CN208204222U - A kind of anti-scratch PE-PPR multiple tube - Google Patents

Abstract

The utility model relates to a kind of anti-scratch PE-PPR multiple tubes, are followed successively by PE layers anti-scratch, elastic cord breaker and PPR sandwich layer from outside to inside；Anti-scratch PE layers of material is polyethylene particles, the ultra-fine mica sheet of polyurethane elastomer and lamellar structure；Mass fraction of the polyurethane elastomer in anti-scratch PE layers of material is 15~20%；Mass fraction of the ultra-fine mica sheet of lamellar structure in anti-scratch PE layers of material is 1~3%.The application plays buffering, resistance to compression, anti-scratch function in stress using polyurethane elastomer；Ultra-fine mica sheet is lamellar structure material, itself has excellent wear-resisting property, and the cortex construction in ultra-fine mica sheet has anisotropy, utilize the structure of lamella, to solve the problems, such as due to inner void caused in process, ultra-fine mica sheet itself inorganic simultaneously is blended in the amorphous region of PE material, has the barrier action of steam for improving amorphous region etc., to assign excellent Scratch Resistance energy.

Description

A kind of anti-scratch PE-PPR multiple tube

Technical field

The utility model relates to PPR pipe production technical fields, are a kind of anti-scratch PE-PPR multiple tubes specifically.

Background technique

Chinese Patent Application No. 201710835825.9 is related to a kind of PPR pipe, belongs to polypropylene pipe field.By weight Number meter, successively takes 100~120 parts of acrylic resins, 20~28 parts of modified charing moss powder, 8~12 parts of modified talc powders, and 3~5 Part toughener, 1~2 part of antioxidant, 2~3 parts of coupling agents, first by acrylic resin, modified charing moss powder and modified talc powder It is mixed in four-hole boiling flask, sequentially adds toughener, antioxidant and coupling agent, after being stirred, injection molding machine is added, is molded into Type is to get PPR pipe.The PPR pipe of technical scheme preparation has excellent toughness, while mechanical strength has obtained significantly mentioning High feature.

Chinese Patent Application No. 201711266705.8 is related to a kind of PPR pipe with copper sense, includes following weight The component of part: 100 parts of PPR, 15-30 parts of graininess copper powder, 1-5 parts of flakey copper powder, 10-15 parts of dispersing agent, carbon fiber 8-18 Part, 1-3 parts of coupling agent, core-shell copolymerized 5-15 parts of object toughener, 1.3-3 parts of antioxidant of soft core hard-shell type.The PPR pipe of the application With good copper sense, low-temperature flexibility is good, no embrittlement phenomena, and heat resistance is good.

Chinese Patent Application No. 201720574206.4 is related to a kind of bridge elbow PPR pipe, the bending section shape of product itself At a bridge elbow domes, each bending section is consistent with the wall thickness of tubing ontology, and stability is high, will not be defective in quality, mentions The high stability and product quality of product, extends product service life.

Chinese Patent Application No. 201710919832.7 is related to a kind of high-intensitive PPR pipe, each component and shared parts by weight Number are as follows: 92-95 parts of PPR raw material, 1-3 parts of matrix resin, 5-10 parts of glass fibre, 1.4-2 parts of propylgallate, additive 0.1-0.5 parts.Production method the following steps are included: (1) by PPR raw material and collective's resin, glass fibre, propylgallate and It is 180-200 DEG C that additive is uniformly mixed temperature setting in mixing machine；(2) it is re-fed into extruder hopper, temperature setting is 210-220 DEG C, it is pushed into the die for molding of moulded products；(3) pipe is cooling, traction, is finally made into tubing article.This Shen Please gained PPR pipe, it is not only environmentally friendly, but also the intensity of tubing improves, and can be applied to in the higher environment of intensity requirement.

Chinese Patent Application No. 201711310199.8 is related to a kind of low-temperature impact-resistant PPR pipe and preparation method thereof, belongs to In PPR pipe preparation technical field.Component comprising following mass fraction: PPR 70~97%, plasticizing mother particle 2~25%, color masterbatch 0.1~6%, it proportionally mixes, extrusion molding is up to the low-temperature impact-resistant PPR pipe.Plasticizing mother particle includes following quality The component of score: PP 29~80%, star rubber 19~70%, antioxidant 0.05-2% are characterized in that PPR plasticizing mother particle Each raw material component mixes in proportion, adds twin-screw extrude extrusion, cooling, is granulated to obtain the PPR plasticizing mother particle.

Chinese Patent Application No. 201711266550.8 is related to a kind of PPR pipe with aluminum metal effect of high-low temperature resistant Material, the component comprising following parts by weight: 100 parts of PPR, 10-25 parts of aluminium powder, 8-18 parts of dispersing agent, soft core hard-shell type is core-shell copolymerized 3-8 parts of object, 5-10 parts of butadiene-styrene rubber, 5-10 parts of carbon fiber, 3-8 parts of acicular wollastonite fiber, 1-3 parts of coupling agent, antioxidant 1.5-3 part.The PPR pipe of the application has uniform aluminum metal effect, and low-temperature flexibility is good, and heat resistance is good.

Chinese Patent Application No. 201711266099.X is related to a kind of preparation side of PPR pipe with stainless steel effect Method, specifically: prepare the raw material of following parts by weight: 100 parts of PPR, 15-30 parts of stainless steel powder, 5-10 parts of acidic dispersion agent, alkali Property 2-6 parts of dispersing agent, maleic anhydride is grafted ethylene propylene diene rubber 5-10 part, 8-15 parts of polypropylene fibre, 1-3 parts of coupling agent, anti- 1.3-3 parts of oxygen agent；Faintly acid coupling agent solution is distributed in polypropylene fibre surface；Acidic dispersion agent solution is distributed in stainless Comminuted steel shot surface, then basic dispersion agent solution is added in stainless steel powder；PPR, maleic anhydride are grafted ethylene propylene diene rubber, antioxidant Modified stainless steel powder mixed liquor is sprayed into while being stirred obtains premix raw material；Premix raw material and modified polypropylene fiber are added Enter extruding pelletization in extruder, obtains PPR pipe.The PPR pipe of the application preparation has uniform stainless steel effect, low-temperature flexibility It is good, no embrittlement phenomena.

Chinese Patent Application No. 201721116188.1 is related to tubing technical field, and in particular a kind of anti-microbial property is good Ppr tubing, including tube body, tube body include the antibiotic layer on the inside of protective layer and protective layer, and antibiotic layer is by inorganic antibacterial layer and nanometer Antibiotic layer composition, tube body are equipped with a seat of honour, are respectively equipped with left fixed plate and right fixed plate, left fixed plate at the both ends of the seat of honour One end be equipped with a left bolt, be equipped with a left discount in one end of left bolt, one end of right fixed plate is equipped with a right side and inserts Pin is equipped with right discount in one end of right pin, and the both ends of the seat of honour are respectively equipped with the slot to match with left bolt and right pin, left Fixed plate and right fixed plate pass through shaft and the seat of honour is rotatablely connected, and elastic plectrum is additionally provided in shaft, the device tubing Antibiotic layer is increased on inner wall, so that tubing be made to reach antibacterial effect, and the unique fixed form used, is not only consolidated, And without matching casing clamp, and when not installing, the fixed plate at both ends is received in tube two sides, reduces its occupied area.

Chinese Patent Application No. 201711266741.4 is related to a kind of good PPR pipe with stainless steel effect of low-temperature flexibility Material, the component comprising following parts by weight: 100 parts of PPR, 15-30 parts of stainless steel powder, 5-10 parts of acidic dispersion agent, alkaline dispersing agent 2-6 parts, ethylene propylene diene rubber 5-10 parts of maleic anhydride grafting, 8-15 parts of polypropylene fibre, 1-3 parts of coupling agent, antioxidant 1.3-3 Part.The PPR pipe of the application has uniform stainless steel effect, and low-temperature flexibility is good, no embrittlement phenomena.

Chinese Patent Application No. 201721102134.X is related to hot-water heating tubing technical field, and specially a kind of four layers of PPR increase Strong toughening temp resistance compound thermal insulating tube, from inside to outside successively including PE-RT layers, glue layer, glass layer and PPR layers, PE-RT layers Tubing toughness, frost resistance and heat-resisting quantity can be enhanced, fiberglass layer can increase tubing intensity hardness, be unlikely to deform tubing； The application's the utility model has the advantages that the application design rationally, stable structure overcomes the problem of PPR pipe toughness and hardness deficiency；It is whole With the resistance to characteristic for freezing obdurability of high temperature resistant, it is unlikely to deform tubing in construction and in.

