CN1560104A - Production of dry type binary liquid shape polyaminoester (pu) resin by waste polyaminoester (pu)resin sole - Google Patents
Production of dry type binary liquid shape polyaminoester (pu) resin by waste polyaminoester (pu)resin sole Download PDFInfo
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- CN1560104A CN1560104A CNA2004100163772A CN200410016377A CN1560104A CN 1560104 A CN1560104 A CN 1560104A CN A2004100163772 A CNA2004100163772 A CN A2004100163772A CN 200410016377 A CN200410016377 A CN 200410016377A CN 1560104 A CN1560104 A CN 1560104A
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- viscosity
- polyurethane
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- sole
- dissolving
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Polyurethanes Or Polyureas (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention relates to a dry two-liquid polyurethane (PU) resin produced by waste PU soles, using waste PU soles as raw material to prepare polyurethane (PU) resin, processing, crushing, drying, stirring and dissolving, cooling and filtering to obtain an intermediate S1, then adding in some raw materials to react and thicken, then diluting, finally cooling and filtering to obtain the dry two-liquid polyurethane (PU) resin. Its process method has the advantages as follows: it adopts waste PU soles as raw material, beneficial to environmental protection. The product has higher peeling strength and solvent resistance in quality, able to meet binding requirements between many materials.
Description
[technical field]
The present invention relates to a kind of dry type two liquid type polyurethane (PU) resin that utilizes waste polyurethane (PU) shoe sole production, its particular content is that main raw material(s) prepares urethane (PU) resin for utilizing waste polyurethane (PU) sole.
[background technology]
The feature of urethane (PU) chemical structure is to contain multiple characteristic group-NH-COO-(carbamate groups), thereby improved the function of itself, be widely used in clothes sporting goods, all kinds of rooms articles for use, automobile transportation means and the industrial starting material.Starting material reactions such as general employing TDI, MDI, polyester polyol, polyether glycol, dibasic alcohol (amine) chainextender and solvent make among the preparation method of the dry type two liquid type polyurethane resin (also claiming the adhesive linkage resin) of known technology.Above-mentioned preparation method is relative, and production cost is higher, by contrast, the invention has the advantages that the recycling of waste polyurethane (PU) sole, can save production cost, and obtains simultaneously that stripping strength is higher, the better product of solvent resistance.
[summary of the invention]
The objective of the invention is to save energy effectively, and obtain that stripping strength is higher, the better dry type binary liquid shape of solvent resistance product.And adopt this technology to can be good at solving the recovery problem of waste polyurethane (PU) sole, thereby obtain good environmental benefit and economic benefit.
In order to achieve the above object, the present invention adopts following scheme to realize: design a kind of dry type two liquid type polyurethane (PU) resin that utilizes waste polyurethane (PU) shoe sole production, comprise N, particle, degradation agents P at the bottom of dinethylformamide (DMF), (waste and old) polyurethane shoe
1, degradation agents P
2, polyol E
1, tolylene diisocyanate (TDI-80), ditan-4,4 '-vulcabond (MDI), catalyzer, toluene raw materials such as (TOL).Its prescription with per-cent is:
(1) the first step: dissolving obtains intermediate S
1
Material name proportioning (weight part)
N, dinethylformamide (DMF) 80～170
Particle 70～130 at the bottom of (waste and old) polyurethane shoe
Degradation agents P
11～45
Degradation agents P
20.5～18
(2) second steps: product is synthetic
Material name proportioning (weight part)
Intermediate S
1150～220
Polyol E
110～155
Tolylene diisocyanate (TDI-80) 5～36
Ditan-4,4 '-vulcabond (MDI) 1～15
Catalyzer 0.01～0.10
Toluene (TOL) 20～300
The processing step of the invention is as follows:
(1) raw-material processing: pick out urethane (PU) sole, remove impurity and dust, sever sole, extract the sole metallic gasket out.
(2) fragmentation: sole is sent into plastic breaker, be broken into the particle of particle diameter≤50 * 50mm.
