CN110408127A - A kind of fiber reinforcement polypropylene random copolymer composite tube and preparation method thereof - Google Patents
A kind of fiber reinforcement polypropylene random copolymer composite tube and preparation method thereof Download PDFInfo
- Publication number
- CN110408127A CN110408127A CN201810398002.9A CN201810398002A CN110408127A CN 110408127 A CN110408127 A CN 110408127A CN 201810398002 A CN201810398002 A CN 201810398002A CN 110408127 A CN110408127 A CN 110408127A
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- Prior art keywords
- layer
- bagasse
- whisker
- polypropylene
- random copolymer
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/14—Compound tubes, i.e. made of materials not wholly covered by any one of the preceding groups
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- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
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- C08J2401/02—Cellulose; Modified cellulose
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Abstract
The present invention relates to a kind of fiber reinforcement polypropylene random copolymer composite tubes and preparation method thereof, which is characterized in that it includes outer layer, middle layer is arranged in middle layer and internal layer between outer layer and internal layer；Polyphenylene sulfide fibre enhancement layer is set between outer layer and middle layer, basalt fibre resistance to compression layer is set between middle layer and internal layer.The fiber-reinforced layer resin of the application uses toughening atactic copolymerized polypropene, improves the low-temperature impact performance of tubing；The application can be used for hot water pipe, building main riser and other industrial pipes.
Description
[technical field]
The present invention relates to tubing technical fields, specifically, be a kind of fiber reinforcement polypropylene random copolymer composite tube and
Preparation method.
[background technique]
Atactic copolymerized polypropene (PP-R) pipeline is because it has health, environmental protection, hot-melt adhesive paste reliable etc. a series of good
Application characteristic received by market, be current China one of dosage maximum kind in building water supply tube material, and it is deep by
Domestic user's favor.But PP-R pipeline, since its linear expansion coefficient is larger, it is easy to be used for pipeline when hot-water heating system in engineer application
Deformation；When simple PP-R pipe is for main riser, compressive resistance slightly dislikes deficiency etc., and above many defects limit PP-R pipeline and exist
The further genralrlization application in China building water supply market.Axial direction fibre enhancing merely is carried out to PP-R pipeline, pipeline can be made
Linear expansion coefficient be decreased obviously, but declined circumferential pressure-resistant performance；And circumferential fiber reinforcement is carried out to PP-R pipe, it can be with
The pressure-resistant performance of pipeline is improved, but the linear expansion coefficient of pipeline cannot be effectively reduced.
Chinese Patent Application No. 201410039301.5 is related to tubing technical field, and in particular to a kind of Antibacterial PPR pipe.
A kind of Antibacterial PPR pipe, is made of following raw material by weight percentage: SiO 2 supported nanometer silver antibacterial agent 0.3~2%,
PPR raw material 94~95.7%, toner 2%, antioxidant 2%；Wherein, the SiO 2 supported nanometer silver antibacterial agent is by by nitre
Sour silver, ethyl orthosilicate, dehydrated alcohol and ammonium hydroxide are mixed and restore through reducing agent and is made.The application realizes nano silver particles
Fine dispersion in PPR pipe, effectively plays the powerful antimicrobial effect of nano silver particles, to reduce nano-silver ionic use
Amount, reduces cost；It is effectively prevent bacteria breed, eliminates bacterium common in water body, guarantees the water hygiene cleaning in pipeline；Technique
Simply, reaction condition is mild, low in cost, greatly facilitates its production and popularization industrially.
Chinese Patent Application No. 201420224337.6 is related to a kind of PPR pipe, including straight tube, horizontal tube and p-type are deposited
Water is curved, and the straight tube has two, wherein the lower part of a straight tube is equipped with the p-type trap, and the side connection of the straight tube
There is lateral nozzle, connects the horizontal tube using the lateral nozzle, one end of the horizontal tube utilizes elbow and other one
The straight tube connection, the bottom of the elbow is provided with the support of triangle, floor drain is mounted at the top of the straight tube, described
P-type trap is then disposed therein the lower section of a floor drain shell, and the bead of the floor drain shell is arranged cock wheel, on the cock wheel
Side's setting castor circle, castor lid, a bottom is arranged in the floor drain inner cavity and peripheral wall is provided with the filter basket of water hole.The utility model structure is closed
Reason, stability is good, can water flowing performance it is good, be not easy deposit dirt, PIPING DESIGN is simple, engineering feed consumption reduce.
Chinese Patent Application No. 201410475728.X is related to copper pipe PPR water supply extruding pipe material pipe fitting, include at least pipe fitting,
Copper connects ring, copper tube, copper and connects muscle, PPR layers and adhesive layer；The pipe fitting is arranged PPR layers of inner end；The fixed insertion of the copper tube
Adhesive layer is provided between copper tube in PPR layers of inner hole, and at PPR layers；The copper connects ring and is arranged in copper tube one end,
And it is connect in copper and is provided with copper on the outside of ring and connects muscle；The PPR water supply extruding pipe material pipe fitting, using seamless T2 copper tube, copper purity reaches
99.9%；This technology structure, tubing and pipe fitting, copper, which connects ring all, in pipe fitting is constructed using copper tube, and performance is equal to copper
Water pipe；Copper pipe-PPR is that copper tube is extruded gluing using hot melt with PP-R pipe to form, and copper connects ring setting in pipe fitting, so that this Shen
Please technology reach full copper touching water effect；Copper is set in pipe fitting and connects ring, reaches a kind of completely new feed pipe of full copper touching water.
Chinese Patent Application No. 201410318662.3 is related to plastic extruding forming technology, supplies for three-dimensional house owner's hidden pipe
Water provides a kind of PPR flat type pipe part.The shortcomings that round pipe part of the PPR supplied currently on the market, hidden pipe supplies water: 1,
Indoor wall fluting is too deep, and steel mesh is truncated；2, the high terrace of duct frame, the exceeded height of ground decoration.To numerous owners, tenant
Lives and properties cause hidden danger.The PPR flat type pipe part of my application, from house lead in water interface, modification enters ground concealed installation, cold
Hot water is by underground flat type pipeline, and upper wall supplies water to each contact, and flat type pipe is reduced into round internal thread interface, in metope dew
Head is installed with sanitary wares, machine coordinations such as existing tap, shower, closets.Novel PPR flat type pipe part, design
Exquisiteness takes benefit to keep away evil, can not only eliminate three-dimensional house hidden danger, also reduce cost for owner's ground decoration.Technical solution
After being converted into actual productivity, economical, societal benefits are good.
Chinese Patent Application No. 201410764651.8 is related to a kind of ageing-resistant PPR pipe and preparation method thereof, the tubing
Be grouped as by each group of following mass parts: PPR80~107 part, 6~19 parts of antioxidant, 12~25 parts of ultraviolet absorber, ethylene is double
4~14 parts of stearmide, 8~21 parts of promotor, 10~19 parts of haloflex.Preparation method: each group mixing that is placed in is stirred
It mixes in machine, 20~26min is mixed at a temperature of 130~150 DEG C, stirring rate is 300~500r/min；It places into cold mixer
35~40 DEG C are cooled to, siccative storehouse is delivered to；By the mixture in siccative storehouse through draw ratio be 32:1 double screw extruder squeeze out,
It is cooled and shaped, fixed length cutting, flare formation, packaging.PPR pipe made from the application has the ageing-resistant performance for improving tubing,
The advantages of prolonging the service life.
Chinese Patent Application No. 201410763214.4 is related to a kind of resistance to compression PPR pipe and preparation method thereof, the tubing by
The each group of following mass parts is grouped as: PPR79~103 part, and 2~13 parts of Masterbatch, plexiglass 15~22
Part, 6~18 parts of anti-impact modifier, 6~20 parts of dioctyl phthalate, 9~17 parts of ethylene~ethyl acrylate copolymer,
5~13 parts of talcum powder, 1~8 part of cumyl peroxide.Preparation method: each component is heated to 120~145 DEG C, in mixing machine
Middle mixing；Spiro rod length and diameter being added than being kneaded in the double screw extruder for 26~34:1, extruder temperature is 200~
260 DEG C, screw speed is 700~1000r/min；It is cooled and shaped, fixed length cutting, flare formation, packs after extrusion.The application system
The PPR pipe obtained has the compressive property for improving tubing, the advantages of prolonging the service life.
Chinese Patent Application No. 201420484130.2 is related to a kind of PPR pipe cooling structure-improved, including is arranged in machine
On frame, it is internal form the cylindrical water body for running through cavity, form the capping that band is open at the both ends of the water body, it is described to open
Mouth connection ennation, water receiving tank is equipped with below the port of the ennation, forms multiple water inlets, institute on the water body
It states water inlet and one water tank is connected by circulation pipe jointly, by return pipe connection water receiving tank on the water tank, in the water receiving tank
It is interior be equipped with refrigerator, on the circulation pipe be equipped with high-pressure hydraulic pump, the water inlet include it is multiple, wait and be evenly distributed on the spray
On the surrounding outer wall of water body, conveyor screw is formed on the inner wall of the water body, the port wall of the ennation is formed at positive lower end
It is open, end edge place opposite with the ennation is equipped with arc groove on the water receiving tank；The utility model reduces rapidly tube surfaces
Temperature, do not influence subsequent tubing hauling operation.
