CN109280241A - A kind of preparation method of modified poly ethylene bellows - Google Patents
A kind of preparation method of modified poly ethylene bellows Download PDFInfo
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- CN109280241A CN109280241A CN201810945797.0A CN201810945797A CN109280241A CN 109280241 A CN109280241 A CN 109280241A CN 201810945797 A CN201810945797 A CN 201810945797A CN 109280241 A CN109280241 A CN 109280241A
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- 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
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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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
- C08L2310/00—Masterbatches
Abstract
The invention discloses a kind of preparation method of modified poly ethylene bellows, which puts into extrusion molding in extruder by compounded mix, polyethylene particle, color masterbatch after mixing, cooling, demoulding, fixed length, and cutting obtains modified poly ethylene bellows；The compounded mix is granulated after being mixed by modified inorganic filler with polyethylene particle and obtains；The modified inorganic filler is polymerize to obtain by the calcium carbonate crystal whisker after silane coupler modified with methyl methacrylate-grafted；Modified calcium carbonate whisker and high density polyethylene (HDPE) are granulated jointly and compounded mix are made by the present invention, compared to base polyethylene resin, the tools such as impact strength, tensile break strength, bending modulus increase significantly, the filler is used for the preparation of polytene corrugated tube, is conducive to intensity, heat resistance, the thermal insulation etc. that improve bellows；Compounded mix and modified poly ethylene bellows of the invention, preparation method is simple, easy to operate, low in cost, good product performance, has good market prospects.
Description
Technical field
The present invention relates to plastic pipe technical fields, more particularly relate to a kind of preparation side of modified poly ethylene bellows
Method.
Background technique
Tubing is a kind of very widely used tool, is mainly used for the transmission of various fluids.According to the difference of raw material,
Metal tube and plastic tube can be substantially divided into.Metal tube intensity is larger, and still, higher cost, weight is larger, and transportation cost is high.
Since plastic tube is at low cost, handling ease, therefore, various plastic tubes are more and more in many industrial applications, especially high density
Polytene corrugated tube, in being used widely for many fields such as electric power, draining, petroleum, chemical industry, steel, mine.Existing wave
The length of every section of line pipe is long, and transport is inconvenient, once damage, maintenance is inconvenient, and replacement cost is high, while existing ripple
Pipe is all that single layer tube wall since tube wall is relatively thin is easy to breakage in use, influences using effect.
Calcium carbonate crystal whisker is a kind of novel needle-like material occurred this year, and because its crystal form is monocrystalline, crystals are several
Zero defect, has that intensity is high, modulus is high, the heat-resisting good characteristics such as good with thermal insulation, with plastics compound tense and matrix resin
Compatibility is good, can improve the processing performance of plastic products, improves mechanical property, so being widely used in automobile, plastics, electrical
The fields such as component manufacture, the manufacture of best bright finish component.But since the carbanion of calcium carbonate surface has sizeable proportion can
It is hydrolyzed, cause particle surface to become hydrophilic and oleophobic there are a large amount of hydroxyl, be difficult in organic media it is evenly dispersed, with base
It is not bound with power between material, be easy to cause boundary defect.According to hydrogen bond action theory, when calcium carbonate particle is dry, surface hydroxyl
Interaction forms hydrogen bond, mutually assembles between particle by hydrogen bond action, to form hard aggregation.So must be to calcium carbonate
It is modified that whisker carries out surface, to drop low-surface-energy, reduces the agglomeration power between calcium carbonate granule, improve dispersibility in the base and
Dispersion stabilization reduces two-phase interface tension, adjusts hydrophobicity, improves wetability and binding force between organic base-material, from
And improve the performance of composite material.
Summary of the invention
It is an object of the invention to overcome defect of the existing technology, a kind of preparation of modified poly ethylene bellows is provided
Method.
To achieve the goals above, The technical solution adopted by the invention is as follows:
The preparation method of modified poly ethylene bellows of the invention, the bellows is by compounded mix, polyethylene particle, color masterbatch
Material puts into extrusion molding in extruder after mixing, cooling, demoulding, fixed length, and cutting obtains modified poly ethylene bellows；Institute
It states to be granulated after compounded mix is mixed by modified inorganic filler with polyethylene particle and obtain；The modified inorganic filler is by through silane idol
The connection modified calcium carbonate crystal whisker of agent polymerize to obtain with methyl methacrylate-grafted.
