CN104877338A - Recycling method for polyurethane elastomer waste - Google Patents
Recycling method for polyurethane elastomer waste Download PDFInfo
- Publication number
- CN104877338A CN104877338A CN201510345321.XA CN201510345321A CN104877338A CN 104877338 A CN104877338 A CN 104877338A CN 201510345321 A CN201510345321 A CN 201510345321A CN 104877338 A CN104877338 A CN 104877338A
- Authority
- CN
- China
- Prior art keywords
- polyurethane elastomer
- waste material
- parts
- waste
- polyether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a recycling method for polyurethane elastomer waste, and belongs to the technical field of waste recycling methods. The method comprises the steps that 100-150 parts of polyurethane elastomer waste particles with the particle size 1-3 mm are instantly heated for 2-3 min in a drying oven at the temperature ranging from 260 DEG C to 275 DEG C, and therefore the surfaces of the polyurethane elastomer waste particles are fused to be sticky; 5-15 parts of polyurethane prepolymer and chain extender mixtures are added into the polyurethane elastomer waste particles to be evenly stirred and then poured into a mold, pressurization molding is performed by using a vulcanizing machine, vulcanization is performed for 30 min at the temperature of 120 DEG C, after demolding is performed, additional vulcanization is performed for 10 hr at the temperature of 100 DEG C, and then compound molding materials of the polyurethane elastomer waste are obtained. According to the method, the production technology is simple, the preparation period is short, the waste recycling rate is high, the energy consumption is little, the production cost is low, and prepared products have good mechanical properties; the method is a new technology and a new method for recycling and reusing the polyurethane elastomer waste, the pollution of the polyurethane elastomer waste to the environment is greatly reduced according to the method, and the prepared products can be used as materials of shock absorption, wear resistance and collision avoidance and the like.
Description
Technical field
The invention belongs to waste recovery Application way technical field, be specifically related to a kind of recoverying and utilizing method of polyurethane elastomer waste material.
Background technology
Polyurethane elastomer raw material is numerous, fill a prescription various, hardness is adjustable, there is inconsistent soft, the hard section two phase structure of thermodynamics, and form microphase-separated, impart the mechanical property of its excellence, wear resisting property, resistance to low temperature, chemical resistance etc., be widely used in industrial production and people's daily life production.The development of polyurethane elastomer is very fast, traditional rubber, nylon, plastics etc. have been instead of at some special dimensions, but meanwhile, also create many polyurethane elastomer waste materials in manufacturing enterprise and application units, topmost is polyether-type and PAUR elastomerics waste material.The method of current process polyurethane elastomer waste material has physiochemical mutagens method, energy recovery method, chemical recycling.Physiochemical mutagens method uses mainly as filler, and the rate of recovery is low; Energy recovery method can produce obnoxious flavour, contaminate environment, and can not Appropriate application waste material, causes the wasting of resources; Chemical recycling step is complicated, and the rate of recovery is low, and Financial cost is higher; So find a kind of not only economy but the method that environmental pollution is little extremely urgent.
Publication number is the moulding process that application discloses a kind of polyurethane composite waste of CN1951511A, specifically for the recycling of automotive trim scrap stock.Polyurethane composite waste is added virgin pp, coupling agent and auxiliary agent Homogeneous phase mixing through pulverizing and makes compound by this invention, compound is through heating, insulation to compound enters molten state, then molten state compound is added mold pressing in mould, obtains goods finished product after cooling and demolding.This invention compound waste leftover material convenient sources, production technique is simple, not easily causes secondary pollution, and can reduce production cost, be conducive to increasing economic efficiency; Through reclaiming shaping goods, there is the excellent performance such as unique elasticity, wear resistance, lower temperature resistance, expandable, resistance to biodeterioration, the industries such as electromechanics, boats and ships, vehicle, civil construction, light industry, weaving and automotive upholstery can be widely used in.The method uses as a kind of filler after polyurethane waste material is pulverized, and belongs to a kind of physical recovery method, there is the technical problem that the rate of recovery is low.
Publication number is the recovery method that application discloses a kind of polyurethane waste material of CN101560309A, technical characteristics is mix with polyvinyl chloride by a certain percentage after the powder being ground into certain ultra-fine order number under polyurethane waste material specific process conditions, under certain plasticization temperature, cause particle through plasticizing completely, utilizing injector, injecting particles or employing being extruded, prolonging the molding modes such as pressure and make goods.This kind of method is both simple, improves the performance of product, again reduces the cost of goods, decreases the pollution to environment.But the method polyurethane waste material used ratio is little, and recovery utilization rate is low.
Publication number is that the method for polyurethane for polyurethane elastomer is reclaimed in a kind of solid phase alcoholysis that application discloses of CN103788335A, namely in polyurethane scrap or waste material: alcoholysis agent: catalyzer be 100 parts: 0.5 ~ 100 part: 0.01 ~ 2 part ratio in intensive mixer, control 160 ~ 220 DEG C, alcoholysis reaction 0.05 ~ 1.5h under 10 ~ 1000r/min, obtain solid alcohol hydrolysis products, again in solid alcohol hydrolysis products: carbon black or white carbon black: dicumyl peroxide: isocyanic ester is after the ratio mixing of 100 parts: 30 ~ 40 parts: 0 ~ 3 part: 0 ~ 8 part, react 3 ~ 15min at controlling 150 ~ 175 DEG C and namely obtain polyurethane elastomer, its tensile strength reaches 8 ~ 26N/mm
2, elongation at break large 150 ~ 500%, Shao A hardness reaches 65 ~ 96.The method belongs to chemical recycling, and recovery process is complicated, if do not classify to polyurethane scrap or waste material, then can produce larger impact to the polyurethane elastomer performance after recovery.