Chinese Patent Application No. 201410343858.8 is related to a kind of three type polypropylene pipe of oxygen-resistance type, the tubing it is outer
Layer is PPR layers, and middle layer is ethylene-vinyl alcohol copolymer oxidation prevention layer, and internal layer is interior PPR layers.It by PPR layers, it is oxidation prevention layer, interior
PPR layers are co-extruded；And the host material molecules structure of each layer is similar, and good compatibility had both been able to achieve without adhesive.It should
Tubing not only has good oxygen barrier effect, the metal part rust corrosion in anti-locking system, and inner wall non-scaling may be implemented,
It is not easy to be layered, does not breed bacterium and algae, keep water quality relatively sanitary, it is easy to spread suitable for the hot water pipe under various environment
Using.
Chinese Patent Application No. 201420318130.5 is related to a kind of novel PPR pipe and for connecting novel PPR pipe
Connector, the novel PPR pipe, the tube body including hollow setting, tube body include the first tube wall being oppositely arranged and second pipe
Wall, the one end and the third tube wall of the one end of the second tube wall that connect the first tube wall, the other end for connecting the first tube wall and
4th tube wall of the other end of the second tube wall, the first tube wall are plane and arranged in parallel, the first pipe with the second tube wall
The outer surface of wall is to the distance between the outer surface of the second tube wall≤20mm.The novel PPR pipe of the utility model, not in application
It needs to slot on wall i.e. mountable, it is easy for installation, easy to operate, the costs such as save human and material resources.
Chinese Patent Application No. 201410218173.0 is related to a kind of natural anti-aging, antibacterial composite plastic particle and its double
The preparation method of layer PPR pipe, by No. 10 0.1-5 parts of white oils, 2-8 parts of polyethylene wax, 0.1-5 parts of silane coupling agent, polyethylene tree
20-40 parts of rouge, it is mixed that high-speed mixer is added in 5-10 parts of the conch meal of 80-100 mesh, 3-6 parts of the load silver bamboo charcoal powder of 80-200 mesh
It closes, after mixing by double screw extruder extruding pelletization to obtain the final product.It is this natural anti-aging, anti-disclosed herein as well is utilizing
The degerming of bacterium composite plastic particle preparation, uvioresistant, antistatic, the fire-retardant double-deck PPR pipe method.The application is easy to operate, real
It is strong, at low cost, environmentally protective with property, obtain it is natural it is anti-aging, antibacterial composite plastic particle dispersion is good, property stablize, institute
Anti-aging, the excellent antibacterial performance of PPR pipe are obtained, cost performance is high, has stronger practical application value and the prospect of marketing.
Chinese Patent Application No. 201410013140.2 is related to a kind of preparation method of porcelain carving tubing, and this method includes by porcelain
Moulding material extrusion molding is the porcelain carving tubing；Porcelain carving material described in the porcelain carving material contains polyolefin and pigment agent, described
Pigment agent is porcelain white, and the polyolefin contains the first polyolefin that weight average molecular weight is 8-15 ten thousand and weight average molecular weight is
The second polyolefin of 5000-20000.The application is by preferably (containing pigment agent and the second polyene for Masterbatch in Masterbatch
Hydrocarbon) it is mixed with the first polyolefin to obtain porcelain carving material, and the porcelain carving material is manufactured into porcelain carving tubing, especially PPR pipe, make
Porcelain carving tubing not only shock resistance with higher is obtained, but also there is opaque characteristic.
201410727274. the application of Chinese Patent Application No. provides a kind of low temperature resistant PP-R pipe, by weight, packet
The raw material of following components is included, 100 parts of PP-R, PP-B1-5 parts, area load there are 1-5 parts of modification color masterbatch of beta nucleater.The application
It is modified by carrying out area load nucleating agent to the inorganic particulate in color masterbatch, while PP-B induction crystallization is added and prepares high β crystalline substance
The PPR pipe of content, compared with prior art, β crystalline substance crystallization effect significantly improve, and can effectively solve the problem that PP-R pipe black brittleness
The problem of.
Chinese Patent Application No. 201410140974.X is related to a kind of PP-R pipe formula and processing technology, including randomly altogether
Poly- polypropylene, tetrapentaerythritol vinegar, nucleating agent TMB-4 and auxiliary antioxidant DLTP, in which: atactic copolymerized polypropene content is
97%-99.65%, tetrapentaerythritol vinegar content are 0.1%-1%, and auxiliary antioxidant DLTP content is 0.2%-1.5%, nucleation
Agent TMB-4 is 0.05%-0.5%.The application is a kind of PP-R pipe formula and processing technology, and in processing, melting temperature is wide,
Molding processibility is preferable, and product has toughness, cold resistance, impact property height and the preferable advantage of transparency, and has poly- third
Outside acidproof, alkaline-resisting, resistant to chemical etching, the heat-resist performance of alkene tubing, also there is low-temperature impact resistance, resistance to ag(e)ing and resistance to
Optical property.
Chinese Patent Application No. 201310678216.9 is related to a kind of High weatherability PPR pipe, is made of the following raw material: 1-2
Part vinyltrimethoxysilane, 2 parts of phthalocyanine greens, 78 parts of atactic copolymerized polypropenes, 3 parts of organic yellows, 3 parts of octadecyl vinyl ethers
With the alternate copolymer of maleic anhydride, 2 parts of light stabilizers, 4 parts of diffusing oils, 1 part of double salicylidenediamine, 1 part of titanium dioxide, 5 parts
Four [methyl-β-(3,5- di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters, 2 parts of spread powders, 2 parts of silane coupling agents,
5 parts of carbon blacks, 2 parts of 2- (2 '-hydroxyls -3 ', 5 '-two tertiary phenyl) -5- chlorination benzotriazole, 2 part three [2.4- di-tert-butyl-phenyl]
Phosphite ester, 3 part 1,3,5- trimethyls -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene, 1 part of polyethylene wax, 1 part
Vinyltrimethoxysilane.The application PPR pipe, oxidation induction time extension, tubing impact strength, tubing hydraulic pressure strength
It increases with tubing ageing-resistant performance.
Chinese Patent Application No. 201320089446.7 is related to a kind of modified PPR pipe, by uvioresistant layer, sandwich layer and resists
Three-decker is combined layer by layer for impact, and wherein uvioresistant layer is the outer layer of tubing, and sandwich layer is the middle layer of tubing, shock resistance
Layer is the internal layer of tubing.The utility model has the advantages that good toughness, rigidity height, good weatherability, the anti-purple in PPR pipe raw material
Its stability of ultraviolet absorbers is good, there is good mechanical performance retentivity and anti-aging property, it and antioxidant have well
Synergistic effect can improve the thermal stability of tubing.Impact modifier and dispersing agent are modified to PPR resin, improve tubing
Rigidity and impact strength improve the weatherability of tubing.The utility model improves that existing PPR pipe rigidity is low, not impact resistance
The shortcomings that, there is good promotional value.
Chinese Patent Application No. 201310590368.3 is related to a kind of PPR pipe special plastic composite assistant and its PPR pipe
The granulation processing method of material is related to a kind of production of PPR pipe and its preparation of composite assistant, the first composite assistant of the application
It proportionally puts into high speed mixer and is stirred, stir 45~60 seconds, then convey mixture by screw feeding machine
Granulation operation is carried out into pelletizer, controls the mixture temperature of pelletizer less than 25 DEG C, two sections of 55 DEG C of temperature, head temperatures 60
DEG C, 25 DEG C of wind chill temperatures, finally by pelletizer squeeze out cylindrical type strip material cooled down by conveyer belt air cooling equipment, to object
By vibration, sieving equipment after material is cooling, powder is removed, finished product is obtained.The oxidation induction period of PPR pipe can be made to be increased to 100
Minute or more, the high/low-temperature impact intensity and the water-fast extracting performance of high temperature of PPR pipe are improved, elasticity capacity extension dialysis is improved and stretches
The latitude of emulsion.
Chinese Patent Application No. 201310500794.3 is related to a kind of PPR pipe with high ageing resistance and its manufacturer
Method chooses PPR raw material, a certain amount of zinc powder is added and is sufficiently mixed uniformly；It is added in uniformly mixed PPR and zinc powder mixture
DOP liquid medicine；It will be added in the PPR and zinc powder mixture merging molding machine of DOP liquid medicine, be heated to 200-230 DEG C, 1-3 points of heat preservation
Clock, until gluey raw material is made in mixture；Manufactured gluey raw material is put into squeeze out in double screw extruder and selects grain, later with single
Screw rod pipe extruder carries out squeezing pipe molding.PPR pipe made of the application can be inside tubing and table due to the addition of zinc powder
Face forms layer of ZnO layer, significantly improves the anti-aging property of tubing；The hardness and black brittleness of tubing, tool can be promoted simultaneously
There is vast market prospect.
