CN105175976B - Composite toughening modifier and its preparation method and application - Google Patents
Composite toughening modifier and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of modified waste polyethylene pipe PP Pipe Compounds and preparation method thereof.The weight group of the PP Pipe Compound becomes：100 parts of waste and old recycle polyethylene, 3~30 parts of composite toughening modifier, 3~5 parts of inorganic filler, 0.02~0.2 part of crosslinking agent, 0.05~0.1 part of antioxidant, 1~7 part of black agglomerate, 0.1~0.5 part of antifoaming agent, the composite toughening modifier is made with scientific and reasonable ratio with rubber powder of waste tire, SBS and LLDPE resins.The present invention utilizes the composite toughening modifier optimized, improve the degree of cross linking of each related component in composite system, composite system tensile strength values are made up, the gel content and mobility of modified material system are controlled, achieve the purpose that optimize composite system mechanical property.The method of the present invention is easy to operate, adaptable, is easy to industrialized production, not only reduces production cost, and reduces pollution of the solid waste to environment, has significant economic benefit and social benefit.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly, to a kind of composite toughening modifier and its preparation
Methods and applications.
Background technology
With extensive use of the new and high technology in Plastics Processing Industry, plastics industry obtains significant progress.However, plastics
The increase of consumption figure causes the yield of waste plastic to surge.Since waste plastic decomposes or degradation speed is slow in nature
Slowly, therefore, waste plastic causes huge environmental pollution（That is " white pollution "）.In addition, with China's rapid development of economy,
Car enters huge numbers of families, it has also become the necessity in people's daily life.However, with the extension of automobile usage time,
Pile up like a mountain for waste tire, has become the important sources of " black pollution ", in order to protect and improve environment, improves the utilization of resources
Efficiency promotes recycling economy development, realizes that sustainable development, the recycling of waste plastic brought China into 2009
Execution from January 1《People's Republic of China's circular economy promotion law》It was promulgated with 2010《Long-term development in science and technology in country
Planning outline (2006-2020)》In important content.Growing day by day with waste plastic rubbish, harm has caused the world
The great attention of various countries, and increase the dynamics that input is studied it.The processing of waste plastic has been basically formed at present and has been compared
Effective 4 kinds of technologies, i.e. burning recover energy, bury, chemistry thermally decomposes and recycling.It was verified that being applicable in, answering the most
What this was advocated energetically is to recycle regeneration techniques.
In plastics industry, polyethylene（PE）Yield is maximum, purposes is most wide, consumption figure is maximum.According to incompletely statistics, waste and old
The amount of PE accounts for the 48% of entire waste plastic amount.Due to molecular structure etc., waste and old PE plastics can not achieve natural decomposition or drop
Solution can cause environment permanent contact scar, while be also the significant wastage to resource.Therefore, its dirt to environment how is solved
Dye, has become today's society urgent problem to be solved.Waste and old recycled plastic be usually because to being dropped after service life,
Mainly due to aging（Also known as chemical aging）Lead to the performance depreciation of material, so that high molecular material is hardened, become fragile, cause
The significantly decline of the mechanical properties such as impact strength, tensile strength, the elongation of material, to influence macromolecule material product
Normal use.Currently, the field of an important application of waste and old recycling PE is tubing, such as double-wall corrugated pipe of draining, blowdown,
Power pipe, communication pipe etc..These usual pipelines are to be embedded in underground, not high to tubing appearance requirement, and it is certain to only require that tubing has
Ring stiffness and the performances such as wear-resisting, corrosion-resistant, and to stretching and the requirement of bending strength is relatively low.Therefore, waste and old recycled plastic is utilized
Produce aforementioned tubes, not only solve the problems, such as to a certain extent or alleviate " white pollution ", have good environmental benefit and
Social benefit, and can also turn waste into wealth, there is good economic benefit.
Authorization Notice No. is CN101899178 B patents of invention, and it is special to disclose a kind of modifying waste plastic water supply line
Material and preparation method, with ethylene octene copolymer（POE）For toughener, cumyl peroxide is crosslinking agent, passes through micro- crosslinking
The gel content and mobility of technical controlling modified materials, meanwhile, nucleating agent is added, plays the work of control crystallite dimension and distribution
With.This method is easy to operate, and toughening effect is preferable, but cost is higher, is unfavorable for it and promotes in the market.Authorization Notice No. point
Not Wei 101549535 B patents of invention of CN, disclose the method for preparing large-caliber double-wall bellow using waste HDPE plastic.
This method is using elastomer POE as the matrix resin of modified master, with the PE resins of sheet, the whisker of threadiness and spherical carbonic acid
Calcium filler is composite modifier, prepares modified master, and the modified master is prepared for the modification to waste HDPE plastic
Bellow.This method operation is fairly simple, but the additive amount due to modified master in waste HDPE plastic more could meet
The performance requirement used causes cost performance higher, it is difficult to extensive use be commercially available.In addition, application publication number is CN
103709485 A patents of invention disclose a kind of polyethylene anticorrosion pipeline modification regeneration PP Pipe Compound and preparation method thereof, toughener
It is changed to use EP rubbers（EPR）, ethylene-propylene diene copolymer（EPDM）, polyolefin elastomer（POE）In one kind, however cost performance is inclined
Therefore height also has certain limitation.
The research and development of new type of toughening agent cheap, best in quality rise emphatically in prepared by the production of modification regeneration PP Pipe Compound
The effect wanted.Presently relevant achievement in research is more rare, has no using thermoplastic styrene butadiene rubber（SBS）It is prepared as one of raw material
New type of toughening agent and applied to prepare waste polyethylene toughening modifying regenerate PP Pipe Compound technology report.
Invention content
It is special the technical problem to be solved by the present invention is to be regenerated for the waste polyethylene toughening modifying for being currently used for pipeline
The technical deficiency of material provides a kind of waste polyethylene toughening modifying regeneration PP Pipe Compound for pipeline, fully not only obtains one
Kind new exclusive material best in quality, and production cost is reduced, reduce pollution of the solid waste to environment.
It is regenerated another technical problem to be solved by the present invention is that providing the waste polyethylene toughening modifying for pipeline
The preparation method of PP Pipe Compound.
The purpose of the present invention is achieved by the following technical programs：
A kind of composite toughening modified waste HDPE special material for pipeline is provided, is made by the component of following parts by weight：
100 parts of waste and old recycle polyethylene；
3~30 parts of composite toughening modifier；
3~5 parts of inorganic filler；
0.02~0.2 part of crosslinking agent；
0.05~0.1 part of antioxidant；
1~7 part of Masterbatch；
0.1~0.5 part of antifoaming agent；
The waste and old recycle polyethylene（HDPE）It is the HDPE regrinding-materials and its product by recycling, through clear using pellet
It washes, be crushed, dry, be granulated, can buy and obtain in conventional market.
