CN104877338B - A kind of recoverying and utilizing method of polyurethane elastomer waste material - Google Patents
A kind of recoverying and utilizing method of polyurethane elastomer waste material Download PDFInfo
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Abstract
The invention discloses a kind of recoverying and utilizing method of polyurethane elastomer waste material, belong to waste recovery Application way technical field, polyurethane elastomer waste granules of this method by 100~150 parts of particle diameters for 1~3mm, 2~3min of transient heating in 260 DEG C~275 DEG C of baking oven, make its melt surface tacky, then 5~15 parts of base polyurethane prepolymer for use as and mixture of chain extenders is added, stir, pour into mould, it is press-formed with vulcanizer, vulcanize 30min at 120 DEG C, the demoulding is after at 100 DEG C, after cure 10hr again, produce polyurethane elastomer waste material composite forming material.This method simple production process, short preparation period, to waste recovery rate height, less energy consumption, production cost be low, product has good mechanical property.It is a kind of new technology recycled to polyurethane elastomer waste recovery, new method, this method considerably reduces pollution of the polyurethane elastomer waste to environment, and the product can be used as the materials'uses such as damping, wear-resisting, anticollision.
Description
Technical field
The invention belongs to waste recovery Application way technical field, and in particular to a kind of recovery of polyurethane elastomer waste material
Application way.
Background technology
Polyurethane elastomer raw material is numerous, and formula is various, and hardness is adjustable, has thermodynamically incompatible soft, hard section two-phase
Structure, and microphase-separated is formed, its excellent mechanical property, anti-wear performance, resistance to low temperature, chemical-resistance etc. are imparted,
It is widely used in industrial production and people's daily life production.The development of polyurethane elastomer is very fast, special at some
Different field instead of traditional rubber, nylon, plastics etc., but at the same time, also be produced in manufacturing enterprise and using unit
Many polyurethane elastomer waste materials, most important be polyether-type and PAUR elastomer waste material.Processing is poly- at present
The method of urethane elastomer waste material has physiochemical mutagens method, energy recovery method, chemical recycling.Physiochemical mutagens method is mainly as filler
Use, the rate of recovery is low；Energy recovery method can produce pernicious gas, pollute environment, and can not rationally utilize waste material, cause resource
Waste；Chemical recycling step is complicated, and the rate of recovery is low, and financial cost is higher；So find a kind of not only economic but also environmental pollution
Small method is extremely urgent.
Publication No. CN1951511A patent application discloses a kind of moulding process of polyurethane composite waste, specifically
Say it is recycling for automotive trim leftover pieces.The invention by polyurethane composite waste through crush add virgin pp,
Coupling agent and auxiliary agent are uniformly mixed and made into compound, and compound is heated, are incubated to compound and enter molten state, then by molten state
Compound is added in mould and is molded, and product finished product is obtained after cooling and demolding.The compound waste leftover material convenient sources of the invention, produce work
Skill is simple, does not easily cause secondary pollution, and can reduce production cost, is advantageous to increase economic efficiency；The product of recovered shaping
The excellent performances such as elasticity, wearability, lower temperature resistance, expandable, resistance to biodeterioration with uniqueness, can be widely applied to
The industries such as electromechanics, ship, vehicle, civil construction, light industry, weaving and automotive upholstery.This method is to crush polyurethane waste material
Used afterwards as a kind of filler, belong to a kind of physical recovery method, the low technical problem of the rate of recovery be present.
Publication No. CN101560309A patent application discloses a kind of recovery method of polyurethane waste material, major technique
Be characterized as polyurethane waste material be ground under specific process conditions after the powder of certain ultra-fine mesh number by a certain percentage with polychlorostyrene second
Alkene mix, under certain plasticization temperature through completely plasticizing cause particle, using injector by particle inject or using extrusion,
Prolong the molding modes such as pressure and product is made.Such a method was both simple and easy, improved the performance of product, reduce again product into
This, reduces the pollution to environment.But polyurethane waste material ratio is small used in this method, and recovery utilization rate is low.