Chinese Patent Application No. 201320700077.0 is related to a kind of noise cancelling type PPR pipe structure comprising PPR pipe pipe
Body, is uniformly provided with spiral fin and groove on the inner wall of the PPR pipe tube body, on the outer tube of the PPR pipe tube body
Compound one layer of noise reduction layer, the noise reduction layer are externally provided with one layer of protective jacket, and the noise reduction layer is the sound-insulating structure of porous foam composition；
The spiral fin and groove that can divide guidance water flow, fin and recessed is arranged in the utility model on the inner wall of PPR pipe
Slot can be split and be oriented in flow process to the water body in drainpipe, utilize the fin and groove absorption water on inner wall
Energy, reduce water body flow hit drainpipe speed, and on the outer wall of PPR pipe increase by one layer of noise reduction layer, thus
Drainage noise is reduced, user's requirement can be greatly met.
Chinese Patent Application No. 201310125917.X is related to a kind of Silane Grafted PPR pipe PP Pipe Compound, by weight
It is made of A material and B material in 90: 10~95: 5 ratio；A material composition are as follows: PPR80~95, high density polyethylene (HDPE) 5~20, insatiable hunger
With silane 1-3, initiator 0.01-0.03, antioxidant 0.1-0.5, auxiliary crosslinking agent 0.1-2；B material composition are as follows: PPR100, catalysis
Agent 1-3, antioxidant 0.1-0.5, cocatalyst 1-5.Preparation method is that A material and B expect respectively independent extruding pelletization, and then A expects
After B material in proportion compounding uniformly, it can be used to directly extrude tubing.The application material impact strength, creep resistance are good, can
It is widely used in the various duct products such as hot water pipe.Preparation method is simple, is not necessarily to long-time high temperature boiling process, convenient for industrialization
Production application.
Chinese Patent Application No. 201310489207.5 is related to a kind of preparation side of acrylic polymers for PPR pipe
Method includes the following steps: that propylene, catalyst are added in the first liquid phase kettle by (1) and reacts, is passed through in the first liquid phase kettle
Ethylene and hydrogen；(2) product that step (1) obtains enters second liquid phase kettle and is reacted, and is passed through ethylene in second liquid phase kettle
(3) product that step (2) obtains enters the first gas phase kettle and is reacted, and is passed through ethylene in the first gas phase kettle；(4) step (3)
Obtained product enters the second gas phase kettle and is reacted, and is passed through ethylene in the second gas phase kettle, obtains acrylic polymers；Pass through this
Apply for that obtained acrylic polymers has xylene soluble part low, molecular weight distribution is wide, and melting temperature is lower, the modulus of polymer
It is higher, the characteristics of good combination property；Acrylic polymers aft-loaded airfoil performance is good, and the inner and outer walls of pipeline of extrusion is especially smooth, Ke Yitong
Cross 1000 hours or less hydrostatic tests and 8760 hours heat stabilization tests.
Chinese Patent Application No. 201320372320.0 is related to a kind of PPR feed pipe, including internal layer copper pipe and outer layer PPR modeling
The bed of material, is equipped with bonding agent middle layer between copper pipe and PPR plastic layer, copper pipe and PPR plastic layer bonding are by bonding agent middle layer
One entirety.The beneficial effects of the utility model are: can be improved the intensity and toughness of tubing and the dimensionally stable under high temperature and resistance to
Croop property；It is easy for construction, it is the sanitary water tubing product for being ideally suited for a variety of application and environments at present, entirely
The full copper touching water of water system designs, and bacterium is died away after entering copper tube in 99% or more water.
Chinese Patent Application No. 201320431805.2 is related to pipe structure technical field, the technical problem to be solved is that
It is embedding to provide a kind of raising pipe fitting quality, the PPR pipe part of extension pipe fitting service life, including main pipe body and copper insert, the copper
Injecting hole is distributed in the surrounding of part, and copper insert after injection molding, hand over full of injecting hole and with copper insert by the plastics of main pipe body
Mistake combination.The PPR pipe part of the utility model mills out injecting hole in the surrounding of copper insert, and copper insert is put into injection mold when production
Middle carry out injection molding, the plastics of main pipe body are full of injecting hole after processing, and staggeredly combine with copper insert, form a barb
Structure, thus prevent pipe fitting from the phenomenon that copper insert is separated with main pipe body occur after expanded by heating deformation in use,
Product quality is improved, pipe fitting service life is extended, reduces customer complaint.
Chinese Patent Application No. 201310509303.1 is related to a kind of toughening modifying PPR extruding pipe material and its preparation side
Method.The tough MODIFIED PP R extruding pipe material includes the component of following mass fraction: PPR58~98%；Toughener 1~20%；Poly- 1-
Butylene 1~20%；Heat stabilizer 0~1%；The dedicated nucleating agent 0~1% of polypropylene.The application is using traditional toughener and novel
The method of toughener poly 1-butene coordination plasticizing, had both improved the low-temperature flexibility of PPR extruding pipe material, in turn ensure weld strength and
Heat resistance, tensile strength (23 DEG C) >=25MPa, elongation at break (23 DEG C) >=500%, tensile strength (95 DEG C) >=10MPa,
Low temperature notched impact strength (- 30 DEG C) >=5KJ/m2, vicat softening temperature (10N) >=125 DEG C.
Chinese Patent Application No. 201310714082.1 is related to high tenacity, high water pressure resistance atactic copolymerized polypropene (PPR) pipe
Material PP Pipe Compound and its preparation process；Using the raw material of mass percent, PPR:85%~90%；PPB-240:10%~15%；β
Nucleating agent: 0.1%~0.3%；Antioxidant: 0.1%~0.3%；Lubricant: 0.3%~0.5%；Preparation process key step
Include: to use low speed mixer, weighs suitable PPR, PPB, beta nucleater, antioxidant, lubricant by formula, successively press in proportion
It is mixed out of more to few sequence investment low speed batch mixer；Respective threaded is arranged to combine；Each section of barrel of double screw extruder is set
Heating temperature；Twin-screw extrusion unit storage hopper is added in mixing raw and auxiliary material；Open grease pump, cooling blower, pelleter,
Cooling water, main motor, feeding motor adjust main motor and feeding motor revolving speed；The material of extrusion passes through cooling trough, drying
Machine, traction to pelleter adjust pelleter revolving speed, so that the material particle size cut out is reached 3, length 3mm；To the material produced and
The detection of Shi Jinhang items physical index.
[summary of the invention]
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of fiber reinforcement atactic copolymerized polypropene is compound
Pipe and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions:
A kind of fiber reinforcement polypropylene random copolymer composite tube, which is characterized in that it includes outer layer, middle layer and interior
Layer, is arranged middle layer between outer layer and internal layer；Polyphenylene sulfide fibre enhancement layer is set between outer layer and middle layer, it is intermediate
Basalt fibre resistance to compression layer is set between layer and internal layer.
Wear-resistant coating is set on outer layer, improves the wear-resisting and service life of tubing.
The material of the wear-resistant coating is quartz sand particle, is adhered on wear-resistant coating by crosslinking agent.
The wearing layer with a thickness of 1~10 millimeter.
The thickness ratio of the outer layer, middle layer, internal layer, polyphenylene sulfide fibre enhancement layer, basalt fibre resistance to compression layer is
1:1:1:1:1。
The material of the outer layer is antibacterial atactic polypropylene agglomerate, thermoplastic polyurethane elastomer rubber and random
Copolymer polypropylene particle, wherein mass fraction of the thermoplastic polyurethane elastomer rubber in cladding material is 5~10%, antibacterial
Mass fraction of the polypropylene agglomerate in cladding material is 1~5%.Thermoplastic polyurethane elastomer rubber has brilliant height
Power, high-tensile strength, tough and ageing-resistant characteristic are a kind of environment-friendly materials of maturation.Currently, have been widely used with health care,
Electronic apparatus, industry and sport etc., with the incomparable intensity height of other plastic materials, good toughness, wear-resisting, resistance to
The characteristics such as cold, oil resistant, water-fast, ageing-resistant, weatherability.
The material of the middle layer is atactic copolymerized polypropene particle.
The material of the internal layer is that antibiotic polypropylene master batch and atactic copolymerized polypropene particle, antibiotic polypropylene master batch exist
Mass fraction in the material of internal layer is 5~15%.
The material of polyphenylene sulfide fibre enhancement layer is polyphenylene sulfide fibre and toughener, and polyphenylene sulfide fibre is in polyphenylene sulfide
Mass fraction in fabric reinforcement is 40~60%, and the length of polyphenylene sulfide fibre is 1~10 millimeter.
