CN108047571A - A kind of method for preparing the PPR pipe with aluminum metal effect - Google Patents

A kind of method for preparing the PPR pipe with aluminum metal effect Download PDF

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CN108047571A
CN108047571A CN201711266548.0A CN201711266548A CN108047571A CN 108047571 A CN108047571 A CN 108047571A CN 201711266548 A CN201711266548 A CN 201711266548A CN 108047571 A CN108047571 A CN 108047571A
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parts
carbon fiber
coupling agent
fiber
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CN108047571B (en
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程东红
陈文其
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Jiangxi Chenshi Technology Group Co.,Ltd.
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SUZHOU SHUOBOSHI BUILDING MATERIALS TECHNOLOGY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/297—Feeding the extrusion material to the extruder at several locations, e.g. using several hoppers or using a separate additive feeding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00—Tubular articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/10—Peculiar tacticity
    • C08L2207/14—Amorphous or atactic polypropylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a kind of methods for preparing the PPR pipe with aluminum metal effect, are specifically：Prepare the raw material of following parts by weight：100 parts of PPR, 10 25 parts of aluminium powder, 8 18 parts of dispersant, soft core-shell copolymerized 38 parts of the object of core hard-shell type, 5 10 parts of butadiene-styrene rubber, 5 10 parts of carbon fiber, 38 parts of acicular wollastonite fiber, 13 parts of coupling agent, 1.5 3 parts of antioxidant；Faintly acid coupling agent solution is distributed in carbon fiber and acicular wollastonite fiber surface；Aluminium powder is added in basic dispersion agent solution；Modified aluminium powder mixed liquor is sprayed into while PPR, the core-shell copolymerized object of soft core hard-shell type, butadiene-styrene rubber, antioxidant are stirred, obtains premix raw material；Premix raw material, modified carbon fiber and modified acicular wollastonite fiber are added in into extruding pelletization in extruder, obtain PPR pipe.PPR pipe prepared by the present invention has uniform aluminum metal effect, and low-temperature flexibility is good, and heat resistance is good.

Description

A kind of method for preparing the PPR pipe with aluminum metal effect
Technical field
The present invention relates to a kind of method for preparing the PPR pipe with aluminum metal effect, the technology of preparing for belonging to PPR pipe is led Domain.
Background technology
PPR is called atactic copolymerized polypropene, is extruded as tubing using atactic copolymerized polypropene, tubing injection becomes pipe Part, PPR pipe part product compared with the pipelines such as traditional cast iron pipe, coating steel pipe, pipe of cement, have energy-saving material-saving, it is environment-protecting and non-poisonous, Heat-resistant pressure-resistant, high-strength light, corrosion-resistant, non-scaling, shock resistance and creep-resistant property it is good, it is easy for installation, be connected firmly, using the longevity The advantages that life is long, material recoverable is widely used in building water supply and drainage, city gas, electric power and cable jacket, industry stream Construction industries, municipal administration, industry and the agriculture fields such as body conveying, agricultural irrigation.
But PPR pipe part, there are the fatal defects of low-temperature flexibility difference, when environment temperature is less than 0 DEG C, toughness drastically declines, Brittleness is shown as, when tubing is subject to impact or the weight of external force, it may appear that straight line cracking phenomena, this cracking can be along pipes The axis direction rapid growth of material be easy to cause the explosion of pipeline, and PPR pipe part is easily used under hot environment, it is easy to Its performance is influenced due to temperature in use is excessively high, and PPR pipe part is caused to soften, in addition, many PPR pipe parts are exposed to build surface, And existing PPR pipe part is common plastics effect, single effect influences beauty.But it manufactures lead in PPR pipe part at present Domain there is no a kind of method to prepare low temperature resistant, high temperature resistant and have the PPR pipe of aluminum metal effect.
The content of the invention
The technical problem to be solved by the present invention is to：To solve, existing PPR pipe low-temperature flexibility is poor, heat resistance is poor, vision The technical issues of single effect, provides a kind of method for preparing the PPR pipe with aluminum metal effect.
The technical solution adopted by the present invention to solve the technical problems is：
A kind of method for preparing the PPR pipe with aluminum metal effect, comprises the following steps：
Prepare the raw material of following parts by weight：100 parts of PPR, 10-25 parts of aluminium powder, 8-18 parts of dispersant, soft core hard-shell type core 3-8 parts of shell copolymer, 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 resist 1.5-3 parts of oxygen agent.
Coupling agent solution is prepared, preferably its pH value is adjusted between 4-5；
Coupling agent solution is distributed in carbon fiber and acicular wollastonite fiber surface, dry, cooling, obtain modified carbon fiber and Modified acicular wollastonite fiber；
Prepare dispersant solution；
Aluminium powder is added in basic dispersion agent solution, obtains modified aluminium powder solution；
Modified aluminium powder is sprayed into while PPR, the core-shell copolymerized object of soft core hard-shell type, butadiene-styrene rubber, antioxidant are stirred Mixed liquor is dried, cooling, obtains premix raw material；
Premix raw material, modified carbon fiber and modified acicular wollastonite fiber are added in into extruding pelletization in extruder, obtain PPR pipe Material.