(3) drying: the sole particle is carried out drying.60～100 ℃ of kiln temperature more than the time of drying 5h, guarantee moisture content≤0.1% in the sole particle.And note stirring the sole particle at any time burned sole when preventing that temperature is higher.
(4) stirring and dissolving: add solvent N earlier in reactor, dinethylformamide (DMF) starts stirring, is warming up to 100～150 ℃, adds sole particle and degradation agents P again
1And P
2, maintain the temperature at 100～150 ℃ of following stirring and dissolving.
(5) viscosity measurements: the intermediate S that obtains after requiring dissolving to finish
1The final viscosity scope be 500～8500mPas/25 ℃.
(6) cooling: intermediate S
1Viscosity close symbol and require after, can lead to water coolant and cool off, cool to below 60 ℃.
(7) filter: material is filtered discharging by 60 or 80 order copper or stainless steel filtering net, and packing obtains intermediate product S
1
(8) rerum natura detects: to intermediate product S
1Carrying out viscosity and solid content detects.
(9) reaction: with intermediate S
1, TDI-80, catalyzer, polyol E
1By reacting in certain condition and the technology adding reactor.
(10) tackify:, in batches add into MDI according to the situation of viscosity.
(11) the sticking accent: when viscosity reaches 10 * 10
4～30 * 10
4Can squeeze into solvent toluene (TOL) in the time of mPas/25 ℃ and dilute, determine whether adding MDI and additional amount thereof according to viscosity size and solid content then.
Repeat above (10), (11) step, total TOL adds by 1～5 time in batches and dilutes.According to the product specification requirement, adjust viscosity 5 * 10
4～15 * 10
4MPas/25 ℃, solid content 30～65%.
(12) cooling: after viscosity and solid content are qualified, can enter the blanking sessions.Open water coolant, product is cooled to below 60 ℃ filters discharging.
(13) filter discharging: product is filtered with 80～120 order copper or stainless steel filtering net.
Processing method of the present invention is compared with existing processing method has following advantage: this technology is that to adopt waste polyurethane (PU) sole be main raw material, help environmental protection so can solve the recovery problem of waste and old PU sole and reduce production costs, and this product has higher stripping strength and solvent resistance on quality, can satisfy the bonding requirements of many storerooms.
[description of drawings]
Fig. 1 is the process flow sheet of these innovation and creation: referring to Fig. 1.
1 is that raw-material processing 2 is that stirring and dissolving 5 is that cooling 7 is that reaction 10 is that sticking accent 12 is to filter discharging for cooling 13 for tackify 11 for filtration 8 for rerum natura detects 9 for viscosity measurements 6 for fragmentation 3 for dry 4
Through raw-material processing, fragmentation is in the dry rear input DMF solvent, at degradation agent P with waste polyurethane (PU) sole1(can be a kind of or dihydroxylic alcohols polyethers such as GE220, the PTMEG etc. in these type of PEPAs such as polyethylene glycol adipate, poly adipate succinic acid ester, poly-adipate glycol butanediol ester, molecular weight 1500～3000, hydroxyl value 75～37mgKOH/g) and P2Carry out stirring and dissolving under the effect of the amino alcohol of (can be aliphatic dihydroxylic alcohols such as ethylene glycol, propane diols, butanediol etc. or diethanol amine and so on etc.), again through supercooling, obtain intermediate S after filtering1 Add then polyol E1(can be dihydroxylic alcohols polyethers such as GE220, PTMEG or poly-Ethylene glycol adipate, poly adipate succinic acid ester, poly-adipate glycol binaryglycol ester etc. This type of PEPA, molecular weight 1500～3000, hydroxyl value 75～37mgKOH/g), TDI, Catalyst (dibutyl tin laurate or stannous octoate) etc. reacts, and adds MDI in good time And toluene (TOL) carries out viscosity and regulates, reach certain requirement after, doing through cooling, after filtering Formula two liquid type polyurethane resin. This kind manufacturing technology and technology are easy realities to brethren person Execute.
