CN105566893B - It is a kind of using spandex waste silk as polyurethane runway of raw material and preparation method thereof - Google Patents
It is a kind of using spandex waste silk as polyurethane runway of raw material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3814—Polyamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of high elastic polyurethane runway, its component and part is as follows：A, performed polymer component：25~40 parts of MDI, 45 parts of polyether polyol；B, curing agent component：5~15 parts of polyether Glycols, 10~20 parts of polyether-tribasic alcohol, 5~10 parts of chain extender, 15~30 parts of plasticizer, 15~30 parts of filler, 5~10 parts of pigment, 0.5~2 part of catalyst, 1~5 part of auxiliary agent, 50~60 parts of spandex waste silk.It with the addition of spandex waste silk component in formula, can prevent sport injury occurred of falling；Phenomena such as compatibility is good, and bonding force is strong, bubble-free, stripping；Impact resistance, elastic recovery rate is high, and abrasion performance is less than 2.5%, meets for a long time, the demand of high frequency of use, and impact force absorption is rapid, and prolonged exercise and match are suitable；Due to the addition of spandex waste silk in preparation process, it is lower to moisture requirement in curing agent component, process conditions requirement is low, not harsh.
Description
Technical field
The invention belongs to polyurethane applied technical field, more particularly to high elastic polyurethane runway and preparation method thereof.
Background technology
Spandex is polyurethane elastomeric fiber abbreviation, has good elastic performance and ultimate strength, therefore be widely used
Textile field.At present, the main method for producing spandex is dry spinning, i.e., carries out polyurethane solutions by spinning appts
Shoot out and be drawn into thread, and be heated through high temperature spinning shaft, the solvent volatilization in stoste, thread is solidified into silk, finally by volume
System for winding, winds finished product.However, the adhesion of spandex thread, silk wind repiece or failure fracture of wire, packaging in process of production
Many waste silks are produced Deng during, therefore the production cost of spandex manufacturer can be added, and because what waste silk processing produced gives up
Water, waste material, also result in environment very big harm.Therefore, waste silk recycles back spinning to reducing spandex production cost, protecting ecology
Environment is respectively provided with important meaning.Spandex is linear block polymers of polyurethane, although theoretically, spandex waste silk can be with
Secondary dissolving is carried out, spinning solution is made again, but tests and finds, spinning solution stability is made very by spandex waste silk again
Difference, easily generate gel and can not spinning, and spandex waste silk has compared with mechanical properties such as spandex finished silk elasticity and significantly damages
Lose.Therefore, spandex waste silk respins that to form spandex thread finished product more difficult.
Polyurethane plastic runway is a kind of casting type polyurethane product, it is widely used in all kinds of sports places, such as
Plastic track-and-field ground, tennis court, basketball court etc., can be used for the laying of family expenses plastic floor and anti-skidding overline bridge of celebrating a festival.Spread with it
If stadium elasticity it is good, anti-skidding, can effectively Protection of the sportsman escape injury, round-the-clock can use.And can be plain to adjust color,
It is beautiful and generous.But polyurethane plastic runway cost is higher.
The content of the invention
The present invention overcomes the shortcomings of that high elastic polyurethane runway cost is high in the prior art, there is provided a kind of high elastic polyurethane
Runway.
The present invention is in order to solve the above technical problems, used technical solution is, a kind of high elastic polyurethane runway, its group
Divide and parts by weight are as follows：
A, performed polymer component：25~40 parts of MDI, 45 parts of polyether polyol；
B, curing agent component：5~15 parts of polyether Glycols, 10~20 parts of polyether-tribasic alcohol, 5~10 parts of chain extender, plasticising
15~30 parts of agent, 15~30 parts of filler, 5~10 parts of pigment, 0.5~2 part of catalyst, 1~5 part of auxiliary agent, spandex waste silk 50~60
Part.
Further, the polyether polyol is polyether Glycols or polyether-tribasic alcohol, and the polyether polyol is divided
Son amount is 2000~3000.Such as polyether Glycols DL-2000 (Mn=2000), Shandong Dong great chemical industry group company, polyethers
Trihydroxylic alcohol：MN3050 (Mn=3000), Shandong Dong great chemical industry group company or polyether polyol N-2020 (Mn=2000),
Liaoning chlor-alkali company of Jin Hua groups, polyether polyol N-330 (Mn=3000), the 3rd petrochemical plant of Tianjin Petrochemical Corp..