Preferably, the parts by weight of component of the raw material is as follows：100 parts of PPR, 15-20 parts of aluminium powder, 10-15 parts of dispersant, Soft core-shell copolymerized object 5-8 parts of core hard-shell type, 8-10 parts of butadiene-styrene rubber, 8-10 parts of carbon fiber, 5-8 parts of acicular wollastonite fiber are even Join 2-3 parts of agent, 2-3 parts of antioxidant.
Preferably, the dispersant is dodecanoic acid, palmitic acid, stearic acid, tetradecylic acid, parinaric acid, 18 carbon At least one of trienic acid, glyceryl tristearate, polyvinylpyrrolidone, polyvinyl alcohol.
Preferably, the soft core-shell copolymerized object of core hard-shell type for the core-shell copolymerized object of methyl methacrylate-butyl acrylate, At least one of methylacrylate- butadiene-styrene core-shell copolymer.
Preferably, the carbon fiber is polyacrylonitrile-based carbon fibre, asphalt base carbon fiber, viscose-based carbon fiber, phenolic aldehyde base At least one of carbon fiber, the average aspect ratio of the carbon fiber is 100-200.
Preferably, the average aspect ratio of the acicular wollastonite fiber is at least 15.
Preferably, the coupling agent is at least one of silane coupling agent or titanate coupling agent；It is described silane coupled The general formula of agent is YSiX3, X is chloro, methoxyl group, ethyoxyl or acetoxyl group, and Y contains vinyl, amino, epoxy group or mercapto Base is preferably γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane；The titanate esters are even Connection agent is monoalkoxy type titanate coupling agent, chelating titanate coupling agent, is coordinated in build titanate coupling agent at least One kind is preferably isopropyl tri(dioctylpyrophosphato)titanate, four octyloxy titaniums [two (tridecyl phosphite)], four Octyloxy titanium [two (dilauryl phosphorite)].
Preferably, the antioxidant is the combination of Hinered phenols antioxidant and monothioester kind antioxidant, the Hinered phenols The mass ratio of antioxidant and monothioester kind antioxidant is 1:0.5-2.
Further, the Hinered phenols antioxidant for β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, Four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, 4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) At least one of benzene, (3- positive decyls are thio for the double octadecyl ester of thio-2 acid or pentaerythrite for the monothioester kind antioxidant At least one of propionic ester).
Preferably, the butadiene-styrene rubber is butadiene-styrene rubber powder of the grain size in 40-100 mesh, and the aluminium powder is 400-800 Mesh.
Preferably, each section of temperature setting of extruder is：One 180-185 DEG C of area, two 185-190 DEG C of areas, three area 190-200 DEG C, four 200-205 DEG C of areas, five 205-210 DEG C of areas, six 210-215 DEG C of areas, seven 215-220 DEG C of areas, eight 210-215 DEG C of areas, 9th area 205-210 DEG C, ten 200-205 DEG C of areas, 200-220 DEG C of head, engine speed 300-450r/min, feeding frequency 5-10r/min.
Further, raw material will be premixed to add in from the main charge door at one area of extruder, by modified carbon fiber and modified acicular Wollastonite fibre is added in from the side loading mouth at 4th area of extruder or 5th area.
The method that modified carbon fiber and modified acicular wollastonite fiber is made is specially：Carbon fiber and acicular wollastonite is fine Atomization sprays into coupling agent solution while dimension stirring, and surface then is impregnated with the carbon fiber of coupling agent and acicular wollastonite fiber When baking 2-3 is small at 90-120 DEG C, it is cooled to room temperature, obtains modified carbon fiber and modified acicular wollastonite fiber；
Be made premix raw material furnace drying method be：When baking 2-3 is small at 60-80 DEG C.
The beneficial effects of the invention are as follows：
(1) PPR pipe for preparing of the present invention adds in 10-25 parts of aluminium powder in the PPR of 100 parts by weight can both make PPR Tubing generates good aluminum metal effect, and PPR pipe embrittlement caused by can avoiding the problem that aluminium powder excess aggravates, and ensures PPR The excellent toughness of tubing, while aluminum metal is lighter, the smaller weight for increasing PPR pipe can obtain apparent metal effect.
(2) dispersant added in can be effectively adsorbed in aluminium powder surface, inhibit the reunion of aluminium powder, finally aluminium powder is made uniformly to divide It is distributed in PPR matrixes, the aluminum metal effect for making each position of PPR pipe is consistent.
(3) select the core-shell copolymerized object of soft core hard-shell type and butadiene-styrene rubber that can subtract crisp aspect in the toughening of PPR pipe and play Synergistic effect, with common ethylene-octene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene in industry- The olefinic copolymers such as polystyrene ternary segmented copolymer are compared as toughener, are had the advantages that：A. soft core hard shell The core-shell copolymerized object of type easily uniformly disperses in PPR matrixes, can give full play to its toughening effect to PPR pipe, effectively carry The resistance to low temperature of high PPR pipe improves the embrittlement phenomena of PPR pipe at low temperature, and the mechanical property of PPR pipe is greatly enhanced Can, it is cracked when being effective against PPR pipe be subject to external impacts or weight；B. the modulus, hardness, heat-resisting temperature of PPR pipe are made The indexs such as degree vary less, and ensure that the excellent performance of forming stability, hardness, the heat resistance of PPR pipe etc..
