fire retardant nanofiber strengthens steel-plastics composite pipe, by wear-resistant antiseepage inner liner (3), middle stress layer (2), the composite bushing structure that surface conductance layer (1) is formed, the sleeve pipe two ends are provided with ring flange fixing or sleeve type (4), every layer of structure is by fiber, resin, and composite curing moulding behind adding fire retardant, the antistatic additive is characterized in that this steel-plastics composite pipe has adopted the said technology of claim 1 to make.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100129530A CN100473518C (en) | 2005-11-07 | 2005-11-07 | Technique for steel-plastic composite tube enhanced by antistatic flame retardant Nano fibers and products therefrom |
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| CNB2005100129530A CN100473518C (en) | 2005-11-07 | 2005-11-07 | Technique for steel-plastic composite tube enhanced by antistatic flame retardant Nano fibers and products therefrom |
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| CN100392306C (en) * | 2006-05-30 | 2008-06-04 | 栗小锋 | Glass fiber reinforced plastic sprinkling tube for desulfurizing tower of electric power plant and preparation method thereof |
| CN100436910C (en) * | 2007-02-05 | 2008-11-26 | 伦慧东 | Antistatic flame-proof light high-intensity resin steel mesh composite tube and production technique |
| CN101493162B (en) * | 2008-01-23 | 2011-02-16 | 核工业第八研究所 | Rectangle thin wall pipe material and method for manufacturing same |
| CN102182880A (en) * | 2011-01-26 | 2011-09-14 | 浙江双林塑料机械有限公司德清分公司 | Water supply pipe wounded by 300-4000 mm steel wire mesh reinforced polyolefin and molding method thereof |
| CN101538802B (en) * | 2009-04-23 | 2011-10-26 | 朱守诚 | High-performance fiber reinforced film composite material |
| CN103104754A (en) * | 2013-01-30 | 2013-05-15 | 河北拓安管业有限公司 | Anti-static flame-retardant steel skeleton fiber reinforced resin pipe and preparation technology thereof |
| CN103453235A (en) * | 2013-08-02 | 2013-12-18 | 伦慧东 | Forming process of underground coal mine steel-lined wire fiber reinforced inorganic gel composite pipe |
| CN104085117A (en) * | 2014-06-16 | 2014-10-08 | 四川航天五源复合材料有限公司 | Preparation method of steel fiber composite bar |
| CN104594382A (en) * | 2014-12-09 | 2015-05-06 | 浙江邦德光电集团有限公司 | Underground communication well |
| CN106090509A (en) * | 2016-07-27 | 2016-11-09 | 山东柏远复合材料科技有限公司 | A kind of thermosetting plastics tube transport system |
| CN106084705A (en) * | 2016-06-09 | 2016-11-09 | 扬州润友复合材料有限公司 | A kind of high intensity antistatic composite material sheet material and preparation method thereof |
| CN107477271A (en) * | 2017-09-29 | 2017-12-15 | 江苏瑞腾涂装科技有限公司 | A kind of high-strength corrosion-resisting plastic-coated composite pipe |
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| JP4733874B2 (en) * | 2001-08-07 | 2011-07-27 | 新日本製鐵株式会社 | Polyolefin coated steel |
| CN1147393C (en) * | 2002-03-05 | 2004-04-28 | 伦慧东 | New technology for anti-electrostatic flame-retarded glass fibre reinforced plastics compound pipe |
| JP4560284B2 (en) * | 2003-04-15 | 2010-10-13 | 新日本製鐵株式会社 | Anticorrosion coating composition for gas transport steel pipe and gas transport steel pipe |
| JP2004323570A (en) * | 2003-04-22 | 2004-11-18 | Osaka Gas Co Ltd | Pipe lining agent |
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| CN100392306C (en) * | 2006-05-30 | 2008-06-04 | 栗小锋 | Glass fiber reinforced plastic sprinkling tube for desulfurizing tower of electric power plant and preparation method thereof |
| CN100436910C (en) * | 2007-02-05 | 2008-11-26 | 伦慧东 | Antistatic flame-proof light high-intensity resin steel mesh composite tube and production technique |
| CN101493162B (en) * | 2008-01-23 | 2011-02-16 | 核工业第八研究所 | Rectangle thin wall pipe material and method for manufacturing same |
| CN101538802B (en) * | 2009-04-23 | 2011-10-26 | 朱守诚 | High-performance fiber reinforced film composite material |
| CN102182880A (en) * | 2011-01-26 | 2011-09-14 | 浙江双林塑料机械有限公司德清分公司 | Water supply pipe wounded by 300-4000 mm steel wire mesh reinforced polyolefin and molding method thereof |
| CN103104754A (en) * | 2013-01-30 | 2013-05-15 | 河北拓安管业有限公司 | Anti-static flame-retardant steel skeleton fiber reinforced resin pipe and preparation technology thereof |
| CN103453235A (en) * | 2013-08-02 | 2013-12-18 | 伦慧东 | Forming process of underground coal mine steel-lined wire fiber reinforced inorganic gel composite pipe |
| CN103453235B (en) * | 2013-08-02 | 2015-06-10 | 伦慧东 | Forming process of underground coal mine steel-lined wire fiber reinforced inorganic gel composite pipe |
| CN104085117A (en) * | 2014-06-16 | 2014-10-08 | 四川航天五源复合材料有限公司 | Preparation method of steel fiber composite bar |
| CN104594382A (en) * | 2014-12-09 | 2015-05-06 | 浙江邦德光电集团有限公司 | Underground communication well |
| CN104594382B (en) * | 2014-12-09 | 2016-06-29 | 浙江邦德光电集团有限公司 | A kind of buried communication well |
| CN106084705A (en) * | 2016-06-09 | 2016-11-09 | 扬州润友复合材料有限公司 | A kind of high intensity antistatic composite material sheet material and preparation method thereof |
| CN106090509A (en) * | 2016-07-27 | 2016-11-09 | 山东柏远复合材料科技有限公司 | A kind of thermosetting plastics tube transport system |
| CN107477271A (en) * | 2017-09-29 | 2017-12-15 | 江苏瑞腾涂装科技有限公司 | A kind of high-strength corrosion-resisting plastic-coated composite pipe |
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Assignee: Tangshan Jiaji Composite Pipe Corp. Ltd. Assignor: Lun Huidong Contract fulfillment period: 2009.5.1 to 2025.11.7 contract change Contract record no.: 2009990000457 Denomination of invention: Technique for steel-plastic composite tube enhanced by antistatic flame retardant Nano fibers Granted publication date: 20090401 License type: Exclusive license Record date: 2009.5.8 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.5.1 TO 2025.11.7; CHANGE OF CONTRACT Name of requester: TANGSHAN JIAJI COMPOSITE PIPE CO., LTD. Effective date: 20090508 |
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Decision date of declaring invalidation: 20130427 Decision number of declaring invalidation: 20509 Granted publication date: 20090401 |