The material of basalt fibre resistance to compression layer is polyphenylene sulfide fibre and toughener, and basalt fibre is anti-in basalt fibre
Mass fraction in the material of pressurized layer is 44~66%, and the length of basalt fibre is 1~10 millimeter.
The material of toughener is HDPE, LLDPE, EVA, PA, POE, PPB etc..
The preparation method of the antibiotic polypropylene master batch, the specific steps are that:
One, the preparation of bagasse whisker:
The bagasse cleaned up is taken, it is molten using the urea liquid progress of sodium hydroxide under the conditions of subzero 10~15 DEG C
Solution after dissolution completely, using the method for ultracentrifugation, collects the sample of centrifugation bottom of the tube, then washed using deionized water
It washs three times, then obtains bagasse whisker for 24 hours in 60 DEG C of vacuum drying；
In the urea liquid of sodium hydroxide, the mass fraction of sodium hydroxide is 3~8%, and the mass fraction of urea is 1.2
~3%；
In ultracentrifugation technique, centrifugal force is 8000~12000g；
Holocellulos or content of lignin are up to 80% in bagasse, and the cellulose itself in bagasse have compared with
The high degree of orientation can be significantly in certain arrangement, while by using hot-cold lysis in the aqueous slkali of current urea
After removal impurity and the aqueous slkali for reducing the crystal whisker materials in cellulose for oriented crystalline, therefore passing through urea dissolve, lysate
Natural cellulose whiskers material in middle reservation bagasse；And crystal whisker materials are being used for PP as a kind of excellent reinforcing material
The fields such as tubing are widely used, and after cellulose whiskers, are reduced due in the glucose molecule structure in cellulose
The dehydration of ehter bond and keep its heat resisting temperature low, easily charing and cause to decompose in plastic processes, cause reinforcing material intensity drop
The problems such as low；Therefore Random fiber element is dissolved by the aqueous slkali of low temperature urea, obtains natural cellulose whiskers material, solved
The low problem of its PP tubing intensity, while having many advantages, such as heat resisting temperature height and high intensity；To extend the service life of tubing.
Two, the preparation of bagasse whisker is activated:
Using the bagasse whisker of step 1 preparation as raw material, acidification activation processing is carried out to bagasse whisker, is then existed again
Under the conditions of 60~80 DEG C, in the aqueous solution of edta edta, edta edta is made to be grafted on bagasse whisker
On, it is dried in vacuo under the conditions of 60 DEG C again after filtering, activation bagasse whisker is prepared；
Acidification activation process is Strong oxdiative acidic mixed solution, and 3~6h is impregnated under the conditions of 80~90 DEG C；Strong oxdiative
Acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the mass concentration of nitric acid solution is 10~15%, hydrogen peroxide
The mass concentration of solution is 10%~15%；
In the aqueous solution of edta edta, the mass fraction of edta edta is 4~8%；
In the grafting process, the graft reaction time is 1.5~2.0h；
Due to the hydroxyl structure containing glucose in the cellulosic structure of bagasse, it is anti-esterification can to occur with carboxylic acid structure
It answers, is improved using esterification and the functionalization of cellulose itself is presently the most effective means；But there is also functions
The function of material itself is difficult to merge with basis material, to influence processing performance；Therefore the application is by carrying out cellulose
Acidification and oxidation processes improve hydroxyl activity in fibre structure using the strong oxidation of nitric acid and hydrogen peroxide, thus be conducive to
Esterification occurs in water phase for EDTA, avoids since the EDTA carboxylic acid structure of aqueous solution is low with hydroxyl structure activity, esterification
The problems such as rate is slow, and enzymatic synthesis condition is harsh；The EDTA structure introduced simultaneously can be good at carrying out complex reaction with metal ion,
To improve the Heat-resistant stable performance of bagasse whisker, and since complex ion itself is in cellulose surface precipitating, to mention
Its high functional effect and reinforcing effect.
Three, the preparation of antibacterial agent:
Activation bagasse whisker prepared by step 2 is added in copper nitrate solution, then adjusts mixed solution with nitric acid
PH is 5.05~5.15, under 45~60 DEG C of stirring conditions, copper ion and activated biomass cellulose whiskers is made be complexed instead
It answers, after being generated again without precipitating in solution to be mixed；Then adjusting pH is 6.0~6.5, then under 45~60 DEG C of stirring conditions, is added
Enter magnesium nitrate solution, so that magnesium ion and activation bagasse whisker is carried out complex reaction, generate and stop without precipitating in solution to be mixed
Reaction is collected sediment and is reacted for 24 hours in 60 DEG C of vacuum drying again, obtains antibacterial agent；
The mass values of the activation bagasse whisker and copper nitrate are 1:0.15~1:0.25；
The mass values of the activation bagasse whisker and magnesium nitrate are 1:0.10~1:0.15；
The mass fraction of the copper nitrate of copper nitrate solution is 15~25%；
The mass fraction of the magnesium nitrate of magnesium nitrate solution is 10~15%；
Bagasse whisker after overactivation due to itself contain can with the amino and carbonyl structure of complexing of metal ion,
By with after complexing of metal ion, avoid amino and carbonyl structure pyrolytic；The copper ion of complexing has excellent simultaneously
Antibacterial effect, but copper ion itself has the function of catalyzed polypropylene degradation, therefore passes through the control and regulation EDTA of pH and gold
The complexing sequence for belonging to ion reaches the first complex copper ion on bagasse whisker, magnesium ion is then complexed again, reaches to copper ion
Cladding purpose, avoid the loss of copper ion and lead to polyacrylic degradation, to improve the intensity of material.And sugarcane
Slag crystal whisker materials are the material with certain draw ratio, by both having and improving bagasse after the complexation of metal ions of surface
The heat-resistant stability of crystal whisker materials, while also there is the roughness for improving surface, improve the compatibility with polypropylene matrix material
Structure plays reinforcing effect；To improve the intensity of tubing.
Four, the preparation of antibacterial atactic polypropylene agglomerate:
With antibacterial agent prepared by step 3, compatilizer, atactic copolymerized polypropene is raw material, and twin-screw extrusion is used after mixing
Machine carries out melting extrusion, and antibiotic polypropylene master batch is prepared.
In antibiotic polypropylene master batch, the mass fraction of antibacterial agent is 1~5%, the mass fraction of compatilizer is 0.1~
1%；
Compatilizer is maleic anhydride inoculated polypropylene type, is conventional polypropylene compatilizer.
The atactic copolymerized polypropene density range: 0.9~1.2g/cm3, melt index is 0.25~1.0g/10min's
Resin；
A kind of preparation method of fiber reinforcement polypropylene random copolymer composite tube, it is total by melting using pipe extruder
Extrusion forming method is prepared.
The application also provides a kind of three-layer polypropylene-polyethylene compound pipe, is divided into internal layer, middle layer and outer layer, internal layer
Glass fiber reinforced layer is set between outer layer, and internal layer, the thickness ratio 3:1:1 of middle layer and outer layer, wherein inner layer material is anti-
Bacterium polypropylene agglomerate, cladding material are polythene material, and the material of glass fiber reinforced layer is staple glass fibre and toughener.
A kind of preparation method of three-layer polypropylene-polyethylene compound pipe, using pipe extruder by melting coextrusion mold
Method is prepared.
The material of toughener is HDPE, LLDPE, EVA, PA, POE, PPB etc..
The application also provides a kind of antibacterial bilayer composite polypropylene, is divided into internal layer and outer layer, and inner layer material is antibacterial
Polypropylene agglomerate, cladding material are polypropylene material.
A kind of preparation method of antibacterial bilayer composite polypropylene, using pipe extruder by melting coextrusion mold method
It is prepared.
Compared with prior art, the positive effect of the present invention is:
The advantages of fiber reinforcement atactic copolymerized polypropene three-layer composite pipe of the present invention with double orientation: by drawing
Enter the pressure-resistant performance that basalt fibre resistance to compression layer improves tubing；The line that introducing polyphenylene sulfide fibre enhancement layer reduces tubing is swollen
Swollen coefficient.By the length for adjusting glass fibre, it is ensured that under the premise of tubing high voltage performance, linear expansion coefficient can drop to 1/3
To 1/4.Fiber-reinforced layer resin uses toughening atactic copolymerized polypropene, improves the low-temperature impact performance of tubing.The invention can
For hot water pipe, building main riser and other industrial pipes.
[Detailed description of the invention]
Fig. 1 is the structural schematic diagram of embodiments herein 1；
The label in accompanying drawing is: 1 internal layer, 2 basalt fibre resistance to compression layers, 3 middle layers, 4 polyphenylene sulfide fibre enhancement layers, 5
Outer layer.
[specific embodiment]
A kind of specific implementation of the fiber reinforcement atactic copolymerized polypropene three-layer composite pipe of double orientation of the present invention presented below
Mode.
