CN107236188A - A kind of modified waste rubber powder and pp intermingling materials and preparation method thereof - Google Patents
A kind of modified waste rubber powder and pp intermingling materials and preparation method thereof Download PDFInfo
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- CN107236188A CN107236188A CN201710491505.6A CN201710491505A CN107236188A CN 107236188 A CN107236188 A CN 107236188A CN 201710491505 A CN201710491505 A CN 201710491505A CN 107236188 A CN107236188 A CN 107236188A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a kind of modified waste rubber powder and pp intermingling materials, include the component of following parts by weight：10 50 parts of shoddy, 50 90 parts of PP, 0.1 0.35 parts of diphenylguanidine, 0.1 0.3 parts of frerrous chloride, 46 parts of methanol, 24 parts of DOP, 24 parts of zinc oxide, 0.5 1.5 parts of paraffin, 1.5 3.5 parts of maleic anhydride.The preparation method of described modified waste rubber powder and pp intermingling materials, comprises the following steps：(1) preparation of dynamic vulcanized comixture；(2) compression molding.The present invention reaches the effect for improving rubber powder and PP comixing compatibilities by the modification to shoddy, rubber passes through its modified compatibility, intensity is all improved, realize the recycling of the new one side of waste old, using Technology of Dynamic Vulcanized technology, experimental period can effectively be shortened, external interference factor is reduced, simplify processing step.
Description
Technical field
Reclaimed the present invention relates to waste old and utilize field, specifically a kind of modified waste rubber powder and pp intermingling materials and its
Preparation method.
Background technology
The rubber sources of current China is very deficient, while China, which is also waste rubber, produces most countries, according to endless
The waste old about 5000kt produced every year is counted entirely, and because the rate of recovery of current China recovery rubber is not high, it is most of useless
Old rubber is all to burn, burial processing, and this, which allows for rubber sources, rationally sufficiently to utilize, and cause to a certain extent
Waste of resource.The limitation of another aspect China prior art is caused, and waste old recycles investment greatly, and recovery utilization rate is not
Height, reclaims the restriction of uneven, etc. the aspect of quality of rubber, limits the development of waste old recovery.Therefore one is developed
The scheme that individual effective waste old is reclaimed, is helped with promoting the protection of environment and recycling for resource.
The world today, resource is nervous, in rubber-consumer amount, second is occupied, while also generating substantial amounts of waste and old rubber
Glue, the annual whole world can produce the junked tire more than 15,000,000 t, but in order to meet requirement of the people to rubber with
And promote the development of Rubber Industry, so researcher improves constantly its performance in terms of material property so that rubber is towards resistance to
Mill, high intensity, stability and ageing-resistant direction are developed, but on the other hand also result in the rubber long-term after discarding not
The phenomenon of energy natural degradation, substantial amounts of waste old is caused than plastic pollution (white pollution) more intractable black pollution.
On the other hand the waste of rubber sources is caused, therefore, waste old how is effectively utilized, how to realize that economy is mutually tied with environmentally friendly
Close, meet the requirement of conservation culture, be both a global problem, be also the new class that china natural resources recycling is faced
Topic is this people early in the seventies begun to how the research to waste old recycling.