Preferably, the inorganic filler selects anhydrite powder, the present invention to give full play to anhydrite powder in submicroscopic structure
The texture structure for having the characteristics that threadiness, can play enhancing well in composite system of the present invention or reinforcement is made
With；Simultaneously, moreover it is possible to which the effect for functioning well as heterogeneous nucleation agent is reached by controlling the size and crystallinity of waste HDPE crystal grain
To the purpose of the mechanical property of optimization material system；In addition, its reasonable addition, not only reduces the cost of material system, may be used also
Solve the problems, such as the bad technical bottleneck of product dimensional stability caused by contraction.It is further preferred that the anhydrite powder
Granular size be 800~2000 mesh.
Preferably, the crosslinking agent selects cumyl peroxide（DCP）, benzoyl peroxide（BPO）In one kind, profit
It is generated free radicals in POE, LLDPE resin and waste HDPE surface energy with its decomposition, micro- crosslinking is formed between realization three, into
And achieve the purpose that reinforcement, thus further improve the compatibility of each component.Furthermore it is possible to control the gel content and stream of modified materials
Dynamic property, and then play the purpose for improving process mobility.
Preferably, it is four [β-(3,5- di-tert-butyl-hydroxy phenyl) third that the antioxidant, which selects Hinered phenols antioxidant,
Acid] pentaerythritol ester, trade name antioxidant 1010.In the present invention, antioxidant is mainly used for slowing down composite material processed
Aging phenomenon in journey improves the stability of material.
The Masterbatch and antifoaming agent are conventional with reference to the art, it is preferable that the present invention selects the Masterbatch grain of black
Material；The antifoaming agent selects organic silicon defoamer.
The present invention uses a kind of composite toughening modifier of optimization.The composite toughening modifier is by following parts by weight
Each component is prepared：
10~50 parts of waste-tyre rubber-powder；
Thermoplastic styrene butadiene rubber（SBS）10~50 parts；
20~50 parts of polyvinyl resin；
0.3~2 part of solubilizer.
The waste-tyre rubber-powder can be obtained through crushing by automobile-used waste tire, can also be obtained through regular market purchase.It is preferred that
The grain size of the waste-tyre rubber-powder is 100~200 mesh.Its dosage institute when being used to prepare composite toughening modifier of the present invention
It is more preferably 25~40 parts to account for parts by weight.
Wherein, the thermoplastic styrene butadiene rubber（SBS）Dosage shared by parts by weight be 30~45 parts.
Its styrene-content is 20~40% ranges.
Preferably, the polyvinyl resin selects ldpe resin（LLDPE）, it is one of principal item of PE.
The present invention uses the polyvinyl resin of rational proportion（LLDPE）, its structure is played in compatibility and there are higher melt flows
Index（MI）The characteristics of, generate the toughening effect of collaboration.It is modified it is further preferred that being used to prepare composite toughening of the present invention
When agent, the polyvinyl resin（LLDPE）Dosage shared by parts by weight be preferably 25~40 parts.
The present invention forms composite toughening by rubber powder of waste tire, SBS and LLDPE resins, with scientific and reasonable ratio and changes
Property agent, on the one hand utilize the coordination plasticizing that rubber powder of waste tire and POE are formed to act on, generate excellent toughening effect, simultaneously
The cost of this material system is also reduced, there is good cost performance；On the other hand, the addition of LLDPE resins can significantly improve
The compatibility of composite toughening modifier and waste HDPE matrix can improve HDPE modification regenerations also because it is with higher MI
The processing flowability of material.Further, the present invention makes said combination of the present invention by the use ratio of accurately determining solubilizer
More preferably technique effect is obtained, parts by weight shared by its dosage are further excellent when being used to prepare composite toughening modifier of the present invention
It is selected as 0.3~1 part.Specifically used solubilizer is the conventional use of solubilizer of the art.It is highly preferred that of the present invention
Solubilizer uses the mixture of one or more of K10H naphthenic oils, EPDM paraffin oil or the special white oil of elastomer.
The present invention also provides the preparation methods of the composite toughening modified waste polyethylene pipe PP Pipe Compound, are used in combination altogether
Micro- crosslinking technological is mixed, is included the following steps：
S1. by waste HDPE pellet drying and processing, 100~110 DEG C of drying temperature, 1~2 h of drying time；
S2. the waste HDPE after above-mentioned S1 steps being dried is modified through solubilizer, then changes inorganic filler and solubilizer
Property after waste HDPE be uniformly mixed；Composite toughening modifier, crosslinking agent, Masterbatch, antifoaming agent and antioxidant are added successively again
Enter, discharging after being sufficiently mixed uniformly；
Waste HDPE after can specifically above-mentioned S1 steps being dried is added in mixing machine, opens mixing machine, will be solubilized
Agent is sprayed onto waste HDPE surface, is uniformly mixed, then anhydrite powder is added in mixing machine, is uniformly mixed；Successively will again
Composite toughening modifier, crosslinking agent, Masterbatch, antifoaming agent and antioxidant are added in mixing machine, are stirred, and are sufficiently mixed
Discharging after even；
S3. the material melts in above-mentioned S2 steps are squeezed out, is granulated, after drying, prepares waste and old for the recycling of pipeline
Polyethylene toughening modifying regenerates PP Pipe Compound.
Wherein, crosslinking agent described in S2 steps is diluted using acetone solution, is added using the method for spraying and is ensured mixing dispersion
Uniformity.
Solubilizer usage amount described in S2 steps is the 5 ‰ of waste HDPE weight fraction.It is sprayed onto in the method for spraying
3~5 min are mixed behind waste HDPE surface, it is ensured that it is uniform in waste HDPE Dispersion on surface.Anhydrite powder is added to mixing
2~5 min are mixed after machine, it is made to be sufficiently mixed uniformly with waste HDPE；Again successively by composite toughening modifier, crosslinking agent, color
Master batch（Black agglomerate）, to be added to the time being stirred after mixing machine be 5~15min for antifoaming agent and antioxidant, be sufficiently mixed
Discharging after uniformly.
Melting extrusion described in S3 steps is that the material in above-mentioned S2 steps is added to double screw extruder melting extrusion；Institute
The barrel temperature control of melting extrusion is stated at 170~210 DEG C, screw speed is 80~250 r/min.
Present invention simultaneously provides the composite toughening modifier preferably preparation methods, the described method comprises the following steps：
S21. waste-tyre rubber-powder is modified through solubilizer；
Waste-tyre rubber-powder is specifically packed into mixing machine, mixing machine is opened, solubilizer is sprayed in mixing machine, is mixed
After uniformly, mixed material is poured out, it is spare after placement.