The first step: dissolving obtains intermediate S1。
At first pick out polyurethane (PU) sole, remove impurity and dust. Cut open sole, take out Go out the sole metallic gasket. Sole is sent into plastic breaker, be broken into particle diameter≤50 * 50mm's Particle. Again the sole particle is put into the hothouse drying. 60～100 ℃ of hothouse temperature are when dry Between more than the 5h, guarantee moisture content≤0.1% in the sole particle. And it is broken to note at any time stirring sole Material, burned sole when preventing that temperature is higher. Sole particle splitting (bucket) dress that drying is good Good, prepare to feed intake dissolving. Degradation agent P1、P
2Respectively vacuum dehydration. Vacuum＜50mmHg, 105～120 ℃ of temperature, 4～6 hours time. Check that whether the solubilizing reaction still is dry clean, closes Good reactor bottom valve. The whole solvent DMFs that add the formula Design amount (DMF), start stirring, be warming up to 100～150 ℃. Reactor condensation pipe valve is half-open, opens Condensed water carries out condensation. In reactor, divide the footwear that add formula ratios for 2～5 times from manhole under stirring End particle is pressed simultaneously formula ratio and is added distintegrant P1And P2, seal manhole cover, maintain the temperature at 100～150 ℃ of lower stirring and dissolving. After the stirring and dissolving 1～6 hour, it is sticking that sampling measures lysate Degree. Intermediate S1The viscosity area requirement at 500～8500mPas/25 ℃. Intermediate S1Viscosity close symbol and require after, can lead to cooling water and cool off, cool to below 60 ℃, sealed reactor, pressurization, 60 or 80 order copper or stainless steel filtering net filter discharging, packing obtains intermediate product S1, and it is carried out the rerum naturas such as viscosity and solid content detect.
Second step: product is synthetic.
Check in the reactor to have or not foreign material, whether various valves are in the switch shape of normal operation Attitude. The intermediate S that adds the formula Design amount1And polyol E1, start stirring, be warming up to 50～70 ℃. Add TDI according to the formula Design amount. The disposable adding of TDI. After TDI adds 20～40min adds the catalyst of formula ratio again. Temperature is controlled at 70～90 ℃, stirring reaction 1～3 hours. Carry out viscosity with MDI and toluene (TOL) and regulate, notice that at any time recording apparatus is to sticking The reflection of degree, and monitor the flow size of sound of feed liquid in the reactor from man-hole opening, estimate to increase Should fill into the quantity of MDI when sticking. Increasing when sticking each MDI, to add the time interval be 20～60min. When viscosity reaches 10 * 104～30×10
4Can squeeze into TOL in the time of mPas/25 ℃ dilutes. Total TOL adds by 1～5 time in batches and dilutes. Repeat the first two step, determine according to viscosity Surely the quantity of the MDI that adds carries out waiting for the second time, for the third time repeatedly dilution and sticking the accent, until All solvents add. All raw materials and solvent add, react finish after, interval 20～40min Twice above viscosity is surveyed in sampling, and last twice viscosity is more or less the same and is in the specification value, simultaneously Confirm then to enter the discharging packing stage after NCO is exhausted; If defective, then fill into MDI or Solvent, until viscosity qualified till. Product quality requirement: viscosity 5 * 104～15×10
4MPas/25 ℃, solid content 30～65%. Open cooling water, be cooled to below 60 ℃ after, Get final product discharging. Stop to stir, lock manhole cover, close other emptying valves, add pressure discharge. Filter discharging with 80～120 order copper or stainless steel filtering net, packing obtains PU resin finished product.