Publication number is the recovery method that application discloses a kind of polyurethane waste material of CN1275587A; it makes polyurethane waste material decompose in aqueous; and in aqueous phase by catalyst separating to recycle; degradation production polyethers and tolylene diamine are separated in equal aqueous phase; simultaneously to tolylene diamine acidylate remaining in polyethers; carry out grafting to polyethers, the polyethers generated can be used to produce urethane.This method process more complicated, production cost is high, can produce hazardous and noxious substances in reaction process, can pollute and injure environment and operator.
Zhong Shiyun was at (Journal of Building Materials 2002 in 2002, No6,194-197) proposition mold pressing and lamination 2 kinds of heat pressing process make sheet material by after the polyurethane foam waste in car roof interior trim production process and the mixing of roof gadget composite waste, have studied the relation between the performance of sheet material and heat pressing process and proportioning raw materials.When hot pressing temperature more than 150 DEG C, the flexural strength of sheet material can reach 15 ~ 23MPa, and the water-intake rate of sheet material is 0.2% ~ 2%, and density is 1.0 ~ 1.6g/cm
3.Foam waste used has certain thermoplasticity, can improve timber intensity, reduces panel density, adds the fire retardant of more than 5 parts, greatly can reduce the incendivity of sheet material.The method step is simple, and waste utilization rate is high, but is only applicable to the recycling of foam waste.
Summary of the invention
There is the technical problem that the rate of recovery is low, the waste of contaminate environment, polyurethane elastomer waste material is serious, recycling step is complicated, Financial cost is high and range of application is narrow in the method that the object of the invention is to solve existing recycling polyurethane elastomer waste material, provides a kind of recoverying and utilizing method of polyurethane elastomer waste material.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A recoverying and utilizing method for polyurethane elastomer waste material, comprises the following steps:
1) metal vessel that mass parts is 100 ~ 150 parts, particle diameter is 1 ~ 3mm polyurethane elastomer waste granules is placed in long × wide × height=300mm × 300mm × 10mm is taken;
2) metal vessel that polyurethane elastomer waste granules is housed is placed in baking oven, at the temperature of 260 DEG C ~ 275 DEG C, heats 2 ~ 3min, now polyurethane elastomer waste granules surface occurs that melting is clamminess phenomenon;
3) be that the base polyurethane prepolymer for use as of 5 ~ 15 parts and the mixture of chainextender are placed in the metal die scribbling releasing agent by mass parts, then polyurethane elastomer waste granules melting be clamminess is poured in metal die, after stirring, extrusion forming is carried out with vulcanizer, sulfuration 30min at the temperature of 120 DEG C, the demoulding, finally revulcanization 10h at the temperature of 100 DEG C, obtains polyurethane elastomer waste material composite forming material.
The preparation method of described base polyurethane prepolymer for use as comprises the following steps:
Be that polyether glycol or the polyester polyol of 100 parts adds in reactor by mass parts, at the temperature of 120 DEG C, dewater 2.5h under the state that vacuum tightness is 0.08 ~ 0.09MPa; Then 50 DEG C are cooled to, the vulcabond that mass parts is 21.3 ~ 46.9 parts is added in reactor, be warming up to 80 DEG C again, insulation reaction 2.5h, the mass percent controlling-NCO ion is 5.0%, deaeration 0.5h under the state being finally 0.8 ~ 0.9MPa in vacuum tightness, obtains polyether-type or PAUR performed polymer.
Described polyurethane elastomer waste material is any one in polyether(poly)urethane elastomerics waste material or PAUR elastomerics; When polyurethane elastomer waste material is polyether(poly)urethane elastomerics waste material, described base polyurethane prepolymer for use as adopts Polyether-Polyol Polyurethane Prepolymer; When polyurethane elastomer waste material is PAUR elastomerics waste material, described base polyurethane prepolymer for use as adopts PAUR performed polymer.
Described chainextender is any one in chloro-4, the 4'-diaminodiphenyl-methanes of 3,3'-bis-or BDO.
The chain extension coefficient of described base polyurethane prepolymer for use as and mixture of chain extenders is 0.9.
Described polyether glycol or polyester polyol to be relative molecular weight be in 1000 or 2000 any one; Or relative molecular weight be 1000 and 2000 two kinds of polyether glycols with arbitrarily than mixture or relative molecular mass be 1000 and 2000 two kinds of polyester polyols with arbitrarily than mixture in any one.
Described vulcabond is any one in TDI-80 type tolylene diisocyanate, TDI-100 type tolylene diisocyanate, MDI-100 type diphenylmethanediisocyanate, MDI-50 type diphenylmethanediisocyanate or liquefied mdi type diphenylmethanediisocyanate.
The present invention adopts above technical scheme, and compared with background technology, the present invention has the following advantages:
1) production unit required for the present invention is simple, substantially conforms to the production unit of polyurethane elastomer, can improve the plant factor of existing polyurethane elastomer manufacturing enterprise;
2) treatment process of the present invention and processing condition simple, broken for polyurethane elastomer waste material essence is only needed to be fine particle shape and to carry out instantaneously heating and composite molding, there is no complicated chemical degradation reaction, waste recovery rate and remanufacture efficiency high, molding time is short, cost recovery is low, significantly reduces the production cost of polyurethane elastomer manufacturing enterprise, improves the economic benefit of enterprise;
3) adopt the present invention to recycle polyurethane elastomer waste material, saved resource, reached the object of cycling and reutilization, not only reduced the pollution of polyurethane elastomer waste material to environment, also beautify the environment of manufacturing enterprise and application units simultaneously;
4) heating treatment time of the present invention is short, and instantaneously heating makes waste granules melt surface be clamminess, and reclaims power consumption of polymer processing low, produce without waste gas slag and effluent waste liquid, removal process does not produce secondary pollution, environmentally friendly, reaches the harmless treatment to refuse;
5) what the present invention was more outstanding is after polyurethane elastomer scraped surface molten mass mixes with base polyurethane prepolymer for use as and mixture of chain extenders, under high temperature and flow state, chemical reaction and the physical entanglement of the intermolecular hydrogen bond of molten mass molecule and performed polymer and chainextender and active group thereof is made by pressurization, reach intermolecular to interpenetrate and act on, elastomerics waste granules is made to form a complete one-piece construction, and granule interior molecular structure is without change, can not be heated and degrade, the polyurethane elastomer Waste Composite Material goods obtained have good hardness, tensile strength and tear strength,
6) adopt the composite property obtained by the present invention good, the requirement of general industrial and mining enterprises can be met, can be used as the materials'uses such as shockproof, crashproof, wear-resistant, anti-skidding.