Publication No. CN103788335A patent application discloses a kind of solid phase alcoholysis and reclaims polyurethane for polyurethane
The method of elastomer, i.e., by polyurethane scrap or waste material：Alcoholysis agent：Catalyst is 100 parts：0.5~100 part：0.01~2 part
Ratio 160~220 DEG C are controlled in forced mixer, 0.05~1.5h of alcoholysis reaction under 10~1000r/min, obtain solid alcohol
Product is solved, then by solid-state alcoholysis product:Carbon black or white carbon:Cumyl peroxide:Isocyanates is 100 parts:30~40 parts:
0~3 part:After 0~8 part of ratio mixing, 3~15min of reaction produces polyurethane elastomer at 150~175 DEG C of control, and it is stretched
Intensity is up to 8~26N/mm2, elongation at break is big by 150~500%, and Shao A hardness is up to 65~96.This method belongs to chemical recycling,
Recovery process is complicated, if to polyurethane scrap or waste material without classification, to the polyurethane elastomer performance meeting after recovery
Produce large effect.
Publication No. CN1275587A patent application discloses a kind of recovery method of polyurethane waste material, and it is water-soluble
Polyurethane waste material is decomposed in liquid, and is separated catalyst to recycle in aqueous phase, catabolite polyethers and toluene two
Amine is separated in equal aqueous phase, while toluenediamine remaining in polyethers is acylated, and polyethers is grafted, the polyethers generated can
For producing polyurethane.The method process is more complicated, and production cost is high, and poisonous and harmful substance can be produced in course of reaction, right
Environment and operating personnel can pollute and injure.
Zhong Shiyun was molded and is laminated 2 kinds of hot pressing works in (Journal of Building Materials 2002, No6,194-197) proposition in 2002
Sheet material is made after mixing the polyurethane foam waste in car roof interior trim production process and headliner composite waste in skill, grinds
The relation between the performance of sheet material and heat pressing process and raw material proportioning is studied carefully.When more than 150 DEG C of hot pressing temperature, the bending of sheet material
Intensity can reach 15~23MPa, and the water absorption rate of sheet material is 0.2%~2%, and density is 1.0~1.6g/cm3.Foam used gives up
Material has certain thermoplasticity, can improve timber intensity, reduces panel density, the fire retardant that more than 5 parts of addition, can drop significantly
The flammability of low sheet material.This method step is simple, and waste utilization rate is high, but is only applicable to the recycling of foam waste.
The content of the invention
Present invention aim to address it is existing recycling polyurethane elastomer waste material method exist the rate of recovery it is low, pollution
Environment, polyurethane elastomer waste material waste the technical problem that serious, recycling step is complicated, financial cost is high and application is narrow,
A kind of recoverying and utilizing method of polyurethane elastomer waste material is provided.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of recoverying and utilizing method of polyurethane elastomer waste material, comprises the following steps：
1) weigh the polyurethane elastomer waste granules that mass parts are 100~150 parts, particle diameter is 1~3mm be placed in it is one long
In × wide × height=300mm × 300mm × 10mm canister；
2) canister equipped with polyurethane elastomer waste granules is placed in baking oven, in 260 DEG C~275 DEG C of temperature
2~3min of lower heating, now polyurethane elastomer waste granules surface appearance melt tacky phenomenon；
3) base polyurethane prepolymer for use as and the mixture of chain extender that mass parts are 5~15 parts are placed in the metal for scribbling releasing agent
In mould, it then will melt tacky polyurethane elastomer waste granules and pour into metal die, after stirring, use vulcanizer
It is press-formed, vulcanizes 30min at a temperature of 120 DEG C, is stripped, most vulcanizes 10h again at a temperature of 100 DEG C, produce
Polyurethane elastomer waste material composite forming material.
The preparation method of the base polyurethane prepolymer for use as comprises the following steps：
PPG or PEPA that mass parts are 100 parts are added in reactor, at a temperature of 120 DEG C,
2.5h is dehydrated in the state of vacuum is 0.08~0.09MPa；Then 50 DEG C are cooled to, mass parts are added into reactor is
21.3~46.9 parts of diisocyanate, then be warming up to 80 DEG C, insulation reaction 2.5h, the mass percent for controlling-NCO ions are
5.0%, finally the deaeration 0.5h in the state of vacuum is 0.8~0.9MPa, obtains polyether-type or PAUR pre-polymerization
Body.
The polyurethane elastomer waste material is in EU elastomer waste material or PAUR elastomer
Any one；When polyurethane elastomer waste material is EU elastomer waste material, described base polyurethane prepolymer for use as uses
Polyether-Polyol Polyurethane Prepolymer；When polyurethane elastomer waste material is PAUR elastomer waste material, described polyurethane
Performed polymer uses PAUR performed polymer.
The chain extender is any one in the chloro- 4,4'- diaminodiphenyl-methanes of 3,3'- bis- or 1,4- butanediols.