Further, the auxiliary agent includes one or more in thixotropic agent, antioxidant, ultra-violet absorber.Wherein touch
Become agent and gas-phase silica can be selected, antioxidant uses antioxidant 1010, and UV-9 can be selected in ultra-violet absorber.
In B component, chain extender can use MOCA or DMTDA etc., and plasticizer can use chlorinated paraffin 52 or DOP etc., filler
Kaolin, montmorillonite or organobentonite etc. can be selected, catalyst can be made at the same time using isooctyl acid lead or zinc Isoocatanoate or two kinds
With.Listed above is for example, those skilled in the art should know that other analogs or similar product are suitable for this
Invention.
Preferably, the spandex waste silk is oil removing and the spandex waste silk after softening agent arranges.Polyether modified silicon oil
Polyether modified silicon oil H-193 (Jiangxi Hito Chemical Co., Ltd.), polyether modified silicon oil ZBH-2070 (Qingdao can be selected in softening agent
Zhong Bao Chemical Co., Ltd.s) or polyether modified silicon oil SM-601 (Laiyang Shunming Chemical Co., Ltd) etc..
Preferably, the spandex waste silk is a diameter of is 25~50 μm, length is 2~5mm
The preparation method of above-mentioned high elastic polyurethane runway, includes the following steps, polyether polyol is 100 in (1) component A
Vacuum dehydration at~110 DEG C, adds MDI after cooling, then react 2~4h at 75~85 DEG C；
(2) by after polyether Glycols, polyether-tribasic alcohol and chain extender mixing in B component, 100~110 DEG C of vacuum are heated to
Degassing, after cooling, adds plasticizer, filler, pigment, auxiliary agent and spandex waste silk, then stirs evenly, then vacuum outgas；
(3) material made from step (1) and step (2) is mixed, and adds catalyst, stirred evenly, through vacuum outgas
Afterwards, cast, high elastic polyurethane runway is made after curing.
Preferably, polyether polyol water content is less than or equal to 0.05% (quality) after step (1) described dehydration.
The invention has the advantages that the present invention with the addition of spandex waste silk component, security in polyurethane runway formula
Height, can prevent sport injury occurred of falling；Phenomena such as compatibility is good, and bonding force is strong, bubble-free, stripping；Impact resistance, tool
There are tough elastic layer and cushion, can absorb powerful impact, surface is not damaged；Elastic recovery rate is high, will not be due to field
The weight of footpath equipment and can not recover elasticity；Abrasion performance is less than 2.5%, meets for a long time, the demand of high frequency of use；Impact
Power absorbs rapid, appropriateness absorption step impact force, reduces sport injury, and prolonged exercise and match are suitable；；In preparation process
Due to the addition of spandex waste silk, it is lower to moisture requirement in curing agent component, simplifies processing step, process conditions requirement
It is low, it is not harsh.
Embodiment
Embodiment 1
A, performed polymer component：25 parts of MDI, 45 parts of polyether polyol (N-2020 (Mn=2000))；
B, curing agent component：15 parts of polyether Glycols (polyether Glycols DL-2000 (Mn=2000)), polyether-tribasic alcohol
10 parts of (MN3050 (Mn=3000)), 5 parts of chain extender MOCA, 52 30 parts of plasticizer chlorinated paraffin, 30 parts of filler kaolin, face
(isooctyl acid lead and zinc Isoocatanoate mass ratio are 1 for 5 parts of material, catalyst:2 mixture) 0.5 part, thixotropic agent (gas-phase silica) 1
(a diameter of 25 μm, length is for part, 0.15 part of antioxidant (antioxidant 1010), 0.1 part of ultraviolet absorber (UV-9), spandex waste silk
5mm) 60 parts.The spandex waste silk is for oil removing and through softening agent (polyether modified silicon oil H-193 (the more limited public affairs of chemical industry in Jiangxi sea
Department)) arrange after spandex waste silk.