[specific embodiment]
Below be the prescription of dry type two liquid type polyurethane (PU) resin:
(1) the first step: dissolving obtains intermediate S
1
Material name proportioning (weight part)
N, dinethylformamide (DMF) 132
Particle 101 at the bottom of (waste and old) polyurethane shoe
Degradation agents P
111.3
Degradation agents P
20.9
(2) second steps: product is synthetic
Material name proportioning (weight part)
Intermediate S
1220
Polyol E
136.2
Tolylene diisocyanate (TDI-80) 9.5
Ditan-4,4 '-vulcabond (MDI) 1.5
Catalyzer 0.02
Toluene (TOL) 33
Preparation method of the present invention fills a prescription according to the above ratio and will pick out an amount of urethane (PU) sole, removes impurity and dust.Sever sole, extract the sole metallic gasket out.Sole is sent into plastic breaker, be broken into the particle of particle diameter≤50 * 50mm.Again the sole particle is put into the kiln drying.The kiln temperature is 80 ℃, time of drying 12h.And note stirring the sole particle at any time burned sole when preventing that temperature is higher.The sole particle splitting (bucket) that drying is good installs, and prepares to feed intake dissolving.Degradation agents P
1, P
2Vacuum hydro-extraction respectively.Vacuum tightness＜50mmHg, 115 ℃ of temperature, 4 hours time.Check that whether the solubilizing reaction still is dry clean, shuts the reactor bottom valve.Add solvent N, dinethylformamide (DMF) 132Kg starts stirring, is warming up to 130 ℃.Reactor condensation pipe valve is half-open, opens water of condensation and carries out condensation.Stir down and in reactor, divide adding 101Kg sole particle 4 times, add decomposition agent P simultaneously from manhole
111.3Kg and P
20.9Kg, seal manhole plate, maintain the temperature at 130 ℃ of following stirring and dissolving.After the stirring and dissolving 3 hours, sampling measures lysate viscosity.Intermediate S
1Range of viscosities require at 500～8500mPas/25 ℃.Intermediate S
1Viscosity close symbol and require after, can lead to water coolant and cool off, cool to 60 ℃, sealed reactor, pressurization, with 60 order copper strainer filtering dischargings are packed, and obtain intermediate product S
1
Checking in the reactor has no-sundries, and whether various valves are in the on off state of works better.The intermediate S that adds the formulating of recipe amount
1220Kg and polyol E
136.2Kg, start stirring, be warming up to 60 ℃.Disposable adding TDI9.5Kg.TDI adds back 20～40min, adds catalyzer 0.02Kg again.Temperature is controlled at 70～90 ℃, stirring reaction 3 hours.Carry out viscosity adjustment with MDI and toluene (TOL), note the reflection of recording meter at any time, and monitor the flow size of sound of feed liquid in the reactor, should mend quantity when estimating tackify into MDI from man-hole opening to viscosity.The about 1.5Kg of total add-on of MDI.Each MDI interpolation timed interval is 40min during tackify.When viscosity reaches 10 * 10
4～30 * 10
4Can squeeze into TOL33Kg in the time of mPas/25 ℃ dilutes.Total TOL adds by 1～2 time in batches and dilutes.Repeat preceding two steps, decide the quantity of the MDI that adds, carry out waiting for the second time, for the third time repeatedly dilution and sticking the accent, add until all solvents according to viscosity.All raw materials and solvent add, react finish after, twice above viscosity is surveyed in 20～40min sampling at interval, last twice viscosity is more or less the same and is in the specification value, confirms simultaneously then to enter the discharging packing stage after NCO is exhausted; If defective, then mend MDI or solvent, till viscosity is qualified.Product quality requirement: viscosity 5 * 10
4～15 * 10
4MPas/25 ℃, solid content 30～65%.Open water coolant, be cooled to 55 ℃.Stop to stir, lock manhole plate, close other emptying valves, add pressure discharge.Filter discharging with 100 order copper or stainless steel filtering net, packing obtains PU resin finished product 300Kg.