The chain extension coefficient of the base polyurethane prepolymer for use as and mixture of chain extenders is 0.9.
The PPG or PEPA be relative molecular weight be 1000 or 2000 in any one；Or phase
Be to molecular weight 1000 and 2000 two kinds of PPGs using the mixture of any ratio or relative molecular mass as 1000 with
2000 two kinds of PEPAs are with any one in the mixture of any ratio.
The diisocyanate is TDI-80 types toluene di-isocyanate(TDI), TDI-100 types toluene di-isocyanate(TDI), MDI-
100 type methyl diphenylene diisocyanates, MDI-50 types methyl diphenylene diisocyanate or liquefied mdi type diphenyl methane two
Any one in isocyanates.
The present invention uses above technical scheme, and compared with background technology, the present invention has advantages below：
1) production equipment needed for the present invention is simple, is consistent substantially with the production equipment of polyurethane elastomer, can improve existing
The utilization rate of equipment and installations of polyurethane elastomer manufacturing enterprise；
2) processing method and process conditions of the invention are simple, it is only necessary to which it is fine particle that polyurethane elastomer waste material is broken into essence
Shape simultaneously carries out transient heating and composite molding, is reacted without the chemical degradation of complexity, waste recovery rate and remanufacture efficiency high,
Molding time is short, and cost recovery is low, significantly reduces the production cost of polyurethane elastomer manufacturing enterprise, improves enterprise
Economic benefit；
3) polyurethane elastomer waste material is recycled using the present invention, has saved resource, it is sharp again to have reached circulation
Purpose, pollution of the polyurethane elastomer waste material to environment is not only reduced, while also beautified manufacturing enterprise and application list
The environment of position；
4) heating treatment time of the present invention is short, and transient heating make it that waste granules melt surface is tacky, recovery processing
Energy consumption is low, and no waste gas slag and effluent waste liquid produces, and removal process does not produce secondary pollution, environmentally friendly, reaches to waste
Harmless treatment；
5) what the present invention was more prominent is polyurethane elastomer scraped surface molten mass and base polyurethane prepolymer for use as and chain extender
After mixture mixing, under high temperature and flow regime, make molten mass molecule and performed polymer and chain extender intermolecular by pressurization
The chemical reaction and physical entanglement of hydrogen bond and its active group, reach intermolecular and interpenetrate and act on, make elastomer waste material
Particle forms a complete overall structure, and particle inner molecular structure is notheated and degraded without change, resulting
Polyurethane elastomer Waste Composite Material product has good hardness, tensile strength and tearing strength；
6) it is good using the composite property obtained by the present invention, the requirement of general industrial and mining enterprises can be met, can conduct
The materials'use such as shockproof, anticollision, wear-resistant, anti-skidding.
Embodiment
Embodiment 1
A kind of recoverying and utilizing method of polyurethane elastomer waste material in the present embodiment, comprises the following steps：
1) the EU elastomer waste granules that mass parts are 100 parts, particle diameter is 1~3mm are weighed and are placed in one
In length × width × height=300mm × 300mm × 10mm canister；
2) canister equipped with EU elastomer waste granules is placed in baking oven, in 260 DEG C of temperature
Lower heating 2min, now EU elastomer waste granules surface appearance melt tacky phenomenon；
3) by Polyether-Polyol Polyurethane Prepolymer and 0.63 part of 3,3'- bis- chloro- 4,4'- diaminourea of the mass parts for 4.37 parts
The mixture of diphenyl methane chain extender is placed in the metal die for scribbling releasing agent, then will melt the poly- ammonia of tacky polyether-type
Ester elastomer waste granules are poured into metal die, after stirring, are press-formed with vulcanizer, in 120 DEG C of temperature
Lower vulcanization 30min, the demoulding, most vulcanizes 10h at a temperature of 100 DEG C, it is compound to produce EU elastomer waste material again
Moulding material.
The preparation method of the Polyether-Polyol Polyurethane Prepolymer comprises the following steps：
It is that the PPG that 100 parts of relative molecular weights are 1000 is added in reactor by mass parts, in 120 DEG C of temperature
Under, it is dehydrated 2.5h in the state of vacuum is 0.08~0.09MPa；Then 50 DEG C are cooled to, quality is added into reactor
Part is 31 parts of TDI-80 type toluene di-isocyanate(TDI)s, then is warming up to 80 DEG C, insulation reaction 2.5h, the quality of control-NCO ions
Percentage is 5.0%, and finally the deaeration 0.5h in the state of vacuum is 0.8~0.9MPa, obtains EU pre-polymerization
Body.