S22. SBS and polyvinyl resin are carried out respectively spare after drying and processing；
S23. by the polyvinyl resin after S22 step drying and processings through solubilizer modification；Then S21 is walked successively
Thermoplastic elastomer (TPE) after rapid modified waste-tyre rubber-powder, S22 step drying and processings is mixed with modified polyvinyl resin,
Discharging after all materials are sufficiently mixed uniformly, it is spare；
Specifically the polyvinyl resin after S22 step drying and processings is added in mixing machine, starts mixing machine, it will be solubilized
Agent（Solubilizer usage amount is the 5 ‰ of LLDPE weight fractions）Be sprayed onto polyvinyl resin surface in the method for spraying, solubilizer and
Polyvinyl resin is uniformly mixed；Then the SBS after the mixed material of S21 steps, S22 step drying and processings is added to successively mixed
In conjunction machine, discharging after all materials are sufficiently mixed uniformly is spare；
S24. the material obtained by above-mentioned S23 steps is added to melting extrusion in double screw extruder, be granulated, after drying i.e.
Obtain composite toughening modifier.
Preferably, it is placed as placement 3~5 days described in S21 steps.
Preferably, drying described in S22 uses dryer.The drying and processing of the SBS is done in 40~60 DEG C of drying temperature
1~2 h of dry time；The drying and processing of the polyvinyl resin is in 90~100 DEG C of drying temperature, 1~2 h of drying time.
Preferably, the time of solubilizer described in S23 steps and polyvinyl resin mixing is 3~5 min.
Preferably, all materials well-mixed time described in S23 steps is 5 min or so.
Preferably, melting extrusion described in S24 steps uses double screw extruder, the barrel temperature control of melting extrusion to exist
130~170 DEG C, screw speed is 40~200 r/min.
Preferably, according to total dosage of ratio-dependent solubilizer of the present invention, wherein leaving and taking a portion solubilizer in S23
Step is sprayed onto polyvinyl resin surface in the method sprayed, and surplus is used in S21 steps and is mixed with waste-tyre rubber-powder.Into
Preferably, S23 steps are sprayed onto the solubilizer on polyvinyl resin surface as polyvinyl resin weight point to one step in the method sprayed
Several 3~8 ‰, it is further preferred that being 5 ‰.
The waste-tyre rubber-powder that the present invention uses comes from tire for vehicles, is the crosslinked product of rubber part, and after being crosslinked
Rubber is generally difficult to dissolve, and therefore, by the method for swelling, its recovered part can be made elastic.The rubber powder of swelling simultaneously, in double spiral shells
Under the effect of bar extruder Strong shear, sulfide cross-linked bond is also partly interrupted, and then the elasticity of rubber powder is made further to be restored,
Vulcanized rubber powder activity can also be improved to a certain extent simultaneously.Especially under process conditions provided by the invention, vulcanized rubber powder
Activity is significantly improved, to play the role of improving the compatibility of itself and basis material.
The beneficial effects of the invention are as follows：
（1）The present invention uses waste-tyre rubber-powder for primary raw material, provides a kind of composite toughening modifier, wherein using
Rubber powder of waste tire, be by automobile-used waste tire through crush obtain, can routinely buy in the market, due to waste and old tyre rubber
Powder is cheap, reduces the production cost of material system, while it is also important one of black pollution source, the present invention utilizes
A kind of new toughener is prepared in it, can not only reduce the cost of material system, turn waste into wealth, transform mode of economic growth,
Be conducive to develop a circular economy, and can also play and economize on resources, the purpose preserved the ecological environment.
It is the crosslinked product of rubber part since these rubber powders come from tire for vehicles, and the rubber after being crosslinked is generally difficult to
Dissolving, therefore, the present invention provides a kind of methods preferably preparing the composite toughening modifier, particular by rationally molten
It is swollen, keep its recovered part elastic, the rubber powder after swelling, under double screw extruder Strong shear force effect, sulfide cross-linked bond also by
Part is interrupted, and therefore, the elasticity of rubber powder obtains further recovery or release, while its surface-active also being made to have to a certain degree
Raising, to play the role of improve itself and basis material interface binding power.
On this basis, the present invention constitutes primary raw material with LLDPE resins with, SBS using waste tire powder and combines, utilization
Coordination plasticizing effect between these main components, has reached the toughness for significantly improving waste HDPE, wherein LLDPE
Other than the effect for playing composite toughening, since it is with higher melt flow index, change in composite toughening of the present invention
Into in the various applications of agent, moreover it is possible to improve the effect of the processing performance of integral material system.In addition, due to itself and waste HDPE base
Body material structure is identical, therefore, composite toughening modifier and waste HDPE is made to have good compatibility, ensures the compound increasing of the present invention
Tough modifier obtains unexpected application effect.
（2）Invention further provides a typical case of composite toughening modifier, by composite toughening modifier with
The reasonable adapted of other materials obtains composite toughening modified waste polyethylene pipe PP Pipe Compound.It is micro- using free radical in the present invention
Crosslinking technological can to a certain extent more on the one hand by the raising of the degree of cross linking of each related component in composite system
The reduction for mending the composite system tensile strength caused by the addition of composite toughing agent, on the other hand can also control modified material
The gel content and mobility of material system, with filler（Anhydrite powder）Together, by controlling the size of waste HDPE crystal grain, being distributed
With crystallinity, achieve the purpose that optimize composite system mechanical property.
（3）Invention also provides the composite toughening modifier and the preparation methods of the PP Pipe Compound, do not change
Existing production equipment, simple and practicable, strong applicability is easy to industrialization promotion and production.
Description of the drawings
Fig. 1 composite toughing agent preparation technology flow charts.
Fig. 2 prepares the implementing process flow chart of multiple elements design toughening modifying waste HDPE PP Pipe Compound.
Specific implementation mode
The invention will be further described in the following with reference to the drawings and specific embodiments, but embodiments of the present invention are only used for
Exemplary illustration is not considered as limiting the invention.Unless stated otherwise, the reagent raw material used in following embodiments is
The reagent or raw material that purchased in market or commercial sources obtain, unless stated otherwise, the method and apparatus used in following embodiments are this
The conventional use of method and apparatus in field.For convenience of description, thermoplastic styrene butadiene rubber used in the embodiment of the present invention（SBS）It is flat
Average molecular weight ranging from 7~120,000, styrene-content is in 20~40% ranges, regular market purchase.
1 composite toughening modifier of embodiment
Composite toughening modifier is prepared with the mixing of each group lease making and melting extrusion of following parts by weight in the present invention：
15 parts of waste-tyre rubber-powder；
Thermoplastic styrene butadiene rubber（SBS）45 parts；
40 parts of polyvinyl resin；
1 part of solubilizer.
The waste-tyre rubber-powder is to be obtained by automobile-used waste tire through crushing, can be obtained through regular market purchase.It is described useless
The grain size of old tire rubber powder is 100~200 mesh.The thermoplastic elastomer (TPE) selects SBS, the polyvinyl resin to select low-density
Polyethylene（LLDPE）Resin, the solubilizer use K10H naphthenic oils（EPDM paraffin oil or elastomer can also be used special
Use white oil）.
The composite toughening modifier preparation method is as follows：
S21. waste-tyre rubber-powder is packed into mixing machine, opens mixing machine, solubilizer is sprayed in mixing machine, mixing is equal
After even, mixed material is poured out, it is spare after placing 3~5 days.