With China's expanding economy, people are increasing to the demand of rubber, then the rubber of social production
It is more and more, cause the storage of the various waste rubber goodses such as waste and old sole, waste old, sole offal more and more, give up
The reusable edible processing of old rubber is one of serious problems that current people face because China is that a rubber resource is relative
Country in short supply, 50% or so of annual reclaimed rubber consumption needs to rely on import, so finding rubber raw materials source and its generation
It is the target that scientific research personnel struggles on without cease with material.Therefore, waste old is conscientiously properly handled, environmental pollution is reduced, and it is right
It makes full use of regenerated resources, breaks away from the scarcity of natural resources, improves the living environment of the people and has extremely far-reaching positive meaning
Justice and realistic meaning.Reclaimed rubber is always the important raw and processed materials of world rubber industry, and on the one hand it can replace rubber, delay
The serious scarcity of natural rubber is solved；On the other hand waste old is realized recycling, solve waste old pollution
The problem of environment；
What the country was reused to waste old at present has following several method；
(1) directly utilize
Old tire is renovated：Under conditions of Normalization rule and good maintenance, rubber sources can be renovated and is used for multiple times, and often be turned over
New 1 time, the service life equivalent to starting rubber 60%~90% can be regained.By being repeatedly remoulded, waste and old rubber can be made
Entire life extension l~2 times of glue.Its cost of waste old of equal unit is renovated equivalent to the rubber for producing new equal unit
L5%~30%, price but be only new rubber 20%~50%；
Directly transform：Waste old such as tire can be used for cladding guardrail after transformation, serve as road sign and buoy etc.,
But this method consumption is less.
(2) rubber powder：Rubber powder refers to that waste or used vulcanized rubber passes through mechanical crushing, and obtained powdered rubber is that one kind has
The powder body material of special elastic, the fundamental property with powder body material.
Three kinds of normal temperature method low-temperature grindings method and wet method are used at present, and interim normal temperature is most-often used because its technological process letter
Single, production cost is low.But different breaking methods would also vary to the performance of rubber powder.
(3) indirect utilization：
Reclaimed rubber：The production method of reclaimed rubber is that rubber is milled into particle, then adds water and chemical substance etc.
Its elasticity is eliminated, plasticity is made it have, then under the conditions of certain temperature and pressure, it is returned to using mechanical presses
It is capable of the state of revulcanization, so as to directly utilize.The use of reclaimed rubber can reduce product cost, and weak point is technique
It is complex, and energy consumption is higher, easily pollutes environment.
Heat utilization：Heat utilization is to use scrap rubber directly as fuel, using its high heat, can reclaim the pairs such as carbon black
Product, but pollute very serious, it is unworthy advocating.
Thermal cracking：Waste old is placed in inert gas environment and thermally decomposed, recyclable carbon black, gas and oil product etc., this
The method of kind can give full play to the value of scrap rubber, better economic benefit, and clean environment firendly, but energy consumption is higher, no
It is adapted to large-scale production.
Low-temperature catalytic pyrolysis：Low-temperature catalytic pyrolysis are different from thermal cracking, and this method is under cryogenic, to utilize catalysis
Agent reaches the purpose of cracking waste old, and the rate of recovery of low-temperature catalytic pyrolysis is very high, and gas is few, oil quality and carbon black product
Matter is higher.
It is to carry out chemical treatment to its surface to reach modified purpose to most of rubber powder modified at present, its utilization can be improved
Value, the activation modifying method of rubber powder is a lot, is divided into：Saturation capacity vulcanization accelerator facture；Liquid polymer material adds vulcanization
Agent facture；Grafting method；Interpenetrating polymer networks (IPN) method；Superficial degradation method of reproduction；Oligomer modification method etc..
(1) saturation capacity vulcanization accelerator facture：It is that mechanization processing is carried out to rubber powder using vulcanization accelerator.Pass through place
The rubber powder of reason so that it uniformly adheres to one layer of vulcanization accelerator, so that rubber powder and the increase of matrix sizing material caking property
Also so that the cross-bond increase of its interface, makes whole rubber mass compounding objects system turn into a uniform cross-linking agent after vulcanizing.This
Plant rubber powder and be applied to tire, its dynamic property and processing characteristics can be lifted.
(2) liquid polymer material adds vulcanizing agent facture：It is high using 11 parts or so of unsaturated vulcanizable liquid
Molecular material is blended with vulcanizing agent, then carries out mechanization processing to waste rubber powder.Adoptable liquid polymer material has
Liquid buna, liquid styrene butadiene rubber, Liquid Ethylene Propylene Methylene etc., the selection of liquid polymer material then can be according to rubber powder kind
Depending on class and rubber powder size size and purposes.
