CN104710666B - A kind of granule modified rubber composite of hard polyaminoester foam and its preparation method and application - Google Patents
A kind of granule modified rubber composite of hard polyaminoester foam and its preparation method and application Download PDFInfo
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- CN104710666B CN104710666B CN201310695681.3A CN201310695681A CN104710666B CN 104710666 B CN104710666 B CN 104710666B CN 201310695681 A CN201310695681 A CN 201310695681A CN 104710666 B CN104710666 B CN 104710666B
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Abstract
The invention provides a kind of granule modified rubber composite of hard polyaminoester foam, by weight, including following components: waste tire rubber granule 30～50, waste and old hard polyaminoester foam granule 30～50, fire retardant 5～10, adhesive 4～10, coloring agent 0.5～3；The present invention uses waste and old scrap tire rubber and polyurethane foam to be prepared as composite, can improve waste and old resource utilization, develops the new technique of a kind of spent high molecular material application simultaneously.Present invention also offers the preparation method of a kind of granule modified rubber composite of hard polyaminoester foam, the method technique is simple, easily operates, and the rubber composite density of preparation is little, and permeability is strong, low cost, excellent performance.Present invention also offers the application in terms of road construction of a kind of granule modified rubber composite of hard polyaminoester foam.
Description
Technical field
The present invention relates to field of compound material, be specifically related to a kind of granule modified rubber of hard polyaminoester foam multiple
Condensation material and its preparation method and application.
Background technology
The mankind enter 21 century, and the recycling of spent high molecular material has become a urgent problem.
The accumulation of a large amount of spent high molecular materials not only causes the waste of resource, and environment is caused pollution.
Waste refrigeration plant (including refrigerator, refrigerator) can produce substantial amounts of waste and old hard polyaminoester foam after disassembling,
Waste and old hard polyaminoester foam is a kind of three-dimensional netted highly cross-linked thermosets, is difficult to dissolve or fusing,
And density is relatively low, it is not easily recycled utilization.In recent years, step into, along with China, the height that waste refrigeration plant is scrapped
The peak phase, the generation of a large amount of Methods for Polyurethane Wastes not only causes the waste of resource, and also produces ecological environment
Adverse effect.Simultaneously because the development of domestic automobile industry, the quantity of junked tire increases year by year how
Reduce junked tire and the pollution of polyurethane foam, and its reasonable recycling has been become currently urgently solve
Problem certainly.
At present the recovery method of polyurethane foam is mainly included comminuting method, physiochemical mutagens, chemical recovery and combustion
Burn and reclaim heat energy etc..To waste tire rubber goods mainly include thermally decompose withdrawal liquid fuels and chemicals,
The utilization of fuel utilization, reclaimed rubber, rubber powder utilization etc..There is method complexity, technology water in existing recycling
Flat low, to consume the energy big, and the problem easily causing secondary pollution；So China is to thermosetting foam plastics
The recycling situation of garbage is unsatisfactory, and the thermoplastic foam just for regenerating easily adds mostly
To develop, lack the recoverying and utilizing method of the thermosetting foam plastics to difficult life.
Summary of the invention
In order to solve existing waste tire rubber and difficult the asking of waste and old hard polyaminoester foam no pollution resource
Topic, the invention provides a kind of granule modified rubber composite of hard polyaminoester foam and preparation method thereof and
Application.Waste and old scrap tire rubber and polyurethane foam granule are prepared as composite, not only by the method
Improve waste and old resource utilization and also developed the new technique of a kind of spent high molecular material application；The party's legal system
The standby granule modified rubber composite of hard polyaminoester foam has the advantage that density is low, permeability is strong, this
Invention additionally provides a kind of granule modified rubber composite of hard polyaminoester foam answering in terms of road construction
With.
First aspect, the invention provides a kind of granule modified rubber composite of hard polyaminoester foam, by weight
Amount part meter, including following components: waste tire rubber granule 30～50, waste and old hard polyaminoester foam granule
30～50, fire retardant 5～10, adhesive 4～10, coloring agent 0.5～3.
Each component in the granule modified rubber composite of hard polyaminoester foam makes this multiple through rational proportion
The function admirable of condensation material.