The preparation method of above-mentioned high elastic polyurethane runway, includes the following steps, polyether polyol is 100 in (1) component A
Vacuum dehydration at DEG C, polyether polyol water content is less than or equal to 0.05% (quality) after ensureing dehydration, MDI is added after cooling, so
Afterwards 2h is reacted at 85 DEG C；
(2) by after polyether Glycols, polyether-tribasic alcohol and chain extender mixing in B component, 110 DEG C of vacuum outgas are heated to,
After cooling, plasticizer, filler, pigment, auxiliary agent and spandex waste silk are added, is then stirred evenly, then vacuum outgas, dehydration (is protected
Card wherein water content is less than or equal to 0.2% (mass fraction, similarly hereinafter))；
(3) material made from step (1) and step (2) is mixed, and adds catalyst, stirred evenly, through vacuum outgas
Afterwards, cast, high elastic polyurethane runway is made after curing.
Embodiment 2
A, performed polymer component：MDI30 parts, 45 parts of polyether polyol (N-2020 (Mn=2000))；
B, curing agent component：10 parts of polyether Glycols (polyether Glycols DL-2000 (Mn=2000)), polyether-tribasic alcohol
20 parts of (MN3050 (Mn=3000)), 10 parts of chain extender MOCA, 52 20 parts of plasticizer chlorinated paraffin, 25 parts of filler kaolin,
(isooctyl acid lead and zinc Isoocatanoate mass ratio are 1 for 8 parts of pigment, catalyst:2 mixture) 1 part, thixotropic agent (gas-phase silica) 3
(a diameter of 35 μm, length is for part, 0.1 part of antioxidant (antioxidant 1010), 0.15 part of ultraviolet absorber (UV-9), spandex waste silk
3mm) 55 parts.((precious chemical industry is limited in Qingdao by polyether modified silicon oil ZBH-2070 for oil removing and through softening agent for the spandex waste silk
Company)) arrange after spandex waste silk.
The preparation method of above-mentioned high elastic polyurethane runway, includes the following steps, polyether polyol is 110 in (1) component A
Vacuum dehydration at DEG C, polyether polyol water content is less than or equal to 0.05% (quality) after ensureing dehydration, MDI is added after cooling, so
Afterwards 3h is reacted at 80 DEG C；
(2) by after polyether Glycols, polyether-tribasic alcohol and chain extender mixing in B component, 100 DEG C of vacuum outgas are heated to,
After cooling, plasticizer, filler, pigment, auxiliary agent and spandex waste silk are added, is then stirred evenly, then vacuum outgas (ensures wherein
0.5%) water content is less than or equal to；
(3) material made from step (1) and step (2) is mixed, and adds catalyst, stirred evenly, through vacuum outgas
Afterwards, cast, high elastic polyurethane runway is made after curing.
Embodiment 3
A, performed polymer component：40 parts of MDI, 45 parts of polyether polyol (N-2020 (Mn=2000))；
B, curing agent component：15 parts of polyether Glycols (polyether Glycols DL-2000 (Mn=2000)), polyether-tribasic alcohol
15 parts of (MN3050 (Mn=3000)), MOCA8 parts of chain extender, 52 30 parts of plasticizer chlorinated paraffin, 30 parts of filler kaolin, face
(isooctyl acid lead and zinc Isoocatanoate mass ratio are 1 for 10 parts of material, catalyst:2 mixture) 2 parts, thixotropic agent (gas-phase silica) 5
(a diameter of 50 μm, length is for part, 0.1 part of antioxidant (antioxidant 1010), 0.1 part of ultraviolet absorber (UV-9), spandex waste silk
5mm) 50 parts.The spandex waste silk is oil removing and ((Laiyang is along the limited public affairs of bright chemical industry by polyether modified silicon oil SM-601 through softening agent
Department)) arrange after spandex waste silk.
The preparation method of above-mentioned high elastic polyurethane runway, includes the following steps, polyether polyol is 100 in (1) component A
Vacuum dehydration at DEG C, polyether polyol water content is less than or equal to 0.05% (quality) after ensureing dehydration, MDI is added after cooling, so
Afterwards 4h is reacted at 85 DEG C；
(2) by after polyether Glycols, polyether-tribasic alcohol and chain extender mixing in B component, 100 DEG C of vacuum outgas are heated to,
After cooling, plasticizer, filler, pigment, auxiliary agent and spandex waste silk are added, is then stirred evenly, then vacuum outgas (ensures wherein
0.8%) water content is less than or equal to；
(3) material made from step (1) and step (2) is mixed, and adds catalyst, stirred evenly, through vacuum outgas
Afterwards, cast, high elastic polyurethane runway is made after curing.