Chinese Patent Application No. 201710364123.7 is related to the PPR pipe that a kind of high temperature resistant is not easy deformation, by giving PPR pipe Layer resistant to high temperatures is added among part inner and outer wall, so that PPR pipe will not be bent in high temperature, plays humidification, removal is applied Security risk in work, use.

Chinese Patent Application No. 201710423339.6 is related to a kind of heat-insulated PPR pipe and its preparation process, from inside to outside according to Secondary includes inner tube, adhesive layer, middle layer and outer layer, which is characterized in that outer layer is EVA film, and middle layer is polyethylene foam heat preservation Layer, internal layer is PPR pipe, and adhesive layer is epoxide-resin glue.Heat loss when the heat-insulated PPR pipe reduces delivery has good Durability, high temperature can be resisted, can be used for a long time.

Chinese Patent Application No. 201711370312.1 is related to a kind of high voltage, high-impact PPR pipe, it is characterised in that described PPR pipe has three-decker, and pipeline middle layer (2) enhances PPR resin using fiber (4), and middle layer introduces flexible compatible simultaneously Agent, Inner tubing layers (3), outer layer raw material (1) use beta nucleater modified PPR resin.The advantages of the application: increased by introducing fiber Tubing intensity can be improved in strong layer；Flexible compatilizer is introduced simultaneously, can further improve the shock resistance of tubing；Pass through It introduces beta nucleater modified, can be further improved the toughness of tubing.By the modification of structure and additive, PPR pipe road ensure that With higher pressure resistance and erosion-resisting characteristics.

Chinese Patent Application No. 201720573609.7 is related to the PPR pipe that a kind of high temperature resistant is not easy deformation, by giving PPR pipe Layer resistant to high temperatures is added among part inner and outer wall, so that PPR pipe will not be bent in high temperature, plays humidification, removal is applied Security risk in work, use.

Chinese Patent Application No. 201720502771.X is related to tubing technical field, and discloses a kind of for beverage conveying Three layers of PPR antibacterial pipe, including tube body, tube body successively includes interior PPR antibiotic layer, middle PPR antibiotic layer and outer PPR anti-from inside to outside Bacterium layer, is provided with refractory layer between interior PPR antibiotic layer and middle PPR antibiotic layer, and the inner and outer wall of refractory layer respectively with interior PPR Antibiotic layer is fixedly connected with middle PPR antibiotic layer outer wall with inner wall, is provided with fever between middle PPR antibiotic layer and outer PPR antibiotic layer Layer, the inner and outer wall of heating layer are fixedly connected with middle PPR antibiotic layer and outer PPR antibiotic layer outer wall and inner wall respectively.This is used for Three layers of PPR antibacterial pipe of beverage conveying, by setting refractory layer and heating layer, high temperature resistant silicon glue-line and glass fiber pellets have compared with Strong heat-resisting ability, internal PPR antibiotic layer are supported and protect, and enhance tube body heat-resisting ability, while lime ball meets water Fever, can preheat tube body in cold snap, prevent tube body fragmentation, more convenient to use.

Chinese Patent Application No. 201720786021.X is related to a kind of high density polyethylene pipe workpiece for water supply, including tube body, The tube body includes PPR pipe, and the outer wall of the PPR pipe is equipped with rubber-plastic sponge layer, set convex block on the inside of second sliding block, institute The outside for stating the second sliding block is equipped with compression bar, the inside of institute's first sliding groove equipped with the first spring base, first spring base Bottom end is connected with disc pad, and first spring base is connected by spring with second spring seat, the top of the second spring seat End is equipped with the first sliding block.The high density polyethylene pipe workpiece for water supply, by the left and right ends in tube body be separately installed with prominent ring and Attachment device is inserted into through-hole by the first sliding block, annulus gasket is fixed on to the inside of cylinder, will by annulus gasket and cylinder Prominent ring clamps to fix on prominent ring, to two water pipes are attached, only when user, which wants to separate two water pipes, is Disc pad is pulled to the right while two compression bars need to be pressed, and attachment device can be split.

Chinese Patent Application No. 201720707308.9 is related to a kind of three-layer co-extruded functional tubing, including internal layer, folder Layer and outer layer, the internal layer is PPR layers of β type, interlayer is CPVC layers, outer layer is MPP layers.The advantages of the application, is: comprehensive performance Preferably.

Chinese Patent Application No. 201710728147.6 is related to a kind of plastic pipe of corrosion resistant antibiotic for sponge city The preparation method of material, main includes assigning the preferable antibiotic property of tubing by adding antibacterial agent, glass, beta nucleater in the base Energy, mechanical strength；PPR is prepared by extruder melt blending and after setting, cooling, traction, winding, technology of the package Tubing.The PPR pipe is a kind of environmentally friendly tubing of low cost, can be largely applied in sponge city；The beta nucleater The mechanical property of balance PPR pipe is cooperateed with glass, balances the toughness of PPR while improving PPR mechanical strength, and improve PPR Corrosion resistance；The antibacterial agent can effectively improve the antibiotic property of PPR, avoid the secondary dirt during sponge city water cycle Dye.The tubing of the application preparation has preferable antibiotic property, and mechanical strength is preferable, and corrosion resistance is preferable, the preparation side of the application Method is easy to operate.

Chinese Patent Application No. 201710882495.9 is related to a kind of low temperature resistant PP-R pipe and preparation method thereof, by with The raw material of lower parts by weight is made: 50-70 parts of PP-R, 10-15 parts of PP-B, 2-3 parts of poly butylene succinates, egg-shell meal 0.5- 6 parts, 1-2 parts of starch, 6-7 parts of block copolymerization polypropylenes, 1-2 parts of maleic anhydride-styrene copolymers, 4-5 parts of sorbierites, 1-2 Part beta crystal-type nucleater, 8-9 parts of phthalic acid dimethyl esters, 1-2 parts of formamides.The application passes through to the inorganic particulate in color masterbatch It carries out area load nucleating agent to be modified, while the PPR pipe that PP-B induction crystallization prepares high-beta crystal content is added, with existing skill The problem of art is compared, and β crystalline substance crystallization effect significantly improves, can effectively solve the problem that PP-R pipe black brittleness.

Chinese Patent Application No. 201710181975.2 is related to a kind of self-cleaning materials in the tube and preparation method thereof and its manufactured multiple Close pipe.The self-cleaning materials in the tube include the raw material of following parts by weight: 50-60 parts of Kynoar, polymethyl methacrylate 35- 46 parts, 2-8 parts of maleic anhydride modified polypropylene and 0.1-0.5 parts of tristerin.The self-cleaning materials in the tube moisture content of the application < 0.3, appearance be it is transparent or semitransparent, with outer layer PPR be coextruded composite molding surface smoothness (or roughness Ra≤0.1 μm) Level is not less than the molded surface of routine PPR material.Self-cleaning materials in the tube molding shrinkage (containing storage and use process expansion and Shrink) it is almost the same with the PPR or intermediate function layer material of coextrusion.Meet national standard with the tubing that self-cleaning materials in the tube produce GB/T18742.2-2002 standard.

Chinese Patent Application No. 201721121239.X is related to a kind of corrosion-resistant stainless steel pipe, including stainless steel tube body, institute It states and is equipped with internal lining pipe in stainless steel tube body, rubber buffer pipe, institute are equipped between the liner pipe outer wall and stainless steel inboard wall of tube body It states rubber buffer pipe outer wall and is evenly equipped with several outer retraction slots, the rubber buffer inside pipe wall is evenly equipped with several contract slots, The outer retraction slot is in the rubber buffer pipe outer wall between two neighboring contract slot, the stainless steel inboard wall of tube body and rubber Glue buffers pipe outer wall interference fit, and the liner pipe outer wall and rubber buffer inside pipe wall are interference fitted.The application passes through stainless Rubber buffer pipe is set between steel tube body and internal lining pipe, when conveying overheat or subcooled liquid, due to internal lining pipe and stainless steel tube The linear expansion coefficient of body is different, and gap size between the two is caused to change, and the gap of this variation is had elasticity The rubber buffer pipe of recovery capability is filled, and the appearance of the failures such as delamination or liner pipe explosion is avoided.