(4) addition of carbon fiber and acicular wollastonite fiber can further improve the resistance to low temperature and mechanics of PPR pipe Performance, and carbon fiber has prominent heat resistance, and the thermal stability that can make PPR pipe is good, and thermal deformation is low, product size Stability is good, but cost is higher, acicular wollastonite fiber can equally improve the resistance to low temperature of PPR pipe, mechanical property and Heat resistance although the effect of acicular wollastonite fiber is less than carbon fiber, wins, carbon fiber and pin lower than carbon fiber in cost Shape wollastonite fibre is combined with rational ratio, in the case that of reasonable cost, can effectively improve the lower temperature resistance of PPR pipe Energy, mechanical property and heat resistance.
(5) carbon fiber and acicular wollastonite fiber and PPR bases can be improved by adding in silane coupling agent or titanate coupling agent The compatibility of body is conducive to PPR pipe and forms homodisperse Phase stracture, avoids the generation of phase separation.
(6) present invention selection Hinered phenols antioxidant is used cooperatively with phosphorous acid esters, and the antioxidant of compounding is in polylactic acid Anti-oxidant aspect be complementary to one another, the oxidative degradations that occur in multiple short time high temperature process of PPR and thus are resisted in collaboration The hydraulic performance decline of generation.
(7) carbon fiber and acicular wollastonite fiber are easy to fracture in process, and to reduce the probability that fractures, selection separates Charging will premix raw material and be added in from the main charge door at one area of extruder, by modified carbon fiber and modified acicular wollastonite fiber It is added in from the side loading mouth at 4th area of extruder or 5th area, premixes raw material herein and melted, modified carbon fiber and modified acicular Shearing force of the wollastonite fibre without element in one area of extruder to 3rd area or four area's half of screw and the collision with premixing raw material, The probability to fracture is reduced, and can effectively improve the efficiency of carbon fiber and acicular wollastonite fiber.
Specific embodiment
The present invention is described in further detail now.
Embodiment 1
The present embodiment provides a kind of methods for preparing the PPR pipe with aluminum metal effect, comprise the following steps：
Prepare the raw material of following parts by weight：100 parts of PPR, 400 15 parts of mesh aluminium powders, 8 parts of dispersant, soft core hard-shell type nucleocapsid 3 parts of copolymer, 100 10 parts of mesh butadiene-styrene rubber, 5 parts of carbon fiber, 8 parts of acicular wollastonite fiber, 2 parts of coupling agent, antioxidant 1.5 Part；The dispersant is dodecanoic acid, and the soft core-shell copolymerized object of core hard-shell type is methyl methacrylate-butyl acrylate core Shell copolymer, the carbon fiber are polyacrylonitrile-based carbon fibre, and the average aspect ratio of the polyacrylonitrile-based carbon fibre is 100, The average aspect ratio of the acicular wollastonite fiber is 15, and the coupling agent is γ-(2,3- the third oxygen of epoxy) propyl trimethoxy Silane, the antioxidant are that mass ratio is 1:0.5 β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecanol ester and sulphur For the double octadecyl esters of dipropionic acid；
Coupling agent solution is prepared, and its pH value is tuned into 4；
Atomization sprays into coupling agent solution while carbon fiber and acicular wollastonite fiber are stirred, and is then impregnated with surface The carbon fiber and acicular wollastonite fiber of coupling agent dried at 90 DEG C 3 it is small when, be cooled to room temperature to get modified carbon fiber and modification Acicular wollastonite fiber；
Prepare dispersant solution；
Aluminium powder is added in basic dispersion agent solution, obtains modified aluminium powder solution；
Modified aluminium powder is sprayed into while PPR, the core-shell copolymerized object of soft core hard-shell type, butadiene-styrene rubber, antioxidant are stirred Solution when then baking 3 is small at 60 DEG C, is cooled to room temperature, and obtains premix raw material；
Raw material will be premixed to add in from the main charge door at one area of extruder, modified carbon fiber and modified acicular wollastonite is fine It ties up and is added in from the side loading mouth at 4th area of extruder, extruding pelletization obtains PPR pipe, and each section of temperature setting of extruder is：One area 180 DEG C, two 185 DEG C of areas, three 190 DEG C of areas, four 200 DEG C of areas, five 205 DEG C of areas, six 210 DEG C of areas, seven 215 DEG C of areas, eight 210 DEG C of areas, Nine 205 DEG C of areas, ten 200 DEG C of areas, 200 DEG C, engine speed 350r/min of head, feeding frequency 5r/min.