(3) mechanical force method：Under the effect such as shearing, the extruding of rubber powder at a certain temperature Jing Guo high speed so that sulphur
Change xanthan molecule three-dimensional network-like structure and be corrupted such that rubber powder carries unsaturated bond, rubber powder energy and rubber with unsaturated bond
Sizing material have good compatibility performance effective and it is close must be combined together, formed co-crosslinking, can be directly added into finished product glue
Begun to pratise, compatibility, point spreading property, good permeability, by modified while improve the tensile strength and tearing strength of finished product,
Reduce initial Mooney, hence it is evident that improve the dynamic fatigue of material, effect is mixed in raising.
Because rubber production cost is expensive, and at present, the mankind are more and more urgent to the demand of rubber, and rubber has incorporated
In the various aspects of life, while waste old is also more and more, therefore research recycling waste old has protection ring
Border, saving capital, save rubber resource and consume excessively, with realistic meaning.
Current waste old application field is most ripe to be used in waste and old rubber modified asphalt direction, such a research direction master
It is used for road pavement.Therefore rubber powder modified can preferably using and play the remaining beautiful jade of its performance such as South China Science ＆ Engineering University and pass through
The method directly kneaded is prepared for rubber powder of good performance/TPV intermingling materials, and improves blending material by adding bulking agent etc.
The combination property of material.The method that Kaynak etc. coats shoddy surface using silane coupler improves epoxy resin and rubber powder
Compatibility, greatly improved fracture toughness.Lee etc. is modified with acrylamide to shoddy surface, in ultraviolet light bar
Under part, WRP/PP blends are prepared for, compared with unmodified system, its tensile property is greatly improved.Li Yan etc. using oxygen etc. from
Daughter is modified to scrap rubber material surface, effectively increases the mechanical property of PVC/ rubber powders
Waste rubber powder major part bond structure so surface is inert, and also mixes all in cross-linked state in rubber powder
Substantial amounts of impurity so that the performance of waste old is much worse than properties, if directly waste old and pp are blended, gained
Blend rubber and plastic blend poor compatibility, boundary have obvious separation situation to occur, and can not play and reclaim rubber
Effect.
The content of the invention
It is above-mentioned to solve it is an object of the invention to provide a kind of modified waste rubber powder and pp intermingling materials and preparation method thereof
The problem of being proposed in background technology.
To achieve the above object, the present invention provides following technical scheme：
A kind of modified waste rubber powder and pp intermingling materials, include the component of following parts by weight：10-50 parts of shoddy, PP 50-
90 parts, 0.1-0.35 parts of diphenylguanidine, 0.1-0.3 parts of frerrous chloride, 4-6 parts of methanol, 2-4 parts of DOP, 2-4 parts of zinc oxide,
0.5-1.5 parts of paraffin, 1.5-3.5 parts of maleic anhydride.
It is used as further scheme of the invention：Include the component of following parts by weight：30 parts of shoddy, 70 parts of PP, accelerator
0.2 part of D, 0.2 part of frerrous chloride, 5 parts of methanol, 3 parts of DOP, 3 parts of zinc oxide, 1 part of paraffin, 2 parts of maleic anhydride.
It is used as further scheme of the invention：The shoddy is that waste old is formed by crushing.
It is used as further scheme of the invention：The shoddy is 50-200 mesh.
It is used as further scheme of the invention：The preparation method of described modified waste rubber powder and pp intermingling materials, including
Following steps：
(1) preparation of dynamic vulcanized comixture：Shoddy and diphenylguanidine, frerrous chloride, methanol are mutually mixed stirring equal
It is even, it is subsequently added into PP and is mixed evenly with other components, said mixture is poured into banburying in banbury with one-step method
10-15min, controls 180 DEG C of mixing temperature, and rotating speed 36r/min takes out the cooling of banburying mixture, and size-reduced machine is ground into particle
Shape, is then placed into drying machine drying 24h, dries 70 DEG C of temperature；
(2) compression molding：Dried mixture is fitted into mould, batten is preheated in the full-automatic tablet press machines of ZG-50
20min, preheating pressure 0MPa, 210 DEG C of temperature；Thin slice preheats 10min, and preheating pressure 0MPa. is vented 10 times, pressurize again
20min, dwell pressure 100Mpa；Then cold moudling on cold press is transferred quickly to, cold pressing pressure 10MPa is cooled to room temperature
After take out finished product.