Embodiment
Embodiment 1
The recoverying and utilizing method of a kind of polyurethane elastomer waste material in the present embodiment, comprises the following steps:
1) metal vessel that mass parts is 100 parts, particle diameter is 1 ~ 3mm polyether(poly)urethane elastomerics waste granules is placed in long × wide × height=300mm × 300mm × 10mm is taken;
2) metal vessel that polyether(poly)urethane elastomerics waste granules is housed is placed in baking oven, at the temperature of 260 DEG C, heats 2min, now polyether(poly)urethane elastomerics waste granules surface occurs that melting is clamminess phenomenon;
3) by mass parts be the Polyether-Polyol Polyurethane Prepolymer of 4.37 parts and 0.63 part 3,3'-bis-chloro-4, the mixture of 4'-diaminodiphenyl-methane chainextender is placed in the metal die scribbling releasing agent, then polyether(poly)urethane elastomerics waste granules melting be clamminess is poured in metal die, after stirring, extrusion forming is carried out with vulcanizer, sulfuration 30min at the temperature of 120 DEG C, the demoulding, finally revulcanization 10h at the temperature of 100 DEG C, obtains polyether(poly)urethane elastomerics waste material composite forming material.
The preparation method of described Polyether-Polyol Polyurethane Prepolymer comprises the following steps:
To be 100 parts of relative molecular weights by mass parts be 1000 polyether glycol add in reactor, at the temperature of 120 DEG C, dewater 2.5h under the state that vacuum tightness is 0.08 ~ 0.09MPa; Then 50 DEG C are cooled to, the TDI-80 type tolylene diisocyanate that mass parts is 31 parts is added in reactor, be warming up to 80 DEG C again, insulation reaction 2.5h, the mass percent controlling-NCO ion is 5.0%, deaeration 0.5h under the state being finally 0.8 ~ 0.9MPa in vacuum tightness, obtains Polyether-Polyol Polyurethane Prepolymer.
After tested, its tensile strength is 6.3MPa to polyether(poly)urethane elastomerics waste material composite forming material prepared by the present embodiment, and elongation is 207%, and tear strength is 48kN/m.
Embodiment 2
The recoverying and utilizing method of a kind of polyurethane elastomer waste material in the present embodiment, comprises the following steps:
1) metal vessel that mass parts is 110 parts, particle diameter is 1 ~ 3mm polyether(poly)urethane elastomerics waste granules is placed in long × wide × height=300mm × 300mm × 10mm is taken;
2) metal vessel that polyether(poly)urethane elastomerics waste granules is housed is placed in baking oven, at the temperature of 265 DEG C, heats 2.5min, now polyether(poly)urethane elastomerics waste granules surface occurs that melting is clamminess phenomenon;
3) by mass parts be the Polyether-Polyol Polyurethane Prepolymer of 7 parts and 1 part 3,3'-bis-chloro-4, the mixture of 4'-diaminodiphenyl-methane chainextender is placed in the metal die scribbling releasing agent, then polyether(poly)urethane elastomerics waste granules melting be clamminess is poured in metal die, after stirring, extrusion forming is carried out with vulcanizer, sulfuration 30min at the temperature of 120 DEG C, the demoulding, finally revulcanization 10h at the temperature of 100 DEG C, obtains polyether(poly)urethane elastomerics waste material composite forming material.
The preparation method of described Polyether-Polyol Polyurethane Prepolymer comprises the following steps:
To be 53.8 parts of relative molecular weights by mass parts be 1000 polyether glycol and 46.2 parts of relative molecular weights be 2000 polyether glycol add in reactor, at the temperature of 120 DEG C, dewater 2.5h under the state that vacuum tightness is 0.08 ~ 0.09MPa; Then 50 DEG C are cooled to, the TDI-100 type diphenylmethanediisocyanate that mass parts is 26.5 parts is added in reactor, be warming up to 80 DEG C again, insulation reaction 2.5h, the mass percent controlling-NCO ion is 5.0%, deaeration 0.5h under the state being finally 0.8 ~ 0.9MPa in vacuum tightness, obtains Polyether-Polyol Polyurethane Prepolymer.
After tested, its tensile strength is 7.4MPa to polyether(poly)urethane elastomerics waste material composite forming material prepared by the present embodiment, and elongation is 226%, and tear strength is 50kN/m.