Claims (10)
1. dry type two liquid type polyurethane (PU) resin that utilizes waste polyurethane (PU) shoe sole production comprises N, dinethylformamide (DMF), waste polyurethane sole particle, degradation agents P
1, degradation agents P
2, polyol E
1, tolylene diisocyanate (TDI-80), ditan-4,4 '-vulcabond (MDI), catalyzer, toluene raw materials such as (TOL); It is characterized in that:
(1) the first step: dissolving obtains intermediate S
1
Material name proportioning (weight part)
N, dinethylformamide (DMF) 80～170
Particle 70～130 at the bottom of (waste and old) polyurethane shoe
Degradation agents P
11～45
Degradation agents P
20.5～18
(2) second steps: product is synthetic
Material name proportioning (weight part)
Intermediate S
1150～220
Polyol E
110～155
Tolylene diisocyanate (TDI-80) 5～36
Ditan-4,4 '-vulcabond (MDI) 1～15
Catalyzer 0.01～0.10
Toluene (TOL) 20～300
2. according to said a kind of dry type two liquid type polyurethane (PU) resin that utilizes waste polyurethane (PU) shoe sole production of claim 1, it is characterized in that its processing step is made up of following:
(1) raw-material processing: pick out urethane (PU) sole, remove impurity and dust, sever sole, extract the sole metallic gasket out.
(2) fragmentation: sole is sent into plastic breaker, be broken into the particle of particle diameter≤50 * 50mm.
(3) drying: the sole particle is carried out drying.60～100 ℃ of kiln temperature more than the time of drying 5h, guarantee moisture content≤0.1% in the sole particle.And note stirring the sole particle at any time burned sole when preventing that temperature is higher.
(4) stirring and dissolving: add solvent N earlier in reactor, dinethylformamide (DMF) starts stirring, is warming up to 100～150 ℃, adds sole particle and degradation agents P again
1And P
2, maintain the temperature at 100～150 ℃ of following stirring and dissolving.
(5) viscosity measurements: the intermediate S that obtains after requiring dissolving to finish
1The final viscosity scope be 500～8500mPas/25 ℃.
(6) cooling: intermediate S
1Viscosity close symbol and require after, can lead to water coolant and cool off, cool to below 60 ℃.
(7) filter: material is filtered discharging by 60 or 80 order copper or stainless steel filtering net, and packing obtains intermediate product S
1
(8) rerum natura detects: to intermediate product S
1Carrying out viscosity and solid content detects.
(9) reaction: with intermediate S
1, TDI-80, catalyzer, polyol E
1By reacting in certain condition and the technology adding reactor.
(10) tackify:, in batches add into MDI according to the situation of viscosity.
(11) the sticking accent: when viscosity reaches 10 * 10
4～30 * 10
4Can squeeze into solvent toluene (TOL) in the time of mPas/25 ℃ and dilute, determine whether adding MDI and additional amount thereof according to viscosity size and solid content then.
Repeat above (10), (11) step, total TOL adds by 1～5 time in batches and dilutes.According to the product specification requirement, adjust viscosity 5 * 10
4～15 * 10
4MPas/25 ℃, solid content 30～65%.
(12) cooling: after viscosity and solid content are qualified, can enter the blanking sessions.Open water coolant, product is cooled to below 60 ℃ filters discharging.
(13) filter discharging: product is filtered with 80～120 order copper or stainless steel filtering net.
3. according to said a kind of dry type two liquid type polyurethane (PU) resin that utilizes waste polyurethane (PU) shoe sole production of claim 1, when carrying out stirring and dissolving, it is characterized in that selecting N, dinethylformamide (DMF) is solvent, P
1And P
2Be degradation agents.
4. according to said a kind of dry type two liquid type polyurethane (PU) resin that utilizes waste polyurethane (PU) shoe sole production of claim 1, when carrying out stirring and dissolving, the solid content that it is characterized in that dissolution phase is 40～60%.
5. according to said a kind of dry type two liquid type polyurethane (PU) resin that utilizes waste polyurethane (PU) shoe sole production of claim 1, when carrying out stirring and dissolving, it is characterized in that material maintains the temperature under 100～150 ℃ when stirring and dissolving carries out, and the time of stirring and dissolving is 1～6 hour.