Embodiment 2
The present embodiment provides a kind of methods for preparing the PPR pipe with aluminum metal effect, comprise the following steps：
Prepare the raw material of following parts by weight：100 parts of PPR, 800 10 parts of mesh aluminium powders, 10 parts of dispersant, soft core hard-shell type core 5 parts of shell copolymer, 5 parts of butadiene-styrene rubber, 8 parts of carbon fiber, 3 parts of acicular wollastonite fiber, 1 part of coupling agent, 2 parts of antioxidant；It is described Dispersant is palmitic acid, and the soft core-shell copolymerized object of core hard-shell type is core-shell copolymerized for methyl methacrylate-butadiene-styrene Object, the carbon fiber are asphalt base carbon fiber, and the average aspect ratio of the asphalt base carbon fiber is 130, the acicular wollastonite The average aspect ratio of fiber is 18, and the coupling agent is γ-mercaptopropyl trimethoxysilane, and the antioxidant is that mass ratio is 1: 1 four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and pentaerythrite (3- positive decyl propane thioic acids Ester)；
Coupling agent solution is prepared, and its pH value is tuned into 5；
Atomization sprays into coupling agent solution while carbon fiber and acicular wollastonite fiber are stirred, and is then impregnated with surface The carbon fiber and acicular wollastonite fiber of coupling agent dried at 120 DEG C 2 it is small when, be cooled to room temperature modified carbon fiber and to change Property acicular wollastonite fiber；
Prepare dispersant solution；
Aluminium powder is added in basic dispersion agent solution, obtains modified aluminium powder solution；
Modified aluminium powder is sprayed into while PPR, the core-shell copolymerized object of soft core hard-shell type, butadiene-styrene rubber, antioxidant are stirred Solution when then baking 2 is small at 80 DEG C, is cooled to room temperature, and obtains premix raw material；
Raw material will be premixed to add in from the main charge door at one area of extruder, modified carbon fiber and modified acicular wollastonite is fine It ties up and is added in from the side loading mouth at 5th area of extruder, extruding pelletization obtains PPR pipe, and each section of temperature setting of extruder is：One area 190 DEG C, two 195 DEG C of areas, three 200 DEG C of areas, four 205 DEG C of areas, five 210 DEG C of areas, six 215 DEG C of areas, seven 220 DEG C of areas, eight 215 DEG C of areas, Nine 210 DEG C of areas, ten 205 DEG C of areas, 220 DEG C, engine speed 450r/min of head, feeding frequency 6r/min.
Embodiment 3
The present embodiment provides a kind of methods for preparing the PPR pipe with aluminum metal effect, comprise the following steps：
Prepare the raw material of following parts by weight：100 parts of PPR, 500 20 parts of mesh aluminium powders, 15 parts of dispersant, soft core hard-shell type core 8 parts of shell copolymer, 8 parts of butadiene-styrene rubber, 10 parts of carbon fiber, 5 parts of acicular wollastonite fiber, 1.5 parts of coupling agent, 2 parts of antioxidant；Institute Dispersant is stated as stearic acid, the soft core-shell copolymerized object of core hard-shell type is core-shell copolymerized for methyl methacrylate-butyl acrylate Object, the carbon fiber are viscose-based carbon fiber, and the average aspect ratio of the viscose-based carbon fiber is 150, the acicular wollastonite The average aspect ratio of fiber is 20, and the coupling agent is isopropyl tri(dioctylpyrophosphato)titanate, and the antioxidant is Mass ratio is 1:The double octadecyl esters of 2 (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene of 4,6- tri- and thio-2 acid；
Coupling agent solution is prepared, and its pH value is tuned into 4.5；
Atomization sprays into coupling agent solution while carbon fiber and acicular wollastonite fiber are stirred, and is then impregnated with surface The carbon fiber and acicular wollastonite fiber of coupling agent dried at 100 DEG C 2 it is small when, be cooled to room temperature modified carbon fiber and to change Property acicular wollastonite fiber；
Prepare dispersant solution；
Aluminium powder is added in basic dispersion agent solution, obtains modified aluminium powder solution；
Modified aluminium powder is sprayed into while PPR, the core-shell copolymerized object of soft core hard-shell type, butadiene-styrene rubber, antioxidant are stirred Solution when then baking 2.5 is small at 70 DEG C, is cooled to room temperature, and obtains premix raw material；
Raw material will be premixed to add in from the main charge door at one area of extruder, modified carbon fiber and modified acicular wollastonite is fine It ties up and is added in from the side loading mouth at 4th area of extruder, extruding pelletization obtains PPR pipe, and each section of temperature setting of extruder is：One area 182 DEG C, two 188 DEG C of areas, three 193 DEG C of areas, four 203 DEG C of areas, five 208 DEG C of areas, six 212 DEG C of areas, seven 217 DEG C of areas, eight 213 DEG C of areas, Nine 206 DEG C of areas, ten 203 DEG C of areas, 210 DEG C, engine speed 300r/min of head, feeding frequency 10r/min.