Embodiment 3
The recoverying and utilizing method of a kind of polyurethane elastomer waste material in the present embodiment, comprises the following steps:
1) metal vessel that mass parts is 120 parts, particle diameter is 1 ~ 3mm polyether(poly)urethane elastomerics waste granules is placed in long × wide × height=300mm × 300mm × 10mm is taken;
2) metal vessel that polyether(poly)urethane elastomerics waste granules is housed is placed in baking oven, at the temperature of 270 DEG C, heats 2.5min, now polyether(poly)urethane elastomerics waste granules surface occurs that melting is clamminess phenomenon;
3) by mass parts be the Polyether-Polyol Polyurethane Prepolymer of 9.54 parts and 0.45 part 1, the mixture of 4-chain expansion of succinic acid agent is placed in the metal die scribbling releasing agent, then polyether(poly)urethane elastomerics waste granules melting be clamminess is poured in metal die, after stirring, extrusion forming is carried out, sulfuration 30min at the temperature of 120 DEG C, the demoulding with vulcanizer, finally revulcanization 10h at the temperature of 100 DEG C, obtains polyether(poly)urethane elastomerics waste material composite forming material.
The preparation method of described Polyether-Polyol Polyurethane Prepolymer comprises the following steps:
To be 33.3 parts of relative molecular weights by mass parts be 1000 polyether glycol and 66.7 parts of relative molecular weights be 2000 polyether glycol add in reactor, at the temperature of 120 DEG C, dewater 2.5h under the state that vacuum tightness is 0.08 ~ 0.09MPa; Then 50 DEG C are cooled to, the MDI-100 type diphenylmethanediisocyanate that mass parts is 37 parts is added in reactor, be warming up to 80 DEG C again, insulation reaction 2.5h, the mass percent controlling-NCO ion is 5.0%, deaeration 0.5h under the state being finally 0.8 ~ 0.9MPa in vacuum tightness, obtains Polyether-Polyol Polyurethane Prepolymer.
After tested, its tensile strength is 10.9MPa to polyether(poly)urethane elastomerics waste material composite forming material prepared by the present embodiment, and elongation is 257%, and tear strength is 58kN/m.
Embodiment 4
The recoverying and utilizing method of a kind of polyurethane elastomer waste material in the present embodiment, comprises the following steps:
1) metal vessel that mass parts is 140 parts, particle diameter is 1 ~ 3mm polyether(poly)urethane elastomerics waste granules is placed in long × wide × height=300mm × 300mm × 10mm is taken;
2) metal vessel that polyether(poly)urethane elastomerics waste granules is housed is placed in baking oven, at the temperature of 270 DEG C, heats 2.5min, now polyether(poly)urethane elastomerics waste granules surface occurs that melting is clamminess phenomenon;
3) by mass parts be the Polyether-Polyol Polyurethane Prepolymer of 11.4 parts and 1.6 parts 3,3'-bis-chloro-4, the mixture of 4'-diaminodiphenyl-methane chainextender is placed in the metal die scribbling releasing agent, then polyether(poly)urethane elastomerics waste granules melting be clamminess is poured in metal die, after stirring, extrusion forming is carried out with vulcanizer, sulfuration 30min at the temperature of 120 DEG C, the demoulding, finally revulcanization 10h at the temperature of 100 DEG C, obtains polyether(poly)urethane elastomerics waste material composite forming material.
The preparation method of described Polyether-Polyol Polyurethane Prepolymer comprises the following steps:
To be 11.1 parts of relative molecular weights by mass parts be 1000 polyether glycol and 88.9 parts of relative molecular weights be 2000 polyether glycol add in reactor, at the temperature of 120 DEG C, dewater 2.5h under the state that vacuum tightness is 0.08 ~ 0.09MPa; Then 50 DEG C are cooled to, the MDI-50 type diphenylmethanediisocyanate that mass parts is 33.8 parts is added in reactor, be warming up to 80 DEG C again, insulation reaction 2.5h, the mass percent controlling-NCO ion is 5.0%, deaeration 0.5h under the state being finally 0.8 ~ 0.9MPa in vacuum tightness, obtains Polyether-Polyol Polyurethane Prepolymer.
After tested, its tensile strength is 12MPa to polyether(poly)urethane elastomerics waste material composite forming material prepared by the present embodiment, and elongation is 298%, and tear strength is 64kN/m.
Embodiment 5
The recoverying and utilizing method of a kind of polyurethane elastomer waste material in the present embodiment, comprises the following steps:
1) metal vessel that mass parts is 150 parts, particle diameter is 1 ~ 3mm polyether(poly)urethane elastomerics waste granules is placed in long × wide × height=300mm × 300mm × 10mm is taken;
2) metal vessel that polyether(poly)urethane elastomerics waste granules is housed is placed in baking oven, at the temperature of 270 DEG C, heats 2.5min, now polyether(poly)urethane elastomerics waste granules surface occurs that melting is clamminess phenomenon;
3) by mass parts be the Polyether-Polyol Polyurethane Prepolymer of 13.1 parts and 1.9 parts 3,3'-bis-chloro-4, the mixture of 4'-diaminodiphenyl-methane chainextender is placed in the metal die scribbling releasing agent, then polyether(poly)urethane elastomerics waste granules melting be clamminess is poured in metal die, after stirring, extrusion forming is carried out with vulcanizer, sulfuration 30min at the temperature of 120 DEG C, the demoulding, finally revulcanization 10h at the temperature of 100 DEG C, obtains polyether(poly)urethane elastomerics waste material composite forming material.
The preparation method of described Polyether-Polyol Polyurethane Prepolymer comprises the following steps:
To be 100 parts of relative molecular weights by mass parts be 2000 polyether glycol add in reactor, at the temperature of 120 DEG C, dewater 2.5h under the state that vacuum tightness is 0.08 ~ 0.09MPa; Then 50 DEG C are cooled to, the liquefied mdi type diphenylmethanediisocyanate that mass parts is 38.33 parts is added in reactor, be warming up to 80 DEG C again, insulation reaction 2.5h, the mass percent controlling-NCO ion is 5.0%, deaeration 0.5h under the state being finally 0.8 ~ 0.9MPa in vacuum tightness, obtains Polyether-Polyol Polyurethane Prepolymer.