6. according to said a kind of dry type two liquid type polyurethane (PU) resin that utilizes waste polyurethane (PU) shoe sole production of claim 1, when intermediate is carried out viscosity measurements, it is characterized in that intermediate S
1The final viscosity scope be 500～8500mPas/25 ℃.
7. according to said a kind of dry type two liquid type polyurethane (PU) resin that utilizes waste polyurethane (PU) shoe sole production of claim 1, when reacting, it is characterized in that temperature of reaction is controlled at 70～90 ℃.
8. according to said a kind of dry type two liquid type polyurethane (PU) resin that utilizes waste polyurethane (PU) shoe sole production of claim 1, when reacting, it is characterized in that intermediate S
1, TDI-80, catalyzer, polyol E
1After adding mixing, carry out polyaddition reaction with TDI-80, late phase reaction MDI tackify early stage.
9. according to said a kind of dry type two liquid type polyurethane (PU) resin that utilizes waste polyurethane (PU) shoe sole production of claim 1, when carrying out viscosity adjustment, it is characterized in that reaching 10 * 10 when viscosity
4～30 * 10
4Can squeeze into TOL in the time of mPas/25 ℃ dilutes.Total solvent TOL adds by 1～5 time in batches and dilutes.
10. according to said a kind of dry type two liquid type polyurethane (PU) resin that utilizes waste polyurethane (PU) shoe sole production of claim 1, when carrying out viscosity adjustment, it is characterized in that general viscosity is 5 * 10 according to the product specification requirement
4～15 * 10
4MPas/25 ℃, solid content are 30～65%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100163772A CN1266181C (en) | 2004-02-17 | 2004-02-17 | Production of dry type binary liquid shape polyaminoester (pu) resin by waste polyaminoester (pu)resin sole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100163772A CN1266181C (en) | 2004-02-17 | 2004-02-17 | Production of dry type binary liquid shape polyaminoester (pu) resin by waste polyaminoester (pu)resin sole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1560104A true CN1560104A (en) | 2005-01-05 |
| CN1266181C CN1266181C (en) | 2006-07-26 |
Family
ID=34440452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100163772A Expired - Fee Related CN1266181C (en) | 2004-02-17 | 2004-02-17 | Production of dry type binary liquid shape polyaminoester (pu) resin by waste polyaminoester (pu)resin sole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1266181C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012037709A1 (en) * | 2010-09-25 | 2012-03-29 | Nike International Ltd. | Regrlnd polyurethane with glycol or polyol additive |
| CN105345986A (en) * | 2015-11-11 | 2016-02-24 | 范焱林 | Recovering and manufacturing process for polyurethane shoe materials and polyurethane-shoe-material injection-molding feeding mechanism for recovering and manufacturing process |
-
2004
- 2004-02-17 CN CNB2004100163772A patent/CN1266181C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012037709A1 (en) * | 2010-09-25 | 2012-03-29 | Nike International Ltd. | Regrlnd polyurethane with glycol or polyol additive |
| CN103154136A (en) * | 2010-09-25 | 2013-06-12 | 耐克国际有限公司 | Regrlnd polyurethane with glycol or polyol additive |
| US9273193B2 (en) | 2010-09-25 | 2016-03-01 | Nike, Inc. | Regrind polyurethane with glycol or polyol additive |
| CN103154136B (en) * | 2010-09-25 | 2016-07-06 | 耐克国际有限公司 | There is the defective material polyurethane of glycol or polyhydric alcohol additive |
| CN105345986A (en) * | 2015-11-11 | 2016-02-24 | 范焱林 | Recovering and manufacturing process for polyurethane shoe materials and polyurethane-shoe-material injection-molding feeding mechanism for recovering and manufacturing process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1266181C (en) | 2006-07-26 |
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Granted publication date: 20060726 Termination date: 20110217 |