Embodiment 4
The present embodiment provides a kind of methods for preparing the PPR pipe with aluminum metal effect, comprise the following steps：
Prepare the raw material of following parts by weight：100 parts of PPR, 700 25 parts of mesh aluminium powders, 18 parts of dispersant, soft core hard-shell type core 6 parts of shell copolymer, 10 parts of butadiene-styrene rubber, 6 parts of carbon fiber, 6 parts of acicular wollastonite fiber, 3 parts of coupling agent, 3 parts of antioxidant；It is described Dispersant is tetradecylic acid, and the soft core-shell copolymerized object of core hard-shell type is core-shell copolymerized for methyl methacrylate-butadiene-styrene Object, the carbon fiber are phenolic aldehyde base carbon fibre, and the average major diameter of the phenolic aldehyde base carbon fibre is 170, and the acicular wollastonite is fine The average aspect ratio of dimension is 20, and the coupling agent is four octyloxy titaniums [two (tridecyl phosphite)], and the antioxidant is Mass ratio is 1:(3- positive decyls are thio for 1 β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecanol ester and pentaerythrite Propionic ester)；
Coupling agent solution is prepared, and its pH value is tuned into 4.5；
Atomization sprays into coupling agent solution while carbon fiber and acicular wollastonite fiber are stirred, and is then impregnated with surface The carbon fiber and acicular wollastonite fiber of coupling agent dried at 110 DEG C 2.5 it is small when, be cooled to room temperature to get modified carbon fiber and Modified acicular wollastonite fiber；
Aluminium powder is added in basic dispersion agent solution, obtains modified aluminium powder solution；
Modified aluminium powder is sprayed into while PPR, the core-shell copolymerized object of soft core hard-shell type, butadiene-styrene rubber, antioxidant are stirred Solution when then baking 2 is small at 70 DEG C, is cooled to room temperature, and obtains premix raw material；
Raw material, modified carbon fiber and modified acicular wollastonite fibre modification polypropylene fibre will be premixed at one area of extruder Main charge door add in, extruding pelletization obtains PPR pipe, and each section of temperature setting of extruder is：One 180 DEG C of area, two 185 DEG C of areas, three 190 DEG C of area, four 200 DEG C of areas, five 205 DEG C of areas, six 210 DEG C of areas, seven 215 DEG C of areas, eight 210 DEG C of areas, nine 205 DEG C of areas, ten areas 200 DEG C, 210 DEG C, engine speed 300r/min of head, feeding frequency 8r/min.
Embodiment 5
The present embodiment provides a kind of methods for preparing the PPR pipe with aluminum metal effect, comprise the following steps：
Prepare the raw material of following parts by weight：100 parts of PPR, 500 15 parts of mesh aluminium powders, 12 parts of dispersant, soft core hard-shell type core 7 parts of shell copolymer, 7 parts of butadiene-styrene rubber, 7 parts of carbon fiber, 7 parts of acicular wollastonite fiber, 1-3 parts of coupling agent, antioxidant 1.5-3 Part；The dispersant is parinaric acid, and the soft core-shell copolymerized object of core hard-shell type is methyl methacrylate-acrylic acid fourth The core-shell copolymerized object of ester, the carbon fiber are polyacrylonitrile-based carbon fibre, and the average aspect ratio of the polyacrylonitrile-based carbon fibre is 200, the average aspect ratio of the acicular wollastonite fiber is 25, and the coupling agent is four octyloxy titaniums [two (dilauryl phosphorous Acid esters)], the antioxidant is that mass ratio is 1:2 four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters With the double octadecyl esters of thio-2 acid；
Coupling agent solution is prepared, and its pH value is tuned into 4.8；
Atomization sprays into coupling agent solution while carbon fiber and acicular wollastonite fiber are stirred, and is then impregnated with surface The carbon fiber and acicular wollastonite fiber of coupling agent dried at 90 DEG C 3 it is small when, be cooled to room temperature to get modified carbon fiber and modification Acicular wollastonite fiber；
Prepare dispersant solution；
Aluminium powder is added in basic dispersion agent solution, obtains modified aluminium powder solution；
Modified aluminium powder is sprayed into while PPR, the core-shell copolymerized object of soft core hard-shell type, butadiene-styrene rubber, antioxidant are stirred Mixed liquor when then baking 3 is small at 60 DEG C, is cooled to room temperature, and obtains premix raw material；
Raw material will be premixed to add in from the main charge door at one area of extruder, modified carbon fiber and modified acicular wollastonite is fine It ties up and is added in from the side loading mouth at 5th area of extruder, extruding pelletization obtains PPR pipe, and each section of temperature setting of extruder is：One area 185 DEG C, two 190 DEG C of areas, three 200 DEG C of areas, four 205 DEG C of areas, five 210 DEG C of areas, six 215 DEG C of areas, seven 220 DEG C of areas, eight 215 DEG C of areas, Nine 210 DEG C of areas, ten 205 DEG C of areas, 210 DEG C, engine speed 400r/min of head, feeding frequency 8r/min.