Chinese Patent Application No. 201710946484.2 is related to managing outside a kind of low temperature resistant PP-R solar energy room and its preparation side Method is prepared from the following raw materials in parts by weight: 50-70 parts of PP-R, 10-15 parts of PP-B, 2-3 parts of poly butylene succinates, 5-6 parts of nanosized SiO_2,1-2 parts of starch, 6-7 parts of long-chain branching polypropylenes, 1-2 parts of maleic anhydride-styrene copolymers, 4-5 parts Sorbierite, 1-2 parts of beta crystal-type nucleaters, 8-9 parts of phthalic acid dimethyl esters, 1-2 parts of formamides.The application passes through in color masterbatch Inorganic particulate carry out that area load nucleating agent is modified, while the PPR pipe that PP-B induction crystallization prepares high-beta crystal content is added Material, compared with prior art, the problem of β crystalline substance crystallization effect significantly improves, can effectively solve the problem that PP-R pipe black brittleness.

Chinese Patent Application No. 201710439229.9 be related to a kind of anti-solarization plastic composition pipeline of novel prefabricated thermal insulation and its The spiral mold for connecting twin-screw is heated to 140 DEG C~180 DEG C by production method, first choice；Ethylene foam extrusion machine is heated to 120 DEG C~160 DEG C inside, which are passed through 0.6~1.0Mpa and compress and liquefy petroleum gas, foams, and after foaming is good, passes through a wherein spiral shell Bar is passed through spiral mold；EVA material is added in protective layer extruder again and is heated to 120 DEG C~150 DEG C, after heating EVA material is passed through spiral mold by another screw rod；Mold temperature is cooled down later to 75 DEG C~90 DEG C, keeps the temperature 0.5~1h；Most Finished product PERT, PEX, PB or PPR pipe are led to the spiral mold for being put into twin-screw by dragger afterwards, are made anti-with heat preservation Shine the plastic composition pipeline of function.External protection of the application using EVA material as pipeline, external protection, insulating layer and work Inner tube very high integrity.

Chinese Patent Application No. 201720042683.6 is related to a kind of heat-insulating pipe, and this application involves heat preservation Manifold technology necks Domain specifically discloses a kind of insulating tube.The insulating tube of the application, including external tube layer, middle tube layer, interior tube layer are additionally equipped with U-shaped solid Determine pipe clamp.Three-layer pipe layer combines closely to form whole pipe structure；Described injection molding of three-layer pipe body structure.The application's Insulating tube produces, is easy to process, and installation cutting technique is simple；It is integral close that the insulating tube of the application is that three-body is combined closely Structure, intermediate seamless, no air layer, has very strong toughness, and resist cold high temperature resistant, will not deform, will not rupture, improve Safety in insulating tube use also increases the service life of insulating tube.

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The purpose of the utility model is to overcome the deficiencies in the prior art, provide a kind of anti-scratch PE-PPR multiple tube and its Manufacturing method.

The purpose of this utility model is achieved through the following technical solutions:

A kind of anti-scratch PE-PPR multiple tube is followed successively by PE layers anti-scratch, elastic cord breaker and PPR core from outside to inside Layer；

Anti-scratch PE layers of outer surface is outer lug structure, the circular configuration unit that outer lug structure is attached most importance to multiple.Utilize evagination knot Structure plays the role of buffering and protection in stress；To protect the sandwich layer of PPR sandwich layer.

Anti-scratch PE layers of inner surface is equipped with groove, and groove is circular configuration, the ultra-fine cloud of setting lamellar structure in groove Master slice.

PE layers anti-scratch, the thickness ratio of elastic cord breaker and PPR sandwich layer is 2:1:2.

Anti-scratch PE layers of material is polyethylene particles, the ultra-fine mica sheet of polyurethane elastomer and lamellar structure.It is poly- Mass fraction of the urethane elastomer in anti-scratch PE layers of material is 15~20%；The ultra-fine mica sheet of lamellar structure is anti-scratch Wiping the mass fraction in PE layers of material is 1~3%.Buffering is played in stress using polyurethane elastomer, resistance to compression is anti-scratch Function.Ultra-fine mica sheet is lamellar structure material, itself has excellent wear-resisting property, and the cortex knot in ultra-fine mica sheet Structure has anisotropy, using the structure of lamella, to solve the problems, such as due to inner void caused in process, while nothing The ultra-fine mica sheet of machine itself is blended in the amorphous region of PE material, has the barrier action of steam for improving amorphous region etc., To assign excellent Scratch Resistance energy.

The material of elastic cord breaker is ptt fiber, glass fibre and toughener.Material of the ptt fiber in elastic cord breaker Mass fraction in material is 10~20%, and mass fraction of the glass fibre in the material of elastic cord breaker is 10~20%, is increased Tough dose is the materials such as low density polyethylene (LDPE).Spring function is provided using ptt fiber, and glass fibre provides enough intensity.Benefit Determine that the fiber has high resiliency and good elastic recovery rate with the macromolecular surprise carbon structure of PTT.For stretching fiber, The relative breaking strength ratio PET (terylene) of ptt fiber wants low 20~30%.Experiments have shown that: when extension at break is 25%, PTT The relative breaking strength of fiber is 3~3.5cN/tex, but higher than wool or cotton, thus with cotton and wool blend when can be improved it is mixed The intensity of spinning.Another outstanding advantages of ptt fiber are that have excellent tensile property.

The material of PPR sandwich layer is antibacterial PPR master batch or multifunctional antibiotic PPR master batch.

The preparation method of antibacterial PPR master batch, the specific steps are that:

One, the preparation of bluish dogbane whisker:

It takes what is cleaned up to spread out the dregs of linseeds or sesame seeds, is dissolved at subzero 10~15 DEG C using the urea liquid of potassium 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 bluish dogbane whisker is obtained for 24 hours in 60 DEG C of vacuum drying；

The mass fraction of sodium hydroxide is 2~8% in the urea liquid of the potassium hydroxide, and the mass fraction of urea is 1.5~4%；

In the ultracentrifugation technique, centrifugal force is 8000~13000g；

Dogbane tea itself is a kind of good natural antibacterial health-care material, is that good fiber crops are fine in bluish dogbane tea grounds itself Dimension has fiber content high, and the cellulosic structure degree of orientation is high in fiber, fiber alignment marshalling, and fibre strength is high, leads to simultaneously Hot-cold lysis in the aqueous slkali using current urea is crossed, impurity can be significantly removed and is reduced in cellulose as orientation knot Brilliant crystal whisker materials, thus by the dissolution of the aqueous slkali of urea after, cellulose whiskers natural in flaxen fiber are retained in lysate Material；And crystal whisker materials enhance as a kind of excellent reinforcing material for construction material, the fields such as enhancing of plastics etc. are answered With extensive, and after cellulose whiskers, reduce the dehydration due to the ehter bond in the glucose molecule structure in cellulose and Keep its heat resisting temperature low, easily carbonizes and cause to decompose in plastic processes, lead to reinforcing material strength reduction；Therefore Random fiber element is dissolved by the aqueous slkali of low temperature urea, obtains natural cellulose whiskers material, has heat resisting temperature high, increases The advantages that potent fruit is good.

Two, it is acidified the preparation of bluish dogbane whisker:

Using the bluish dogbane whisker of step 1 preparation as raw material, bluish dogbane whisker is carried out acidification activation processing, is then existed again Under the conditions of 60~80 DEG C, in the aqueous solution of 1,3- trimethylen-edinitrilo-tetraacetic acid, 1,3- trimethylen-edinitrilo-tetraacetic acid is made to be grafted on bluish dogbane whisker On, filtering is dried in vacuo under the conditions of 60 DEG C again, and acidification bluish dogbane whisker is prepared；

The acidification activation process of the acidification bluish dogbane whisker is Strong oxdiative acidic mixed solution, at 80~90 DEG C Under the conditions of impregnate 3~6h；

The Strong oxdiative acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the quality of nitric acid solution is dense Degree is 10~16%, and the mass concentration of hydrogen peroxide solution is 10%~16%；

The mass fraction of 1,3- trimethylen-edinitrilo-tetraacetic acid is 5~9% in the aqueous solution of the 1,3- trimethylen-edinitrilo-tetraacetic acid；

The graft reaction time is 1.5~2.0h；

Containing the hydroxyl structure of glucose in cellulosic structure, esterification can occur with carboxylic acid structure, utilize esterification Reaction is presently the most effective means to raising and the functionalization of cellulose itself；But there is also the function of functional material itself It can be difficult to merge with material, especially influence function and processing performance；Therefore the application is by being acidified cellulose and oxygen Change processing improves hydroxyl activity in fibre structure using the strong oxidation of nitric acid and hydrogen peroxide, to be conducive to and 1,3- the third two Esterification occurs in water phase for amine tetraacethyl, avoid carboxylic acid structure in 1, the 3- trimethylen-edinitrilo-tetraacetic acid due to aqueous solution with The problems such as hydroxyl structure activity is low, and esterification rate is slow, and enzymatic synthesis condition is harsh；The 1,3- trimethylen-edinitrilo-tetraacetic acid structure energy introduced simultaneously It is enough to carry out complex reaction with metal ion well, to improve the Heat-resistant stable performance of cellulose whiskers, and due to complexing Ion itself is precipitated in cellulose surface, to improve its functional effect and reinforcing effect.