S22. by thermoplastic styrene butadiene rubber（SBS）It is carried out respectively with polyvinyl resin spare after drying and processing；The drying
Using dryer.The drying and processing of the thermoplastic elastomer (TPE) is in 40~60 DEG C of drying temperature, 1~2 h of drying time；It is described
The drying and processing of polyvinyl resin is in 90~100 DEG C of drying temperature, 1~2h of drying time；
S23. the polyvinyl resin after S22 step drying and processings is added in mixing machine, starts mixing machine, by solubilizer
（Solubilizer usage amount is the 3 ‰ of LLDPE weight fractions）It is sprayed onto polyvinyl resin surface in the method for spraying, solubilizer and poly-
Vinyl, which mixes 3~5 min, to be made to be uniformly mixed；It then successively will be after the mixed material of S21 steps, S22 step drying and processings
Thermoplastic styrene butadiene rubber（SBS）It is added in mixing machine, all materials, which are sufficiently mixed 5min or so, to be made to discharge after mixing,
It is spare；
S24. the material obtained by above-mentioned S23 steps is added to melting extrusion in double screw extruder, be granulated, after drying i.e.
Obtain composite toughening modifier.The technological parameter of double screw extruder is：Host frequency is 90 r/min, and feeding frequency is 50 r/
Min, extruder temperature of each section are respectively 165 DEG C of 1 area's temperature, 165 DEG C of 2 area's temperature, 170 DEG C of 3 area's temperature, 175 DEG C of 4 area's temperature, 5
175 DEG C of area's temperature, 172 DEG C of 6 area's temperature, 170 DEG C of 7 area's temperature, head temperature are 180 DEG C.
The tensile strength for the composite toughening modifier that the present embodiment is prepared is 13.7MPa, and elongation at break is
423.8%, melt flow rate (MFR) 1.86g/10min.
Embodiment 2
Composite toughening modifier is prepared with the mixing of each group lease making and melting extrusion of following parts by weight in the present invention：
20 parts of waste-tyre rubber-powder；
Thermoplastic styrene butadiene rubber（SBS）40 parts；
40 parts of polyvinyl resin；
1 part of solubilizer.
The waste-tyre rubber-powder is to be obtained by automobile-used waste tire through crushing, can be obtained through regular market purchase.It is described useless
The grain size of old tire rubber powder is 100~200 mesh.The thermoplastic elastomer (TPE) selects SBS, the polyvinyl resin to select low-density
Polyethylene（LLDPE）Resin, the solubilizer use EPDM paraffin oil（K10H naphthenic oils or elastomer can also be used special
Use white oil）.
The composite toughening modifier preparation method is as follows：
S21. waste-tyre rubber-powder is packed into mixing machine, opens mixing machine, solubilizer is sprayed in mixing machine, mixing is equal
After even, mixed material is poured out, it is spare after placing 3~5 days.
S22. by thermoplastic styrene butadiene rubber（SBS）It is carried out respectively with polyvinyl resin spare after drying and processing；The drying
Using dryer.The drying and processing of the thermoplastic elastomer (TPE) is in 40~60 DEG C of drying temperature, 1~2 h of drying time；It is described
The drying and processing of polyvinyl resin is in 90~100 DEG C of drying temperature, 1~2h of drying time；
S23. the polyvinyl resin after S22 step drying and processings is added in mixing machine, starts mixing machine, by solubilizer
（Solubilizer usage amount is the 3 ‰ of LLDPE weight fractions）It is sprayed onto polyvinyl resin surface in the method for spraying, solubilizer and poly-
Vinyl, which mixes 3~5 min, to be made to be uniformly mixed；It then successively will be after the mixed material of S21 steps, S22 step drying and processings
Thermoplastic styrene butadiene rubber（SBS）It is added in mixing machine, all materials, which are sufficiently mixed 5min or so, to be made to discharge after mixing,
It is spare；
S24. the material obtained by above-mentioned S23 steps is added to melting extrusion in double screw extruder, be granulated, after drying i.e.
Obtain composite toughening modifier.The technological parameter of double screw extruder is：Host frequency is 90 r/min, and feeding frequency is 50 r/
Min, extruder temperature of each section are respectively 165 DEG C of 1 area's temperature, 165 DEG C of 2 area's temperature, 170 DEG C of 3 area's temperature, 175 DEG C of 4 area's temperature, 5
175 DEG C of area's temperature, 172 DEG C of 6 area's temperature, 170 DEG C of 7 area's temperature, head temperature are 175 DEG C.
The tensile strength for the composite toughening modifier that the present embodiment is prepared is 13.4MPa, and elongation at break is
417.8%, melt flow rate (MFR) 1.97g/10min.
Embodiment 3
Composite toughening modifier is prepared with the mixing of each group lease making and melting extrusion of following parts by weight in the present invention：
30 parts of waste-tyre rubber-powder；
Thermoplastic styrene butadiene rubber（SBS）30 parts of body；
40 parts of polyvinyl resin；
1.5 parts of solubilizer.
The waste-tyre rubber-powder is to be obtained by automobile-used waste tire through crushing, can be obtained through regular market purchase.It is described useless
The grain size of old tire rubber powder is 100~200 mesh.The polyvinyl resin selects low density polyethylene (LDPE)（LLDPE）Resin, the increasing
Solvent uses the special white oil of elastomer（K10H naphthenic oils or EPDM paraffin oil can also be used）.
The composite toughening modifier preparation method is as follows：
S21. waste-tyre rubber-powder is packed into mixing machine, opens mixing machine, solubilizer is sprayed in mixing machine, mixing is equal
After even, mixed material is poured out, it is spare after placing 3~5 days.
S22. by thermoplastic styrene butadiene rubber（SBS）It is carried out respectively with polyvinyl resin spare after drying and processing；The drying
Using dryer.The drying and processing of the thermoplastic elastomer (TPE) is in 40~60 DEG C of drying temperature, 1~2 h of drying time；It is described
The drying and processing of polyvinyl resin is in 90~100 DEG C of drying temperature, 1~2h of drying time；
S23. the polyvinyl resin after S22 step drying and processings is added in mixing machine, starts mixing machine, by solubilizer
（Solubilizer usage amount is the 3 ‰ of LLDPE weight fractions）It is sprayed onto polyvinyl resin surface in the method for spraying, solubilizer and poly-
Vinyl, which mixes 3~5 min, to be made to be uniformly mixed；It then successively will be after the mixed material of S21 steps, S22 step drying and processings
Thermoplastic styrene butadiene rubber（SBS）It is added in mixing machine, all materials, which are sufficiently mixed 5min or so, to be made to discharge after mixing,
It is spare；
S24. the material obtained by above-mentioned S23 steps is added to melting extrusion in double screw extruder, be granulated, after drying i.e.