Embodiment 6
The present embodiment provides a kind of method for preparing the PPR pipe with aluminum metal effect, the group of following parts by weight is included Point：100 parts of PPR, 700 15 parts of mesh aluminium powders, 10 parts of dispersant, soft core-shell copolymerized 3 parts of the object of core hard-shell type, 5 parts of butadiene-styrene rubber, carbon 5 parts of fiber, 3 parts of acicular wollastonite fiber, 1 part of coupling agent, 1.5 parts of antioxidant；The dispersant be glyceryl tristearate, institute The soft core-shell copolymerized object of core hard-shell type is stated as methylacrylate- butadiene-styrene core-shell copolymer, the carbon fiber is drip Blue or green base carbon fibre, the average aspect ratio of the asphalt base carbon fiber is 130, and the average aspect ratio of the acicular wollastonite fiber is 20, the coupling agent is four octyloxy titaniums [two (dilauryl phosphorite)], and the antioxidant is that mass ratio is 1:2 4,6- Three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene and pentaerythrite (3- positive decyls thiopropionate)；
Coupling agent solution is prepared, and its pH value is tuned into 4.6；
Atomization sprays into coupling agent solution while carbon fiber and acicular wollastonite fiber are stirred, and is then impregnated with surface The carbon fiber and acicular wollastonite fiber of coupling agent dried at 120 DEG C 2 it is small when, be cooled to room temperature modified carbon fiber and to change Property acicular wollastonite fiber；
Prepare dispersant solution；
Aluminium powder is added in basic dispersion agent solution, obtains modified aluminium powder solution；
Modified aluminium powder is sprayed into while PPR, the core-shell copolymerized object of soft core hard-shell type, butadiene-styrene rubber, antioxidant are stirred Solution when then baking 2 is small at 80 DEG C, is cooled to room temperature, and obtains premix raw material；
Raw material will be premixed to add in from the main charge door at one area of extruder, modified carbon fiber and modified acicular wollastonite is fine It ties up and is added in from the side loading mouth at 5th area of extruder, extruding pelletization obtains PPR pipe, and each section of temperature setting of extruder is：One area 185 DEG C, two 190 DEG C of areas, three 200 DEG C of areas, four 205 DEG C of areas, five 210 DEG C of areas, six 215 DEG C of areas, seven 220 DEG C of areas, eight 215 DEG C of areas, Nine 210 DEG C of areas, ten 205 DEG C of areas, 210 DEG C, engine speed 400r/min of head, feeding frequency 8r/min.
Embodiment 7
The present embodiment provides a kind of method for preparing the PPR pipe with aluminum metal effect, the group of following parts by weight is included Point：100 parts of PPR, 800 15 parts of mesh aluminium powders, 12 parts of dispersant, soft core-shell copolymerized 8 parts of the object of core hard-shell type, 10 parts of butadiene-styrene rubber, carbon 10 parts of fiber, 8 parts of acicular wollastonite fiber, 3 parts of coupling agent, 3 parts of antioxidant；The dispersant be polyvinylpyrrolidone, institute The soft core-shell copolymerized object of core hard-shell type is stated as the core-shell copolymerized object of methyl methacrylate-butyl acrylate, the carbon fiber is viscose glue Base carbon fibre, phenolic aldehyde base carbon fibre, the average aspect ratio of the viscose-based carbon fiber is 180, the acicular wollastonite fiber Average aspect ratio is 15, and the coupling agent is γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, and the antioxidant is quality Than for 1:0.5 β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecanol ester and the double octadecyl esters of thio-2 acid；
Coupling agent solution is prepared, and its pH value is tuned into 4.6；
Atomization sprays into coupling agent solution while carbon fiber and acicular wollastonite fiber are stirred, and is then impregnated with surface The carbon fiber and acicular wollastonite fiber of coupling agent dried at 100 DEG C 2.5 it is small when, be cooled to room temperature to get modified carbon fiber and Modified acicular wollastonite fiber；
Prepare dispersant solution；
Aluminium powder is added in basic dispersion agent solution, obtains modified aluminium powder solution；
Modified aluminium powder is sprayed into while PPR, the core-shell copolymerized object of soft core hard-shell type, butadiene-styrene rubber, antioxidant are stirred Solution when then baking 2.5 is small at 70 DEG C, is cooled to room temperature, and obtains premix raw material；
Raw material will be premixed to add in from the main charge door at one area of extruder, modified carbon fiber and modified acicular wollastonite is fine It ties up and is added in from the side loading mouth at 5th area of extruder, extruding pelletization obtains PPR pipe, and each section of temperature setting of extruder is：One area 185 DEG C, two 190 DEG C of areas, three 200 DEG C of areas, four 205 DEG C of areas, five 210 DEG C of areas, six 215 DEG C of areas, seven 220 DEG C of areas, eight 215 DEG C of areas, Nine 210 DEG C of areas, ten 205 DEG C of areas, 210 DEG C, engine speed 400r/min of head, feeding frequency 8r/min.