Embodiment 1
Refer to attached drawing 1, a kind of fiber reinforcement polypropylene random copolymer composite tube and preparation method thereof, which is characterized in that
It includes outer layer, middle layer 3 is arranged in middle layer and internal layer between outer layer 5 and internal layer 1；Between outer layer and middle layer
Polyphenylene sulfide fibre enhancement layer 4 is set, basalt fibre resistance to compression layer 2 is set between middle layer and internal layer.
Wear-resistant coating is set on outer layer, improves the wear-resisting and service life of tubing.
The material of the wear-resistant coating is quartz sand particle, is adhered on wear-resistant coating by crosslinking agent.
The wearing layer with a thickness of 1~10 millimeter.
The thickness ratio of the outer layer, middle layer, internal layer, polyphenylene sulfide fibre enhancement layer, basalt fibre resistance to compression layer is
1:1:1:1:1。
The material of the outer layer is antibacterial atactic polypropylene agglomerate, thermoplastic polyurethane elastomer rubber and random
Copolymer polypropylene particle, wherein mass fraction of the thermoplastic polyurethane elastomer rubber in cladding material is 5%, antibacterial poly- third
Mass fraction of the alkene master batch in cladding material is 1%.Thermoplastic polyurethane elastomer rubber has brilliant high-tension, Gao La
Power, tough and ageing-resistant characteristic are a kind of environment-friendly materials of maturation.Currently, having been widely used and health care, electronics electricity
Device, industry and sport etc., with the incomparable intensity height of other plastic materials, good toughness, wear-resisting, cold-resistant, resistance to
The characteristics such as oily, water-fast, ageing-resistant, weatherability.
The material of the middle layer is atactic copolymerized polypropene particle.
The material of the internal layer is that antibiotic polypropylene master batch and atactic copolymerized polypropene particle, antibiotic polypropylene master batch exist
Mass fraction in the material of internal layer is 5%.
The material of polyphenylene sulfide fibre enhancement layer is polyphenylene sulfide fibre and toughener, and polyphenylene sulfide fibre is in polyphenylene sulfide
Mass fraction in fabric reinforcement is 40%, and the length of polyphenylene sulfide fibre is 1~10 millimeter.
The material of basalt fibre resistance to compression layer is polyphenylene sulfide fibre and toughener, and basalt fibre is anti-in basalt fibre
Mass fraction in the material of pressurized layer is 44%, and the length of basalt fibre is 1~10 millimeter.
The material of toughener is HDPE, LLDPE, EVA, PA, POE, PPB etc..
The preparation method of the antibiotic polypropylene master batch, the specific steps are that:
One, the preparation of bagasse whisker:
The bagasse cleaned up is taken, it is molten using the urea liquid progress of sodium hydroxide under the conditions of subzero 10~15 DEG C
Solution after dissolution completely, using the method for ultracentrifugation, collects the sample of centrifugation bottom of the tube, then washed using deionized water
It washs three times, then obtains bagasse whisker for 24 hours in 60 DEG C of vacuum drying；
In the urea liquid of sodium hydroxide, the mass fraction of sodium hydroxide is 3~8%, and the mass fraction of urea is 1.2
~3%；
In ultracentrifugation technique, centrifugal force is 8000~12000g；
Two, the preparation of bagasse whisker is activated:
Using the bagasse whisker of step 1 preparation as raw material, acidification activation processing is carried out to bagasse whisker, is then existed again
Under the conditions of 60~80 DEG C, in the aqueous solution of edta edta, edta edta is made to be grafted on bagasse whisker
On, it is dried in vacuo under the conditions of 60 DEG C again after filtering, activation bagasse whisker is prepared；
Acidification activation process is Strong oxdiative acidic mixed solution, and 3~6h is impregnated under the conditions of 80~90 DEG C；Strong oxdiative
Acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the mass concentration of nitric acid solution is 10%, hydrogen peroxide solution
Mass concentration be 10%；
In the aqueous solution of edta edta, the mass fraction of edta edta is 4%；
In the grafting process, the graft reaction time is 1.5~2.0h；
Three, the preparation of antibacterial agent:
Activation bagasse whisker prepared by step 2 is added in copper nitrate solution, then adjusts mixed solution with nitric acid
PH is 5.05~5.15, under 45~60 DEG C of stirring conditions, copper ion and activated biomass cellulose whiskers is made be complexed instead
It answers, after being generated again without precipitating in solution to be mixed；Then adjusting pH is 6.0~6.5, then under 45~60 DEG C of stirring conditions, is added
Enter magnesium nitrate solution, so that magnesium ion and activation bagasse whisker is carried out complex reaction, generate and stop without precipitating in solution to be mixed
Reaction is collected sediment and is reacted for 24 hours in 60 DEG C of vacuum drying again, obtains antibacterial agent；
The mass values of the activation bagasse whisker and copper nitrate are 1:0.15；
The mass values of the activation bagasse whisker and magnesium nitrate are 1:0.10；
The mass fraction of the copper nitrate of copper nitrate solution is 15%；
The mass fraction of the magnesium nitrate of magnesium nitrate solution is 10%；
Four, the preparation of antibacterial atactic polypropylene agglomerate:
With antibacterial agent prepared by step 3, compatilizer, atactic copolymerized polypropene is raw material, and twin-screw extrusion is used after mixing
Machine carries out melting extrusion, and antibiotic polypropylene master batch is prepared.
In antibiotic polypropylene master batch, the mass fraction of antibacterial agent is 1%, and the mass fraction of compatilizer is 0.1%；
Compatilizer is maleic anhydride inoculated polypropylene type, is conventional polypropylene compatilizer.
Performance test:
The anti-microbial property of the internal layer of fiber reinforcement polypropylene random copolymer composite tube is the antibiotic property > to Escherichia coli
93%, the antibiotic property > 93% of staphylococcus glucose coccus.
The hydrostatic test result of fiber reinforcement polypropylene random copolymer composite tube are as follows: 95 DEG C, 5Mpa, 165h, no destruction,
Without infiltration.
The room temperature impact strength of fiber reinforcement polypropylene random copolymer composite tube is 8.2KJ/m2, room temperature impact strength position
6.6KJ/m2, tensile strength 36MPa, bending strength 66MPa, after ultraviolet light 700 hours, each intensity refers to
Mark probably has dropped 10%.
Embodiment 2
A kind of fiber reinforcement polypropylene random copolymer composite tube and preparation method thereof, which is characterized in that it includes outer layer, in
Interbed and internal layer, are arranged middle layer between outer layer and internal layer；Polyphenylene sulfide fibre is set between outer layer and middle layer
Basalt fibre resistance to compression layer is arranged in enhancement layer between middle layer and internal layer.
Wear-resistant coating is set on outer layer, improves the wear-resisting and service life of tubing.
The material of the wear-resistant coating is quartz sand particle, is adhered on wear-resistant coating by crosslinking agent.
The wearing layer with a thickness of 1~10 millimeter.
The thickness ratio of the outer layer, middle layer, internal layer, polyphenylene sulfide fibre enhancement layer, basalt fibre resistance to compression layer is
1:1:1:1:1。
The material of the outer layer is antibacterial atactic polypropylene agglomerate, thermoplastic polyurethane elastomer rubber and random
Copolymer polypropylene particle, wherein mass fraction of the thermoplastic polyurethane elastomer rubber in cladding material is 7.5%, and antibacterial is poly-
Mass fraction of the propylene master batch in cladding material is 2.5%.Thermoplastic polyurethane elastomer rubber have brilliant high-tension,
High-tensile strength, tough and ageing-resistant characteristic are a kind of environment-friendly materials of maturation.Currently, having been widely used and health care, electronics
Electric appliance, industry and sport etc., with the incomparable intensity height of other plastic materials, good toughness, it is wear-resisting, cold-resistant,
The characteristics such as oil resistant, water-fast, ageing-resistant, weatherability.
The material of the middle layer is atactic copolymerized polypropene particle.
The material of the internal layer is that antibiotic polypropylene master batch and atactic copolymerized polypropene particle, antibiotic polypropylene master batch exist
Mass fraction in the material of internal layer is 10%.
The material of polyphenylene sulfide fibre enhancement layer is polyphenylene sulfide fibre and toughener, and polyphenylene sulfide fibre is in polyphenylene sulfide
Mass fraction in fabric reinforcement is 50%, and the length of polyphenylene sulfide fibre is 1~10 millimeter.
The material of basalt fibre resistance to compression layer is polyphenylene sulfide fibre and toughener, and basalt fibre is anti-in basalt fibre
Mass fraction in the material of pressurized layer is 55%, and the length of basalt fibre is 1~10 millimeter.
The material of toughener is HDPE, LLDPE, EVA, PA, POE, PPB etc..