Obtain composite toughening modifier.The technological parameter of double screw extruder is：Host frequency is 95 r/min, and feeding frequency is 50 r/
Min, extruder temperature of each section are respectively 165 DEG C of 1 area's temperature, 165 DEG C of 2 area's temperature, 170 DEG C of 3 area's temperature, 175 DEG C of 4 area's temperature, 5
175 DEG C of area's temperature, 172 DEG C of 6 area's temperature, 170 DEG C of 7 area's temperature, head temperature are 175 DEG C.
The tensile strength for the composite toughening modifier that the present embodiment is prepared is 14.3MPa, and elongation at break is
400.6%, melt flow rate (MFR) 1.74g/10min.
Embodiment 4
Composite toughening modifier is prepared with each component of following parts by weight in the present invention：
40 parts of waste-tyre rubber-powder；
Thermoplastic styrene butadiene rubber（SBS）30 parts；
30 parts of polyvinyl resin；
0.8 part of solubilizer.
The waste-tyre rubber-powder is to be obtained by automobile-used waste tire through crushing, can be obtained through regular market purchase.It is described useless
The grain size of old tire rubber powder is 100~200 mesh.The polyvinyl resin selects low density polyethylene (LDPE)（LLDPE）Resin, the increasing
Solvent uses EPDM paraffin oil（K10H naphthenic oils or the special white oil of elastomer can also be used）.
The composite toughening modifier preparation method is as follows：
S21. waste-tyre rubber-powder is packed into mixing machine, opens mixing machine, solubilizer is sprayed in mixing machine, mixing is equal
After even, mixed material is poured out, it is spare after placing 3~5 days.
S22. by thermoplastic styrene butadiene rubber（SBS）It is carried out respectively with polyvinyl resin spare after drying and processing；The drying
Using dryer.The drying and processing of the thermoplastic elastomer (TPE) is in 40~60 DEG C of drying temperature, 1~2 h of drying time；It is described
The drying and processing of polyvinyl resin is in 90~100 DEG C of drying temperature, 1~2h of drying time；
S23. the polyvinyl resin after S22 step drying and processings is added in mixing machine, starts mixing machine, by solubilizer
（Solubilizer usage amount is the 3 ‰ of LLDPE weight fractions）It is sprayed onto polyvinyl resin surface in the method for spraying, solubilizer and poly-
Vinyl, which mixes 3~5 min, to be made to be uniformly mixed；It then successively will be after the mixed material of S21 steps, S22 step drying and processings
Thermoplastic styrene butadiene rubber（SBS）It is added in mixing machine, all materials, which are sufficiently mixed 5min or so, to be made to discharge after mixing,
It is spare；
S24. the material obtained by above-mentioned S23 steps is added to melting extrusion in double screw extruder, be granulated, after drying i.e.
Obtain composite toughening modifier.The technological parameter of double screw extruder is：Host frequency is 85 r/min, and feeding frequency is 40 r/
Min, extruder temperature of each section are respectively 162 DEG C of 1 area's temperature, 168 DEG C of 2 area's temperature, 168 DEG C of 3 area's temperature, 173 DEG C of 4 area's temperature, 5
173 DEG C of area's temperature, 168 DEG C of 6 area's temperature, 165 DEG C of 7 area's temperature, head temperature are 170 DEG C.
The tensile strength for the composite toughening modifier that the present embodiment is prepared is 12.7MPa, and elongation at break is
381.5%, melt flow rate (MFR) 1.63/10min.
Embodiment 5
Composite toughening modifier is prepared with each component of following parts by weight in the present invention：
45 parts of waste-tyre rubber-powder；
Thermoplastic styrene butadiene rubber（SBS）25 parts；
30 parts of polyvinyl resin；
1 part of solubilizer.
The waste-tyre rubber-powder is to be obtained by automobile-used waste tire through crushing, can be obtained through regular market purchase.It is described useless
The grain size of old tire rubber powder is 100~200 mesh.The polyvinyl resin selects low density polyethylene (LDPE)（LLDPE）Resin, the increasing
Solvent uses K10H naphthenic oils（EPDM paraffin oil or the special white oil of elastomer can also be used）.
The present invention forms composite toughening by rubber powder of waste tire, SBS and LLDPE resins, with scientific and reasonable ratio and changes
Property agent, on the one hand utilize the coordination plasticizing that rubber powder of waste tire and SBS are formed to act on, generate excellent toughening effect, simultaneously
The cost of this material system is also reduced, there is good cost performance；On the other hand, the addition of LLDPE resins can significantly improve
The compatibility of composite toughening modifier and waste HDPE matrix can improve HDPE modification regenerations also because it is with higher MI
The processing flowability of material.
The composite toughening modifier preparation method process flow diagram is as shown in Fig. 1（The same technique of embodiment 2 to 4
The same the present embodiment of flow diagram）, the specific method is as follows：
S21. waste-tyre rubber-powder is packed into mixing machine, opens mixing machine, solubilizer is sprayed in mixing machine, mixing is equal
After even, mixed material is poured out, it is spare after placing 3~5 days.
S22. by thermoplastic styrene butadiene rubber（SBS）It is carried out respectively with polyvinyl resin spare after drying and processing；The drying
Using dryer.The thermoplastic styrene butadiene rubber（SBS）Drying and processing be in 40~60 DEG C of drying temperature, drying time 1~2
h；The drying and processing of the polyvinyl resin is in 90~100 DEG C of drying temperature, 1~2h of drying time；
S23. the polyvinyl resin after S22 step drying and processings is added in mixing machine, starts mixing machine, by solubilizer
（Solubilizer usage amount is the 5 ‰ of LLDPE weight fractions）It is sprayed onto polyvinyl resin surface in the method for spraying, solubilizer and poly-
Vinyl, which mixes 3~5 min, to be made to be uniformly mixed；It then successively will be after the mixed material of S21 steps, S22 step drying and processings
Thermoplastic styrene butadiene rubber（SBS）It is added in mixing machine, all materials, which are sufficiently mixed 5min or so, to be made to discharge after mixing,
It is spare；
S24. the material obtained by above-mentioned S23 steps is added to melting extrusion in double screw extruder, be granulated, after drying i.e.
Obtain composite toughening modifier.The technological parameter of double screw extruder is：Host frequency is 80 r/min, and feeding frequency is 40 r/
The temperature of min, each warm area of extruder are followed successively by 160 DEG C, 165 DEG C, 165 DEG C, 170 DEG C, 170 DEG C, 165 DEG C, 160 DEG C, head temperature
Degree is 170 DEG C.
The tensile strength for the composite toughening modifier that the present embodiment is prepared is 10.8MPa, and elongation at break is
315.7%, melt flow rate (MFR) 1.41g/10min.