Embodiment 8
The present embodiment provides a kind of methods for preparing the PPR pipe with aluminum metal effect, comprise the following steps：
Prepare the raw material of following parts by weight：100 parts of PPR, 700 20 parts of mesh aluminium powders, 8 parts of dispersant, soft core hard-shell type nucleocapsid 8 parts of copolymer, 10 parts of butadiene-styrene rubber, 10 parts of carbon fiber, 8 parts of acicular wollastonite fiber, 3 parts of coupling agent, 3 parts of antioxidant；It is described Dispersant is polyvinyl alcohol, and the soft core-shell copolymerized object of core hard-shell type is core-shell copolymerized for methyl methacrylate-butyl acrylate Object, the carbon fiber are phenolic aldehyde base carbon fibre, and the average aspect ratio of the phenolic aldehyde base carbon fibre is 150, the acicular wollastonite The average aspect ratio of fiber be 20, the coupling agent be γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, the antioxidant It is 1 for mass ratio:1 β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecanol ester and the double octadecyl esters of thio-2 acid；
Coupling agent solution is prepared, and its pH value is tuned into 4.8；
Atomization sprays into coupling agent solution while carbon fiber and acicular wollastonite fiber are stirred, and is then impregnated with surface The carbon fiber and acicular wollastonite fiber of coupling agent dried at 100 DEG C 2.5 it is small when, be cooled to room temperature to get modified carbon fiber and Modified acicular wollastonite fiber；
Aluminium powder is added in basic dispersion agent solution, obtains modified aluminium powder solution；
Modified aluminium powder is sprayed into while PPR, the core-shell copolymerized object of soft core hard-shell type, butadiene-styrene rubber, antioxidant are stirred Solution when then baking 2.5 is small at 70 DEG C, is cooled to room temperature, and obtains premix raw material；
Raw material will be premixed to add in from the main charge door at one area of extruder, modified carbon fiber and modified acicular wollastonite is fine It ties up and is added in from the side loading mouth at 5th area of extruder, extruding pelletization obtains PPR pipe, and each section of temperature setting of extruder is：One area 185 DEG C, two 190 DEG C of areas, three 200 DEG C of areas, four 205 DEG C of areas, five 210 DEG C of areas, six 215 DEG C of areas, seven 220 DEG C of areas, eight 215 DEG C of areas, Nine 210 DEG C of areas, ten 205 DEG C of areas, 210 DEG C, engine speed 400r/min of head, feeding frequency 8r/min.
Comparative example 1
With being different only in that for embodiment 8,18 parts by weight of methylmethacrylate-butyl acrylate is contained in PPR pipe Core-shell copolymerized object, no butadiene-styrene rubber.
Comparative example 2
With being different only in that for embodiment 8, containing 18 parts by weight butadiene-styrene rubber in PPR pipe, no methyl methacrylate- The core-shell copolymerized object of butyl acrylate.
Comparative example 3
With being different only in that for embodiment 8,18 parts by weight of carbon fibers are contained in PPR pipe, without needle-shaped wollastonite fibre.
Comparative example 4
With being different only in that for embodiment 8,18 parts by weight acicular wollastonite fibers, no carbon fiber are contained in PPR pipe.
The present invention carries out performance measurement, testing standard to the PPR pipe of Examples 1 to 6 and comparative example 1-2：Tensile strength： ISO527/2-93；Low temperature notched impact strength：ISO180-93；Elongation at break：ISO527/2-93；Vicat softening temperature ISO306.Test result is shown in Table 1.
Table 1 prepares the performance indicator of the method for the PPR pipe with aluminum metal effect
It can be seen that PPR pipe prepared by the present invention is respectively provided with by the outer surface for the PPR pipe for observing Examples 1 to 6 Good aluminum metal effect can be seen that the tool of the invention prepared by the performance measurement result of the PPR pipe of Examples 1 to 8 There is the PPR pipe good toughness of aluminum metal effect, there is good resistance to low temperature, mechanical property and heat resistance.
It can be seen that by the performance measurement result of embodiment 8 and the PPR pipe of comparative example 1-2：Select soft core hard-shell type Core-shell copolymerized object and butadiene-styrene rubber can subtract crisp aspect in the toughening of PPR pipe and play synergistic effect, and soft core hard shell is used alone The core-shell copolymerized object of type or butadiene-styrene rubber cannot reach good toughening and subtract crisp effect, resistance to low temperature and poor mechanical property, go out Embrittlement phenomena under existing low temperature, it is easy to crack when being subject to external impacts or weight.
The comparison that performance measurement result is carried out by embodiment 8 and the PPR pipe of comparative example 1-2 can be seen that：Independent carbon Fiber compared with using carbon fiber and acicular wollastonite fiber simultaneously, resistance to low temperature, mechanical property and the heat resistance of PPR pipe It can be not much different, but individually carbon fiber cost compared with using carbon fiber and acicular wollastonite fiber simultaneously is higher, and it is independent Declined using the resistance to low temperature and mechanical property of PPR pipe during acicular wollastonite fiber, especially PPR pipe is heat-resisting Hydraulic performance decline is more, it is therefore desirable to which carbon fiber and acicular wollastonite fiber are combined with rational ratio, in situation of reasonable cost Under, resistance to low temperature, mechanical property and the heat resistance of PPR pipe can be effectively improved.
Using above-mentioned desirable embodiment according to the invention as enlightenment, by above-mentioned description, relevant staff is complete Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention Property scope is not limited to the content on specification, it is necessary to determine its technical scope according to right.

Claims (10)

  1. A kind of 1. method for preparing the PPR pipe with aluminum metal effect, which is characterized in that comprise the following steps：
    Prepare the raw material of following parts by weight：100 parts of PPR, 10-25 parts of aluminium powder, 8-18 parts of dispersant, soft core hard-shell type nucleocapsid are total to 3-8 parts of polymers, 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；
    Prepare coupling agent solution；
    Coupling agent solution is distributed in carbon fiber and acicular wollastonite fiber surface, is dried, cooling obtains modified carbon fiber and modification Acicular wollastonite fiber；
    Prepare dispersant solution；
    Aluminium powder is added in basic dispersion agent solution, obtains modified aluminium powder solution；
    Modified aluminium powder mixing is sprayed into while PPR, the core-shell copolymerized object of soft core hard-shell type, butadiene-styrene rubber, antioxidant are stirred Liquid is dried, cooling, obtains premix raw material；
    Premix raw material, modified carbon fiber and modified acicular wollastonite fiber are added in into extruding pelletization in extruder, obtain PPR pipe.