Three, the preparation of biomass antibacterial agent:

Acidification bluish dogbane whisker prepared by step 2 is added in cuprous nitrate solution, then with the pH of nitre acid-conditioning solution It is 5.05~5.15, under 45~60 DEG C of stirring conditions, so that cuprous ion and acidification bluish dogbane whisker is carried out complex reaction, to molten After generating without precipitating again in liquid, obtain just precipitating；Then Adlerika is added, is 6.0~6.5 with sulphur acid for adjusting pH, then Under 45~60 DEG C of stirring conditions, makes magnesium ion and just precipitate to carry out complex reaction, generate and stop instead without precipitating in solution to be mixed It answers, collects sediment and reacted for 24 hours in 60 DEG C of vacuum drying again, obtain biomass antibacterial agent；

The mass values of the acidification bluish dogbane whisker and cuprous nitrate are 1:0.15~1:0.26；

The mass values of the acidification bluish dogbane whisker and magnesium sulfate are 1:0.10~1:0.16；

The cuprous nitrate mass fraction of the cuprous nitrate solution is 15~27%；

The magnesium sulfate mass fraction of the Adlerika is 10~17%.

Biomass cellulose whisker after acidified itself contains can be with the amino and carbonyl knot of complexing of metal ion Structure, by with after complexing of metal ion, avoid amino and carbonyl structure pyrolytic；The zinc ion of complexing has excellent simultaneously Different antibacterial effect, but copper ion itself has the function of catalyst, polyester degradation, therefore by the control and regulation 1 of pH, 3- the third two The complexing sequence of amine tetraacethyl and metal ion, reaches and cuprous ion is first complexed on biomass cellulose whisker, then network again Magnesium ion is closed, achievees the purpose that the cladding to zinc ion, the loss of cuprous ion is avoided and leads to the degradation of substrate, to mention The intensity of superpolyester.And crystal whisker materials are the material with certain draw ratio, by after the complexation of metal ions of surface, both With the heat-resistant stability for improving crystal whisker materials, while also there is the roughness for improving surface, improves compatible with substrate material Property structure, to improve reinforcing effect.

Four, the preparation of antibacterial PPR master batch:

Biomass antibacterial agent prepared by step 3, polyethylene glycol and PPR particle are raw material, are prepared by melt blending Obtain antibacterial PPR master batch.Mass fraction of the biomass antibacterial agent in antibacterial PPR master batch is 1~3%, and polyethylene glycol is in antibacterial Mass fraction in PPR master batch is 1~3%.

The preparation method of dual antibacterial PPR master batch, the specific steps are that:

One, the preparation of bluish dogbane whisker:

It takes what is cleaned up to spread out the dregs of linseeds or sesame seeds, is dissolved at subzero 10~15 DEG C using the urea liquid of potassium 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 bluish dogbane whisker is obtained for 24 hours in 60 DEG C of vacuum drying；

The mass fraction of sodium hydroxide is 2~8% in the urea liquid of the potassium hydroxide, and the mass fraction of urea is 1.5~4%；

In the ultracentrifugation technique, centrifugal force is 8000~13000g；

Two, it is acidified the preparation of bluish dogbane whisker:

Using the bluish dogbane whisker of step 1 preparation as raw material, bluish dogbane whisker is carried out acidification activation processing, is then existed again Under the conditions of 60~80 DEG C, in the aqueous solution of 1,3- trimethylen-edinitrilo-tetraacetic acid, 1,3- trimethylen-edinitrilo-tetraacetic acid is made to be grafted on bluish dogbane whisker On, filtering is dried in vacuo under the conditions of 60 DEG C again, and acidification bluish dogbane whisker is prepared；

The acidification activation process of the acidification bluish dogbane whisker is Strong oxdiative acidic mixed solution, at 80~90 DEG C Under the conditions of impregnate 3~6h；

The Strong oxdiative acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the quality of nitric acid solution is dense Degree is 10~16%, and the mass concentration of hydrogen peroxide solution is 10%~16%；

The mass fraction of 1,3- trimethylen-edinitrilo-tetraacetic acid is 5~9% in the aqueous solution of the 1,3- trimethylen-edinitrilo-tetraacetic acid；

The graft reaction time is 1.5~2.0h；

Three, the preparation of biomass antibacterial agent:

Acidification bluish dogbane whisker prepared by step 2 is added in cuprous nitrate solution, then with the pH of nitre acid-conditioning solution It is 5.05~5.15, under 45~60 DEG C of stirring conditions, so that cuprous ion and acidification bluish dogbane whisker is carried out complex reaction, to molten After generating without precipitating again in liquid, obtain just precipitating；Then Adlerika is added, is 6.0~6.5 with sulphur acid for adjusting pH, then Under 45~60 DEG C of stirring conditions, makes magnesium ion and just precipitate to carry out complex reaction, generate and stop instead without precipitating in solution to be mixed It answers, collects sediment and reacted for 24 hours in 60 DEG C of vacuum drying again, obtain biomass antibacterial agent；

The mass values of the acidification bluish dogbane whisker and cuprous nitrate are 1:0.15~1:0.26；

The mass values of the acidification bluish dogbane whisker and magnesium sulfate are 1:0.10~1:0.16；

The cuprous nitrate mass fraction of the cuprous nitrate solution is 15~27%；

The magnesium sulfate mass fraction of the Adlerika is 10~17%.

Four, chitin modified antibacterial agent

Superparamagnetic nickel colloidal nanocrystals cluster is dissolved in the aqueous solution of ethyl alcohol, citric acid solution is then added, is led to It crosses microwave to be dispersed with stirring after mixing, then isolated product, is finally cleaned to obtain hydrophily superparamagnetic with deionized water Nickel colloidal nanocrystals cluster；Hydrophily superparamagnetic nickel colloidal nanocrystals cluster and chitosan material are subjected to mixed grinding, obtained Chitin modified antibacterial agent；

The time that microwave is dispersed with stirring mixing is 2~4 hours, speed 2000-24000r/min.

The molar ratio of citric acid and superparamagnetic nickel colloidal nanocrystals cluster in citric acid solution is 1:0.12~1:0.6；

The application carries out surface to superparamagnetic nickel colloidal nanocrystals cluster using citric acid and is modified, and mainly utilizes citric acid In citrate and reacted with the hydroxyl in hydroxylated superparamagnetic nickel colloidal nanocrystals cluster, in superparamagnetic nickel colloid Nanocrystal cluster surface forms adsorption layer, because hydroxyl is contained on its surface, is easy to combine with the amino in chitosan material, be formed Absorption is to prepare chitin modified antibacterial agent.Chitosan and its derivative has preferable antibacterial activity, can inhibit some true The growth and breeding of bacterium, bacterium and virus.Therefore chitin modified antibacterial agent has good biological antibiotic effect.

Five, the preparation of dual antibacterial PPR master batch:

By biological antibiosis agent, chitin modified antibacterial agent, dual antibacterial is prepared by melt blending in polyvinyl alcohol PPR master batch.Mass fraction of the biomass antibacterial agent in dual antibacterial PPR master batch is 1~3%, and polyethylene glycol is in dual antibacterial Mass fraction in PPR master batch is 1~3%, and mass fraction of the polyethylene glycol in dual antibacterial PPR master batch is 1~3%.

A kind of manufacturing method of anti-scratch PE-PPR multiple tube, every layer of conventional extrusion molding process by tubing, and layer Hot-melt adhesive paste is carried out by hot melt adhesive between layer, this is the technical conditions of mature technique.

Compared with prior art, the good effect of the utility model is:

Anti-scratch PE layers of material is polyethylene particles, the ultra-fine mica sheet of polyurethane elastomer and lamellar structure.It is poly- Mass fraction of the urethane elastomer in anti-scratch PE layers of material is 15~20%；The ultra-fine mica sheet of lamellar structure is anti-scratch Wiping the mass fraction in PE layers of material is 1~3%.Buffering is played in stress using polyurethane elastomer, resistance to compression is anti-scratch Function.Ultra-fine mica sheet is lamellar structure material, itself has excellent wear-resisting property, and the cortex knot in ultra-fine mica sheet Structure has anisotropy, using the structure of lamella, to solve the problems, such as due to inner void caused in process, while nothing The ultra-fine mica sheet of machine itself is blended in the amorphous region of PE material, has the barrier action of steam for improving amorphous region etc., To assign excellent Scratch Resistance energy.