Preferably, the method for modifying of the calcium carbonate crystal whisker is as follows: calcium carbonate crystal whisker being dispersed in dehydrated alcohol, nothing is made
The solid content of water-ethanol is 15-35%, is ultrasonically treated 20-90min, and then instilling mass fraction under agitation is 3-8%
Silane coupling agent, control temperature of reaction system be 75-86 DEG C, be stirred to react 1.5-3h, filter, take filter residue, dry, obtain table
The alkylated modified calcium carbonate whisker in face.
Preferably, the additive amount of the silane coupling agent is the 0.5-2% of calcium carbonate crystal whisker weight；The silane coupling agent
For any one in silane coupling agent kh550, silane coupling agent kh560, silane coupling agent kh570.
Preferably, the method that the modified calcium carbonate crystal whisker polymerize with methyl methacrylate-grafted is as follows: will change
Property after calcium carbonate crystal whisker be dispersed in the ethanol solution that volume fraction is 30-50%, and water soluble starter persulfuric acid is added
Potassium or ammonium persulfate, are then added methyl methacrylate under agitation, make calcium carbonate crystal whisker and methyl methacrylate
Graft polymerization reaction occurs, the temperature for controlling reaction system is 75-80 DEG C, and reaction time 4-5h is filtered after reaction, taken
Filter residue is rinsed 2-3 times with deionized water, and dry 1-1.5h, obtains modified inorganic filler at 115-120 DEG C.
Preferably, the molar ratio of the modified calcium carbonate crystal whisker and methyl methacrylate is 1:0.7-0.9.
Preferably, the compounded mix the preparation method is as follows: modified inorganic filler and polyethylene particle are put into plastics
In extruder, the temperature of heated material melts polyethylene particle to 135-170 DEG C, and material is uniformly mixed, is squeezed out, is granulated,
Obtain compounded mix.
Preferably, the mass ratio of the modified inorganic filler and polyethylene particle is 15-25:100.
Preferably, the modified poly ethylene bellows the preparation method is as follows: by compounded mix, polyethylene particle, color masterbatch
Material presses the mass ratio of 15-25:80-120:1-5 after mixing, is put into the barrel of extruder, controls the mixed material and expecting
Temperature in cylinder is 204-212 DEG C, and then extrusion molding is cooling, demoulding, fixed length, and cutting obtains modified poly ethylene bellows.
Preferably, the polyethylene particle is high density polyethylene (HDPE) particle.
The present invention is by adopting the above-described technical solution, have the advantages that
1, the present invention is modified calcium carbonate crystal whisker using silane coupling agent, wraps modified calcium carbonate crystal whisker surface
One layer of organic coating that can generate preferable affinity with polyolefin is covered, its oleophilic drainage, the good dispersion in organic matter are made.With
Water soluble starter potassium peroxydisulfate or ammonium persulfate cause methyl methacrylate and calcium carbonate and carbon modified in ethanol solution
Sour calcium pyroborate carries out surface grafting polymerization, and the pattern of modified calcium carbonate whisker is made to obtain intact preservation, surface modification
Calcium carbonate crystal whisker and polyethylene compound tense can form evenly dispersed stabilising system.Through testing, the additive amount of silane coupling agent is 1%
When, the activation index of calcium carbonate crystal whisker can reach 100%, efficiently use calcium carbonate crystal whisker, save raw material.
2, modified calcium carbonate whisker and high density polyethylene (HDPE) are granulated jointly and compounded mix are made by the present invention, compare polyethylene
Matrix resin, the tools such as impact strength, tensile break strength, bending modulus increase significantly, of the invention compound to fill out through testing
Material compares base polyethylene resin, and impact strength improves 31.5% or more, and tensile break strength improves 35.7% or more, bending die
Amount improves 117% or more, and has substantially no effect on melt flow rate (MFR), which is used for the preparation of polytene corrugated tube, favorably
In intensity, heat resistance, the thermal insulation etc. that improve bellows.The precipitated calcium carbonate filler material of UPVC, PVC feed pipe is replaced with this
The modified calcium carbonate whisker of invention, tubing intensity increase by 500 above, can significantly improve the rigidity of material.