After tested, its tensile strength is EU elastomer waste material composite forming material manufactured in the present embodiment
6.3MPa, elongation 207%, tearing strength 48kN/m.
Embodiment 2
A kind of recoverying and utilizing method of polyurethane elastomer waste material in the present embodiment, comprises the following steps：
1) the EU elastomer waste granules that mass parts are 110 parts, particle diameter is 1~3mm are weighed and are placed in one
In length × width × height=300mm × 300mm × 10mm canister；
2) canister equipped with EU elastomer waste granules is placed in baking oven, in 265 DEG C of temperature
Lower heating 2.5min, now EU elastomer waste granules surface appearance melt tacky phenomenon；
3) by Polyether-Polyol Polyurethane Prepolymer and 1 part of 3,3'- bis- chloro- 4,4'- diamino-diphenyl of the mass parts for 7 parts
The mixture of methane chain extender is placed in the metal die for scribbling releasing agent, then will melt tacky EU elasticity
Body waste granules are poured into metal die, after stirring, are press-formed with vulcanizer, are vulcanized at a temperature of 120 DEG C
30min, the demoulding, most vulcanizes 10h at a temperature of 100 DEG C, produces EU elastomer waste material combined shaping material again
Material.
The preparation method of the Polyether-Polyol Polyurethane Prepolymer comprises the following steps：
By mass parts be PPG that 53.8 parts of relative molecular weights are 1000 and 46.2 parts of relative molecular weights are 2000
PPG add reactor in, at a temperature of 120 DEG C, vacuum be 0.08~0.09MPa in the state of be dehydrated
2.5h；Then 50 DEG C are cooled to, the TDI-100 type diphenylmethane diisocyanates that mass parts are 26.5 parts are added into reactor
Ester, then 80 DEG C are warming up to, insulation reaction 2.5h, the mass percent for controlling-NCO ions is 5.0%, is in vacuum finally
Deaeration 0.5h in the state of 0.8~0.9MPa, obtains Polyether-Polyol Polyurethane Prepolymer.
After tested, its tensile strength is EU elastomer waste material composite forming material manufactured in the present embodiment
7.4MPa, elongation 226%, tearing strength 50kN/m.
Embodiment 3
A kind of recoverying and utilizing method of polyurethane elastomer waste material in the present embodiment, comprises the following steps：
1) the EU elastomer waste granules that mass parts are 120 parts, particle diameter is 1~3mm are weighed and are placed in one
In length × width × height=300mm × 300mm × 10mm canister；
2) canister equipped with EU elastomer waste granules is placed in baking oven, in 270 DEG C of temperature
Lower heating 2.5min, now EU elastomer waste granules surface appearance melt tacky phenomenon；
3) by the mixed of Polyether-Polyol Polyurethane Prepolymer that mass parts are 9.54 parts and 0.45 part of 1,4- chain expansion of succinic acid agent
Compound is placed in the metal die for scribbling releasing agent, then will be melted tacky EU elastomer waste granules and is poured into
In metal die, after stirring, it is press-formed with vulcanizer, vulcanizes 30min at a temperature of 120 DEG C, is stripped, finally
Vulcanize 10h again at a temperature of 100 DEG C, produce EU elastomer waste material composite forming material.
The preparation method of the Polyether-Polyol Polyurethane Prepolymer comprises the following steps：
By mass parts be PPG that 33.3 parts of relative molecular weights are 1000 and 66.7 parts of relative molecular weights are 2000
PPG add reactor in, at a temperature of 120 DEG C, vacuum be 0.08~0.09MPa in the state of be dehydrated
2.5h；Then 50 DEG C are cooled to, the MDI-100 type diphenylmethane diisocyanates that mass parts are 37 parts are added into reactor
Ester, then 80 DEG C are warming up to, insulation reaction 2.5h, the mass percent for controlling-NCO ions is 5.0%, is in vacuum finally
Deaeration 0.5h in the state of 0.8~0.9MPa, obtains Polyether-Polyol Polyurethane Prepolymer.
After tested, its tensile strength is EU elastomer waste material composite forming material manufactured in the present embodiment
10.9MPa, elongation 257%, tearing strength 58kN/m.