The preparation method of the antibiotic polypropylene master batch, the specific steps are that:
One, the preparation of bagasse whisker:
The bagasse cleaned up is taken, it is molten using the urea liquid progress of sodium hydroxide under the conditions of subzero 10~15 DEG C
Solution after dissolution completely, using the method for ultracentrifugation, collects the sample of centrifugation bottom of the tube, then washed using deionized water
It washs three times, then obtains bagasse whisker for 24 hours in 60 DEG C of vacuum drying；
In the urea liquid of sodium hydroxide, the mass fraction of sodium hydroxide is 5%, and the mass fraction of urea is 1.9%；
In ultracentrifugation technique, centrifugal force is 8000~12000g；
Two, the preparation of bagasse whisker is activated:
Using the bagasse whisker of step 1 preparation as raw material, acidification activation processing is carried out to bagasse whisker, is then existed again
Under the conditions of 60~80 DEG C, in the aqueous solution of edta edta, edta edta is made to be grafted on bagasse whisker
On, it is dried in vacuo under the conditions of 60 DEG C again after filtering, activation bagasse whisker is prepared；
Acidification activation process is Strong oxdiative acidic mixed solution, and 3~6h is impregnated under the conditions of 80~90 DEG C；Strong oxdiative
Acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the mass concentration of nitric acid solution is 12.5%, and dioxygen is water-soluble
The mass concentration of liquid is 12.5%；
In the aqueous solution of edta edta, the mass fraction of edta edta is 6%；
In the grafting process, the graft reaction time is 1.5~2.0h；
Three, the preparation of antibacterial agent:
Activation bagasse whisker prepared by step 2 is added in copper nitrate solution, then adjusts mixed solution with nitric acid
PH is 5.05~5.15, under 45~60 DEG C of stirring conditions, copper ion and activated biomass cellulose whiskers is made be complexed instead
It answers, after being generated again without precipitating in solution to be mixed；Then adjusting pH is 6.0~6.5, then under 45~60 DEG C of stirring conditions, is added
Enter magnesium nitrate solution, so that magnesium ion and activation bagasse whisker is carried out complex reaction, generate and stop without precipitating in solution to be mixed
Reaction is collected sediment and is reacted for 24 hours in 60 DEG C of vacuum drying again, obtains antibacterial agent；
The mass values of the activation bagasse whisker and copper nitrate are 1:0.2；
The mass values of the activation bagasse whisker and magnesium nitrate are 1:0.12；
The mass fraction of the copper nitrate of copper nitrate solution is 20%；
The mass fraction of the magnesium nitrate of magnesium nitrate solution is 12%；
Four, the preparation of antibacterial atactic polypropylene agglomerate:
With antibacterial agent prepared by step 3, compatilizer, atactic copolymerized polypropene is raw material, and twin-screw extrusion is used after mixing
Machine carries out melting extrusion, and antibiotic polypropylene master batch is prepared.
In antibiotic polypropylene master batch, the mass fraction of antibacterial agent is 2%, and the mass fraction of compatilizer is 0.5%；
Compatilizer is maleic anhydride inoculated polypropylene type, is conventional polypropylene compatilizer.
The atactic copolymerized polypropene density range: 0.9~1.2g/cm3, melt index is 0.25~1.0g/10min's
Resin；
Performance test:
The anti-microbial property of the internal layer of fiber reinforcement polypropylene random copolymer composite tube is the antibiotic property > to Escherichia coli
95%, the antibiotic property > 95% of staphylococcus glucose coccus.
The hydrostatic test result of fiber reinforcement polypropylene random copolymer composite tube are as follows: 95 DEG C, 5Mpa, 165h, no destruction,
Without infiltration.
The room temperature impact strength of fiber reinforcement polypropylene random copolymer composite tube is 8.5KJ/m2, room temperature impact strength position
6.6KJ/m2, tensile strength 38MPa, bending strength 68MPa, after ultraviolet light 700 hours, each intensity refers to
Mark probably has dropped 10%.
Embodiment 3
A kind of fiber reinforcement polypropylene random copolymer composite tube and preparation method thereof, which is characterized in that it includes outer layer, in
Interbed and internal layer, are arranged middle layer between outer layer and internal layer；Polyphenylene sulfide fibre is set between outer layer and middle layer
Basalt fibre resistance to compression layer is arranged in enhancement layer between middle layer and internal layer.
Wear-resistant coating is set on outer layer, improves the wear-resisting and service life of tubing.
The material of the wear-resistant coating is quartz sand particle, is adhered on wear-resistant coating by crosslinking agent.
The wearing layer with a thickness of 1~10 millimeter.
The thickness ratio of the outer layer, middle layer, internal layer, polyphenylene sulfide fibre enhancement layer, basalt fibre resistance to compression layer is
1:1:1:1:1。
The material of the outer layer is antibacterial atactic polypropylene agglomerate, thermoplastic polyurethane elastomer rubber and random
Copolymer polypropylene particle, wherein mass fraction of the thermoplastic polyurethane elastomer rubber in cladding material is 10%, and antibacterial is poly-
Mass fraction of the propylene master batch in cladding material is 5%.
The material of the middle layer is atactic copolymerized polypropene particle.
The material of the internal layer is that antibiotic polypropylene master batch and atactic copolymerized polypropene particle, antibiotic polypropylene master batch exist
Mass fraction in the material of internal layer is 15%.
The material of polyphenylene sulfide fibre enhancement layer is polyphenylene sulfide fibre and toughener, and polyphenylene sulfide fibre is in polyphenylene sulfide
Mass fraction in fabric reinforcement is 60%, and the length of polyphenylene sulfide fibre is 1~10 millimeter.
The material of basalt fibre resistance to compression layer is polyphenylene sulfide fibre and toughener, and basalt fibre is anti-in basalt fibre
Mass fraction in the material of pressurized layer is 66%, and the length of basalt fibre is 1~10 millimeter.
The material of toughener is HDPE, LLDPE, EVA, PA, POE, PPB etc..
The preparation method of the antibiotic polypropylene master batch, the specific steps are that:
One, the preparation of bagasse whisker:
The bagasse cleaned up is taken, it is molten using the urea liquid progress of sodium hydroxide under the conditions of subzero 10~15 DEG C
Solution after dissolution completely, using the method for ultracentrifugation, collects the sample of centrifugation bottom of the tube, then washed using deionized water
It washs three times, then obtains bagasse whisker for 24 hours in 60 DEG C of vacuum drying；
In the urea liquid of sodium hydroxide, the mass fraction of sodium hydroxide is 8%, and the mass fraction of urea is 3%；
In ultracentrifugation technique, centrifugal force is 8000~12000g；
Two, the preparation of bagasse whisker is activated:
Using the bagasse whisker of step 1 preparation as raw material, acidification activation processing is carried out to bagasse whisker, is then existed again
Under the conditions of 60~80 DEG C, in the aqueous solution of edta edta, edta edta is made to be grafted on bagasse whisker
On, it is dried in vacuo under the conditions of 60 DEG C again after filtering, activation bagasse whisker is prepared；
Acidification activation process is Strong oxdiative acidic mixed solution, and 3~6h is impregnated under the conditions of 80~90 DEG C；Strong oxdiative
Acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the mass concentration of nitric acid solution is 15%, hydrogen peroxide solution
Mass concentration be 15%；
In the aqueous solution of edta edta, the mass fraction of edta edta is 8%；
In the grafting process, the graft reaction time is 1.5~2.0h；
Three, the preparation of antibacterial agent:
Activation bagasse whisker prepared by step 2 is added in copper nitrate solution, then adjusts mixed solution with nitric acid
PH is 5.05~5.15, under 45~60 DEG C of stirring conditions, copper ion and activated biomass cellulose whiskers is made be complexed instead
It answers, after being generated again without precipitating in solution to be mixed；Then adjusting pH is 6.0~6.5, then under 45~60 DEG C of stirring conditions, is added
Enter magnesium nitrate solution, so that magnesium ion and activation bagasse whisker is carried out complex reaction, generate and stop without precipitating in solution to be mixed
Reaction is collected sediment and is reacted for 24 hours in 60 DEG C of vacuum drying again, obtains antibacterial agent；
The mass values of the activation bagasse whisker and copper nitrate are 1:0.25；
The mass values of the activation bagasse whisker and magnesium nitrate are 1:0.15；
The mass fraction of the copper nitrate of copper nitrate solution is 25%；
The mass fraction of the magnesium nitrate of magnesium nitrate solution is 15%；
Four, the preparation of antibacterial atactic polypropylene agglomerate:
With antibacterial agent prepared by step 3, compatilizer, atactic copolymerized polypropene is raw material, and twin-screw extrusion is used after mixing
Machine carries out melting extrusion, and antibiotic polypropylene master batch is prepared.
In antibiotic polypropylene master batch, the mass fraction of antibacterial agent is 5%, and the mass fraction of compatilizer is 1%；
Compatilizer is maleic anhydride inoculated polypropylene type, is conventional polypropylene compatilizer.
The atactic copolymerized polypropene density range: 0.9~1.2g/cm3, melt index is 0.25~1.0g/10min's
Resin；
Performance test:
The anti-microbial property of the internal layer of fiber reinforcement polypropylene random copolymer composite tube is the antibiotic property > 94% of Escherichia coli,
The antibiotic property > 94% of staphylococcus glucose coccus.