3, compounded mix of the invention can method by the way that master batch or PP Pipe Compound is made, also may be directly applied to plastics
In production of articles, it can be widely used for the plastic products such as production injection molding, extrusion, product has excellent service performance.
It can be seen that compounded mix and modified poly ethylene bellows of the invention, preparation method is simple, easy to operate,
Low in cost, good product performance has good market prospects.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, preferred embodiment is enumerated below, to this hair
Bright further description.However, it is necessary to illustrate, many details listed in specification are used for the purpose of making reader to this
The one or more aspects of invention have a thorough explanation, also may be implemented even without these specific details of the invention
These aspects.
Embodiment 1
The preparation method of modified poly ethylene bellows of the present invention, includes the following steps:
(1) calcium carbonate crystal whisker is dispersed in dehydrated alcohol, makes the solid content 15% of dehydrated alcohol, be ultrasonically treated
20min, then instills the silane coupling agent kh550 that mass fraction is 3% under agitation, and dripping quantity is calcium carbonate crystal whisker weight
The 2% of amount；Controlling temperature of reaction system is 75 DEG C, is stirred to react 1.5h, filters, takes filter residue, dries, it is alkylated to obtain surface
Modified calcium carbonate whisker；
(2) the modified calcium carbonate whisker of step (1) is dispersed in the ethanol solution that volume fraction is 30%, and water is added
Soluble initiator potassium peroxydisulfate, is then added methyl methacrylate under agitation, makes calcium carbonate crystal whisker and metering system
Graft polymerization reaction occurs for sour methyl esters, and the temperature for controlling reaction system is 75 DEG C, and reaction time 5h is filtered after reaction,
Filter residue is taken, is rinsed 2 times with deionized water, dry 1.5h, obtains modified inorganic filler at 115 DEG C；The modified calcium carbonate is brilliant
It must be 1:0.9 with the molar ratio of methyl methacrylate；
(3) the modified inorganic filler of step (2) and high density polyethylene (HDPE) particle are put into plastics by the mass ratio of 15:100
In extruder, the temperature of heated material makes high density polyethylene (HDPE) particle fusion to 135 DEG C, and material is uniformly mixed, squeezes out, makes
Grain, obtains compounded mix；
(4) compounded mix of step (3) and high density polyethylene (HDPE) particle and color masterbatch are pressed to the mass ratio of 15:80:1
After mixing, it is put into the barrel of extruder, controlling temperature of the mixed material in barrel is 205 DEG C, is then extruded into
Type, cooling, demoulding, fixed length, cutting obtain modified poly ethylene bellows.
Embodiment 2
The preparation method of modified poly ethylene bellows of the present invention, includes the following steps:
(1) calcium carbonate crystal whisker is dispersed in dehydrated alcohol, makes the solid content 17% of dehydrated alcohol, be ultrasonically treated
Then 27min instills the silane coupling agent kh560 that mass fraction is 3.5% under agitation, dripping quantity is calcium carbonate crystal whisker
The 1.9% of weight；Controlling temperature of reaction system is 77 DEG C, is stirred to react 1.6h, filters, takes filter residue, dries, obtains surface alkyl
The modified calcium carbonate whisker of change；
(2) the modified calcium carbonate whisker of step (1) is dispersed in the ethanol solution that volume fraction is 32%, and water is added
Soluble initiator potassium peroxydisulfate, is then added methyl methacrylate under agitation, makes calcium carbonate crystal whisker and metering system
Graft polymerization reaction occurs for sour methyl esters, and the temperature for controlling reaction system is 75.5 DEG C, reaction time 4.9h, after reaction mistake
Filter, takes filter residue, is rinsed 3 times with deionized water, and dry 1.45h, obtains modified inorganic filler at 115.5 DEG C；The carbon modified
The molar ratio of sour calcium pyroborate and methyl methacrylate is 1:0.88；
(3) compounded mix of step (3) and high density polyethylene (HDPE) particle and color masterbatch are put by the mass ratio of 16:100
Enter in plastic extruder, the temperature of heated material makes high density polyethylene (HDPE) particle fusion to 138 DEG C, and material is uniformly mixed, is squeezed
Out, it is granulated, obtains compounded mix；
(4) mass ratio that compounded mix, high density polyethylene (HDPE) particle, color masterbatch are pressed 16:84:1.4 after mixing, is put
Enter in the barrel of extruder, controlling temperature of the mixed material in barrel is 205 DEG C, and then extrusion molding is cooling, demoulding,
Fixed length, cutting, obtains modified poly ethylene bellows.