Embodiment 4
A kind of recoverying and utilizing method of polyurethane elastomer waste material in the present embodiment, comprises the following steps：
1) the EU elastomer waste granules that mass parts are 140 parts, particle diameter is 1~3mm are weighed and are placed in one
In length × width × height=300mm × 300mm × 10mm canister；
2) canister equipped with EU elastomer waste granules is placed in baking oven, in 270 DEG C of temperature
Lower heating 2.5min, now EU elastomer waste granules surface appearance melt tacky phenomenon；
3) by Polyether-Polyol Polyurethane Prepolymer and 1.6 part of 3,3'- bis- chloro- 4,4'- diaminourea of the mass parts for 11.4 parts
The mixture of diphenyl methane chain extender is placed in the metal die for scribbling releasing agent, then will melt the poly- ammonia of tacky polyether-type
Ester elastomer waste granules are poured into metal die, after stirring, are press-formed with vulcanizer, in 120 DEG C of temperature
Lower vulcanization 30min, the demoulding, most vulcanizes 10h at a temperature of 100 DEG C, it is compound to produce EU elastomer waste material again
Moulding material.
The preparation method of the Polyether-Polyol Polyurethane Prepolymer comprises the following steps：
By mass parts be PPG that 11.1 parts of relative molecular weights are 1000 and 88.9 parts of relative molecular weights are 2000
PPG add reactor in, at a temperature of 120 DEG C, vacuum be 0.08~0.09MPa in the state of be dehydrated
2.5h；Then 50 DEG C are cooled to, the MDI-50 type diphenylmethane diisocyanates that mass parts are 33.8 parts are added into reactor
Ester, then 80 DEG C are warming up to, insulation reaction 2.5h, the mass percent for controlling-NCO ions is 5.0%, is in vacuum finally
Deaeration 0.5h in the state of 0.8~0.9MPa, obtains Polyether-Polyol Polyurethane Prepolymer.
After tested, its tensile strength is EU elastomer waste material composite forming material manufactured in the present embodiment
12MPa, elongation 298%, tearing strength 64kN/m.
Embodiment 5
A kind of recoverying and utilizing method of polyurethane elastomer waste material in the present embodiment, comprises the following steps：
1) the EU elastomer waste granules that mass parts are 150 parts, particle diameter is 1~3mm are weighed and are placed in one
In length × width × height=300mm × 300mm × 10mm canister；
2) canister equipped with EU elastomer waste granules is placed in baking oven, in 270 DEG C of temperature
Lower heating 2.5min, now EU elastomer waste granules surface appearance melt tacky phenomenon；
3) by Polyether-Polyol Polyurethane Prepolymer and 1.9 part of 3,3'- bis- chloro- 4,4'- diaminourea of the mass parts for 13.1 parts
The mixture of diphenyl methane chain extender is placed in the metal die for scribbling releasing agent, then will melt the poly- ammonia of tacky polyether-type
Ester elastomer waste granules are poured into metal die, after stirring, are press-formed with vulcanizer, in 120 DEG C of temperature
Lower vulcanization 30min, the demoulding, most vulcanizes 10h at a temperature of 100 DEG C, it is compound to produce EU elastomer waste material again
Moulding material.
The preparation method of the Polyether-Polyol Polyurethane Prepolymer comprises the following steps：
It is that the PPG that 100 parts of relative molecular weights are 2000 is added in reactor by mass parts, in 120 DEG C of temperature
Under, it is dehydrated 2.5h in the state of vacuum is 0.08~0.09MPa；Then 50 DEG C are cooled to, quality is added into reactor
Part is 38.33 parts of liquefied mdi type methyl diphenylene diisocyanate, then is warming up to 80 DEG C, insulation reaction 2.5h, control-NCO
The mass percent of ion is 5.0%, and finally the deaeration 0.5h in the state of vacuum is 0.8~0.9MPa, obtains polyether-type
Base polyurethane prepolymer for use as.
After tested, its tensile strength is EU elastomer waste material composite forming material manufactured in the present embodiment
12MPa, elongation 318%, tearing strength 71kN/m.
Embodiment 6
A kind of recoverying and utilizing method of polyurethane elastomer waste material in the present embodiment, comprises the following steps：
1) the PAUR elastomer waste granules that mass parts are 100 parts, particle diameter is 1~3mm are weighed and are placed in one
In length × width × height=300mm × 300mm × 10mm canister；
2) canister equipped with PAUR elastomer waste granules is placed in baking oven, in 265 DEG C of temperature
Lower heating 3min, now PAUR elastomer waste granules surface appearance melt tacky phenomenon；
3) by the mixed of PAUR performed polymer that mass parts are 4.77 parts and 0.23 part of 1,4- chain expansion of succinic acid agent
Compound is placed in the metal die for scribbling releasing agent, then will be melted tacky PAUR elastomer waste granules and is poured into
In metal die, after stirring, it is press-formed with vulcanizer, vulcanizes 30min at a temperature of 120 DEG C, is stripped, finally
Vulcanize 10h again at a temperature of 100 DEG C, produce PAUR elastomer waste material composite forming material.