Described waste tire rubber granule is that the junked tire of automobile dismounting or daily recovery is after disassembling and crushing
Granule.Preferably, the particle diameter of described waste tire rubber granule is grade.Preferably, described waste and old take turns
The particle size range of tire rubber granule is 1～5mm.
Described waste and old hard polyaminoester foam granule is the waste and old rigid polyurethane foam that electron wastes disassembles generation
Cotton, warp is broken and obtains.Preferably, the particle diameter of described hard polyaminoester foam granule is grade.Preferably,
The particle size range of described waste and old hard polyaminoester foam granule is 0.5～4mm.
Waste and old hard polyaminoester foam granule is directly over simple broken prepared, so having big lump waste materials density
Low advantage.
Preferably, described fire retardant includes that tetraphenyl (bisphenol-A) bisphosphate (BDP), resorcinol are double
One in (diphenyl) phosphate ester (RDP), APP (APP) and triphenyl phosphate (TPP)
Or two or more combinations.
Described fire retardant is phosphorus-nitrogen containing flame retardant, and phosphorus-nitrogen containing flame retardant is environmental protection fire retarding agent, has fire-retardant and plasticising
Dual-use function, flame retarding efficiency is high, can realize fire retardant non-halogen, and the amount of being fuming is relatively low；Plasticising function is permissible
When making plastic shaping, flow processability improves, and can suppress the residue after burning, the poisonous gas of generation and corruption
Erosion property gas is less, and especially phosphate ester is fine with the compatibility of polyurethane；Additionally, phosphorus-nitrogen containing flame retardant is easy
Hydrolysis, biodegradable, there is no environmental persistence and bioaccumulation.
Preferably, described adhesive is polyurethane-type adhesive.
Described polyurethane adhesive is environment-protecting polyurethane type adhesive, be generally of highly filled, low viscosity,
The advantages such as the technique suitability is good, bonding force is strong, nontoxic；Also there is good machining property and wettability
Can, after being combined, the most viscous effect is obvious especially, has good transparency and elasticity, ageing-resistant, and economy is real
Use environmental protection.
Preferably, during described coloring agent is titanium dioxide, white carbon black, iron oxide red, iron oxide yellow, titanium viridescent and titanium ultramarine
At least one.
The component of the described granule modified rubber composite of hard polyaminoester foam be waste tire rubber granule and
Waste and old hard polyaminoester foam granule, it is close that described waste and old hard polyaminoester foam granule can retain big lump waste materials
Spend low advantage, simultaneously open-celled structure and rubber grain and poly-ammonia present in hard polyaminoester foam granule
Space between ester foam void among particles, rubber grain and rubber grain and polyurethane foam granule and poly-ammonia
Ester foam void among particles makes the hard polyaminoester foam granule modified rubber composite density obtained little,
Permeability is strong, and the described granule modified rubber composite of hard polyaminoester foam is used for road construction aspect,
Make surface rain water can well leak into underground, can effectively solve urban road drainage problem；
And, at the compositing range of the granule modified rubber composite of hard polyaminoester foam that the present invention provides
In, according to different regions precipitation, by regulation waste and old rubber particle and waste and old hard polyaminoester foam granule
Size and consumption proportion can prepare and various there is different densities and infiltrative hard polyurethane
The granule modified rubber composite of ester foam, can meet the road construction demand of different regions, therefore be suitable for
Property and practicality are the strongest；
Further, since the raw material that the granule modified rubber composite of hard polyaminoester foam uses is all garbage,
So the advantage with low cost.
Second aspect, the invention provides the preparation of a kind of granule modified rubber composite of hard polyaminoester foam
Method, comprises the following steps:
(1) waste tire rubber granule is provided；
(2) waste and old hard polyaminoester foam granule is provided；
(3) mixing banburying: by weight: waste tire rubber granule 30～50, waste and old hard polyaminoester
Foam granule 30～50, fire retardant 5～10, adhesive 4～10, coloring agent 0.5～3 weighs material, then depends on
Secondary respectively by described waste tire rubber granule, waste and old hard polyaminoester foam granule, fire retardant, adhesive
Join in mill with coloring agent, mix banburying 5～10min, to be mixed uniformly after, obtain lamellar material base；
(4) hot-forming: the lamellar material base that step (3) obtains is put in mould, hot-forming obtain hard
Matter polyurethane foam granule modified rubber composite semi-finished product, then take out that product is clipped, after deburring
To the described granule modified rubber composite of hard polyaminoester foam.