Embodiment 3
The preparation method of modified poly ethylene bellows of the present invention, includes the following steps:
(1) calcium carbonate crystal whisker is dispersed in dehydrated alcohol, makes the solid content 19% of dehydrated alcohol, be ultrasonically treated
34min, then instills the silane coupling agent kh570 that mass fraction is 4% under agitation, and dripping quantity is calcium carbonate crystal whisker weight
The 1.8% of amount；Controlling temperature of reaction system is 78 DEG C, is stirred to react 1.8h, filters, takes filter residue, is dried, and surface alkylation is obtained
Modified calcium carbonate whisker；
(2) the modified calcium carbonate whisker of step (1) is dispersed in the ethanol solution that volume fraction is 34%, and water is added
Soluble initiator potassium peroxydisulfate, is then added methyl methacrylate under agitation, makes calcium carbonate crystal whisker and metering system
Graft polymerization reaction occurs for sour methyl esters, and the temperature for controlling reaction system is 76 DEG C, reaction time 4.8h, after reaction mistake
Filter, takes filter residue, is rinsed 2 times with deionized water, and dry 1.4h, obtains modified inorganic filler at 116 DEG C；The modified calcium carbonate
The molar ratio of whisker and methyl methacrylate is 1:0.86；
(3) the modified inorganic filler of step (2) and high density polyethylene (HDPE) particle are put into plastics by the mass ratio of 17:100
In extruder, the temperature of heated material makes high density polyethylene (HDPE) particle fusion to 142 DEG C, and material is uniformly mixed, squeezes out, makes
Grain, obtains compounded mix；
(4) compounded mix of step (3) and high density polyethylene (HDPE) particle and color masterbatch are pressed to the quality of 17:88:1.8
Than after mixing, being put into the barrel of extruder, controlling temperature of the mixed material in barrel is 206 DEG C, is then squeezed out
Molding, cooling, demoulding, fixed length, cutting obtain modified poly ethylene bellows.
Embodiment 4
The preparation method of modified poly ethylene bellows of the present invention, includes the following steps:
(1) calcium carbonate crystal whisker is dispersed in dehydrated alcohol, makes the solid content 21% of dehydrated alcohol, be ultrasonically treated
Then 41min instills the silane coupling agent kh550 that mass fraction is 4.5% under agitation, dripping quantity is calcium carbonate crystal whisker
The 1.6% of weight；Controlling temperature of reaction system is 79 DEG C, is stirred to react 1.9h, filters, takes filter residue, dries, obtains surface alkyl
The modified calcium carbonate whisker of change；
(2) the modified calcium carbonate whisker of step (1) is dispersed in the ethanol solution that volume fraction is 36%, and water is added
Soluble initiator potassium peroxydisulfate, is then added methyl methacrylate under agitation, makes calcium carbonate crystal whisker and metering system
Graft polymerization reaction occurs for sour methyl esters, and the temperature for controlling reaction system is 76.5 DEG C, reaction time 4.7h, after reaction mistake
Filter, takes filter residue, is rinsed 3 times with deionized water, and dry 1.35h, obtains modified inorganic filler at 116.5 DEG C；The carbon modified
The molar ratio of sour calcium pyroborate and methyl methacrylate is 1:0.84；
(3) the modified inorganic filler of step (2) and high density polyethylene (HDPE) particle are put into plastics by the mass ratio of 18:100
In extruder, the temperature of heated material makes high density polyethylene (HDPE) particle fusion to 145 DEG C, and material is uniformly mixed, squeezes out, makes
Grain, obtains compounded mix；
(4) compounded mix of step (3) and high density polyethylene (HDPE) particle and color masterbatch are pressed to the quality of 18:92:2.2
Than after mixing, being put into the barrel of extruder, controlling temperature of the mixed material in barrel is 207 DEG C, is then squeezed out
Molding, cooling, demoulding, fixed length, cutting obtain modified poly ethylene bellows.