The preparation method of the PAUR performed polymer comprises the following steps：
It is that the PEPA that 100 parts of relative molecular weights are 1000 is added in reactor by mass parts, in 120 DEG C of temperature
Under, it is dehydrated 2.5h in the state of vacuum is 0.08~0.09MPa；Then 50 DEG C are cooled to, quality is added into reactor
Part is 46.9 parts of MDI-100 type toluene di-isocyanate(TDI)s, then is warming up to 80 DEG C, insulation reaction 2.5h, control-NCO ions
Mass percent is 5.0%, and finally the deaeration 0.5h in the state of vacuum is 0.8~0.9MPa, obtains PAUR
Performed polymer.
After tested, its tensile strength is EU elastomer waste material composite forming material manufactured in the present embodiment
8.5MPa, elongation 217%, tearing strength 57kN/m.
Embodiment 7
A kind of recoverying and utilizing method of polyurethane elastomer waste material in the present embodiment, comprises the following steps：
1) the PAUR elastomer waste granules that mass parts are 110 parts, particle diameter is 1~3mm are weighed and are placed in one
In length × width × height=300mm × 300mm × 10mm canister；
2) canister equipped with PAUR elastomer waste granules is placed in baking oven, in 270 DEG C of temperature
Lower heating 3min, now PAUR elastomer waste granules surface appearance melt tacky phenomenon；
3) by the mixed of PAUR performed polymer that mass parts are 7.63 parts and 0.37 part of 1,4- chain expansion of succinic acid agent
Compound is placed in the metal die for scribbling releasing agent, then will be melted tacky PAUR elastomer waste granules and is poured into
In metal die, after stirring, it is press-formed with vulcanizer, vulcanizes 30min at a temperature of 120 DEG C, is stripped, finally
Vulcanize 10h again at a temperature of 100 DEG C, produce PAUR elastomer waste material composite forming material.
The preparation method of the PAUR performed polymer comprises the following steps：
By mass parts be PEPA that 53.8 parts of relative molecular weights are 1000 and 46.2 parts of relative molecular weights are 2000
PEPA add reactor in, at a temperature of 120 DEG C, vacuum be 0.08~0.09MPa in the state of be dehydrated
2.5h；Then 50 DEG C are cooled to, the MDI-50 type diphenylmethane diisocyanates that mass parts are 40.1 parts are added into reactor
Ester, then 80 DEG C are warming up to, insulation reaction 2.5h, the mass percent for controlling-NCO ions is 5.0%, is in vacuum finally
Deaeration 0.5h in the state of 0.8~0.9MPa, obtain PAUR performed polymer.
After tested, its tensile strength is EU elastomer waste material composite forming material manufactured in the present embodiment
10.2MPa, elongation 302%, tearing strength 66kN/m.
Embodiment 8
A kind of recoverying and utilizing method of polyurethane elastomer waste material in the present embodiment, comprises the following steps：
1) the PAUR elastomer waste granules that mass parts are 130 parts, particle diameter is 1~3mm are weighed and are placed in one
In length × width × height=300mm × 300mm × 10mm canister；
2) canister equipped with PAUR elastomer waste granules is placed in baking oven, in 275 DEG C of temperature
Lower heating 3min, now PAUR elastomer waste granules surface appearance melt tacky phenomenon；
3) by the mixed of PAUR performed polymer that mass parts are 9.54 parts and 0.46 part of 1,4- chain expansion of succinic acid agent
Compound is placed in the metal die for scribbling releasing agent, then will be melted tacky PAUR elastomer waste granules and is poured into
In metal die, after stirring, it is press-formed with vulcanizer, vulcanizes 30min at a temperature of 120 DEG C, is stripped, finally
Vulcanize 10h again at a temperature of 100 DEG C, produce PAUR elastomer waste material composite forming material.