Preferably, in described step (1) by the junked tire of automobile dismounting or daily recovery through over cleaning, dry in the air
Do, cut, crush, sieve, the rubber grain screened is carried out activation processing, then cleans, dry,
Obtain described waste tire rubber granule standby.
Preferably, described in step (1), the particle size range of waste tire rubber granule is 1～5mm.
Preferably, the polyurethane foam that electron wastes disassembles in described step (2) generation is cleaned, dry in the air
It is dry, broken that to obtain waste and old hard polyaminoester foam granule standby.
Preferably, described in step (2), the particle size range of waste and old hard polyaminoester foam granule is 0.5～4mm.
Preferably, fire retardant described in step (3) include tetraphenyl (bisphenol-A) bisphosphate (BDP),
Double (diphenyl) phosphate ester (RDP) of resorcinol, APP (APP) and triphenyl phosphate (TPP)
In one or more combination.
Preferably, described in step (3), adhesive is polyurethane-type adhesive.
Preferably, coloring agent described in step (3) is titanium dioxide, white carbon black, iron oxide red, iron oxide yellow, titanium viridescent
With at least one in titanium ultramarine.
Preferably, described in step (4), the technological parameter of hot-forming process is: tablet machine temperature is 50～150
DEG C, pressure is 3～10MPa, and the dwell time is 5～10min.
The preparation method of the described granule modified rubber composite of hard polyaminoester foam uses waste tire rubber
With waste and old hard polyaminoester foam granule as raw material, one is that the preparation of particulate material is more simple and easy to do, technique
Simply, energy consumption is low, production cost is low；Two is that particulate material remains the low density advantage of big lump waste materials, and
Space between particulate material and particulate material makes the composite density of preparation little, and permeability is strong.On the other hand,
Described preparation method achieves waste tire rubber and the harmless resource utilization of waste and old rigid polyurethane foam cotton material
Utilize, there is the advantages such as inexpensive, environmental protection, economic benefit are high.
The third aspect, the invention provides a kind of granule modified rubber composite of hard polyaminoester foam at road
Application in terms of construction.
Compared with prior art, there is advantages that
1, to have density little for the granule modified rubber composite of hard polyaminoester foam that the present invention provides, infiltration
Property strong, low cost, excellent performance, the advantage of high financial profit；
2, the preparation method of the granule modified rubber composite of hard polyaminoester foam that the present invention provides, utilizes
Waste tire rubber granule and polyurethane foam granule are that raw material is prepared as composite, turn waste into wealth, reach
Innoxious, the recycling of waste and scrap, this preparation method have environmental protection, raw material supply extensively, work
Skill is simple, easily operate, energy consumption is low, be prone to the advantages such as large-scale production；
3, the invention provides a kind of granule modified rubber composite of hard polyaminoester foam in road construction side
The application in face, due in waste and old hard polyaminoester foam modified rubber floor tile hard polyaminoester foam addition and
The design of structure, surface rain water can well leak into underground, can effectively solve urban groundwater disappearance
Problem.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, the present invention is entered one
Step describes in detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, not
For limiting the present invention.
Embodiment 1
The preparation method of a kind of granule modified rubber composite of hard polyaminoester foam, comprises the following steps:
(1) junked tire of automobile dismounting or recovery is put in clear water clean up, remove booty, take out
Dry, then carry out cutting, crush, sieve after select the rubber grain that particle size range is 1～5mm；Will sieve
The rubber grain chosen is put in hydrochloric acid solution, and after carrying out activation processing 15 minutes, taking-up clean water is done
Clean and dry, obtain described waste tire rubber granule standby；
(2) electron wastes being disassembled the polyurethane foam of generation put in clear water and clean up, taking-up is dried,
Then the waste and old hard polyaminoester foam granule that particle size range is 0.5～4mm it is broken into standby；
(3) by weight: waste tire rubber granule 44 parts, waste and old hard polyaminoester foam granule 40
Part, APP 8 parts, adhesive for polyurethane 6 parts, coloring agent 2 parts weigh material, distinguish the most successively
By described waste tire rubber granule, waste and old hard polyaminoester foam granule, APP, polyurethane gluing
Agent and coloring agent join in mill, mix banburying 8min, to be mixed uniformly after, exist according to die size
Lamellar material base is prepared in mill；
(4) the lamellar material base that step (3) obtains is put in mould, hot-forming obtain rigid polyurethane foam
Cotton granule modified rubber composite semi-finished product, wherein, tablet machine temperature is 75 DEG C, and pressure is 3MPa, protects
The pressure time is 5min, then takes out that product is clipped, obtains described hard polyaminoester foam granule after deburring and change
Property rubber composite.