Embodiment 5
The preparation method of modified poly ethylene bellows of the present invention, includes the following steps:
(1) calcium carbonate crystal whisker is dispersed in dehydrated alcohol, makes the solid content 23% of dehydrated alcohol, be ultrasonically treated
48min, then instills the silane coupling agent kh560 that mass fraction is 5% under agitation, and dripping quantity is calcium carbonate crystal whisker weight
The 1.4% of amount；Controlling temperature of reaction system is 80 DEG C, is stirred to react 2.1h, filters, takes filter residue, is dried, and surface alkylation is obtained
Modified calcium carbonate whisker；
(2) the modified calcium carbonate whisker of step (1) is dispersed in the ethanol solution that volume fraction is 38%, and water is added
Soluble initiator potassium peroxydisulfate, is then added methyl methacrylate under agitation, makes calcium carbonate crystal whisker and metering system
Graft polymerization reaction occurs for sour methyl esters, and the temperature for controlling reaction system is 77 DEG C, reaction time 4.6h, after reaction mistake
Filter, takes filter residue, is rinsed 2 times with deionized water, and dry 1.3h, obtains modified inorganic filler at 117 DEG C；The modified calcium carbonate
The molar ratio of whisker and methyl methacrylate is 1:0.82；
(3) the modified inorganic filler of step (2) and high density polyethylene (HDPE) particle are put into plastics by the mass ratio of 19:100
In extruder, the temperature of heated material makes high density polyethylene (HDPE) particle fusion to 149 DEG C, and material is uniformly mixed, squeezes out, makes
Grain, obtains compounded mix；
(4) compounded mix of step (3) and high density polyethylene (HDPE) particle and color masterbatch are pressed to the quality of 20:96:2.6
Than after mixing, being put into the barrel of extruder, controlling temperature of the mixed material in barrel is 208 DEG C, is then squeezed out
Molding, cooling, demoulding, fixed length, cutting obtain modified poly ethylene bellows.
Embodiment 6
The preparation method of modified poly ethylene bellows of the present invention, includes the following steps:
(1) calcium carbonate crystal whisker is dispersed in dehydrated alcohol, makes the solid content 25% of dehydrated alcohol, be ultrasonically treated
Then 55min instills the silane coupling agent kh570 that mass fraction is 5.5% under agitation, dripping quantity is calcium carbonate crystal whisker
The 1.2% of weight；Controlling temperature of reaction system is 81 DEG C, is stirred to react 2.3h, filters, takes filter residue, dries, obtains surface alkyl
The modified calcium carbonate whisker of change；
(2) the modified calcium carbonate whisker of step (1) is dispersed in the ethanol solution that volume fraction is 40%, and water is added
Soluble initiator potassium peroxydisulfate, is then added methyl methacrylate under agitation, makes calcium carbonate crystal whisker and metering system
Graft polymerization reaction occurs for sour methyl esters, and the temperature for controlling reaction system is 77.5 DEG C, reaction time 4.5h, after reaction mistake
Filter, takes filter residue, is rinsed 3 times with deionized water, and dry 1.25h, obtains modified inorganic filler at 117.5 DEG C；The carbon modified
The molar ratio of sour calcium pyroborate and methyl methacrylate is 1:0.8；
(3) the modified inorganic filler of step (2) and high density polyethylene (HDPE) particle are put into plastics by the mass ratio of 20:100
In extruder, the temperature of heated material makes high density polyethylene (HDPE) particle fusion to 152 DEG C, and material is uniformly mixed, squeezes out, makes
Grain, obtains compounded mix；
(4) compounded mix of step (3) and high density polyethylene (HDPE) particle and color masterbatch are pressed to the mass ratio of 21:100:3
After mixing, it is put into the barrel of extruder, controlling temperature of the mixed material in barrel is 209 DEG C, is then extruded into
Type, cooling, demoulding, fixed length, cutting obtain modified poly ethylene bellows.