After tested, its tensile strength is 12MPa to polyether(poly)urethane elastomerics waste material composite forming material prepared by the present embodiment, and elongation is 318%, and tear strength is 71kN/m.
Embodiment 6
The recoverying and utilizing method of a kind of polyurethane elastomer waste material in the present embodiment, comprises the following steps:
1) metal vessel that mass parts is 100 parts, particle diameter is 1 ~ 3mm PAUR elastomerics waste granules is placed in long × wide × height=300mm × 300mm × 10mm is taken;
2) metal vessel that PAUR elastomerics waste granules is housed is placed in baking oven, at the temperature of 265 DEG C, heats 3min, now PAUR elastomerics waste granules surface occurs that melting is clamminess phenomenon;
3) by mass parts be the PAUR performed polymer of 4.77 parts and 0.23 part 1, the mixture of 4-chain expansion of succinic acid agent is placed in the metal die scribbling releasing agent, then PAUR elastomerics waste granules melting be clamminess is poured in metal die, after stirring, extrusion forming is carried out, sulfuration 30min at the temperature of 120 DEG C, the demoulding with vulcanizer, finally revulcanization 10h at the temperature of 100 DEG C, obtains PAUR elastomerics waste material composite forming material.
The preparation method of described PAUR performed polymer comprises the following steps:
To be 100 parts of relative molecular weights by mass parts be 1000 polyester polyol add in reactor, at the temperature of 120 DEG C, dewater 2.5h under the state that vacuum tightness is 0.08 ~ 0.09MPa; Then 50 DEG C are cooled to, the MDI-100 type tolylene diisocyanate that mass parts is 46.9 parts is added in reactor, be warming up to 80 DEG C again, insulation reaction 2.5h, the mass percent controlling-NCO ion is 5.0%, deaeration 0.5h under the state being finally 0.8 ~ 0.9MPa in vacuum tightness, obtains PAUR performed polymer.
After tested, its tensile strength is 8.5MPa to polyether(poly)urethane elastomerics waste material composite forming material prepared by the present embodiment, and elongation is 217%, and tear strength is 57kN/m.
Embodiment 7
The recoverying and utilizing method of a kind of polyurethane elastomer waste material in the present embodiment, comprises the following steps:
1) metal vessel that mass parts is 110 parts, particle diameter is 1 ~ 3mm PAUR elastomerics waste granules is placed in long × wide × height=300mm × 300mm × 10mm is taken;
2) metal vessel that PAUR elastomerics waste granules is housed is placed in baking oven, at the temperature of 270 DEG C, heats 3min, now PAUR elastomerics waste granules surface occurs that melting is clamminess phenomenon;
3) by mass parts be the PAUR performed polymer of 7.63 parts and 0.37 part 1, the mixture of 4-chain expansion of succinic acid agent is placed in the metal die scribbling releasing agent, then PAUR elastomerics waste granules melting be clamminess is poured in metal die, after stirring, extrusion forming is carried out, sulfuration 30min at the temperature of 120 DEG C, the demoulding with vulcanizer, finally revulcanization 10h at the temperature of 100 DEG C, obtains PAUR elastomerics waste material composite forming material.
The preparation method of described PAUR performed polymer comprises the following steps:
To be 53.8 parts of relative molecular weights by mass parts be 1000 polyester polyol and 46.2 parts of relative molecular weights be 2000 polyester polyol add in reactor, at the temperature of 120 DEG C, dewater 2.5h under the state that vacuum tightness is 0.08 ~ 0.09MPa; Then 50 DEG C are cooled to, the MDI-50 type diphenylmethanediisocyanate that mass parts is 40.1 parts is added in reactor, be warming up to 80 DEG C again, insulation reaction 2.5h, the mass percent controlling-NCO ion is 5.0%, deaeration 0.5h under the state being finally 0.8 ~ 0.9MPa in vacuum tightness, obtains PAUR performed polymer.
After tested, its tensile strength is 10.2MPa to polyether(poly)urethane elastomerics waste material composite forming material prepared by the present embodiment, and elongation is 302%, and tear strength is 66kN/m.
Embodiment 8
The recoverying and utilizing method of a kind of polyurethane elastomer waste material in the present embodiment, comprises the following steps:
1) metal vessel that mass parts is 130 parts, particle diameter is 1 ~ 3mm PAUR elastomerics waste granules is placed in long × wide × height=300mm × 300mm × 10mm is taken;
2) metal vessel that PAUR elastomerics waste granules is housed is placed in baking oven, at the temperature of 275 DEG C, heats 3min, now PAUR elastomerics waste granules surface occurs that melting is clamminess phenomenon;
3) by mass parts be the PAUR performed polymer of 9.54 parts and 0.46 part 1, the mixture of 4-chain expansion of succinic acid agent is placed in the metal die scribbling releasing agent, then PAUR elastomerics waste granules melting be clamminess is poured in metal die, after stirring, extrusion forming is carried out, sulfuration 30min at the temperature of 120 DEG C, the demoulding with vulcanizer, finally revulcanization 10h at the temperature of 100 DEG C, obtains PAUR elastomerics waste material composite forming material.
The preparation method of described PAUR performed polymer comprises the following steps:
To be 33.3 parts of relative molecular weights by mass parts be 1000 polyester polyol and 66.7 parts of relative molecular weights be 2000 polyester polyol add in reactor, at the temperature of 120 DEG C, dewater 2.5h under the state that vacuum tightness is 0.08 ~ 0.09MPa; Then 50 DEG C are cooled to, the liquefied mdi type diphenylmethanediisocyanate that mass parts is 44.2 parts is added in reactor, be warming up to 80 DEG C again, insulation reaction 2.5h, the mass percent controlling-NCO ion is 5.0%, deaeration 0.5h under the state being finally 0.8 ~ 0.9MPa in vacuum tightness, obtains PAUR performed polymer.