The hydrostatic test result of fiber reinforcement polypropylene random copolymer composite tube are as follows: 95 DEG C, 5Mpa, 165h, no destruction,
Without infiltration.
The room temperature impact strength of fiber reinforcement polypropylene random copolymer composite tube is 8.4KJ/m2, room temperature impact strength position
6.4KJ/m2, tensile strength 37MPa, bending strength 67MPa, after ultraviolet light 700 hours, each intensity refers to
Mark probably has dropped 10%.
Embodiment 4
A kind of fiber reinforcement polypropylene random copolymer composite tube and preparation method thereof, which is characterized in that it includes outer layer, in
Interbed and internal layer, are arranged middle layer between outer layer and internal layer；Polyphenylene sulfide fibre is set between outer layer and middle layer
Basalt fibre resistance to compression layer is arranged in enhancement layer between middle layer and internal layer.
Wear-resistant coating is set on outer layer, improves the wear-resisting and service life of tubing.
The material of the wear-resistant coating is quartz sand particle, is adhered on wear-resistant coating by crosslinking agent.
The wearing layer with a thickness of 1~10 millimeter.
The thickness ratio of the outer layer, middle layer, internal layer, polyphenylene sulfide fibre enhancement layer, basalt fibre resistance to compression layer is
1:1:1:1:1。
The material of the outer layer is antibacterial atactic polypropylene agglomerate, thermoplastic polyurethane elastomer rubber and random
Copolymer polypropylene particle, wherein mass fraction of the thermoplastic polyurethane elastomer rubber in cladding material is 7.5%, and antibacterial is poly-
Mass fraction of the propylene master batch in cladding material is 2.5%.
The material of the middle layer is atactic copolymerized polypropene particle.
The material of the internal layer is that antibiotic polypropylene master batch and atactic copolymerized polypropene particle, antibiotic polypropylene master batch exist
Mass fraction in the material of internal layer is 10%.
The material of polyphenylene sulfide fibre enhancement layer is polyphenylene sulfide fibre and toughener, and polyphenylene sulfide fibre is in polyphenylene sulfide
Mass fraction in fabric reinforcement is 50%, and the length of polyphenylene sulfide fibre is 1~10 millimeter.
The material of basalt fibre resistance to compression layer is polyphenylene sulfide fibre and toughener, and basalt fibre is anti-in basalt fibre
Mass fraction in the material of pressurized layer is 55%, and the length of basalt fibre is 1~10 millimeter.
The material of toughener is HDPE, LLDPE, EVA, PA, POE, PPB etc..
The preparation method of the antibiotic polypropylene master batch, the specific steps are that:
One, the preparation of bagasse whisker:
The bagasse cleaned up is taken, it is molten using the urea liquid progress of sodium hydroxide under the conditions of subzero 10~15 DEG C
Solution after dissolution completely, using the method for ultracentrifugation, collects the sample of centrifugation bottom of the tube, then washed using deionized water
It washs three times, then obtains bagasse whisker for 24 hours in 60 DEG C of vacuum drying；
In the urea liquid of sodium hydroxide, the mass fraction of sodium hydroxide is 5%, and the mass fraction of urea is 1.9%；
In ultracentrifugation technique, centrifugal force is 8000~12000g；
Two, the preparation of bagasse whisker is activated:
Using the bagasse whisker of step 1 preparation as raw material, acidification activation processing is carried out to bagasse whisker, is then existed again
Under the conditions of 60~80 DEG C, in the aqueous solution of edta edta, edta edta is made to be grafted on bagasse whisker
On, it is dried in vacuo under the conditions of 60 DEG C again after filtering, activation bagasse whisker is prepared；
Acidification activation process is Strong oxdiative acidic mixed solution, and 3~6h is impregnated under the conditions of 80~90 DEG C；Strong oxdiative
Acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the mass concentration of nitric acid solution is 12.5%, and dioxygen is water-soluble
The mass concentration of liquid is 12.5%；
In the aqueous solution of edta edta, the mass fraction of edta edta is 6%；
In the grafting process, the graft reaction time is 1.5~2.0h；
Three, the preparation of antibacterial agent:
Activation bagasse whisker prepared by step 2 is added in copper nitrate solution, then adjusts mixed solution with nitric acid
PH is 5.05~5.15, under 45~60 DEG C of stirring conditions, copper ion and activated biomass cellulose whiskers is made be complexed instead
It answers, after being generated again without precipitating in solution to be mixed；It collects sediment to react for 24 hours in 60 DEG C of vacuum drying again, obtains antibacterial agent；
The mass values of the activation bagasse whisker and copper nitrate are 1:0.2；
The mass fraction of the copper nitrate of copper nitrate solution is 20%；
Four, the preparation of antibacterial atactic polypropylene agglomerate:
With antibacterial agent prepared by step 3, compatilizer, atactic copolymerized polypropene is raw material, and twin-screw extrusion is used after mixing
Machine carries out melting extrusion, and antibiotic polypropylene master batch is prepared.
In antibiotic polypropylene master batch, the mass fraction of antibacterial agent is 2%, and the mass fraction of compatilizer is 0.5%；
Compatilizer is maleic anhydride inoculated polypropylene type, is conventional polypropylene compatilizer.
The atactic copolymerized polypropene density range: 0.9~1.2g/cm3, melt index is 0.25~1.0g/10min's
Resin；
Performance test:
The anti-microbial property of the internal layer of fiber reinforcement polypropylene random copolymer composite tube is the antibiotic property > 78% of Escherichia coli,
The antibiotic property > 78% of staphylococcus glucose coccus.
The hydrostatic test result of fiber reinforcement polypropylene random copolymer composite tube are as follows: 95 DEG C, 5Mpa, 165h, no destruction,
Without infiltration.
The room temperature impact strength of fiber reinforcement polypropylene random copolymer composite tube is 7.5KJ/m2, room temperature impact strength position
5.6KJ/m2, tensile strength 32MPa, bending strength 60MPa, after ultraviolet light 700 hours, each intensity refers to
Mark probably has dropped 10%.The application lacks this processing step of the package of magnesium ion, it is seen that compared with Example 2, asks antibacterial
Performance is decreased obviously, and each intensity index is also to be declined.
Embodiment 5
The application also provides a kind of three-layer polypropylene-polyethylene compound pipe, is divided into internal layer, middle layer and outer layer, internal layer
Glass fiber reinforced layer is set between outer layer, and internal layer, the thickness ratio 3:1:1 of middle layer and outer layer, wherein inner layer material is anti-
Bacterium polypropylene agglomerate, cladding material are polythene material, and the material of glass fiber reinforced layer is staple glass fibre and toughener.
The material of toughener is HDPE, LLDPE, EVA, PA, POE, PPB etc..
The preparation of antibiotic polypropylene master batch is referring to embodiment 1.
Performance test:
The anti-microbial property of the internal layer of fiber reinforcement polypropylene random copolymer composite tube is the antibiotic property > 95% of Escherichia coli,
The antibiotic property > 95% of staphylococcus glucose coccus.
The hydrostatic test result of fiber reinforcement polypropylene random copolymer composite tube are as follows: 95 DEG C, 5Mpa, 165h, no destruction,
Without infiltration.
The room temperature impact strength of fiber reinforcement polypropylene random copolymer composite tube is 7.8KJ/m2, room temperature impact strength position
5.8KJ/m2, tensile strength 38MPa, bending strength 60MPa, after ultraviolet light 700 hours, each intensity refers to
Mark probably has dropped 10%.
Embodiment 6
The application also provides a kind of three-layer polypropylene-polyethylene compound pipe, is divided into internal layer, middle layer and outer layer, internal layer
Glass fiber reinforced layer is set between outer layer, and internal layer, the thickness ratio 3:1:1 of middle layer and outer layer, wherein inner layer material is anti-
Bacterium polypropylene agglomerate, cladding material are polythene material, and the material of glass fiber reinforced layer is staple glass fibre and toughener.
The material of toughener is HDPE, LLDPE, EVA, PA, POE, PPB etc..
The preparation of antibiotic polypropylene master batch is referring to embodiment 2.
Performance test:
The anti-microbial property of the internal layer of fiber reinforcement polypropylene random copolymer composite tube is the antibiotic property > 96% of Escherichia coli,
The antibiotic property > 96% of staphylococcus glucose coccus.
The hydrostatic test result of fiber reinforcement polypropylene random copolymer composite tube are as follows: 95 DEG C, 5Mpa, 165h, no destruction,
Without infiltration.
The room temperature impact strength of fiber reinforcement polypropylene random copolymer composite tube is 7.9KJ/m2, room temperature impact strength position
5.9KJ/m2, tensile strength 34MPa, bending strength 61MPa, after ultraviolet light 700 hours, each intensity refers to
Mark probably has dropped 10%.It is compared with embodiment 1,2,3, and intensity is declined, and is due to lacking fiber reinforcement and resistance to compression layer
Reason.