Embodiment 7
The preparation method of modified poly ethylene bellows of the present invention, includes the following steps:
(1) calcium carbonate crystal whisker is dispersed in dehydrated alcohol, makes the solid content 27% of dehydrated alcohol, be ultrasonically treated
62min, then instills the silane coupling agent kh550 that mass fraction is 6% under agitation, and dripping quantity is calcium carbonate crystal whisker weight
The 1.1% of amount；Controlling temperature of reaction system is 82 DEG C, is stirred to react 2.5h, filters, takes filter residue, is dried, and surface alkylation is obtained
Modified calcium carbonate whisker；
(2) the modified calcium carbonate whisker of step (1) is dispersed in the ethanol solution that volume fraction is 42%, and water is added
Soluble initiator ammonium persulfate, is then added methyl methacrylate under agitation, makes calcium carbonate crystal whisker and metering system
Graft polymerization reaction occurs for sour methyl esters, and the temperature for controlling reaction system is 78 DEG C, reaction time 4.4h, after reaction mistake
Filter, takes filter residue, is rinsed 2 times with deionized water, and dry 1.2h, obtains modified inorganic filler at 118 DEG C；The modified calcium carbonate
The molar ratio of whisker and methyl methacrylate is 1:0.78；
(3) the modified inorganic filler of step (2) and high density polyethylene (HDPE) particle are put into plastics by the mass ratio of 21:100
In extruder, the temperature of heated material makes high density polyethylene (HDPE) particle fusion to 156 DEG C, and material is uniformly mixed, squeezes out, makes
Grain, obtains compounded mix；
(4) compounded mix of step (3) and high density polyethylene (HDPE) particle and color masterbatch are pressed to the quality of 22:104:3.4
Than after mixing, being put into the barrel of extruder, controlling temperature of the mixed material in barrel is 210 DEG C, is then squeezed out
Molding, cooling, demoulding, fixed length, cutting obtain modified poly ethylene bellows.
Embodiment 8
The preparation method of modified poly ethylene bellows of the present invention, includes the following steps:
(1) calcium carbonate crystal whisker is dispersed in dehydrated alcohol, makes the solid content 29% of dehydrated alcohol, be ultrasonically treated
Then 69min instills the silane coupling agent kh560 that mass fraction is 6.5% under agitation, dripping quantity is calcium carbonate crystal whisker
The 0.9% of weight；Controlling temperature of reaction system is 83 DEG C, is stirred to react 2.6h, filters, takes filter residue, dries, obtains surface alkyl
The modified calcium carbonate whisker of change；
(2) the modified calcium carbonate whisker of step (1) is dispersed in the ethanol solution that volume fraction is 44%, and water is added
Soluble initiator ammonium persulfate, is then added methyl methacrylate under agitation, makes calcium carbonate crystal whisker and metering system
Graft polymerization reaction occurs for sour methyl esters, and the temperature for controlling reaction system is 78.5 DEG C, reaction time 4.3h, after reaction mistake
Filter, takes filter residue, is rinsed 3 times with deionized water, and dry 1.15h, obtains modified inorganic filler at 118.5 DEG C；The carbon modified
The molar ratio of sour calcium pyroborate and methyl methacrylate is 1:0.76；
(3) the modified inorganic filler of step (2) and high density polyethylene (HDPE) particle are put into plastics by the mass ratio of 22:100
In extruder, the temperature of heated material makes high density polyethylene (HDPE) particle fusion to 159 DEG C, and material is uniformly mixed, squeezes out, makes
Grain, obtains compounded mix；
(4) compounded mix of step (3) and high density polyethylene (HDPE) particle and color masterbatch are pressed to the quality of 23:108:3.8
Than after mixing, being put into the barrel of extruder, controlling temperature of the mixed material in barrel is 211 DEG C, is then squeezed out
Molding, cooling, demoulding, fixed length, cutting obtain modified poly ethylene bellows.