The preparation method of the PAUR performed polymer comprises the following steps：
By mass parts be PEPA that 33.3 parts of relative molecular weights are 1000 and 66.7 parts of relative molecular weights are 2000
PEPA add reactor in, at a temperature of 120 DEG C, vacuum be 0.08~0.09MPa in the state of be dehydrated
2.5h；Then 50 DEG C are cooled to, the liquefied mdi type diphenylmethane diisocyanate that mass parts are 44.2 parts is added into reactor
Ester, then 80 DEG C are warming up to, insulation reaction 2.5h, the mass percent for controlling-NCO ions is 5.0%, is in vacuum finally
Deaeration 0.5h in the state of 0.8~0.9MPa, obtain PAUR performed polymer.
After tested, its tensile strength is EU elastomer waste material composite forming material manufactured in the present embodiment
11MPa, elongation 307%, tearing strength 69kN/m.
Embodiment 9
A kind of recoverying and utilizing method of polyurethane elastomer waste material in the present embodiment, comprises the following steps：
1) the PAUR elastomer waste granules that mass parts are 140 parts, particle diameter is 1~3mm are weighed and are placed in one
In length × width × height=300mm × 300mm × 10mm canister；
2) canister equipped with PAUR elastomer waste granules is placed in baking oven, in 275 DEG C of temperature
Lower heating 3min, now PAUR elastomer waste granules surface appearance melt tacky phenomenon；
3) it is 11.4 parts of PAUR performed polymer and the chloro- 4,4'- diaminourea of 1.6 parts of 3,3'- bis- by mass parts
The mixture of diphenyl methane chain extender is placed in the metal die for scribbling releasing agent, then will melt the poly- ammonia of tacky polyester-type
Ester elastomer waste granules are poured into metal die, after stirring, are press-formed with vulcanizer, in 120 DEG C of temperature
Lower vulcanization 30min, the demoulding, most vulcanizes 10h at a temperature of 100 DEG C, it is compound to produce PAUR elastomer waste material again
Moulding material.
The preparation method of the PAUR performed polymer comprises the following steps：
By mass parts be PEPA that 11.1 parts of relative molecular weights are 1000 and 88.9 parts of relative molecular weights are 2000
PEPA add reactor in, at a temperature of 120 DEG C, vacuum be 0.08~0.09MPa in the state of be dehydrated
2.5h；Then 50 DEG C are cooled to, mass parts are added into reactor and are 22.4 parts of TDI-80 type toluene di-isocyanate(TDI)s, then are risen
Temperature to 80 DEG C, insulation reaction 2.5h, control-NCO ions mass percent be 5.0%, finally vacuum be 0.8~
Deaeration 0.5h in the state of 0.9MPa, obtain PAUR performed polymer.
After tested, its tensile strength is EU elastomer waste material composite forming material manufactured in the present embodiment
10.5MPa, elongation 267%, tearing strength 61kN/m.
Embodiment 10
A kind of recoverying and utilizing method of polyurethane elastomer waste material in the present embodiment, comprises the following steps：
1) the PAUR elastomer waste granules that mass parts are 150 parts, particle diameter is 1~3mm are weighed and are placed in one
In length × width × height=300mm × 300mm × 10mm canister；
2) canister equipped with PAUR elastomer waste granules is placed in baking oven, in 275 DEG C of temperature
Lower heating 3min, now PAUR elastomer waste granules surface appearance melt tacky phenomenon；
3) it is 13.1 parts of PAUR performed polymer and the chloro- 4,4'- diaminourea of 1.9 parts of 3,3'- bis- by mass parts
The mixture of diphenyl methane chain extender is placed in the metal die for scribbling releasing agent, then will melt the poly- ammonia of tacky polyester-type
Ester elastomer waste granules are poured into metal die, after stirring, are press-formed with vulcanizer, in 120 DEG C of temperature
Lower vulcanization 30min, the demoulding, most vulcanizes 10h at a temperature of 100 DEG C, it is compound to produce PAUR elastomer waste material again
Moulding material.
The preparation method of the PAUR performed polymer comprises the following steps：
It is that the PEPA that 100 parts of relative molecular weights are 2000 is added in reactor by mass parts, in 120 DEG C of temperature
Under, it is dehydrated 2.5h in the state of vacuum is 0.08~0.09MPa；Then 50 DEG C are cooled to, quality is added into reactor
Part is 21.3 parts of TDI-100 type toluene di-isocyanate(TDI)s, then is warming up to 80 DEG C, insulation reaction 2.5h, control-NCO ions
Mass percent is 5.0%, and finally the deaeration 0.5h in the state of vacuum is 0.8~0.9MPa, obtains PAUR
Performed polymer.