The granule modified rubber composite of hard polyaminoester foam prepared by the present embodiment, can be used as floor tile, institute
State floor tile and can be applicable to road construction.Property to the described granule modified rubber composite of hard polyaminoester foam
Can test, recording apparent density is 0.76g/cm3, elongation at break is 54%, and seepage rate is 46%,
The hard polyaminoester foam granule modified rubber composite density that the visible present invention provides is low, and permeability is strong,
Excellent performance.
Embodiment 2
The preparation method of a kind of granule modified rubber composite of hard polyaminoester foam, comprises the following steps:
(1) junked tire of automobile dismounting or recovery is put in clear water clean up, remove booty, take out
Dry, then carry out cutting, crush, sieve after select the rubber grain that particle size range is 1～5mm；Will sieve
The rubber grain chosen is put in hydrochloric acid solution, and after carrying out activation processing 12 minutes, taking-up clean water is done
Clean and dry, obtain described waste tire rubber granule standby；
(2) electron wastes being disassembled the polyurethane foam of generation put in clear water and clean up, taking-up is dried,
Then the waste and old hard polyaminoester foam granule that particle size range is 0.5～4mm it is broken into standby；
(3) by weight: waste tire rubber granule 36 parts, waste and old hard polyaminoester foam granule 46
Part, triphenyl phosphate 7.5 parts, adhesive for polyurethane 10 parts, coloring agent 0.5 part weigh material, then depend on
Secondary respectively by described waste tire rubber granule, waste and old hard polyaminoester foam granule, triphenyl phosphate, poly-
Urethane adhesive and coloring agent join in mill, mix banburying 8min, to be mixed uniformly after, according to mould
Tool size prepares lamellar material base on a mill until；
(4) the lamellar material base that step (3) obtains is put in mould, hot-forming obtain rigid polyurethane foam
Cotton granule modified rubber composite semi-finished product, wherein, tablet machine temperature is 65 DEG C, and pressure is 4MPa, protects
The pressure time is 6min, then takes out that product is clipped, obtains described hard polyaminoester foam granule after deburring and change
Property rubber composite.
The granule modified rubber composite of hard polyaminoester foam prepared by the present embodiment, can be used as floor tile, institute
State floor tile and can be applicable to road construction.Property to the described granule modified rubber composite of hard polyaminoester foam
Can test, recording apparent density is 0.71g/cm3, elongation at break is 64%, and seepage rate is 51%,
The hard polyaminoester foam granule modified rubber composite density that the visible present invention provides is low, and permeability is strong,
Excellent performance.
Embodiment 3
The preparation method of a kind of granule modified rubber composite of hard polyaminoester foam, comprises the following steps:
(1) junked tire of automobile dismounting or recovery is put in clear water clean up, remove booty, take out
Dry, then carry out cutting, crush, sieve after select the rubber grain that particle size range is 1～5mm；Will sieve
The rubber grain chosen is put in hydrochloric acid solution, and after carrying out activation processing 7 minutes, taking-up clean water is done
Clean and dry, obtain described waste tire rubber granule standby；
(2) electron wastes being disassembled the polyurethane foam of generation put in clear water and clean up, taking-up is dried,
Then the waste and old hard polyaminoester foam granule that particle size range is 0.5～4mm it is broken into standby；
(3) by weight: waste tire rubber granule 30 parts, waste and old hard polyaminoester foam granule 50
Part, triphenyl phosphate 10 parts, adhesive for polyurethane 7 parts, coloring agent 3 parts weigh material, divide the most successively
Not by described waste tire rubber granule, waste and old hard polyaminoester foam granule, triphenyl phosphate, polyurethane
Adhesive and coloring agent join in mill, mix banburying 5min, to be mixed uniformly after, according to mould chi
Very little prepare lamellar material base on a mill until；
(4) the lamellar material base that step (3) obtains is put in mould, hot-forming obtain rigid polyurethane foam
Cotton granule modified rubber composite semi-finished product, wherein, tablet machine temperature is 50 DEG C, and pressure is 3MPa, protects
The pressure time is 5min, then takes out that product is clipped, obtains described hard polyaminoester foam granule after deburring and change
Property rubber composite.