Embodiment 7
The application also provides a kind of three-layer polypropylene-polyethylene compound pipe, is divided into internal layer, middle layer and outer layer, internal layer
Glass fiber reinforced layer is set between outer layer, and internal layer, the thickness ratio 3:1:1 of middle layer and outer layer, wherein inner layer material is anti-
Bacterium polypropylene agglomerate, cladding material are polythene material, and the material of glass fiber reinforced layer is staple glass fibre and toughener.
The material of toughener is HDPE, LLDPE, EVA, PA, POE, PPB etc..
The preparation of antibiotic polypropylene master batch is referring to embodiment 3.
Performance test:
The anti-microbial property of the internal layer of fiber reinforcement polypropylene random copolymer composite tube is the antibiotic property > 94% of Escherichia coli,
The antibiotic property > 94% of staphylococcus glucose coccus.
The hydrostatic test result of fiber reinforcement polypropylene random copolymer composite tube are as follows: 95 DEG C, 5Mpa, 165h, no destruction,
Without infiltration.
The room temperature impact strength of fiber reinforcement polypropylene random copolymer composite tube is 8.0KJ/m2, room temperature impact strength position
6.0KJ/m2, tensile strength 34MPa, bending strength 62MPa, after ultraviolet light 700 hours, each intensity refers to
Mark probably has dropped 10%.
Embodiment 8
The application also provides a kind of antibacterial bilayer composite polypropylene, is divided into internal layer and outer layer, and inner layer material is antibacterial
Polypropylene agglomerate, cladding material are polypropylene material.
The preparation of antibiotic polypropylene master batch is the same as embodiment 1.
Performance test:
The anti-microbial property of the internal layer of fiber reinforcement polypropylene random copolymer composite tube is the antibiotic property > 94% of Escherichia coli,
The antibiotic property > 94% of staphylococcus glucose coccus.
The hydrostatic test result of fiber reinforcement polypropylene random copolymer composite tube are as follows: 95 DEG C, 5Mpa, 165h, no destruction,
Without infiltration.
The room temperature impact strength of fiber reinforcement polypropylene random copolymer composite tube is 7.0KJ/m2, room temperature impact strength position
5.5KJ/m2, tensile strength 31MPa, bending strength 58MPa, after ultraviolet light 700 hours, each intensity refers to
Mark probably has dropped 10%.It is compared with embodiment 1,2,3, and intensity is declined, and is due to lacking fiber reinforcement and resistance to compression layer
Reason.
Embodiment 9
The application also provides a kind of antibacterial bilayer composite polypropylene, is divided into internal layer and outer layer, and inner layer material is antibacterial
Polypropylene agglomerate, cladding material are polypropylene material.
The preparation of antibiotic polypropylene master batch is the same as embodiment 2.
Performance test:
The anti-microbial property of the internal layer of fiber reinforcement polypropylene random copolymer composite tube is the antibiotic property > 95% of Escherichia coli,
The antibiotic property > 95% of staphylococcus glucose coccus.
The hydrostatic test result of fiber reinforcement polypropylene random copolymer composite tube are as follows: 95 DEG C, 5Mpa, 165h, no destruction,
Without infiltration.
The room temperature impact strength of fiber reinforcement polypropylene random copolymer composite tube is 7.2KJ/m2, room temperature impact strength position
5.7KJ/m2, tensile strength 33MPa, bending strength 59MPa, after ultraviolet light 700 hours, each intensity refers to
Mark probably has dropped 10%.
Embodiment 10
The application also provides a kind of antibacterial bilayer composite polypropylene, is divided into internal layer and outer layer, and inner layer material is antibacterial
Polypropylene agglomerate, cladding material are polypropylene material.
The preparation of antibiotic polypropylene master batch is the same as embodiment 3.
Performance test:
The anti-microbial property of the internal layer of fiber reinforcement polypropylene random copolymer composite tube is the antibiotic property > 95% of Escherichia coli,
The antibiotic property > 95% of staphylococcus glucose coccus.
The hydrostatic test result of fiber reinforcement polypropylene random copolymer composite tube are as follows: 95 DEG C, 5Mpa, 165h, no destruction,
Without infiltration.
The room temperature impact strength of fiber reinforcement polypropylene random copolymer composite tube is 7.1KJ/m2, room temperature impact strength position
5.5KJ/m2, tensile strength 32MPa, bending strength 59MPa, after ultraviolet light 700 hours, each intensity refers to
Mark probably has dropped 10%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (8)
1. a kind of fiber reinforcement polypropylene random copolymer composite tube, which is characterized in that it includes outer layer, middle layer and internal layer,
Middle layer is set between outer layer and internal layer；Polyphenylene sulfide fibre enhancement layer, middle layer are set between outer layer and middle layer
And basalt fibre resistance to compression layer is set between internal layer.
2. a kind of fiber reinforcement polypropylene random copolymer composite tube as described in claim 1, which is characterized in that described is outer
Layer, middle layer, internal layer, polyphenylene sulfide fibre enhancement layer, the thickness ratio of basalt fibre resistance to compression layer are 1:1:1:1:1.
3. a kind of fiber reinforcement polypropylene random copolymer composite tube as described in claim 1, which is characterized in that the outer layer
Material be antibacterial atactic polypropylene agglomerate, thermoplastic polyurethane elastomer rubber and atactic copolymerized polypropene particle,
Mass fraction of the middle thermoplastic polyurethane elastomer rubber in cladding material is 5~10%, and antibiotic polypropylene master batch is in outer layer
Mass fraction in material is 1~5%.
4. a kind of fiber reinforcement polypropylene random copolymer composite tube as described in claim 1, which is characterized in that the centre
The material of layer is atactic copolymerized polypropene particle.
5. a kind of fiber reinforcement polypropylene random copolymer composite tube as described in claim 1, which is characterized in that the internal layer
Material be antibiotic polypropylene master batch and atactic copolymerized polypropene particle, quality of the antibiotic polypropylene master batch in the material of internal layer
Score is 5~15%.
6. a kind of fiber reinforcement polypropylene random copolymer composite tube as described in claim 1, which is characterized in that polyphenylene sulfide is fine
The material for tieing up enhancement layer is polyphenylene sulfide fibre and toughener, matter of the polyphenylene sulfide fibre in polyphenylene sulfide fibre enhancement layer
Measuring score is 40~60%, and the length of polyphenylene sulfide fibre is 1~10 millimeter.
7. a kind of fiber reinforcement polypropylene random copolymer composite tube as described in claim 1, which is characterized in that basalt fibre
The material of resistance to compression layer is polyphenylene sulfide fibre and toughener, quality of the basalt fibre in the material of basalt fibre resistance to compression layer
Score is 44~66%, and the length of basalt fibre is 1~10 millimeter.
8. a kind of fiber reinforcement polypropylene random copolymer composite tube as described in claim 3 or 5, which is characterized in that described
Antibiotic polypropylene master batch preparation method, the specific steps are that:
One, the preparation of bagasse whisker:
The bagasse cleaned up is taken, is dissolved under the conditions of subzero 10~15 DEG C using the urea liquid of sodium hydroxide, it is molten
After solution is complete, using the method for ultracentrifugation, the sample of centrifugation bottom of the tube is collected, then washing three is carried out using deionized water
It is secondary, then bagasse whisker is obtained for 24 hours in 60 DEG C of vacuum drying；
Two, the preparation of bagasse whisker is activated:
Using the bagasse whisker of step 1 preparation as raw material, acidification activation processing is carried out to bagasse whisker, then again 60~
Under the conditions of 80 DEG C, in the aqueous solution of edta edta, it is grafted on edta edta on bagasse whisker, mistake
It is dried in vacuo under the conditions of 60 DEG C again after filter, activation bagasse whisker is prepared；
Three, the preparation of antibacterial agent:
Activation bagasse whisker prepared by step 2 is added in copper nitrate solution, then is with the pH that nitric acid adjusts mixed solution
5.05~5.15, under 45~60 DEG C of stirring conditions, copper ion and activated biomass cellulose whiskers is made to carry out complex reaction, to
After being generated again without precipitating in mixed solution；Then adjusting pH is 6.0~6.5, then under 45~60 DEG C of stirring conditions, nitric acid is added
Magnesium solution makes magnesium ion and activation bagasse whisker carry out complex reaction, generates in solution to be mixed without precipitating and stop reaction, receive
Collect sediment to react for 24 hours in 60 DEG C of vacuum drying again, obtains antibacterial agent；
Four, the preparation of antibacterial atactic polypropylene agglomerate:
With step 3 prepare antibacterial agent, compatilizer, atactic copolymerized polypropene is raw material, after mixing using double screw extruder into
Row melting extrusion, is prepared antibiotic polypropylene master batch；
In antibiotic polypropylene master batch, the mass fraction of antibacterial agent is 1~5%, and the mass fraction of compatilizer is 0.1~1%.
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