Rubber powder is generated after mechanical crushing, and it derives from the rubber (mainly automobile tire) scrapped, and rubber powder is
A kind of dusty material containing crosslinking, therefore the fundamental characteristics with powder body material, due to the unsaturation of rubber, except a part
, then just can be common with rubber also containing certain unreacted unsaturated bond outside unsaturated bond is crosslinked during vulcanization reaction
Rubber equally can also use peroxide cure simultaneously using sulphur-accelerator vulcanization.
The scope difference of its application of different rubber powder particle diameters is classified by particle size, the applicable cases such as table 1 of rubber powder：
The different-grain diameter rubber powder application of table 1
Polypropylene (Polypropylene, PP) molecular formula is (C3H6) n, it is a kind of common high polymer material, fusing point is high,
Density is low, with preferable mechanical property, and its electrical insulating property and chemical resistance are excellent, and its is resistance in all general-purpose plastics
Hot best, fatigue durability is good, price is minimum in all resins.Its preparation technology is relatively simple, and with low cost, raw material
Wide material sources, therefore it is widely used in industry.
In terms of processing characteristics, polypropylene does not need drying, because its water absorption rate is very low, soaks one day and absorbs water in water
Rate only has a ten thousandth or so.Melt polypropylene is more sensitive to shear rate and temperature, similar to non-newtonian fluid, improves
Pressure and temperature can improve its fluidity of molten.Polypropylene is especially sensitive to oxygen at high temperature, be heated oxidizable degraded, institute
To need to add antioxidant often in processing and reduce the heat time.
Polypropylene has higher crystallinity, and its impact resistance is also poor, therefore is commonly used to be blended with other materials, warp
Product of good performance is made in the modified and addition class material of solubilizer one.
Compared with prior art, the beneficial effects of the invention are as follows：Reached by the modification to shoddy raising rubber powder with
The effect of PP comixing compatibilities, rubber passes through its modified compatibility, and intensity is all improved, and realizes one of waste old newly
The recycling of individual aspect, using Technology of Dynamic Vulcanized technology, can effectively shorten experimental period, reduce external interference because
Element, simplifies processing step.
Brief description of the drawings
Fig. 1 is modified waste rubber powder and the flow chart of pp intermingling material preparation methods.
Fig. 2 is shoddy and PP infrared spectrograms in modified waste rubber powder and pp intermingling materials and preparation method thereof.
Fig. 3 is different content, different-grain diameter rubber powder in modified waste rubber powder and pp intermingling materials and preparation method thereof to compound
The influence figure of tensile strength of material.
Fig. 4 is different content, different-grain diameter rubber powder in modified waste rubber powder and pp intermingling materials and preparation method thereof to compound
The influence figure of Materials Fracture elongation and tensile strength.
Fig. 5 is the sem analysis figure in modified waste rubber powder and pp intermingling materials and preparation method thereof during rubber powder content 50%.
Fig. 6 is the sem analysis figure in modified waste rubber powder and pp intermingling materials and preparation method thereof during rubber powder content 40%.
Fig. 7 is the sem analysis figure in modified waste rubber powder and pp intermingling materials and preparation method thereof during rubber powder content 30%.
Fig. 8 is the sem analysis figure in modified waste rubber powder and pp intermingling materials and preparation method thereof during rubber powder content 20%.