Embodiment 9
The preparation method of modified poly ethylene bellows of the present invention, includes the following steps:
(1) calcium carbonate crystal whisker is dispersed in dehydrated alcohol, makes the solid content 31% of dehydrated alcohol, be ultrasonically treated
75min, then instills the silane coupling agent kh570 that mass fraction is 7% under agitation, and dripping quantity is calcium carbonate crystal whisker weight
The 0.7% of amount；Controlling temperature of reaction system is 84 DEG C, is stirred to react 2.7h, filters, takes filter residue, is dried, and surface alkylation is obtained
Modified calcium carbonate whisker；
(2) the modified calcium carbonate whisker of step (1) is dispersed in the ethanol solution that volume fraction is 46%, and water is added
Soluble initiator ammonium persulfate, is then added methyl methacrylate under agitation, makes calcium carbonate crystal whisker and metering system
Graft polymerization reaction occurs for sour methyl esters, and the temperature for controlling reaction system is 79 DEG C, reaction time 4.2h, after reaction mistake
Filter, takes filter residue, is rinsed 2 times with deionized water, and dry 1.1h, obtains modified inorganic filler at 119 DEG C；The modified calcium carbonate
The molar ratio of whisker and methyl methacrylate is 1:0.74；
(3) the modified inorganic filler of step (2) and high density polyethylene (HDPE) particle are put into plastics by the mass ratio of 23:100
In extruder, the temperature of heated material makes high density polyethylene (HDPE) particle fusion to 163 DEG C, and material is uniformly mixed, squeezes out, makes
Grain, obtains compounded mix；
(4) compounded mix of step (3) and high density polyethylene (HDPE) particle and color masterbatch are pressed to the quality of 24:112:4.2
Than after mixing, being put into the barrel of extruder, controlling temperature of the mixed material in barrel is 212 DEG C, is then squeezed out
Molding, cooling, demoulding, fixed length, cutting obtain modified poly ethylene bellows.
Embodiment 10
The preparation method of modified poly ethylene bellows of the present invention, includes the following steps:
(1) calcium carbonate crystal whisker is dispersed in dehydrated alcohol, makes the solid content 33% of dehydrated alcohol, be ultrasonically treated
Then 83min instills the silane coupling agent kh550 that mass fraction is 7.5% under agitation, dripping quantity is calcium carbonate crystal whisker
The 0.6% of weight；Controlling temperature of reaction system is 85 DEG C, is stirred to react 2.8h, filters, takes filter residue, dries, obtains surface alkyl
The modified calcium carbonate whisker of change；
(2) the modified calcium carbonate whisker of step (1) is dispersed in the ethanol solution that volume fraction is 48%, and water is added
Soluble initiator ammonium persulfate, is then added methyl methacrylate under agitation, makes calcium carbonate crystal whisker and metering system
Graft polymerization reaction occurs for sour methyl esters, and the temperature for controlling reaction system is 79.5 DEG C, reaction time 4.1h, after reaction mistake
Filter, takes filter residue, is rinsed 3 times with deionized water, and dry 1.05h, obtains modified inorganic filler at 119.5 DEG C；The carbon modified
The molar ratio of sour calcium pyroborate and methyl methacrylate is 1:0.72；
(3) the modified inorganic filler of step (2) and high density polyethylene (HDPE) particle are put into plastics by the mass ratio of 24:100
In extruder, the temperature of heated material makes high density polyethylene (HDPE) particle fusion to 167 DEG C, and material is uniformly mixed, squeezes out, makes
Grain, obtains compounded mix；
(4) compounded mix of step (3) and high density polyethylene (HDPE) particle and color masterbatch are pressed to the quality of 25:116:4.6
Than after mixing, being put into the barrel of extruder, controlling temperature of the mixed material in barrel is 210 DEG C, is then squeezed out
Molding, cooling, demoulding, fixed length, cutting obtain modified poly ethylene bellows.
Embodiment 11
The preparation method of modified poly ethylene bellows of the present invention, includes the following steps:
(1) calcium carbonate crystal whisker is dispersed in dehydrated alcohol, makes the solid content 35% of dehydrated alcohol, be ultrasonically treated
90min, then instills the silane coupling agent kh550 that mass fraction is 8% under agitation, and dripping quantity is calcium carbonate crystal whisker weight
The 0.5% of amount；Controlling temperature of reaction system is 86 DEG C, is stirred to react 3h, filters, takes filter residue, dries, it is alkylated to obtain surface
Modified calcium carbonate whisker；
(2) the modified calcium carbonate whisker of step (1) is dispersed in the ethanol solution that volume fraction is 50%, and water is added
Soluble initiator ammonium persulfate, is then added methyl methacrylate under agitation, makes calcium carbonate crystal whisker and metering system
Graft polymerization reaction occurs for sour methyl esters, and the temperature for controlling reaction system is 80 DEG C, and reaction time 4h is filtered after reaction,
Filter residue is taken, is rinsed 3 times with deionized water, dry 1h, obtains modified inorganic filler at 120 DEG C；The modified calcium carbonate whisker
Molar ratio with methyl methacrylate is 1:0.7；
(3) the modified inorganic filler of step (2) and high density polyethylene (HDPE) particle are put into plastics by the mass ratio of 25:100
In extruder, the temperature of heated material makes high density polyethylene (HDPE) particle fusion to 170 DEG C, and material is uniformly mixed, squeezes out, makes
Grain, obtains compounded mix；
(4) compounded mix of step (3) and high density polyethylene (HDPE) particle and color masterbatch are pressed to the mass ratio of 19:120:5
After mixing, it is put into the barrel of extruder, controlling temperature of the mixed material in barrel is 207 DEG C, is then extruded into
Type, cooling, demoulding, fixed length, cutting obtain modified poly ethylene bellows.