The granule modified rubber composite of hard polyaminoester foam prepared by the present embodiment, can be used as floor tile, institute
State floor tile and can be applicable to road construction.Property to the described granule modified rubber composite of hard polyaminoester foam
Can test, recording apparent density is 0.65g/cm3, elongation at break is 46%, and seepage rate is 53%,
The hard polyaminoester foam granule modified rubber composite density that the visible present invention provides is low, and permeability is strong,
Excellent performance.
Embodiment 4
The preparation method of a kind of granule modified rubber composite of hard polyaminoester foam, comprises the following steps:
(1) junked tire of automobile dismounting or recovery is put in clear water clean up, remove booty, take out
Dry, then carry out cutting, crush, sieve after select the rubber grain that particle size range is 1～5mm；Will sieve
The rubber grain chosen is put in hydrochloric acid solution, and after carrying out activation processing 15 minutes, taking-up clean water is done
Clean and dry, obtain described waste tire rubber granule standby；
(2) electron wastes being disassembled the polyurethane foam of generation put in clear water and clean up, taking-up is dried,
Then the waste and old hard polyaminoester foam granule that particle size range is 0.5～4mm it is broken into standby；
(3) by weight: waste tire rubber granule 50 parts, waste and old hard polyaminoester foam granule 38
Part, tetraphenyl (bisphenol-A) bisphosphate 5 parts, adhesive for polyurethane 4 parts, coloring agent 3 parts weigh thing
Material, the most respectively by described waste tire rubber granule, waste and old hard polyaminoester foam granule, four benzene
Base (bisphenol-A) bisphosphate, adhesive for polyurethane and coloring agent join in mill, mix banburying 10min,
To be mixed uniformly after, prepare lamellar material base on a mill until according to die size；
(4) the lamellar material base that step (3) obtains is put in mould, hot-forming obtain rigid polyurethane foam
Cotton granule modified rubber composite semi-finished product, wherein, tablet machine temperature is 150 DEG C, and pressure is 10MPa,
Dwell time is 10min, then takes out that product is clipped, obtains described hard polyaminoester foam granule after deburring
Modified rubber composite.
The granule modified rubber composite of hard polyaminoester foam prepared by the present embodiment, can be used as floor tile, institute
State floor tile and can be applicable to road construction.Property to the described granule modified rubber composite of hard polyaminoester foam
Can test, recording apparent density is 0.86g/cm3, elongation at break is 63%, and seepage rate is 47%,
The hard polyaminoester foam granule modified rubber composite density that the visible present invention provides is low, and permeability is strong,
Excellent performance.
Embodiment 5
The preparation method of a kind of granule modified rubber composite of hard polyaminoester foam, comprises the following steps:
(1) junked tire of automobile dismounting or recovery is put in clear water clean up, remove booty, take out
Dry, then carry out cutting, crush, sieve after select the rubber grain that particle size range is 1～5mm；Will sieve
The rubber grain chosen is put in hydrochloric acid solution, and after carrying out activation processing 15 minutes, taking-up clean water is done
Clean and dry, obtain described waste tire rubber granule standby；
(2) electron wastes being disassembled the polyurethane foam of generation put in clear water and clean up, taking-up is dried,
Then the waste and old hard polyaminoester foam granule that particle size range is 0.5～4mm it is broken into standby；
(3) by weight: waste tire rubber granule 50 parts, waste and old hard polyaminoester foam granule 30
Part, triphenyl phosphate 6 parts, resorcinol double (diphenyl) phosphate ester 3 parts, adhesive for polyurethane 8
Part, coloring agent 3 parts weigh material, the most respectively by described waste tire rubber granule, waste and old hard
Double (diphenyl) phosphate ester of polyurethane foam granule, triphenyl phosphate and resorcinol, adhesive for polyurethane,
Coloring agent joins in mill, mixes banburying 10min, to be mixed uniformly after, according to die size in mill
Lamellar material base is prepared on machine；
(4) the lamellar material base that step (3) obtains is put in mould, hot-forming obtain rigid polyurethane foam
Cotton granule modified rubber composite semi-finished product, wherein, tablet machine temperature is 150 DEG C, and pressure is 10MPa,
Dwell time is 10min, then takes out that product is clipped, obtains described hard polyaminoester foam granule after deburring
Modified rubber composite.