Chitosan source the Nature, pollution-free and do not injure to human body, chitosan and its derivative has preferable antibacterial Activity can inhibit the growth and breeding of some fungies, bacterium and virus.Therefore chitin modified antibacterial agent has good biology Antibacterial effect.

Detailed description of the invention

The structural schematic diagram of Fig. 1 embodiments herein 1；

The label in accompanying drawing is: 1PPR sandwich layer, 2 elastic cord breakers, 3 is PE layers anti-scratch, 31 outer lug structures, 32 grooves.

Specific embodiment

The specific embodiment of a kind of anti-scratch PE-PPR multiple tube of the utility model presented below and its manufacturing method.

Embodiment 1

Attached drawing 1 is referred to, a kind of anti-scratch PE-PPR multiple tube is followed successively by anti-scratch PE layer 3, elastic buffer from outside to inside 2 and PPR of layer sandwich layer 1；

Anti-scratch PE layers of outer surface is outer lug structure 31, the circular configuration unit that outer lug structure is attached most importance to multiple.Utilize evagination Structure plays the role of buffering and protection in stress；To protect the sandwich layer of PPR sandwich layer.

Anti-scratch PE layers of inner surface is equipped with groove 32, and groove is circular configuration, and setting lamellar structure is ultra-fine in groove Mica sheet.

PE layers anti-scratch, the thickness ratio of elastic cord breaker and PPR sandwich layer is 2:1:2.

Anti-scratch PE layers of material is polyethylene particles, the ultra-fine mica sheet of polyurethane elastomer and lamellar structure.It is poly- Mass fraction of the urethane elastomer in anti-scratch PE layers of material is 15%；The ultra-fine mica sheet of lamellar structure is in anti-scratch PE Mass fraction in the material of layer is 1%.Buffering, resistance to compression, anti-scratch function are played in stress using polyurethane elastomer.It is super Thin mica sheet is lamellar structure material, itself has excellent wear-resisting property, and the cortex construction in ultra-fine mica sheet has Anisotropy, using the structure of lamella, to solve the problems, such as due to inner void caused in process, and meanwhile it is inorganic super Thin mica sheet itself is blended in the amorphous region of PE material, has the barrier action of steam for improving amorphous region etc., to assign Give excellent Scratch Resistance energy.

The material of elastic cord breaker is ptt fiber, glass fibre and toughener.Material of the ptt fiber in elastic cord breaker Mass fraction in material is 10%, and mass fraction of the glass fibre in the material of elastic cord breaker is 10%, and toughener is low The materials such as density polyethylene.Spring function is provided using ptt fiber, and glass fibre provides enough intensity.Utilize the big of PTT Molecule surprise carbon structure determines that the fiber has high resiliency and good elastic recovery rate.For stretching fiber, ptt fiber Relative breaking strength ratio PET (terylene) wants low 20~30%；Another outstanding advantages of ptt fiber are that there is excellent stretching to return Elasticity.

The material of PPR sandwich layer is antibacterial PPR master batch or multifunctional antibiotic PPR master batch.

The preparation method of antibacterial PPR master batch, the specific steps are that:

One, the preparation of bluish dogbane whisker:

It takes what is cleaned up to spread out the dregs of linseeds or sesame seeds, is dissolved at subzero 10~15 DEG C using the urea liquid of potassium 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 bluish dogbane whisker is obtained for 24 hours in 60 DEG C of vacuum drying；

The mass fraction of sodium hydroxide is 2% in the urea liquid of the potassium hydroxide, and the mass fraction of urea is 1.5%；

In the ultracentrifugation technique, centrifugal force is 8000~13000g；

Two, it is acidified the preparation of bluish dogbane whisker:

Using the bluish dogbane whisker of step 1 preparation as raw material, bluish dogbane whisker is carried out acidification activation processing, is then existed again Under the conditions of 60~80 DEG C, in the aqueous solution of 1,3- trimethylen-edinitrilo-tetraacetic acid, 1,3- trimethylen-edinitrilo-tetraacetic acid is made to be grafted on bluish dogbane whisker On, filtering is dried in vacuo under the conditions of 60 DEG C again, and acidification bluish dogbane whisker is prepared；

The acidification activation process of the acidification bluish dogbane whisker is Strong oxdiative acidic mixed solution, at 80~90 DEG C Under the conditions of impregnate 3~6h；

The Strong oxdiative acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the quality of nitric acid solution is dense Degree is 10%, and the mass concentration of hydrogen peroxide solution is 10%%；

The mass fraction of 1,3- trimethylen-edinitrilo-tetraacetic acid is 5% in the aqueous solution of the 1,3- trimethylen-edinitrilo-tetraacetic acid；

The graft reaction time is 1.5~2.0h；

Three, the preparation of biomass antibacterial agent:

Acidification bluish dogbane whisker prepared by step 2 is added in cuprous nitrate solution, then with the pH of nitre acid-conditioning solution It is 5.05~5.15, under 45~60 DEG C of stirring conditions, so that cuprous ion and acidification bluish dogbane whisker is carried out complex reaction, to molten After generating without precipitating again in liquid, obtain just precipitating；Then Adlerika is added, is 6.0~6.5 with sulphur acid for adjusting pH, then Under 45~60 DEG C of stirring conditions, makes magnesium ion and just precipitate to carry out complex reaction, generate and stop instead without precipitating in solution to be mixed It answers, collects sediment and reacted for 24 hours in 60 DEG C of vacuum drying again, obtain biomass antibacterial agent；

The mass values of the acidification bluish dogbane whisker and cuprous nitrate are 1:0.15；

The mass values of the acidification bluish dogbane whisker and magnesium sulfate are 1:0.10；

The cuprous nitrate mass fraction of the cuprous nitrate solution is 15%；

The magnesium sulfate mass fraction of the Adlerika is 10%.

Four, the preparation of antibacterial PPR master batch:

Biomass antibacterial agent prepared by step 3, polyethylene glycol and PPR particle are raw material, are prepared by melt blending Obtain antibacterial PPR master batch.Mass fraction of the biomass antibacterial agent in antibacterial PPR master batch is 1%, and polyethylene glycol is in antibacterial PPR Mass fraction in master batch is 1%.

The preparation method of dual antibacterial PPR master batch, the specific steps are that:

One, the preparation of bluish dogbane whisker:

It takes what is cleaned up to spread out the dregs of linseeds or sesame seeds, is dissolved at subzero 10~15 DEG C using the urea liquid of potassium 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 bluish dogbane whisker is obtained for 24 hours in 60 DEG C of vacuum drying；

The mass fraction of sodium hydroxide is 2% in the urea liquid of the potassium hydroxide, and the mass fraction of urea is 1.5%；

In the ultracentrifugation technique, centrifugal force is 8000~13000g；

Two, it is acidified the preparation of bluish dogbane whisker:

Using the bluish dogbane whisker of step 1 preparation as raw material, bluish dogbane whisker is carried out acidification activation processing, is then existed again Under the conditions of 60~80 DEG C, in the aqueous solution of 1,3- trimethylen-edinitrilo-tetraacetic acid, 1,3- trimethylen-edinitrilo-tetraacetic acid is made to be grafted on bluish dogbane whisker On, filtering is dried in vacuo under the conditions of 60 DEG C again, and acidification bluish dogbane whisker is prepared；

The acidification activation process of the acidification bluish dogbane whisker is Strong oxdiative acidic mixed solution, at 80~90 DEG C Under the conditions of impregnate 3~6h；

The Strong oxdiative acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the quality of nitric acid solution is dense Degree is 10%, and the mass concentration of hydrogen peroxide solution is 10%%；

The mass fraction of 1,3- trimethylen-edinitrilo-tetraacetic acid is 5% in the aqueous solution of the 1,3- trimethylen-edinitrilo-tetraacetic acid；

The graft reaction time is 1.5~2.0h；

Three, the preparation of biomass antibacterial agent:

Acidification bluish dogbane whisker prepared by step 2 is added in cuprous nitrate solution, then with the pH of nitre acid-conditioning solution It is 5.05~5.15, under 45~60 DEG C of stirring conditions, so that cuprous ion and acidification bluish dogbane whisker is carried out complex reaction, to molten After generating without precipitating again in liquid, obtain just precipitating；Then Adlerika is added, is 6.0~6.5 with sulphur acid for adjusting pH, then Under 45~60 DEG C of stirring conditions, makes magnesium ion and just precipitate to carry out complex reaction, generate and stop instead without precipitating in solution to be mixed It answers, collects sediment and reacted for 24 hours in 60 DEG C of vacuum drying again, obtain biomass antibacterial agent；

The mass values of the acidification bluish dogbane whisker and cuprous nitrate are 1:0.15；

The mass values of the acidification bluish dogbane whisker and magnesium sulfate are 1:0.10；

The cuprous nitrate mass fraction of the cuprous nitrate solution is 15%；

The magnesium sulfate mass fraction of the Adlerika is 10%.