Embodiment 4
A, performed polymer component：MDI35 parts, 45 parts of polyether polyol (N-2020 (Mn=2000))；
B, curing agent component：8 parts of polyether Glycols (polyether Glycols DL-2000 (Mn=2000)), polyether-tribasic alcohol
18 parts of (MN3050 (Mn=3000)), 8 parts of chain extender MOCA, 52 25 parts of plasticizer chlorinated paraffin, 25 parts of filler kaolin, face
(isooctyl acid lead and zinc Isoocatanoate mass ratio are 1 for 7 parts of material, catalyst:2 mixture) 1.5 parts, thixotropic agent (gas-phase silica) 1
(a diameter of 30 μm, length is for part, 0.15 part of antioxidant (antioxidant 1010), 0.1 part of ultraviolet absorber (UV-9), spandex waste silk
2mm) 60 parts.The spandex waste silk is oil removing and ((Laiyang is along the limited public affairs of bright chemical industry by polyether modified silicon oil SM-601 through softening agent
Department)) arrange after spandex waste silk.
The preparation method of above-mentioned high elastic polyurethane runway, includes the following steps, polyether polyol is 100 in (1) component A
Vacuum dehydration at DEG C, polyether polyol water content is less than or equal to 0.05% (quality) after ensureing dehydration, MDI is added after cooling, so
Afterwards 2h is reacted at 85 DEG C；
(2) by after polyether Glycols, polyether-tribasic alcohol and chain extender mixing in B component, 110 DEG C of vacuum outgas are heated to,
After cooling, plasticizer, filler, pigment, auxiliary agent and spandex waste silk are added, is then stirred evenly, then vacuum outgas, dehydration (is protected
0.6%) card wherein water content is less than or equal to；
(3) material made from step (1) and step (2) is mixed, and adds catalyst, stirred evenly, through vacuum outgas
Afterwards, cast, high elastic polyurethane runway is made after curing.
Comparative example 1
Spandex waste silk in embodiment 1 is replaced with to a diameter of 20 μm of spandex waste silk, other conditions are constant.
Comparative example 2
Spandex waste silk in embodiment 1 is replaced with into the spandex waste silk that length is 8mm, other conditions are constant.
Comparative example 3
Spandex waste silk in embodiment 3 is replaced with to a diameter of 55 μm of spandex waste silk, other conditions are constant.
Comparative example 4
Spandex waste silk replaces with the spandex waste silk that length is 1mm in comparative example 4, and other conditions are constant.
Comparative example 5
Spandex waste silk number in embodiment 1 is adjusted to 65 parts, other conditions are constant.
Comparative example 6
Spandex waste silk number in embodiment 3 is adjusted to 45 parts, other conditions are constant.
Comparative example 7
Spandex waste silk in embodiment 1 is replaced with to the spandex waste silk without oil removing and softening agent arrangement.
Performance test
Poly- ammonia in embodiment 1~4 is can be seen that from the performance test for the polyurethane runway being prepared with last embodiment
The mechanical property of ester runway has relative to traditional polyurethane runway to be obviously improved, and spandex waste silk has played the performance of itself
Advantage, is effectively utilized.If in addition, from comparative example 1~4 as can be seen that changing the spandex waste silk added in the application
Diameter and length, then can to the mechanical property of final products produce large effect；Secondly, the addition on spandex waste silk
Also there is large effect to final polyurethane runway performance, although comparative example 5 and 6 can be seen that spandex waste silk from upper table
Diameter and length are in the framework of the present definition, but addition is slightly more or less slightly will have to final products mechanical property
Large effect, results even in polyurethane runway and situation about foaming occurs, this is probably that spandex waste silk and polyurethane runway are pre-
The compatibility of aggressiveness etc. is related.Although from comparative example 7 as can be seen that only replacing with the spandex waste silk added in embodiment 1 not
Waste silk is arranged by oil removing and softening agent, but its final mechanical property reduces very much, this is probably removing spandex waste silk
Upper remaining finish greatly reduces influence of the finish on spandex waste silk to track performance, and soft using polyether modified silicon oil
Soft dose compensate for the mechanical property loss of energy such as spandex waste silk elasticity, so as to improve runway with polyurethane runway raw material collective effect
Comprehensive performance.