  2. 2. the method according to claim 1 for preparing the PPR pipe with aluminum metal effect, which is characterized in that the original The parts by weight of component of material is as follows：100 parts of PPR, 15-20 parts of aluminium powder, 10-15 parts of dispersant, the soft core-shell copolymerized object 5- of core hard-shell type 8 parts, 8-10 parts of butadiene-styrene rubber, 8-10 parts of carbon fiber, 5-8 parts of acicular wollastonite fiber, 2-3 parts of coupling agent, 2-3 parts of antioxidant.
  3. 3. the method according to claim 1 or 2 for preparing the PPR pipe with aluminum metal effect, which is characterized in that described Dispersant is dodecanoic acid, palmitic acid, stearic acid, tetradecylic acid, parinaric acid, octatecatrienoic acid, three glycerol stearates At least one of ester, polyvinylpyrrolidone, polyvinyl alcohol.
  4. 4. preparing the method for the PPR pipe with aluminum metal effect according to claim 1-3 any one of them, feature exists In the soft core-shell copolymerized object of core hard-shell type is the core-shell copolymerized object of methyl methacrylate-butyl acrylate, methyl methacrylate At least one of core-shell copolymerized object of ester-butadiene-styrene.
  5. 5. preparing the method for the PPR pipe with aluminum metal effect according to claim 1-4 any one of them, feature exists In, the carbon fiber be polyacrylonitrile-based carbon fibre, in asphalt base carbon fiber, viscose-based carbon fiber, phenolic aldehyde base carbon fibre extremely Few one kind, the average aspect ratio of the carbon fiber is 100-200, and the average aspect ratio of the acicular wollastonite fiber is at least 15。
  6. 6. preparing the method for the PPR pipe with aluminum metal effect according to claim 1-5 any one of them, feature exists In the coupling agent is at least one of silane coupling agent or titanate coupling agent；The general formula of the silane coupling agent is YSiX3, X is chloro, methoxyl group, ethyoxyl or acetoxyl group, and Y contains vinyl, amino, epoxy group or sulfydryl, preferably γ- (the third oxygen of 2,3- epoxies) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane；The titanate coupling agent is single alcoxyl At least one of fundamental mode titanate coupling agent, chelating titanate coupling agent, coordination build titanate coupling agent, are preferably three (dioctyl pyrophosphoryl oxygroup) isopropyl titanate, four octyloxy titaniums [two (tridecyl phosphite)], four octyloxy titaniums [two (dilauryl phosphorite)].
  7. 7. preparing the method for the PPR pipe with aluminum metal effect according to claim 1-6 any one of them, feature exists In, the antioxidant be the combination of Hinered phenols antioxidant and monothioester kind antioxidant, the Hinered phenols antioxidant with it is thio The mass ratio of esters antioxidant is 1:0.5-2, the Hinered phenols antioxidant are preferably β-(3,5- di-t-butyl -4- hydroxy benzenes Base) propionic acid octadecanol ester, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, 4,6- tri- (3,5- bis- At least one of tertiary butyl-4-hydroxy benzyl) benzene, the monothioester kind antioxidant is preferably for the double octadecyl esters of thio-2 acid Or at least one of pentaerythrite (3- positive decyls thiopropionate).
  8. 8. preparing the method for the PPR pipe with aluminum metal effect according to claim 1-7 any one of them, feature exists In the butadiene-styrene rubber is butadiene-styrene rubber powder of the grain size in 40-100 mesh, and the aluminium powder is 400-800 mesh.
  9. 9. preparing the method for the PPR pipe with aluminum metal effect according to claim 1-8 any one of them, feature exists In each section of temperature setting of extruder is：One 180-185 DEG C of area, two 185-190 DEG C of areas, three 190-200 DEG C of areas, four area 200-205 DEG C, five 205-210 DEG C of areas, six 210-215 DEG C of areas, seven 215-220 DEG C of areas, eight 210-215 DEG C of areas, nine 205-210 DEG C of areas, tenth area 200-205 DEG C, 200-220 DEG C of head, engine speed 300-450r/min, feeding frequency 5-10r/min；Will premix raw material from squeeze Main charge door at mono- areas of Chu Ji adds in, by modified carbon fiber and modified acicular wollastonite fiber at 4th area of extruder or 5th area Side loading mouth add in.
  10. 10. preparing the method for the PPR pipe with aluminum metal effect according to claim 1-9 any one of them, feature exists In the method that modified carbon fiber and modified acicular wollastonite fiber is made is specially：Carbon fiber and acicular wollastonite fiber are stirred Atomization sprays into coupling agent solution while mixing, and surface then is impregnated with the carbon fiber of coupling agent and acicular wollastonite fiber exists When baking 2-3 is small at 90-120 DEG C, it is cooled to room temperature, obtains modified carbon fiber and modified acicular wollastonite fiber；Premix raw material is made Furnace drying method be：When baking 2-3 is small at 60-80 DEG C.
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