After tested, its tensile strength is 11MPa to polyether(poly)urethane elastomerics waste material composite forming material prepared by the present embodiment, and elongation is 307%, and tear strength is 69kN/m.
Embodiment 9
The recoverying and utilizing method of a kind of polyurethane elastomer waste material in the present embodiment, comprises the following steps:
1) metal vessel that mass parts is 140 parts, particle diameter is 1 ~ 3mm PAUR elastomerics waste granules is placed in long × wide × height=300mm × 300mm × 10mm is taken;
2) metal vessel that PAUR elastomerics waste granules is housed is placed in baking oven, at the temperature of 275 DEG C, heats 3min, now PAUR elastomerics waste granules surface occurs that melting is clamminess phenomenon;
3) by mass parts be the PAUR performed polymer of 11.4 parts and 1.6 parts 3,3'-bis-chloro-4, the mixture of 4'-diaminodiphenyl-methane chainextender is placed in the metal die scribbling releasing agent, then PAUR elastomerics waste granules melting be clamminess is poured in metal die, after stirring, extrusion forming is carried out with vulcanizer, sulfuration 30min at the temperature of 120 DEG C, the demoulding, finally revulcanization 10h at the temperature of 100 DEG C, obtains PAUR elastomerics waste material composite forming material.
The preparation method of described PAUR performed polymer comprises the following steps:
To be 11.1 parts of relative molecular weights by mass parts be 1000 polyester polyol and 88.9 parts of relative molecular weights be 2000 polyester polyol add in reactor, at the temperature of 120 DEG C, dewater 2.5h under the state that vacuum tightness is 0.08 ~ 0.09MPa; Then 50 DEG C are cooled to, the TDI-80 type tolylene diisocyanate that mass parts is 22.4 parts is added in reactor, be warming up to 80 DEG C again, insulation reaction 2.5h, the mass percent controlling-NCO ion is 5.0%, deaeration 0.5h under the state being finally 0.8 ~ 0.9MPa in vacuum tightness, obtains PAUR performed polymer.
After tested, its tensile strength is 10.5MPa to polyether(poly)urethane elastomerics waste material composite forming material prepared by the present embodiment, and elongation is 267%, and tear strength is 61kN/m.
Embodiment 10
The recoverying and utilizing method of a kind of polyurethane elastomer waste material in the present embodiment, comprises the following steps:
1) metal vessel that mass parts is 150 parts, particle diameter is 1 ~ 3mm PAUR elastomerics waste granules is placed in long × wide × height=300mm × 300mm × 10mm is taken;
2) metal vessel that PAUR elastomerics waste granules is housed is placed in baking oven, at the temperature of 275 DEG C, heats 3min, now PAUR elastomerics waste granules surface occurs that melting is clamminess phenomenon;
3) by mass parts be the PAUR performed polymer of 13.1 parts and 1.9 parts 3,3'-bis-chloro-4, the mixture of 4'-diaminodiphenyl-methane chainextender is placed in the metal die scribbling releasing agent, then PAUR elastomerics waste granules melting be clamminess is poured in metal die, after stirring, extrusion forming is carried out with vulcanizer, sulfuration 30min at the temperature of 120 DEG C, the demoulding, finally revulcanization 10h at the temperature of 100 DEG C, obtains PAUR elastomerics waste material composite forming material.
The preparation method of described PAUR performed polymer comprises the following steps:
To be 100 parts of relative molecular weights by mass parts be 2000 polyester polyol add in reactor, at the temperature of 120 DEG C, dewater 2.5h under the state that vacuum tightness is 0.08 ~ 0.09MPa; Then 50 DEG C are cooled to, the TDI-100 type tolylene diisocyanate that mass parts is 21.3 parts is added in reactor, be warming up to 80 DEG C again, insulation reaction 2.5h, the mass percent controlling-NCO ion is 5.0%, deaeration 0.5h under the state being finally 0.8 ~ 0.9MPa in vacuum tightness, obtains PAUR performed polymer.
After tested, its tensile strength is 14.5MPa to polyether(poly)urethane elastomerics waste material composite forming material prepared by the present embodiment, and elongation is 313%, and tear strength is 76kN/m.
By the composite property that the polyurethane elastomer waste material obtained by above-mentioned specific embodiment and base polyurethane prepolymer for use as and mixture of chain extenders press vulcanization obtained by molding arrive, testing method is carried out with reference to the standard such as GB/T6031 " vulcanized rubber or thermoplastic elastomer measurement of hardness " GB/T528 " vulcanized rubber or thermoplastic elastomer tear strength measure ", GB/T5723 " vulcanized rubber or thermoplastic elastomer test sample and product size mensuration ", GB/T 2568 " resin-cast body stretching test method ".
Claims (7)
1. a recoverying and utilizing method for polyurethane elastomer waste material, is characterized in that: comprise the following steps:
1) metal vessel that mass parts is 100 ~ 150 parts, particle diameter is 1 ~ 3mm polyurethane elastomer waste granules is placed in long × wide × height=300mm × 300mm × 10mm is taken;
2) metal vessel that polyurethane elastomer waste granules is housed is placed in baking oven, at the temperature of 260 DEG C ~ 275 DEG C, heats 2 ~ 3min, now polyurethane elastomer waste granules surface occurs that melting is clamminess phenomenon;
3) be that the base polyurethane prepolymer for use as of 5 ~ 15 parts and the mixture of chainextender are placed in the metal die scribbling releasing agent by mass parts, then polyurethane elastomer waste granules melting be clamminess is poured in metal die, after stirring, extrusion forming is carried out with vulcanizer, sulfuration 30min at the temperature of 120 DEG C, the demoulding, finally revulcanization 10h at the temperature of 100 DEG C, obtains polyurethane elastomer waste material composite forming material.