Claims (9)
1. a kind of preparation method of modified poly ethylene bellows, which is characterized in that the bellows is by compounded mix, polyethylene
Grain, color masterbatch put into extrusion molding in extruder after mixing, cooling, demoulding, fixed length, and cutting obtains modified poly ethylene wave
Line pipe；The compounded mix is granulated after being mixed by modified inorganic filler with polyethylene particle and obtains；The modified inorganic filler by
Calcium carbonate crystal whisker after silane coupler modified polymerize to obtain with methyl methacrylate-grafted.
2. the preparation method of modified poly ethylene bellows according to claim 1, which is characterized in that the calcium carbonate crystal whisker
Method of modifying it is as follows: calcium carbonate crystal whisker is dispersed in dehydrated alcohol, the solid content 15-35% of dehydrated alcohol is made, ultrasound
20-90min is handled, the silane coupling agent that mass fraction is 3-8% is then instilled under agitation, controls temperature of reaction system
It is 75-86 DEG C, is stirred to react 1.5-3h, filter, take filter residue, dries, obtain the alkylated modified calcium carbonate whisker in surface.
3. the preparation method of modified poly ethylene bellows according to claim 2, which is characterized in that the silane coupling agent
Additive amount be calcium carbonate crystal whisker weight 0.5-2%；The silane coupling agent is silane coupling agent kh550, silane coupling agent
Any one in kh560, silane coupling agent kh570.
4. the preparation method of modified poly ethylene bellows according to claim 1, which is characterized in that the modified carbon
The method that sour calcium pyroborate polymerize with methyl methacrylate-grafted is as follows: modified calcium carbonate crystal whisker is dispersed in volume fraction
For in the ethanol solution of 30-50%, and water soluble starter potassium peroxydisulfate or ammonium persulfate is added, then under agitation plus
Enter methyl methacrylate, makes calcium carbonate crystal whisker and methyl methacrylate that graft polymerization reaction occur, control reaction system
Temperature is 75-80 DEG C, and reaction time 4-5h filters after reaction, takes filter residue, is rinsed 2-3 times with deionized water, in 115-
Dry 1-1.5h, obtains modified inorganic filler at 120 DEG C.
5. the preparation method of modified poly ethylene bellows according to claim 4, which is characterized in that the modified carbon
The molar ratio of sour calcium pyroborate and methyl methacrylate is 1:0.7-0.9.
6. the preparation method of modified poly ethylene bellows according to claim 1, which is characterized in that the compounded mix
The preparation method is as follows: modified inorganic filler and polyethylene particle are put into plastic extruder, the temperature of heated material to 135-
170 DEG C melt polyethylene particle, and material is uniformly mixed, and squeeze out, and are granulated, obtain compounded mix.
7. the preparation method of modified poly ethylene bellows according to claim 6, which is characterized in that the modified inorganic is filled out
The mass ratio of material and polyethylene particle is 15-25:100.
8. the preparation method of modified poly ethylene bellows according to claim 1, which is characterized in that the modified poly ethylene
Bellows the preparation method is as follows: compounded mix, polyethylene particle, color masterbatch are mixed by the mass ratio of 15-25:80-120:1-5
It after closing uniformly, is put into the barrel of extruder, controlling temperature of the mixed material in barrel is 204-212 DEG C, is then squeezed out
Molding, cooling, demoulding, fixed length, cutting obtain modified poly ethylene bellows.
9. according to claim 1 or the preparation method of the described in any item modified poly ethylene bellowss of 6-8, which is characterized in that institute
The polyethylene particle stated is high density polyethylene (HDPE) particle.
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