Fig. 9 is the sem analysis figure in modified waste rubber powder and pp intermingling materials and preparation method thereof during rubber powder content 10%.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art obtained under the premise of creative work is not made it is all its
His embodiment, belongs to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, a kind of modified waste rubber powder and pp intermingling materials include the component of following parts by weight：Shoddy
10 parts, 90 parts of PP, 0.1 part of diphenylguanidine, 0.1-0.3 parts of frerrous chloride, 5 parts of methanol, 2 parts of DOP, 2 parts of zinc oxide, paraffin 1
Part, 1.5 parts of maleic anhydride.
Embodiment 2
In the embodiment of the present invention, a kind of modified waste rubber powder and pp intermingling materials include the component of following parts by weight：Shoddy
20 parts, 80 parts of PP, 0.2 part of diphenylguanidine, 0.15 part of frerrous chloride, 5 parts of methanol, 2.5 parts of DOP, 2.5 parts of zinc oxide, paraffin
1 part, 2 parts of maleic anhydride.
Embodiment 3
In the embodiment of the present invention, a kind of modified waste rubber powder and pp intermingling materials include the component of following parts by weight：Shoddy
30 parts, 70 parts of PP, 0.25 part of diphenylguanidine, 0.2 part of frerrous chloride, 5 parts of methanol, 3 parts of DOP, 3 parts of zinc oxide, 1 part of paraffin,
2.5 parts of maleic anhydride.
Embodiment 4
In the embodiment of the present invention, a kind of modified waste rubber powder and pp intermingling materials include the component of following parts by weight：Shoddy
40 parts, 60 parts of PP, 0.3 part of diphenylguanidine, 0.25 part of frerrous chloride, 5 parts of methanol, 3.5 parts of DOP, 3.5 parts of zinc oxide, paraffin
1 part, 3 parts of maleic anhydride.
Embodiment 5
In the embodiment of the present invention, a kind of modified waste rubber powder and pp intermingling materials include the component of following parts by weight：Shoddy
50 parts, 50 parts of PP, 0.35 part of diphenylguanidine, 0.3 part of frerrous chloride, 5 parts of methanol, 4 parts of DOP, 4 parts of zinc oxide, 1 part of paraffin,
3.5 parts of maleic anhydride.
Prepare modified waste rubber powder and pp intermingling materials respectively by said ratio, as shown in Figure 1：
(1) preparation of dynamic vulcanized comixture：Shoddy and diphenylguanidine, frerrous chloride, methanol are mutually mixed stirring equal
It is even, it is subsequently added into PP and is mixed evenly with other components, said mixture is poured into banburying in banbury with one-step method
10-15min, controls 180 DEG C of mixing temperature, and rotating speed 36r/min takes out the cooling of banburying mixture, and size-reduced machine is ground into particle
Shape, is then placed into drying machine drying 24h, dries 70 DEG C of temperature；
(2) compression molding：Dried mixture is fitted into mould, batten is preheated in the full-automatic tablet press machines of ZG-50
20min, preheating pressure 0MPa, 210 DEG C of temperature；Thin slice preheats 10min, and preheating pressure 0MPa. is vented 10 times, pressurize again
20min, dwell pressure 100Mpa；Then cold moudling on cold press is transferred quickly to, cold pressing pressure 10MPa is cooled to room temperature
After take out finished product.
Experiment：
First, elongation at break and tensile strength：
Dumbbell shaped print is cut with sheet-punching machine, extension at break is tested with CMT-4104 microcomputer controlled electronic universal testers
Rate and tensile strength.Draw speed is 20mm/min, and test sample print every group five is taken the mean.
Elongation at break is to weigh sample toughness (elasticity) index, refers to effective graticule part (two fixtures during tensile sample
Between) length incrementss Δ l and initial effectively graticule part (between two fixtures) length l when breaking0Percentage, i.e.,
Elongation at break=Δ l/l0×100
Tensile strength is under defined test temperature, humidity and speed of experiment, to apply vertically on standard specimen and draw
Load is stretched until the maximum load P that sample is born before fracture and the ratio of sample cross (product of width b and thickness d), lead to
Conventional σtRepresent, i.e.,
Its unit is Newton/meter2, N/m2Or Pa.