2. the recoverying and utilizing method of a kind of polyurethane elastomer waste material according to claim 1, is characterized in that: the preparation method of described base polyurethane prepolymer for use as comprises the following steps:
Be that polyether glycol or the polyester polyol of 100 parts adds in reactor by mass parts, at the temperature of 120 DEG C, dewater 2.5h under the state that vacuum tightness is 0.08 ~ 0.09MPa; Then 50 DEG C are cooled to, the vulcabond that mass parts is 21.3 ~ 46.9 parts is added in reactor, be warming up to 80 DEG C again, insulation reaction 2.5h, the mass percent controlling-NCO ion is 5.0%, deaeration 0.5h under the state being finally 0.8 ~ 0.9MPa in vacuum tightness, obtains polyether-type or PAUR performed polymer.
3. the recoverying and utilizing method of a kind of polyurethane elastomer waste material according to claim 1, is characterized in that: described polyurethane elastomer waste material is any one in polyether(poly)urethane elastomerics waste material or PAUR elastomerics; When polyurethane elastomer waste material is polyether(poly)urethane elastomerics waste material, described base polyurethane prepolymer for use as adopts Polyether-Polyol Polyurethane Prepolymer; When polyurethane elastomer waste material is PAUR elastomerics waste material, described base polyurethane prepolymer for use as adopts PAUR performed polymer.
4. the recoverying and utilizing method of a kind of polyurethane elastomer waste material according to claim 1, is characterized in that: described chainextender is any one in chloro-4, the 4'-diaminodiphenyl-methanes of 3,3'-bis-or BDO.
5. the recoverying and utilizing method of a kind of polyurethane elastomer waste material according to claim 1, is characterized in that: the chain extension coefficient of described base polyurethane prepolymer for use as and mixture of chain extenders is 0.9.
6. the recoverying and utilizing method of a kind of polyurethane elastomer waste material according to claim 2, is characterized in that: described polyether glycol or polyester polyol to be relative molecular weight be in 1000 or 2000 any one; Or relative molecular weight be 1000 and 2000 two kinds of polyether glycols with arbitrarily than mixture or relative molecular mass be 1000 and 2000 two kinds of polyester polyols with arbitrarily than mixture in any one.
7. the recoverying and utilizing method of a kind of polyurethane elastomer waste material according to claim 2, is characterized in that: described vulcabond is any one in TDI-80 type tolylene diisocyanate, TDI-100 type tolylene diisocyanate, MDI-100 type diphenylmethanediisocyanate, MDI-50 type diphenylmethanediisocyanate or liquefied mdi type diphenylmethanediisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510345321.XA CN104877338B (en) | 2015-06-19 | 2015-06-19 | A kind of recoverying and utilizing method of polyurethane elastomer waste material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510345321.XA CN104877338B (en) | 2015-06-19 | 2015-06-19 | A kind of recoverying and utilizing method of polyurethane elastomer waste material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104877338A true CN104877338A (en) | 2015-09-02 |
| CN104877338B CN104877338B (en) | 2018-03-13 |
Family
ID=53945032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510345321.XA Active CN104877338B (en) | 2015-06-19 | 2015-06-19 | A kind of recoverying and utilizing method of polyurethane elastomer waste material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104877338B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483855A (en) * | 2015-12-21 | 2016-04-13 | 长乐恒申合纤科技有限公司 | Method for producing spandex filaments by utilizing spandex prepolymer waste liquid |
| CN106883591A (en) * | 2017-04-24 | 2017-06-23 | 广东工业大学 | The Application way and elastomer of a kind of polyurethane waste material |
| CN107090174A (en) * | 2017-06-15 | 2017-08-25 | 海洋石油工程股份有限公司 | A kind of preparation method of the casting type polyurethane composite layer of anti-skid wearable |
| CN107446345A (en) * | 2017-08-29 | 2017-12-08 | 河北科技大学 | A kind of filled-type flexible polyurethane foams based on vamp leftover pieces and preparation method thereof |
| CN107686630A (en) * | 2017-08-29 | 2018-02-13 | 河北科技大学 | A kind of preparation technology of vamp leftover pieces polymer composite and its application |
| CN111500053A (en) * | 2020-04-20 | 2020-08-07 | 江苏建筑职业技术学院 | Method for preparing composite heat-preservation vibration-damping material by regenerating elastomer waste |
| CN111635627A (en) * | 2020-06-01 | 2020-09-08 | 丁震 | Meyer sedge sports insole and manufacturing method thereof |
| CN111995725A (en) * | 2020-09-07 | 2020-11-27 | 江苏湘园化工有限公司 | Environment-friendly liquid polyurethane curing agent and application method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05287257A (en) * | 1992-04-08 | 1993-11-02 | Dai Ichi Kogyo Seiyaku Co Ltd | Binder for constituting elastic rubber chip and preparation of elastic rubber chip |
| CN101041725A (en) * | 2006-03-24 | 2007-09-26 | 陈书怡 | Reproduction new method for waste elastomer and plastic |
| CN101376718A (en) * | 2008-08-13 | 2009-03-04 | 刘建平 | Method for recycling waste polyurethane |
| CN101440171A (en) * | 2008-10-22 | 2009-05-27 | 无锡吉兴汽车部件有限公司 | Process for recovering polyurethane composite waste material for automobile roof liner |
-
2015