Four, chitin modified antibacterial agent

Superparamagnetic nickel colloidal nanocrystals cluster is dissolved in the aqueous solution of ethyl alcohol, citric acid solution is then added, is led to It crosses microwave to be dispersed with stirring after mixing, then isolated product, is finally cleaned to obtain hydrophily superparamagnetic with deionized water Nickel colloidal nanocrystals cluster；Hydrophily superparamagnetic nickel colloidal nanocrystals cluster and chitosan material are subjected to mixed grinding, obtained Chitin modified antibacterial agent；

The time that microwave is dispersed with stirring mixing is 2~4 hours, speed 2000-24000r/min.

The molar ratio of citric acid and superparamagnetic nickel colloidal nanocrystals cluster in citric acid solution is 1:0.12；

The application carries out surface to superparamagnetic nickel colloidal nanocrystals cluster using citric acid and is modified, and mainly utilizes citric acid In citrate and reacted with the hydroxyl in hydroxylated superparamagnetic nickel colloidal nanocrystals cluster, in superparamagnetic nickel colloid Nanocrystal cluster surface forms adsorption layer, because hydroxyl is contained on its surface, is easy to combine with the amino in chitosan material, be formed Absorption is to prepare chitin modified antibacterial agent.Chitosan and its derivative has preferable antibacterial activity, can inhibit some true The growth and breeding of bacterium, bacterium and virus.Therefore chitin modified antibacterial agent has good biological antibiotic effect.Superparamagnetic nickel The preparation method of colloidal nanocrystals cluster, by NiCl₂It is synthesized with NaOH by liquid phase method, the technique specifically synthesized in detail Route is referring to Superparamagnetic nickel colloidal nanocrystal clusters with antibacterial activity and bacteria binding ability(Nat.Nanotech.2018

doi:10.1038/s41565-018-0108-0)。

Five, the preparation of dual antibacterial PPR master batch:

By biological antibiosis agent, chitin modified antibacterial agent, dual antibacterial is prepared by melt blending in polyvinyl alcohol PPR master batch.Mass fraction of the biomass antibacterial agent in dual antibacterial PPR master batch is 1%, and polyethylene glycol is in dual antibacterial PPR Mass fraction in master batch is 1%, and mass fraction of the polyethylene glycol in dual antibacterial PPR master batch is 1%.

When the material of sandwich layer is antibacterial PPR master batch, the sandwich layer anti-microbial property of the tubing of the application is to Escherichia coli Antibiotic property > 90%, to the antibiotic property > 90% of staphylococcus glucose coccus.The sandwich layer anti-microbial property of the tubing of the application is pair The later antibiotic property > 90% in 48 hours of Escherichia coli, to 48 hours of staphylococcus glucose coccus later antibiotic property > 90%.

When the material of sandwich layer is dual antibacterial PPR master batch, the sandwich layer anti-microbial property of the tubing of the application is to large intestine bar The antibiotic property > 97% of bacterium, to the antibiotic property > 97% of staphylococcus glucose coccus.The sandwich layer anti-microbial property of the tubing of the application For the later antibiotic property > 97% in 48 hours to Escherichia coli, 48 hours to staphylococcus glucose coccus later antibiotic properties > 97%.It can be seen that the antibacterial effect of dual antibacterial matrices is preferable.

Embodiment 2

A kind of anti-scratch PE-PPR multiple tube is followed successively by PE layers anti-scratch, elastic cord breaker and PPR core from outside to inside Layer；

Anti-scratch PE layers of outer surface is outer lug structure, the circular configuration unit that outer lug structure is attached most importance to multiple.Utilize evagination knot Structure plays the role of buffering and protection in stress；To protect the sandwich layer of PPR sandwich layer.

Anti-scratch PE layers of inner surface is equipped with groove, and groove is circular configuration, the ultra-fine cloud of setting lamellar structure in groove Master slice.

PE layers anti-scratch, the thickness ratio of elastic cord breaker and PPR sandwich layer is 2:1:2.

Anti-scratch PE layers of material is polyethylene particles, the ultra-fine mica sheet of polyurethane elastomer and lamellar structure.It is poly- Mass fraction of the urethane elastomer in anti-scratch PE layers of material is 17%；The ultra-fine mica sheet of lamellar structure is in anti-scratch PE Mass fraction in the material of layer is 2%.Buffering, resistance to compression, anti-scratch function are played in stress using polyurethane elastomer.It is super Thin mica sheet is lamellar structure material, itself has excellent wear-resisting property, and the cortex construction in ultra-fine mica sheet has Anisotropy, using the structure of lamella, to solve the problems, such as due to inner void caused in process, and meanwhile it is inorganic super Thin mica sheet itself is blended in the amorphous region of PE material, has the barrier action of steam for improving amorphous region etc., to assign Give excellent Scratch Resistance energy.

The material of elastic cord breaker is ptt fiber, glass fibre and toughener.Material of the ptt fiber in elastic cord breaker Mass fraction in material is 15%, and mass fraction of the glass fibre in the material of elastic cord breaker is 15%, and toughener is low The materials such as density polyethylene.Spring function is provided using ptt fiber, and glass fibre provides enough intensity.Utilize the big of PTT Molecule surprise carbon structure determines that the fiber has high resiliency and good elastic recovery rate.For stretching fiber, ptt fiber Relative breaking strength ratio PET (terylene) wants low 20~30%.Experiments have shown that: when extension at break be 25% when, ptt fiber it is opposite Breaking strength is 3~3.5cN/tex, but higher than wool or cotton, thus with intensity that mixed yarn can be improved when cotton and wool blend. Another outstanding advantages of ptt fiber are that have excellent tensile property.

The material of PPR sandwich layer is antibacterial PPR master batch or multifunctional antibiotic PPR master batch.

The preparation method of antibacterial PPR master batch, the specific steps are that:

One, the preparation of bluish dogbane whisker:

It takes what is cleaned up to spread out the dregs of linseeds or sesame seeds, is dissolved at subzero 10~15 DEG C using the urea liquid of potassium 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 bluish dogbane whisker is obtained for 24 hours in 60 DEG C of vacuum drying；

The mass fraction of sodium hydroxide is 5% in the urea liquid of the potassium hydroxide, and the mass fraction of urea is 2.5%；

In the ultracentrifugation technique, centrifugal force is 8000~13000g；

Two, it is acidified the preparation of bluish dogbane whisker:

Using the bluish dogbane whisker of step 1 preparation as raw material, bluish dogbane whisker is carried out acidification activation processing, is then existed again Under the conditions of 60~80 DEG C, in the aqueous solution of 1,3- trimethylen-edinitrilo-tetraacetic acid, 1,3- trimethylen-edinitrilo-tetraacetic acid is made to be grafted on bluish dogbane whisker On, filtering is dried in vacuo under the conditions of 60 DEG C again, and acidification bluish dogbane whisker is prepared；

The acidification activation process of the acidification bluish dogbane whisker is Strong oxdiative acidic mixed solution, at 80~90 DEG C Under the conditions of impregnate 3~6h；

The Strong oxdiative acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the quality of nitric acid solution is dense Degree is 14%, and the mass concentration of hydrogen peroxide solution is 14%；

The mass fraction of 1,3- trimethylen-edinitrilo-tetraacetic acid is 7% in the aqueous solution of the 1,3- trimethylen-edinitrilo-tetraacetic acid；

The graft reaction time is 1.5~2.0h；

Three, the preparation of biomass antibacterial agent:

Acidification bluish dogbane whisker prepared by step 2 is added in cuprous nitrate solution, then with the pH of nitre acid-conditioning solution It is 5.05~5.15, under 45~60 DEG C of stirring conditions, so that cuprous ion and acidification bluish dogbane whisker is carried out complex reaction, to molten After generating without precipitating again in liquid, obtain just precipitating；Then Adlerika is added, is 6.0~6.5 with sulphur acid for adjusting pH, then Under 45~60 DEG C of stirring conditions, makes magnesium ion and just precipitate to carry out complex reaction, generate and stop instead without precipitating in solution to be mixed It answers, collects sediment and reacted for 24 hours in 60 DEG C of vacuum drying again, obtain biomass antibacterial agent；

The mass values of the acidification bluish dogbane whisker and cuprous nitrate are 1:0.2；

The mass values of the acidification bluish dogbane whisker and magnesium sulfate are 1:0.14；

The cuprous nitrate mass fraction of the cuprous nitrate solution is 22%；

The magnesium sulfate mass fraction of the Adlerika is 14%.