After tested, its tensile strength is EU elastomer waste material composite forming material manufactured in the present embodiment
14.5MPa, elongation 313%, tearing strength 76kN/m.
Mixed by the polyurethane elastomer waste material obtained by above-mentioned specific embodiment with base polyurethane prepolymer for use as and chain extender
The composite property that thing press cure obtained by molding arrives, method of testing is with reference to GB/T6031《Vulcanize rubber or thermoplastic elastomer
Determination of Hardness》GB/T528《Vulcanize rubber or thermoplastic elastomer tearing strength measure》、GB/T5723《Vulcanize rubber or thermoplasticity
Rubber experiment sample and product size measure》、GB/T 2568《Resin-cast body stretching test method》Enter etc. standard
OK.
Claims (6)
- A kind of 1. recoverying and utilizing method of polyurethane elastomer waste material, it is characterised in that：Comprise the following steps：1) weigh the polyurethane elastomer waste granules that mass parts are 100~150 parts, particle diameter is 1~3mm be placed in it is one long × wide In × height=300mm × 300mm × 10mm canister；2) canister equipped with polyurethane elastomer waste granules is placed in baking oven, added at a temperature of 260 DEG C~275 DEG C 2~3min of heat, now polyurethane elastomer waste granules surface appearance melt tacky phenomenon；3) base polyurethane prepolymer for use as and the mixture of chain extender that mass parts are 5~15 parts are placed in the metal die for scribbling releasing agent In, it then will melt tacky polyurethane elastomer waste granules and pour into metal die, after stirring, carried out with vulcanizer Extrusion forming, vulcanizes 30min at a temperature of 120 DEG C, is stripped, most vulcanizes 10h again at a temperature of 100 DEG C, produce poly- ammonia Ester elastomer waste material composite forming material, the preparation method of the base polyurethane prepolymer for use as comprise the following steps：PPG or PEPA that mass parts are 100 parts are added in reactor, at a temperature of 120 DEG C, true Reciprocal of duty cycle is dehydrated 2.5h in the state of being 0.08~0.09MPa；Then 50 DEG C are cooled to, it is 21.3 that mass parts are added into reactor ~46.9 parts of diisocyanate, then be warming up to 80 DEG C, insulation reaction 2.5h, the mass percent for controlling-NCO ions are 5.0%, finally the deaeration 0.5h in the state of vacuum is 0.8~0.9MPa, obtains polyether-type or PAUR pre-polymerization Body.
- A kind of 2. recoverying and utilizing method of polyurethane elastomer waste material according to claim 1, it is characterised in that：It is described poly- Urethane elastomer waste material is any one in EU elastomer waste material or PAUR elastomer；When poly- ammonia When ester elastomer waste material is EU elastomer waste material, described base polyurethane prepolymer for use as uses EU pre-polymerization Body；When polyurethane elastomer waste material is PAUR elastomer waste material, described base polyurethane prepolymer for use as uses polyester-type Base polyurethane prepolymer for use as.
- A kind of 3. recoverying and utilizing method of polyurethane elastomer waste material according to claim 1, it is characterised in that：The expansion Chain agent is any one in the chloro- 4,4'- diaminodiphenyl-methanes of 3,3'- bis- or 1,4- butanediols.
- A kind of 4. recoverying and utilizing method of polyurethane elastomer waste material according to claim 1, it is characterised in that：It is described poly- The chain extension coefficient of urethane performed polymer and mixture of chain extenders is 0.9.
- A kind of 5. recoverying and utilizing method of polyurethane elastomer waste material according to claim 1, it is characterised in that：It is described poly- Ethoxylated polyhydric alcohol or PEPA be relative molecular weight be 1000 or 2000 in any one；Or relative molecular weight is 1000 Two kinds of PPGs with 2000 are more as 1000 and 2,000 two kinds of polyester using the mixture of any ratio or relative molecular mass First alcohol is with any one in the mixture of any ratio.
- A kind of 6. recoverying and utilizing method of polyurethane elastomer waste material according to claim 1, it is characterised in that：Described two Isocyanates is TDI-80 types toluene di-isocyanate(TDI), TDI-100 types toluene di-isocyanate(TDI), MDI-100 type diphenyl methanes Appointing in diisocyanate, MDI-50 types methyl diphenylene diisocyanate or liquefied mdi type methyl diphenylene diisocyanate Meaning is a kind of.
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| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
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