In addition, the addition of spandex waste silk is so that the requirement in preparation process to water content reduces, such as 1 step of embodiment (2)
The middle water content after dehydration is 0.2%, and water content is at maximum up to 0.8% in 2~4 step of embodiment (2).But from above-mentioned table
As can be seen that the performance of polyurethane runway prepared by embodiment 1~4 is not much different, it is essentially identical.And in the prior art, due to
Raw material can react with water, therefore, have strict requirements to each step reaction water content, general to require particularly in step (1)
Water content is less than 0.1% in step (1), requires water content to be less than 0.2% in step (2).To aqueous in step (2) in the application
Measure it is of less demanding, may be with spandex waste silk be added in the form of staple fiber formula in it is related.
Claims (4)
- A kind of 1. high elastic polyurethane runway, it is characterised in that：Its component and part is as follows,A, performed polymer component25 ~ 40 parts of MDI, 45 parts of polyether polyol；B, curing agent component5 ~ 15 parts of polyether Glycols, 10 ~ 20 parts of polyether-tribasic alcohol, 5 ~ 10 parts of chain extender, 15 ~ 30 parts of plasticizer, filler 15 ~ 30 Part, 5 ~ 10 parts of pigment, 0.5 ~ 2 part of catalyst, 1 ~ 5 part of auxiliary agent, 50 ~ 60 parts of spandex waste silk,The auxiliary agent is thixotropic agent, one or more in antioxidant, ultra-violet absorber,The spandex waste silk is oil removing and the spandex waste silk after softening agent arranges,The spandex waste silk is 25 ~ 50 μm a diameter of, length is 2 ~ 5mm.
- 2. high elastic polyurethane runway according to claim 1, it is characterised in that：The polyether polyol is polyethers two First alcohol or polyether-tribasic alcohol, the polyether polyol molecular weight are 2000 ~ 3000.
- A kind of 3. preparation method according to claim 1 ~ 2 any one of them high elastic polyurethane runway, it is characterised in that：Bag Include following steps,（1）Polyether polyol vacuum dehydration at 100 ~ 110 DEG C in component A, adds MDI after cooling, then in 75 ~ 85 DEG C of reactions 2~4h；（2）After polyether Glycols, polyether-tribasic alcohol and chain extender mix in B component, 100 ~ 110 DEG C of vacuum outgas are heated to, After cooling, plasticizer, filler, pigment, auxiliary agent and spandex waste silk are added, is then stirred evenly, then vacuum outgas；（3）By step（1）And step（2）Obtained material mixing, and catalyst is added, stir evenly, after vacuum outgas, pour Casting, is made high elastic polyurethane runway after curing.
- 4. the preparation method of high elastic polyurethane runway according to claim 3, it is characterised in that：Step（1）After dehydration, Water quality content in polyether polyol is less than or equal to 0.05%.
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| SU1286670A1 (en) * | 1984-06-26 | 1987-01-30 | Волгоградский Политехнический Институт | Coating for field tracks and sports grounds |
| CN1352213A (en) * | 2000-11-15 | 2002-06-05 | 北京中商世纪纳米塑胶材料有限公司 | Spreading material for sports ground prepared from polyurethane/nanometer montorillonoid and its preparing method |
| CN101245184A (en) * | 2007-02-15 | 2008-08-20 | 天津市景鸿体育设施技术有限公司 | Nano-environment protection type polyurethane paving material for athletic ground and manufacture method thereof |
| CN102485797A (en) * | 2010-12-06 | 2012-06-06 | 王诚 | Plastic ground paving material |
| CN103073882A (en) * | 2012-12-28 | 2013-05-01 | 郑州大学 | Nylon-6/spandex waste silk compound material and preparation method thereof |
| CN105131568A (en) * | 2015-09-01 | 2015-12-09 | 江门市长河化工实业集团有限公司 | Polyurethane foam for all-plastic plastic runway and preparation method thereof |
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