2nd, impact strength
Batten is produced into breach through breach sampling machine, gap width is 6.5mm, with GT-7045-HML numerical digit impact tests
Machine tests impact strength, from the pendulum that specification is 3.5V-2.75J, test sample batten every group five.
Impact strength σiIt is a kind of index for weighing toughness of material, it is defined as sample in the presence of shock loading W
Fracture or during jackknifing absorption per unit area energy, i.e.,
W in formula --- the work(that sample is consumed is thrust, b is width, and d is thickness.
3rd, SEM image observation analysis
Batten is placed in liquid nitrogen and cooled down, then by batten brittle failure.Under 20 DEG C of room temperature conditions, with vacuum evaporator to crisp
Disconnected sample section carries out metal spraying processing, and observes cross-section morphology with SEM.
The main content that rubber powder in a. blends is determined by following factor of the impact strength of blend；B.pp melt
Index；C. test temperature；Table 2 is, to modified glue powder/pp blend impact strength performance test datas, rubber powder to be understood from data
Content from high to low but its sample rushes energy and first increases and then reduce, interim impact energy is up to positioned at 70:30 deals
Than.When batten is pure rubber powder (blank control) due to there is impurity inside it, and then should containing substantial amounts of cross-linked structure
The mechanical property of batten is poor, therefore its impact strength is minimum.Its impact strength increases when 10phr pp has been blended
Nearly 10 times, reason is rubber powder to be improved such as shock resistance by its modified performance, while also containing in batten
Its shock resistance of pp events is highly improved.Raised with the content of rubber powder, the impact strength of material also progressively on
Rise, the comparison that on the one hand explanation rubber powder is combined with pp of such situation occur fully, batten inside rubber powder is dispersed and pp
With reference to the mechanical property of enhancing blend, on the other hand also illustrate that the rise of pp contents can aid in the improvement of blending physical performance.
Table 2 is to modified glue powder/pp blend impact strength performance test datas
But as can be seen from Figure 4 as rubber content is raised and batten impact strength after rubber powder/PP ratios are 30/70
Gradually reduce, this be due to rubber phase in blend internal structure rubber powder particle internal layer mainly play a part of expand volume, with
PP effect is not obvious, the outer layer for the mainly rubber phase being had an effect with polypropylene, therefore, when rubber powder content is relatively low,
The increase of rubber powder content can promote the increase of intermingling material toughness, but increasing when more than 1 boundary's point with rubber content
Wait, rubber powder particle undertakes the limited in one's ability of stress, rigidity is poor, by larger deformation is easily produced during external force, to whole multiple
The intensity and rigidity of condensation material cause certain loss, and this also reflects the increase of rubber powder particle to material bending intensity simultaneously
There is the phenomenon of impact strength decreased in decline with tensile strength.When rubber powder and pp content ratios are 50:It is (more empty than pure pp when 50
White control) impact strength is also low, illustrate that now batten can embodies the performance of modified glue powder using excessive rubber powder, with regard to not
To default effect.