The granule modified rubber composite of hard polyaminoester foam prepared by the present embodiment, can be used as floor tile, institute
State floor tile and can be applicable to road construction.Property to the described granule modified rubber composite of hard polyaminoester foam
Can test, recording apparent density is 0.87g/cm3, elongation at break is 61%, and seepage rate is 45%,
The hard polyaminoester foam granule modified rubber composite density that the visible present invention provides is low, and permeability is strong,
Excellent performance.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (6)
1. the granule modified rubber composite of hard polyaminoester foam, it is characterised in that by weight,
Including following components: waste tire rubber granule 30～50, waste and old hard polyaminoester foam granule 30～50, resistance
Combustion agent 5～10, adhesive 4～10, coloring agent 0.5～3；The particle size range of described waste tire rubber granule is
1～5mm, the particle size range of described waste and old hard polyaminoester foam granule is 0.5～4mm.
The granule modified rubber composite of hard polyaminoester foam the most according to claim 1, its feature
Being, described fire retardant includes double (diphenyl) phosphorus of tetraphenyl (bisphenol-A) bisphosphate, resorcinol
One or more combination in acid esters, APP and triphenyl phosphate.
The granule modified rubber composite of hard polyaminoester foam the most according to claim 1, its feature
Being, described adhesive is polyurethane-type adhesive.
4. the preparation method of the granule modified rubber composite of hard polyaminoester foam, it is characterised in that
Comprise the following steps:
(1) providing waste tire rubber granule, the particle size range of described waste tire rubber granule is 1～5mm；
(2) waste and old hard polyaminoester foam granule is provided, the particle diameter of described waste and old hard polyaminoester foam granule
Scope is 0.5～4mm；
(3) mixing banburying: by weight: waste tire rubber granule 30～50, waste and old hard polyaminoester
Foam granule 30～50, fire retardant 5～10, adhesive 4～10, coloring agent 0.5～3 weighs material, then depends on
Secondary respectively by described waste tire rubber granule, waste and old hard polyaminoester foam granule, fire retardant, adhesive
Join in mill with coloring agent, mix banburying 5～10min, to be mixed uniformly after, obtain lamellar material base；
(4) hot-forming: the lamellar material base that step (3) obtains is put in mould, hot-forming obtain hard
Matter polyurethane foam granule modified rubber composite semi-finished product, then take out that product is clipped, after deburring
To the described granule modified rubber composite of hard polyaminoester foam.
The preparation side of the granule modified rubber composite of hard polyaminoester foam the most according to claim 4
Method, it is characterised in that described in step (4), the technological parameter of hot-forming process is: tablet machine temperature is
50～150 DEG C, pressure is 3～10MPa, and the dwell time is 5～10min.
6. the granule modified rubber composite of hard polyaminoester foam as claimed in claim 1 is at road
Application in terms of construction.
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| CN107459691A (en) * | 2017-06-13 | 2017-12-12 | 东莞市汇如涞电能科技有限公司 | A kind of modified plastic particles and its homogenization process |
| CN108115876A (en) * | 2017-12-15 | 2018-06-05 | 南京志绿声学科技有限公司 | A kind of preparation method of floating build floor heat preservation and soundproof pad |
| CN109517363A (en) * | 2018-11-12 | 2019-03-26 | 金陵科技学院 | A kind of nylon fiber enhancing compound polyurethane material and preparation method thereof |
| CN115368651B (en) * | 2022-09-14 | 2023-11-28 | 交通运输部公路科学研究所 | Sound absorption material for recycling waste tire rubber and preparation method thereof |
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| CN101629025A (en) * | 2009-08-07 | 2010-01-20 | 天津大学 | Plastic material prepared by using waste thermosetting foam plastics and preparation method thereof |
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