Embodiment 6
The present embodiment using composite toughening modifier obtained by any embodiment in the embodiment of the present invention 1 to 5 as one of raw material, with
Other raw material reasonable compatibilities, are prepared a kind of composite toughening modified waste HDPE special material for pipeline, the special material for pipeline by
The mixing of group lease making and melting extrusion of following parts by weight are made：
100 parts of waste and old recycle polyethylene；
5 parts of composite toughening modifier；
3 parts of inorganic particle filler；
0.02 part of crosslinking agent；
0.05 part of antioxidant；
2 parts of Masterbatch；
0.3 part of antifoaming agent.
The waste and old recycle polyethylene（HDPE）It is the HDPE regrinding-materials and its product by recycling, through clear using pellet
It washes, be crushed, dry, be granulated, can be obtained through regular market purchase.Following embodiments are same.
Inorganic filler described in the present embodiment selects anhydrite powder, under the conditions of reasonable compatibility of the present invention, give full play to anhydrite
The texture structure in powder submicroscopic structure with threadiness can play preferable in composite system of the present invention
Enhancing or strengthening action；Simultaneously, moreover it is possible to the effect for functioning well as heterogeneous nucleation agent, by the size for controlling waste HDPE crystal grain
With crystallinity, achieve the purpose that the mechanical property for optimizing material system；In addition, its addition, not only reduce material system at
This, can also solve the problems, such as the bad technical bottleneck of product dimensional stability caused by contraction.The particle of the anhydrite powder
It is preferably sized to 800~2000 mesh.
The crosslinking agent selects cumyl peroxide（DCP）, the present invention using its decomposition in SBS, LLDPE resin and
Waste HDPE surface energy generates free radicals, and forms micro- crosslinking between realization three, and then achieve the purpose that reinforcement, thus also improves
The compatibility of each component.Furthermore it is possible to control the gel content and mobility of modified materials.
It was four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] seasons penta that the antioxidant, which selects Hinered phenols antioxidant,
Four alcohol esters, trade name antioxidant 1010.In the present invention, antioxidant is mainly used for slowing down composite material in process old
Change phenomenon, improves the stability of material.
The selection of the Masterbatch and antifoaming agent is conventional with reference to this field.Preferably, the present embodiment Masterbatch selects black
Masterbatch pellet；The preferred organic silicon defoamer of antifoaming agent.
The preparation method of the composite toughening modified waste polyethylene pipe PP Pipe Compound is as follows：
S1. waste HDPE pellet is put into dryer and is dried, 100~110 DEG C of drying temperature, 1~2 h of drying time.
S2. the waste HDPE after above-mentioned S1 steps being dried is added in mixing machine, opens mixing machine, solubilizer is sprayed
To waste HDPE surface, anhydrite powder is then added in mixing machine by mixing, is uniformly mixed；Composite toughening is changed successively again
Property agent, crosslinking agent, Masterbatch（Black agglomerate）, antifoaming agent and antioxidant be added in mixing machine, be stirred, be sufficiently mixed
Discharging after even；
S3. the material melts in above-mentioned S2 steps are squeezed out, is granulated, after drying, prepares waste and old for the recycling of pipeline
Polyethylene toughening modifying regenerates PP Pipe Compound.Wherein, the technological parameter of double screw extruder is：Host frequency is 80 r/min, is fed
Material frequency is 40 r/min, the temperature of each warm area of extruder be followed successively by 170 DEG C, 170 DEG C, 180 DEG C, 185 DEG C, 185 DEG C, 190 DEG C,
190 DEG C, head temperature is 200 DEG C.
Crosslinking agent described in S2 steps is diluted using acetone solution, is added using the method for spraying and is ensured the uniform of mixing dispersion
Property.
Solubilizer usage amount described in S2 steps is the 3 ‰ of waste HDPE weight fraction.It is sprayed onto in the method for spraying
3~5 min are mixed behind waste HDPE surface, it is ensured that it is uniform in waste HDPE Dispersion on surface.Anhydrite powder is added to mixing
2~5 min are mixed after machine, it is made to be sufficiently mixed uniformly with waste HDPE；Again successively by composite toughening modifier, crosslinking agent, color
Master batch（Black agglomerate）, to be added to the time being stirred after mixing machine be 5~15min for antifoaming agent and antioxidant, be sufficiently mixed
Discharging after uniformly.
Embodiment 7
The present embodiment using composite toughening modifier obtained by any embodiment in the embodiment of the present invention 1 to 5 as one of raw material, with
Other raw material reasonable compatibilities, are prepared a kind of composite toughening modified waste HDPE special material for pipeline, the special material for pipeline by
The mixing of group lease making and melting extrusion of following parts by weight are made：
100 parts of waste and old recycle polyethylene；
10 parts of composite toughening modifier；
4 parts of inorganic particle filler；
0.02 part of crosslinking agent；
0.05 part of antioxidant；
2 parts of black agglomerate；
0.3 part of antifoaming agent.
The waste and old recycle polyethylene（HDPE）It is the HDPE regrinding-materials and its product by recycling, through clear using pellet
It washes, be crushed, dry, be granulated, can be obtained through regular market purchase.Anhydrite powder, institute are selected in inorganic filler described in the present embodiment
The granular size for stating anhydrite powder is preferably 800~2000 mesh.The crosslinking agent selects benzoyl peroxide（BPO）, utilize it
Decomposition is generated free radicals in SBS, LLDPE resin and waste HDPE surface energy, and micro- crosslinking, Jin Erda are formed between realization three
To the purpose of reinforcement, the compatibility of each component is thus further improved.Furthermore it is possible to control gel content and the flowing of modified materials
Property.The selection of the Masterbatch and antifoaming agent is conventional with reference to this field.Preferably, the present embodiment Masterbatch selects the color masterbatch of black
Grain pellet；The preferred organic silicon defoamer of antifoaming agent.
The preparation process flow schematic diagram of the composite toughening modified waste polyethylene pipe PP Pipe Compound is as shown in Fig. 2,
The specific method is as follows：
S1. waste HDPE pellet is put into dryer and is dried, 100~110 DEG C of drying temperature, 1~2 h of drying time.
S2. the waste HDPE after above-mentioned S1 steps being dried is added in mixing machine, opens mixing machine, solubilizer is sprayed
To waste HDPE surface, anhydrite powder is then added in mixing machine by mixing, is uniformly mixed；Composite toughening is changed successively again
Property agent, crosslinking agent, Masterbatch（Black agglomerate）, antifoaming agent and antioxidant be added in mixing machine, be stirred, be sufficiently mixed
Discharging after even；
S3. the material melts in above-mentioned S2 steps are squeezed out, is granulated, after drying, prepares waste and old for the recycling of pipeline
Polyethylene toughening modifying regenerates PP Pipe Compound.Wherein, the technological parameter of double screw extruder is：Host frequency is 80 r/min, is fed
Material frequency is 40 r/min, and extruder temperature of each section is respectively 180 DEG C of 1 area's temperature, 185 DEG C of 2 area's temperature, 188 DEG C of 3 area's temperature, 4
188 DEG C of area's temperature, 195 DEG C of 5 area's temperature, 195 DEG C of 6 area's temperature, 190 DEG C of 7 area's temperature, head temperature are 200 DEG C.