The present invention carries out toughness reinforcing by main toughener of modified glue powder to matrix resin polypropylene, so as to prepare with Gao Mo
Amount, high performance advanced composite material (ACM), wherein, some characteristics of the addition of rubber powder and selected rubber powder in itself, to compound
The influence of material is different.Fig. 3, Fig. 4 are different content, different-grain diameter rubber powder to fracture of composite materials elongation and stretched strong
The influence of degree.The reason for tensile strength general trend is gradually reduction as can be seen from Figure 3 is due to when rubber powder content is less
When, the overall performance of blend is based on PP proper property, while rubber powder is the polymer that vulcanization crosslinking is crossed, it is again
It is not remelted during processing, isolated phase is easily formed in the material, and the content for especially working as rubber powder is more, its orphan formed
Vertical phase is more, isolates the presence of phase, leverages the integrality of material, under stress, easy performance deficiency is caused
The reduction of intensity.With the increase of rubber powder content, the tensile strength of blend material significantly decreases, especially for part
The more rubber powder of amount ratio, when its addition reaches 50%, its tensile strength is reduced to 6MPa by 35MPa；When its addition is
When 20%, tensile strength is 15MPa；The rubber powder size is the rubber powder of 120 mesh, but when rubber powder addition reaches 30%, it draws
Intensity is stretched but to get a promotion, its reason be modified glue powder as the elastomer to polypropylene (PP) toughness reinforcing, in modified glue powder content
When relatively low, rubber powder elasticity in co-mixing system is sufficiently embodied, when material receives external impacts, the formation of rubber powder particle
Rubber, which meets to be formed much, tiny rubber powder granule aggregation stress concentration point, promotes the formation of small crazing and shear band, this
Process along with big energy consumption.When the addition amount of rubber powder is excessive, fusion faculty of the matrix resin to rubber powder particle
It is limited, and rubber powder is not remelted during intermingling material is processed, but mutually exist with isolated, the increase of rubber powder particle is big
The big overall caking property for reducing intermingling material, causes the globality of material to decline, when by external impacts, composite
Stress concentration can not be produced to stress, material is destroyed.
Table 3
Equally face the different effects to intermingling material of rubber powder content in each middle different rubber powder of in the market, co-mixing system
Also be not quite similar, with SEM to five kinds of different rubber and plastics than the impact brittle failure face of co-mixing system observe, can
To be clearly visible that branch situation of the rubber powder of different content in co-mixing system, from Fig. 5-9 can from obtain sizing material and contain
Rubber powder and pp compatibilities are best in blend at 30% for amount, and possible rubber powder such a ratio after modified active is optimal excellent
Change proportioning, the rise of modified glue powder surface-active improves the interface binding intensity between rubber powder and pp so that rubber powder and pp's
Compatibility improves.Effect of the rubber powder granule in intermingling material simultaneously has two, and first is stress collection as intermingling material
Center, can induce substantial amounts of crazing or shear band absorbs energy；Second is that can effectively control the development of crazing
And crazing timely terminates and is unlikely to develop into destructive crackle.When as shown in Figure 5,6 due to rubber powder too high levels
The effect of rubber powder and polypropylene (pp) gradually increases, but rubber powder particle undertakes the limited in one's ability of stress, causes to bond weakness
Rubber powder particle can not control the development of crazing and crazing is terminated in time under stress conditions, can not then control stationary crack,
A Crack is formed between two-phase interface and causes fracture, causing the mechanical property of intermingling material reduces.From processing technology side
It is more smooth to compared for Fig. 7,8, Fig. 7 surfaces, without sags and crests, it also illustrate that when rubber and plastic ratio is 30/70 now blend
Compatibility performance preferably, processing when can effectively lift blend material processing characteristics
Conclusion：
(1) it is compared in multigroup different rubber and plastic ratios, summarizes, grope by repetition test by many experiments, determine glue
The optimal proportion of powder and PP, when the ratio is 30/70, intermingling material mechanical property, processing characteristics are optimal.
(2) activation modification is the key factor that rubber industry wastewater is recycled, impact strength test analysis, SEM section shapes
Looks are analyzed, and blank control surface, and rubber passes through its modified compatibility, and intensity is all improved, and realizes that waste old is new
One side recycling.
(3) Technology of Dynamic Vulcanized technology is used, can effectively shorten experimental period, external interference factor is reduced, simplifies work
Skill step.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, nothing
By from the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by institute
Attached claim rather than described above are limited, it is intended that will fall in the implication and scope of the equivalency of claim
All changes include in the present invention.Any reference in claim should not be considered as to the right involved by limitation
It is required that.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art should
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It may be appreciated other embodiment.