Four, the preparation of antibacterial PPR master batch:

Biomass antibacterial agent prepared by step 3, polyethylene glycol and PPR particle are raw material, are prepared by melt blending Obtain antibacterial PPR master batch.Mass fraction of the biomass antibacterial agent in antibacterial PPR master batch is 2%, and polyethylene glycol is in antibacterial PPR Mass fraction in master batch is 2%.

The preparation method of dual antibacterial PPR master batch, the specific steps are that:

One, the preparation of bluish dogbane whisker:

It takes what is cleaned up to spread out the dregs of linseeds or sesame seeds, is dissolved at subzero 10~15 DEG C using the urea liquid of potassium 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 bluish dogbane whisker is obtained for 24 hours in 60 DEG C of vacuum drying；

The mass fraction of sodium hydroxide is 5% in the urea liquid of the potassium hydroxide, and the mass fraction of urea is 2.5%；

In the ultracentrifugation technique, centrifugal force is 8000~13000g；

Two, it is acidified the preparation of bluish dogbane whisker:

Using the bluish dogbane whisker of step 1 preparation as raw material, bluish dogbane whisker is carried out acidification activation processing, is then existed again Under the conditions of 60~80 DEG C, in the aqueous solution of 1,3- trimethylen-edinitrilo-tetraacetic acid, 1,3- trimethylen-edinitrilo-tetraacetic acid is made to be grafted on bluish dogbane whisker On, filtering is dried in vacuo under the conditions of 60 DEG C again, and acidification bluish dogbane whisker is prepared；

The acidification activation process of the acidification bluish dogbane whisker is Strong oxdiative acidic mixed solution, at 80~90 DEG C Under the conditions of impregnate 3~6h；

The Strong oxdiative acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the quality of nitric acid solution is dense Degree is 14%, and the mass concentration of hydrogen peroxide solution is 14%；

The mass fraction of 1,3- trimethylen-edinitrilo-tetraacetic acid is 7% in the aqueous solution of the 1,3- trimethylen-edinitrilo-tetraacetic acid；

The graft reaction time is 1.5~2.0h；

Three, the preparation of biomass antibacterial agent:

Acidification bluish dogbane whisker prepared by step 2 is added in cuprous nitrate solution, then with the pH of nitre acid-conditioning solution It is 5.05~5.15, under 45~60 DEG C of stirring conditions, so that cuprous ion and acidification bluish dogbane whisker is carried out complex reaction, to molten After generating without precipitating again in liquid, obtain just precipitating；Then Adlerika is added, is 6.0~6.5 with sulphur acid for adjusting pH, then Under 45~60 DEG C of stirring conditions, makes magnesium ion and just precipitate to carry out complex reaction, generate and stop instead without precipitating in solution to be mixed It answers, collects sediment and reacted for 24 hours in 60 DEG C of vacuum drying again, obtain biomass antibacterial agent；

The mass values of the acidification bluish dogbane whisker and cuprous nitrate are 1:0.2；

The mass values of the acidification bluish dogbane whisker and magnesium sulfate are 1:0.14；

The cuprous nitrate mass fraction of the cuprous nitrate solution is 22%；

The magnesium sulfate mass fraction of the Adlerika is 14%.

Four, chitin modified antibacterial agent

Superparamagnetic nickel colloidal nanocrystals cluster is dissolved in the aqueous solution of ethyl alcohol, citric acid solution is then added, is led to It crosses microwave to be dispersed with stirring after mixing, then isolated product, is finally cleaned to obtain hydrophily superparamagnetic with deionized water Nickel colloidal nanocrystals cluster；Hydrophily superparamagnetic nickel colloidal nanocrystals cluster and chitosan material are subjected to mixed grinding, obtained Chitin modified antibacterial agent；

The time that microwave is dispersed with stirring mixing is 2~4 hours, speed 2000-24000r/min.

The molar ratio of citric acid and superparamagnetic nickel colloidal nanocrystals cluster in citric acid solution is 1:0.22；

The application carries out surface to superparamagnetic nickel colloidal nanocrystals cluster using citric acid and is modified, and mainly utilizes citric acid In citrate and reacted with the hydroxyl in hydroxylated superparamagnetic nickel colloidal nanocrystals cluster, in superparamagnetic nickel colloid Nanocrystal cluster surface forms adsorption layer, because hydroxyl is contained on its surface, is easy to combine with the amino in chitosan material, be formed Absorption is to prepare chitin modified antibacterial agent.Chitosan and its derivative has preferable antibacterial activity, can inhibit some true The growth and breeding of bacterium, bacterium and virus.Therefore chitin modified antibacterial agent has good biological antibiotic effect.

Five, the preparation of dual antibacterial PPR master batch:

By biological antibiosis agent, chitin modified antibacterial agent, dual antibacterial is prepared by melt blending in polyvinyl alcohol PPR master batch.Mass fraction of the biomass antibacterial agent in dual antibacterial PPR master batch is 2%, and polyethylene glycol is in dual antibacterial PPR Mass fraction in master batch is 2%, and mass fraction of the polyethylene glycol in dual antibacterial PPR master batch is 2%.

When the material of sandwich layer is antibacterial PPR master batch, the sandwich layer anti-microbial property of the tubing of the application is to Escherichia coli Antibiotic property > 91%, to the antibiotic property > 91% of staphylococcus glucose coccus.The sandwich layer anti-microbial property of the tubing of the application is pair The later antibiotic property > 91% in 48 hours of Escherichia coli, to 48 hours of staphylococcus glucose coccus later antibiotic property > 91%.

When the material of sandwich layer is dual antibacterial PPR master batch, the sandwich layer anti-microbial property of the tubing of the application is to large intestine bar The antibiotic property > 98% of bacterium, to the antibiotic property > 98% of staphylococcus glucose coccus.The sandwich layer anti-microbial property of the tubing of the application For the later antibiotic property > 98% in 48 hours to Escherichia coli, 48 hours to staphylococcus glucose coccus later antibiotic properties > 98%.

Embodiment 3

A kind of anti-scratch PE-PPR multiple tube is followed successively by PE layers anti-scratch, elastic cord breaker and PPR core from outside to inside Layer；

Anti-scratch PE layers of outer surface is outer lug structure, the circular configuration unit that outer lug structure is attached most importance to multiple.Utilize evagination knot Structure plays the role of buffering and protection in stress；To protect the sandwich layer of PPR sandwich layer.

Anti-scratch PE layers of inner surface is equipped with groove, and groove is circular configuration, the ultra-fine cloud of setting lamellar structure in groove Master slice.

PE layers anti-scratch, the thickness ratio of elastic cord breaker and PPR sandwich layer is 2:1:2.

Anti-scratch PE layers of material is polyethylene particles, the ultra-fine mica sheet of polyurethane elastomer and lamellar structure.It is poly- Mass fraction of the urethane elastomer in anti-scratch PE layers of material is 17%；The ultra-fine mica sheet of lamellar structure is in anti-scratch PE Mass fraction in the material of layer is 2%.

The material of elastic cord breaker is ptt fiber, glass fibre and toughener.Material of the ptt fiber in elastic cord breaker Mass fraction in material is 15%, and mass fraction of the glass fibre in the material of elastic cord breaker is 15%, and toughener is low The materials such as density polyethylene.

The material of PPR sandwich layer is antibacterial PPR master batch or multifunctional antibiotic PPR master batch.