- 2015-06-19 CN CN201510345321.XA patent/CN104877338B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05287257A (en) * | 1992-04-08 | 1993-11-02 | Dai Ichi Kogyo Seiyaku Co Ltd | Binder for constituting elastic rubber chip and preparation of elastic rubber chip |
| CN101041725A (en) * | 2006-03-24 | 2007-09-26 | 陈书怡 | Reproduction new method for waste elastomer and plastic |
| CN101376718A (en) * | 2008-08-13 | 2009-03-04 | 刘建平 | Method for recycling waste polyurethane |
| CN101440171A (en) * | 2008-10-22 | 2009-05-27 | 无锡吉兴汽车部件有限公司 | Process for recovering polyurethane composite waste material for automobile roof liner |
Non-Patent Citations (6)
| Title |
|---|
| 山西省化工研究所编: "《聚氨酯弹性体手册》", 31 January 2001 * |
| 张洪雁等: "《高性能橡胶密封材料》", 31 July 2007 * |
| 张玉龙: "《塑料配方及其组分设计宝典》", 31 January 2006 * |
| 方园等: "废旧聚氨酯的回收利用", 《中国聚氨酯工业协会第十次年会论文集》 * |
| 黄永炳: "聚氨酯的回收利用技术", 《环境技术》 * |
| 齐贵亮: "《废旧塑料回收利用实用技术》", 30 September 2011 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483855A (en) * | 2015-12-21 | 2016-04-13 | 长乐恒申合纤科技有限公司 | Method for producing spandex filaments by utilizing spandex prepolymer waste liquid |
| CN106883591A (en) * | 2017-04-24 | 2017-06-23 | 广东工业大学 | The Application way and elastomer of a kind of polyurethane waste material |
| CN106883591B (en) * | 2017-04-24 | 2020-04-28 | 广东工业大学 | Method for utilizing polyurethane waste material and elastomer |
| CN107090174A (en) * | 2017-06-15 | 2017-08-25 | 海洋石油工程股份有限公司 | A kind of preparation method of the casting type polyurethane composite layer of anti-skid wearable |
| CN107446345A (en) * | 2017-08-29 | 2017-12-08 | 河北科技大学 | A kind of filled-type flexible polyurethane foams based on vamp leftover pieces and preparation method thereof |
| CN107686630A (en) * | 2017-08-29 | 2018-02-13 | 河北科技大学 | A kind of preparation technology of vamp leftover pieces polymer composite and its application |
| CN111500053A (en) * | 2020-04-20 | 2020-08-07 | 江苏建筑职业技术学院 | Method for preparing composite heat-preservation vibration-damping material by regenerating elastomer waste |
| CN111635627A (en) * | 2020-06-01 | 2020-09-08 | 丁震 | Meyer sedge sports insole and manufacturing method thereof |
| CN111995725A (en) * | 2020-09-07 | 2020-11-27 | 江苏湘园化工有限公司 | Environment-friendly liquid polyurethane curing agent and application method thereof |
| CN111995725B (en) * | 2020-09-07 | 2022-02-11 | 江苏湘园化工有限公司 | Environment-friendly liquid polyurethane curing agent and application method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104877338B (en) | 2018-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104877338A (en) | Recycling method for polyurethane elastomer waste | |
| Nikje et al. | Polyurethane waste reduction and recycling: From bench to pilot scales | |
| CN101376718B (en) | Method for recycling waste polyurethane | |
| CN102382406B (en) | Polyvinyl butyral foamed material | |
| CN101440171B (en) | Process for recovering polyurethane composite waste material for automobile roof liner | |
| Modesti et al. | Chemical recycling of reinforced polyurethane from the automotive industry | |
| CN105017581B (en) | A kind of modified abandoned RPUF activity micro mist strengthens the preparation method of elastomeric material | |
| CN109705563B (en) | Flame retardant thermoplastic polyurethane composition and expanded beads thereof | |
| Modesti | Recycling of polyurethane polymers | |
| CN106147036A (en) | The expanded material of a kind of recyclable recycling and manufacture method thereof | |
| EP2115042B1 (en) | Rubber | |
| CA2043057A1 (en) | Compositions prepared using finely-divided isocyanate based thermoset polymers | |
| CN106279760A (en) | A kind of recovery processing technique of waste polyurethane | |
| CN100336867C (en) | Recovery and shaping technology of polyurethane composite waste material | |
| WO2014020532A1 (en) | Process for recycling thermosetting composite materials, and thermosetting composite materials obtained thereby | |
| CN109749229A (en) | A kind of automotive upholstery leftover pieces recovery and reuse technology | |
| CN1050392A (en) | Waste old, waste or used plastics, wood powder composition and manufacture method thereof | |
| Shojaei et al. | Polymer foams waste management: a focus on mechanical and chemical recycling | |
| CN103160024B (en) | Method of utilizing waste polyurethane foaming plastic and nonmetal powder to prepare composite materials | |
| US5648431A (en) | Process for the utilization of plastics | |
| CN109422943B (en) | Raw material for inflation-free manpower vehicle tire, inflation-free manpower vehicle tire and preparation method thereof | |
| CN104494006A (en) | Process for processing waste polyurethane | |
| KR20010008243A (en) | The method and its products of used polyuretane foam | |
| KR20150057649A (en) | Manufacturing Method and Apparatus of Sound Insulation Material Using Waste Polymer Compound | |
| CN115322435B (en) | Environment-friendly recycling method for waste rubber and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220126 Address after: 030000 0113, No. 1, No. 2 Road, Wusu comprehensive free trade zone, No. 19 Qingyun street, Shanxi comprehensive reform demonstration zone, Taiyuan City, Shanxi Province Patentee after: Taiyuan yingkeao pen and ink technology Co.,Ltd. Address before: 037500 Pingcheng village, zuotan Township, Guangling County, Datong City, Shanxi Province Patentee before: SHANXI LINGYUN POLYURETHANE Co.,Ltd. |