Claims (5)
1. a kind of modified waste rubber powder and pp intermingling materials, it is characterised in that include the component of following parts by weight：Shoddy 10-50
Part, 50-90 parts of PP, 0.1-0.35 parts of diphenylguanidine, 0.1-0.3 parts of frerrous chloride, 4-6 parts of methanol, 2-4 parts of DOP, zinc oxide
2-4 parts, 0.5-1.5 parts of paraffin, 1.5-3.5 parts of maleic anhydride.
2. modified waste rubber powder according to claim 1 and pp intermingling materials, it is characterised in that include the group of following parts by weight
Point：30 parts of shoddy, 70 parts of PP, 0.2 part of diphenylguanidine, 0.2 part of frerrous chloride, 5 parts of methanol, 3 parts of DOP, 3 parts of zinc oxide,
1 part of paraffin, 2 parts of maleic anhydride.
3. modified waste rubber powder according to claim 1 or 2 and pp intermingling materials, it is characterised in that the shoddy is useless
Old rubber is formed by crushing.
4. modified waste rubber powder according to claim 1 or 2 and pp intermingling materials, it is characterised in that the shoddy is 50-
200 mesh.
5. the preparation method of a kind of modified waste rubber powder as described in claim 1-4 is any and pp intermingling materials, it is characterised in that
Comprise the following steps：
(1) preparation of dynamic vulcanized comixture：Shoddy is mutually mixed with diphenylguanidine, frerrous chloride, methanol and stirred,
It is subsequently added into PP to be mixed evenly with other components, said mixture is poured into banburying 10- in banbury with one-step method
15min, controls 180 DEG C of mixing temperature, and rotating speed 36r/min takes out the cooling of banburying mixture, and size-reduced machine is ground into graininess,
It is then placed into drying machine drying 24h, dries 70 DEG C of temperature；
(2) compression molding：Dried mixture is fitted into mould, batten is preheated in the full-automatic tablet press machines of ZG-50
20min, preheating pressure 0MPa, 210 DEG C of temperature；Thin slice preheats 10min, and preheating pressure 0MPa. is vented 10 times again, pressurize 20min,
Dwell pressure 100Mpa；Then cold moudling on cold press is transferred quickly to, cold pressing pressure 10MPa is cooled to after room temperature and taken out
Finished product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| PL425051A1 (en) * | 2018-03-28 | 2019-10-07 | Sieć Badawcza Łukasiewicz-Instytut Inżynierii Materiałów Polimerowych I Barwników | Method for modification of the polar rubber mix |
| CN110901124A (en) * | 2018-09-18 | 2020-03-24 | 北京斯科瑞新材料科技股份有限公司 | Preparation of environment-friendly rubber floor mat |
| CN110936534A (en) * | 2018-09-21 | 2020-03-31 | 临沂斯科瑞聚氨酯材料有限公司 | Preparation of green environment-friendly rubber brick |
| CN115926436A (en) * | 2023-02-16 | 2023-04-07 | 河北华密新材科技股份有限公司 | Super-wear-resistant rubber and plastic material and preparation method and application thereof |
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| CN1281000A (en) * | 1999-07-15 | 2001-01-24 | 四川大学 | Process for desulfurizing used rubber |
| CN1425708A (en) * | 2002-12-19 | 2003-06-25 | 上海交通大学 | Process for preparing waste rubber powder/poly olefine resin blend |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| PL425051A1 (en) * | 2018-03-28 | 2019-10-07 | Sieć Badawcza Łukasiewicz-Instytut Inżynierii Materiałów Polimerowych I Barwników | Method for modification of the polar rubber mix |
| CN110901124A (en) * | 2018-09-18 | 2020-03-24 | 北京斯科瑞新材料科技股份有限公司 | Preparation of environment-friendly rubber floor mat |
| CN110936534A (en) * | 2018-09-21 | 2020-03-31 | 临沂斯科瑞聚氨酯材料有限公司 | Preparation of green environment-friendly rubber brick |
| CN115926436A (en) * | 2023-02-16 | 2023-04-07 | 河北华密新材科技股份有限公司 | Super-wear-resistant rubber and plastic material and preparation method and application thereof |
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