Crosslinking agent described in S2 steps is diluted using acetone solution, is added using the method for spraying and is ensured the uniform of mixing dispersion
Property.
Solubilizer usage amount described in S2 steps is the 3 ‰ of waste HDPE weight fraction.It is sprayed onto in the method for spraying
3~5 min are mixed behind waste HDPE surface, it is ensured that it is uniform in waste HDPE Dispersion on surface.Anhydrite powder is added to mixing
2~5 min are mixed after machine, it is made to be sufficiently mixed uniformly with waste HDPE；Again successively by composite toughening modifier, crosslinking agent, color
Master batch（Black agglomerate）, to be added to the time being stirred after mixing machine be 5~15min for antifoaming agent and antioxidant, be sufficiently mixed
Discharging after uniformly.
Embodiment 8
The present embodiment using composite toughening modifier obtained by any embodiment in the embodiment of the present invention 1 to 5 as one of raw material, with
Other raw material reasonable compatibilities, are prepared a kind of composite toughening modified waste HDPE special material for pipeline, the special material for pipeline by
The mixing of group lease making and melting extrusion of following parts by weight are made：
100 parts of waste and old recycle polyethylene；
20 parts of composite toughening modifier；
4 parts of inorganic particle filler；
0.03 part of crosslinking agent；
0.05 part of antioxidant；
2 parts of black agglomerate；
0.3 part of antifoaming agent.
The waste and old recycle polyethylene（HDPE）It is the HDPE regrinding-materials and its product by recycling, through clear using pellet
It washes, be crushed, dry, be granulated, can be obtained through regular market purchase.Anhydrite powder, institute are selected in inorganic filler described in the present embodiment
The granular size for stating anhydrite powder is preferably 800~2000 mesh..The crosslinking agent selects cumyl peroxide（DCP）And mistake
Benzoyl Oxide（BPO）Mixture, mixed proportion do not do considered critical.Using crosslinking agent decompose SBS, LLDPE resin with
And waste HDPE surface energy generates free radicals, and forms micro- crosslinking between realization three, and then achieve the purpose that reinforcement, thus also changes
It has been apt to the compatibility of each component.Furthermore it is possible to control the gel content and mobility of modified materials.The Masterbatch and antifoaming agent
It selects conventional with reference to this field.Preferably, the present embodiment Masterbatch selects the Masterbatch pellet of black；The antifoaming agent preferably has
Machine silicon defoaming agent.
The preparation method of the composite toughening modified waste polyethylene pipe PP Pipe Compound is as follows：
S1. waste HDPE pellet is put into dryer and is dried, 100~110 DEG C of drying temperature, 1~2 h of drying time.
S2. the waste HDPE after above-mentioned S1 steps being dried is added in mixing machine, opens mixing machine, solubilizer is sprayed
To waste HDPE surface, anhydrite powder is then added in mixing machine by mixing, is uniformly mixed；Composite toughening is changed successively again
Property agent, crosslinking agent, Masterbatch（Black agglomerate）, antifoaming agent and antioxidant be added in mixing machine, be stirred, be sufficiently mixed
Discharging after even；
S3. the material melts in above-mentioned S2 steps are squeezed out, is granulated, after drying, prepares waste and old for the recycling of pipeline
Polyethylene toughening modifying regenerates PP Pipe Compound.Wherein, the technological parameter of double screw extruder is：Host frequency is 95 r/min, is fed
Material frequency is 55 r/min, and extruder temperature of each section is respectively 185 DEG C of 1 area's temperature, 188 DEG C of 2 area's temperature, 190 DEG C of 3 area's temperature, 4
195 DEG C of area's temperature, 195 DEG C of 5 area's temperature, 190 DEG C of 6 area's temperature, 190 DEG C of 7 area's temperature, head temperature are 200 DEG C.
Crosslinking agent described in S2 steps is diluted using acetone solution, is added using the method for spraying and is ensured the uniform of mixing dispersion
Property.
Solubilizer usage amount described in S2 steps is the 3 ‰ of waste HDPE weight fraction.It is sprayed onto in the method for spraying
3~5 min are mixed behind waste HDPE surface, it is ensured that it is uniform in waste HDPE Dispersion on surface.Anhydrite powder is added to mixing
2~5 min are mixed after machine, it is made to be sufficiently mixed uniformly with waste HDPE；Again successively by composite toughening modifier, crosslinking agent, color
Master batch（Black agglomerate）, to be added to the time being stirred after mixing machine be 5~15min for antifoaming agent and antioxidant, be sufficiently mixed
Discharging after uniformly.
Embodiment 9
The present embodiment using composite toughening modifier obtained by any embodiment in the embodiment of the present invention 1 to 5 as one of raw material, with
Other raw material reasonable compatibilities（The selection of other raw materials is with reference to embodiment 8）, a kind of composite toughening modified waste HDPE is prepared
Special material for pipeline, the special material for pipeline are made by the mixing of group lease making and melting extrusion of following parts by weight：
100 parts of waste and old recycle polyethylene；
30 parts of composite toughening modifier；
5 parts of inorganic particle filler；
0.04 part of crosslinking agent；
0.05 part of antioxidant；
2 parts of black agglomerate；
0.3 part of antifoaming agent；
The preparation method of the composite toughening modified waste polyethylene pipe PP Pipe Compound is as follows：
S1. waste HDPE pellet is put into dryer and is dried, 100~110 DEG C of drying temperature, 1~2 h of drying time.
S2. the waste HDPE after above-mentioned S1 steps being dried is added in mixing machine, opens mixing machine, solubilizer is sprayed
To waste HDPE surface, anhydrite powder is then added in mixing machine by mixing, is uniformly mixed；Composite toughening is changed successively again
Property agent, crosslinking agent, Masterbatch（Black agglomerate）, antifoaming agent and antioxidant be added in mixing machine, be stirred, be sufficiently mixed
Discharging after even；
S3. the material melts in above-mentioned S2 steps are squeezed out, is granulated, after drying, prepares waste and old for the recycling of pipeline
Polyethylene toughening modifying regenerates PP Pipe Compound.Wherein, the technological parameter of double screw extruder is：Host frequency is 100 r/min, is fed
Material frequency is 50 r/min, and extruder temperature of each section is respectively 188 DEG C of 1 area's temperature, 188 DEG C of 2 area's temperature, 195 DEG C of 3 area's temperature, 4
195 DEG C of area's temperature, 200 DEG C of 5 area's temperature, 195 DEG C of 6 area's temperature, 190 DEG C of 7 area's temperature, head temperature are 200 DEG C.
Crosslinking agent described in S2 steps is diluted using acetone solution, is added using the method for spraying and is ensured the uniform of mixing dispersion
Property.