The preparation method of antibacterial PPR master batch, the specific steps are that:

One, the preparation of bluish dogbane whisker:

It takes what is cleaned up to spread out the dregs of linseeds or sesame seeds, is dissolved at subzero 10~15 DEG C using the urea liquid of potassium 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 bluish dogbane whisker is obtained for 24 hours in 60 DEG C of vacuum drying；

The mass fraction of sodium hydroxide is 5% in the urea liquid of the potassium hydroxide, and the mass fraction of urea is 2.5%；

In the ultracentrifugation technique, centrifugal force is 8000~13000g；

Two, it is acidified the preparation of bluish dogbane whisker:

Using the bluish dogbane whisker of step 1 preparation as raw material, bluish dogbane whisker is carried out acidification activation processing, is then existed again Under the conditions of 60~80 DEG C, in the aqueous solution of 1,3- trimethylen-edinitrilo-tetraacetic acid, 1,3- trimethylen-edinitrilo-tetraacetic acid is made to be grafted on bluish dogbane whisker On, filtering is dried in vacuo under the conditions of 60 DEG C again, and acidification bluish dogbane whisker is prepared；

The acidification activation process of the acidification bluish dogbane whisker is Strong oxdiative acidic mixed solution, at 80~90 DEG C Under the conditions of impregnate 3~6h；

The Strong oxdiative acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the quality of nitric acid solution is dense Degree is 14%, and the mass concentration of hydrogen peroxide solution is 14%；

The mass fraction of 1,3- trimethylen-edinitrilo-tetraacetic acid is 7% in the aqueous solution of the 1,3- trimethylen-edinitrilo-tetraacetic acid；

The graft reaction time is 1.5~2.0h；

Three, the preparation of biomass antibacterial agent:

Acidification bluish dogbane whisker prepared by step 2 is added in cuprous nitrate solution, then with the pH of nitre acid-conditioning solution It is 5.05~5.15, under 45~60 DEG C of stirring conditions, so that cuprous ion and acidification bluish dogbane whisker is carried out complex reaction, to molten After being generated again without precipitating in liquid, collects sediment and reacted for 24 hours in 60 DEG C of vacuum drying again, obtain biomass antibacterial agent；

The mass values of the acidification bluish dogbane whisker and cuprous nitrate are 1:0.2；

The cuprous nitrate mass fraction of the cuprous nitrate solution is 22%；

Four, the preparation of antibacterial PPR master batch:

Biomass antibacterial agent prepared by step 3, polyethylene glycol and PPR particle are raw material, are prepared by melt blending Obtain antibacterial PPR master batch.Mass fraction of the biomass antibacterial agent in antibacterial PPR master batch is 2%, and polyethylene glycol is in antibacterial PPR Mass fraction in master batch is 2%.

The preparation method of dual antibacterial PPR master batch, the specific steps are that:

One, the preparation of bluish dogbane whisker:

It takes what is cleaned up to spread out the dregs of linseeds or sesame seeds, is dissolved at subzero 10~15 DEG C using the urea liquid of potassium 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 bluish dogbane whisker is obtained for 24 hours in 60 DEG C of vacuum drying；

The mass fraction of sodium hydroxide is 5% in the urea liquid of the potassium hydroxide, and the mass fraction of urea is 2.5%；

In the ultracentrifugation technique, centrifugal force is 8000~13000g；

Two, it is acidified the preparation of bluish dogbane whisker:

Using the bluish dogbane whisker of step 1 preparation as raw material, bluish dogbane whisker is carried out acidification activation processing, is then existed again Under the conditions of 60~80 DEG C, in the aqueous solution of 1,3- trimethylen-edinitrilo-tetraacetic acid, 1,3- trimethylen-edinitrilo-tetraacetic acid is made to be grafted on bluish dogbane whisker On, filtering is dried in vacuo under the conditions of 60 DEG C again, and acidification bluish dogbane whisker is prepared；

The acidification activation process of the acidification bluish dogbane whisker is Strong oxdiative acidic mixed solution, at 80~90 DEG C Under the conditions of impregnate 3~6h；

The Strong oxdiative acidic mixed solution is the mixed solution of nitric acid and hydrogen peroxide, and wherein the quality of nitric acid solution is dense Degree is 14%, and the mass concentration of hydrogen peroxide solution is 14%；

The mass fraction of 1,3- trimethylen-edinitrilo-tetraacetic acid is 7% in the aqueous solution of the 1,3- trimethylen-edinitrilo-tetraacetic acid；

The graft reaction time is 1.5~2.0h；

Three, the preparation of biomass antibacterial agent:

Acidification bluish dogbane whisker prepared by step 2 is added in cuprous nitrate solution, then with the pH of nitre acid-conditioning solution It is 5.05~5.15, under 45~60 DEG C of stirring conditions, so that cuprous ion and acidification bluish dogbane whisker is carried out complex reaction, to molten After being generated again without precipitating in liquid, collects sediment and reacted for 24 hours in 60 DEG C of vacuum drying again, obtain biomass antibacterial agent；

The mass values of the acidification bluish dogbane whisker and cuprous nitrate are 1:0.2；

The cuprous nitrate mass fraction of the cuprous nitrate solution is 22%；

Four, chitin modified antibacterial agent

Superparamagnetic nickel colloidal nanocrystals cluster is dissolved in the aqueous solution of ethyl alcohol, citric acid solution is then added, is led to It crosses microwave to be dispersed with stirring after mixing, then isolated product, is finally cleaned to obtain hydrophily superparamagnetic with deionized water Nickel colloidal nanocrystals cluster；Hydrophily superparamagnetic nickel colloidal nanocrystals cluster and chitosan material are subjected to mixed grinding, obtained Chitin modified antibacterial agent；

The time that microwave is dispersed with stirring mixing is 2~4 hours, speed 2000-24000r/min.

The molar ratio of citric acid and superparamagnetic nickel colloidal nanocrystals cluster in citric acid solution is 1:0.22；

Five, the preparation of dual antibacterial PPR master batch:

By biological antibiosis agent, chitin modified antibacterial agent, dual antibacterial is prepared by melt blending in polyvinyl alcohol PPR master batch.Mass fraction of the biomass antibacterial agent in dual antibacterial PPR master batch is 2%, and polyethylene glycol is in dual antibacterial PPR Mass fraction in master batch is 2%, and mass fraction of the polyethylene glycol in dual antibacterial PPR master batch is 2%.

When the material of sandwich layer is antibacterial PPR master batch, the sandwich layer anti-microbial property of the tubing of the application is to Escherichia coli Antibiotic property > 84%, to the antibiotic property > 84% of staphylococcus glucose coccus.The sandwich layer anti-microbial property of the tubing of the application is pair The later antibiotic property > 81% in 48 hours of Escherichia coli, to 48 hours of staphylococcus glucose coccus later antibiotic property > 81%.

When the material of sandwich layer is dual antibacterial PPR master batch, the sandwich layer anti-microbial property of the tubing of the application is to large intestine bar The antibiotic property > 90% of bacterium, to the antibiotic property > 90% of staphylococcus glucose coccus.The sandwich layer anti-microbial property of the tubing of the application For the later antibiotic property > 90% in 48 hours to Escherichia coli, 48 hours to staphylococcus glucose coccus later antibiotic properties > 90%.Essentially identical with embodiment 2, unique difference is just the absence of this technique of the package of magnesium ion, for final The persistence of the antibacterial of product produces significant impact, specially in being decreased obviously, probably has dropped 10% or so.

The above is only the preferred embodiment of the utility model, it is noted that for the common skill of the art Art personnel can also make several improvements and modifications without departing from the concept of the premise utility, these improvements and modifications Also it should be regarded as in the protection scope of the utility model.

Claims (5)

1. a kind of anti-scratch PE-PPR multiple tube, which is characterized in that be followed successively by from outside to inside it is PE layers anti-scratch, elastic cord breaker with And PPR sandwich layer；Elastic cord breaker is set between anti-scratch PE layers and PPR sandwich layer；Anti-scratch PE layers of outer surface is evagination knot Structure, the circular configuration unit that outer lug structure is attached most importance to multiple；Anti-scratch PE layers of inner surface is equipped with groove, and groove is circular configuration, recessed The ultra-fine mica sheet of setting lamellar structure in slot.

2. a kind of anti-scratch PE-PPR multiple tube as described in claim 1, which is characterized in that PE layers anti-scratch, elastic buffer The thickness ratio of layer and PPR sandwich layer is 2:1:2.

3. a kind of anti-scratch PE-PPR multiple tube as described in claim 1, which is characterized in that anti-scratch PE layers of material is poly- The ultra-fine mica sheet of beta particles, polyurethane elastomer and lamellar structure.

4. a kind of anti-scratch PE-PPR multiple tube as described in claim 1, which is characterized in that the material of elastic cord breaker is Ptt fiber, glass fibre and toughener.

5. a kind of anti-scratch PE-PPR multiple tube as described in claim 1, which is characterized in that the material of PPR sandwich layer is antibacterial PPR master batch or multifunctional antibiotic PPR master batch.