Solubilizer usage amount described in S2 steps is the 3 ‰ of waste HDPE weight fraction.It is sprayed onto in the method for spraying
3~5 min are mixed behind waste HDPE surface, it is ensured that it is uniform in waste HDPE Dispersion on surface.Anhydrite powder is added to mixing
2~5 min are mixed after machine, it is made to be sufficiently mixed uniformly with waste HDPE；Again successively by composite toughening modifier, crosslinking agent, color
Master batch（Black agglomerate）, to be added to the time being stirred after mixing machine be 5~15min for antifoaming agent and antioxidant, be sufficiently mixed
Discharging after uniformly.
It is special for the waste polyethylene plasticized modifier of pipeline and regeneration that Tables 1 and 2 each provides the present invention
The performance test results of materials.
The performance test results of 1 composite toughening modifier of table
| Performance | Test method | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Tensile strength（MPa） | GB/T1040.5-2008 | 13.7 | 13.4 | 14.3 | 12.7 | 10.8 |
| Elongation at break（%） | GB/T1040.5-2008 | 423.8 | 417.8 | 400.6 | 381.5 | 315.7 |
| Melt index（g/10min） | GB/T3682-2000 | 1.86 | 1.97 | 1.74 | 1.63 | 1.41 |
Performance test results of the table 2 for the waste polyethylene toughening modifying regeneration PP Pipe Compound of pipeline
| Performance | Test method | Waste HDPE | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Impact strength（Notch）（KJ/m2） | GB/T 1043-2000 | 38.5 | 58.3 | 64.6 | 69.4 | 73.8 |
| Elongation at break（%） | GB/T1040.5-2008 | 89.4 | 157.8 | 178.7 | 190.1 | 195.5 |
| Tensile strength（MPa） | GB/T1040.5-2008 | 28.6 | 28.0 | 27.8 | 27.1 | 27.5 |
| Bending strength（MPa） | GB/T9341-2008 | 23.5 | 23.2 | 22.7 | 22.3 | 21.6 |
By table 1 as it can be seen that the present invention uses waste-tyre rubber-powder for primary raw material, a kind of composite toughening modifier is obtained,
Reduce the cost of material system, it is often more important that, it is applied to and prepares composite toughening modified waste polyethylene pipe PP Pipe Compound,
Achieve the purpose that optimize composite system mechanical property.
Claims (10)
1. a kind of composite toughening modified waste HDPE special material for pipeline, which is characterized in that be made by the component of following parts by weight：
100 parts of waste and old recycle polyethylene；
3~30 parts of composite toughening modifier；
3~5 parts of inorganic filler；
0.02~0.2 part of crosslinking agent；
0.05~0.1 part of antioxidant；
1~7 part of Masterbatch；
0.1~0.5 part of antifoaming agent；
Wherein, the composite toughening modifier is prepared by each component of following parts by weight：
10~50 parts of waste-tyre rubber-powder；
10~50 parts of thermoplastic styrene butadiene rubber；
20~50 parts of polyvinyl resin；
0.3~2 part of solubilizer.
2. composite toughening modified waste HDPE special material for pipeline according to claim 1, which is characterized in that the inorganic filler
For anhydrite powder；The crosslinking agent is cumyl peroxide or benzoyl peroxide；The antioxidant selects Hinered phenols anti-
Oxygen agent is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters；The Masterbatch is the Masterbatch of black
Pellet；The antifoaming agent is organic silicon defoamer.
3. composite toughening modified waste HDPE special material for pipeline according to claim 1, which is characterized in that the anhydrite powder
Granular size be 800~2000 mesh.
4. composite toughening modified waste HDPE special material for pipeline according to claim 1, which is characterized in that the waste tire
The grain size of rubber powder is 100~200 mesh.
5. composite toughening modified waste HDPE special material for pipeline according to claim 1, which is characterized in that the polyethylene tree
Fat is ldpe resin.
6. composite toughening modified waste HDPE special material for pipeline according to claim 1, which is characterized in that the solubilizer is
The mixture of one or more of naphthenic oil, ethylene propylene diene rubber paraffin oil or the special white oil of elastomer of model K10H.
7. the preparation method of any one of claim 1 to the 6 composite toughening modified waste HDPE special material for pipeline, feature exist
In including the following steps：
S1. by waste HDPE pellet drying and processing, 100~110 DEG C of drying temperature, 1~2h of drying time；
S2. the waste HDPE after above-mentioned S1 steps being dried is modified through solubilizer, then that inorganic filler is modified with solubilizer
Waste HDPE be uniformly mixed；Composite toughening modifier, crosslinking agent, Masterbatch, antifoaming agent and antioxidant are added successively again, filled
Divide and discharges after mixing；
S3. the material melts in above-mentioned S2 steps are squeezed out, is granulated, after drying, prepares for the waste and old poly- second of the recycling of pipeline
Alkene toughening modifying regenerates PP Pipe Compound.
8. the preparation method of composite toughening modified waste HDPE special material for pipeline according to claim 7, which is characterized in that S2
Crosslinking agent described in step is diluted using acetone solution, is added using the method for spraying；Solubilizer usage amount described in S2 steps is
The 3 of waste HDPE weight fraction~5 ‰ mix 3~5min after being sprayed onto waste HDPE surface in the method for spraying；It is described to incite somebody to action
Inorganic filler mixes 2~5min after being added to mixing machine.
9. the preparation method of composite toughening modified waste HDPE special material for pipeline according to claim 7, which is characterized in that S2
The preparation method of composite toughening modifier described in step includes the following steps：
S21. waste-tyre rubber-powder is modified through solubilizer；
S22. thermoplastic styrene butadiene rubber and polyvinyl resin are carried out respectively spare after drying and processing；
S23. by the polyvinyl resin after S22 step drying and processings through solubilizer modification；Then successively by S21 steps through changing
Property waste-tyre rubber-powder, the thermoplastic styrene butadiene rubber after S22 step drying and processings mixed with modified polyvinyl resin, own
Discharging after material is sufficiently mixed uniformly, it is spare；
S24. the material melts obtained by above-mentioned S23 steps are squeezed out, is granulated, up to composite toughening modifier after drying.
10. the preparation method of composite toughening modified waste HDPE special material for pipeline according to claim 7, which is characterized in that
At 170~210 DEG C, screw speed is 80~250r/min for the barrel temperature control of melting extrusion described in S3 steps.
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| WO2018094527A1 (en) * | 2016-11-24 | 2018-05-31 | Multy Home Limited Partnership | Process for making shaped articles |
| CN107057147B (en) * | 2017-06-07 | 2018-03-02 | 深圳市深士达实业有限公司 | Utilize the method for waste old processing thermoplastic elastomeric material |
| CN108676223A (en) * | 2018-04-19 | 2018-10-19 | 安徽华远节水灌溉器材有限公司 | A kind of talc modified waste polyethylene |
| CN112920494A (en) * | 2021-02-05 | 2021-06-08 | 保定风帆美新蓄电池隔板制造有限公司 | Method for preparing regenerated substance by using waste PE (polyethylene) partition plate of lead-acid storage battery |
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