CN106750897B - The preparation method of crystals of calcium salts modified polypropene cortex for bimodal polyethylene pipe - Google Patents
The preparation method of crystals of calcium salts modified polypropene cortex for bimodal polyethylene pipe Download PDFInfo
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- CN106750897B CN106750897B CN201611056171.1A CN201611056171A CN106750897B CN 106750897 B CN106750897 B CN 106750897B CN 201611056171 A CN201611056171 A CN 201611056171A CN 106750897 B CN106750897 B CN 106750897B
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/466—Conversion of one form of calcium sulfate to another
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The present invention relates to a kind of preparation methods of crystals of calcium salts modified polypropene cortex for bimodal polyethylene pipe, it is characterized in that using the isotactic polypropylene (iPP) that metallocene catalysis synthesizes, be raw material be blended with the calcium sulfate crystal whiskers of modification as filler that cortical material is prepared, the cortical material is coextruded one layer of crystals of calcium salts modified polypropene cortex by coextrusion processes, on the bimodal polyethylene surface (BPE) that the metallocene catalysis of extrusion synthesizes.The beneficial effects of the present invention are: 1, process is environmentally protective, processing performance is good, at low cost.2, solve the problems, such as that whisker dehydration is disintegrated under the hot conditions in coextrusion stage, improves the extraneous service life of PE pipeline.3, waste is subjected to higher value application, it can be achieved that inexpensive multifunction, reduces the modification cost of PE pipeline.
Description
Technical field
The present invention relates to a kind of preparation methods of crystals of calcium salts modified polypropene cortex for bimodal polyethylene pipe, belong to
Polymer matrix composites and product technique field.
Background technique
With extensive use of polyethylene (PE) pipeline in the plumbing of China cities and towns, gas ductwork construction, PE pipeline
It is increasingly becoming the achievement that social production every field attracts people's attention.PE pipeline compares traditional steel, cement tube road, has corrosion resistant
Erosion, the features such as easy to install, flexibility is good, and processing performance is excellent, environmentally friendly, safe.But PE resin is as a kind of pair of ultraviolet light and height
The high molecular material of temperature sensitive, under strong ultraviolet radiation and hot conditions, PE can fast degradation aging, that there are surfaces is crisp for pipeline
The danger such as change, mechanical strength reduce, welding point fails.
China's PE pipeline was grown rapidly since the 1980s.Nineteen eighty-two Shanghai has begun to use PE pipe to convey city
Combustion gas.As the special equipment of fuel gas transmission, PE pipeline focused primarily upon the optimization design of mechanical property at that time, and pipeline squeezes out life
The efficiency and strict control of producing line squeeze out the size etc. of pipeline.Period, have the novel PE resin of high stress crack resistant into
Enter market, high-efficiency pipeline extrusion technique emerges, and rate of extrusion can reach one tonne or more per hour.These development are being given
The public spheres such as draining, gas pipeline play an important role.During " 12th Five-Year Plan ", China's plastic conduit industry, which still maintains, is held
Continuous, stable development, yield rise to 13,800,000 tons of year ends 2015 by 840.2 ten thousand tons of 2010, and average annual growth rate is
10.43%.But current PE pipeline ageing failure complicated mechanism, novel PE duct products flood the market, the ageing failure of PE pipeline
Journal of Sex Research relatively lags behind.
Foreign countries are in phase early 1990s, medium density polyethylene (PE-MD) fuel gas conduit and high density polyethylene (HDPE) (PE-HD)
Fuel gas conduit is used widely.At the same time, pipeline production company starts to lead using multilayer PE multiple tube applied to public work
Domain.Representational product includes the research and development of Radius-Systems pipeline company, Britain in PE pipe surface layer coextrusion polypropylene
(PP) double-layer compound pipeline of cortex.Its PP skin thickness is lower than the 10% of pipeline wall thickness, and the PP cortex of outer layer can protect PE
Inner tube is in non-excavation traction installation process damage, and in addition PP cortex can be stripped easily from PE pipeline, to obtain
The pure surface PE is obtained in order to electric fusion weld, welding installation effectiveness is greatly improved and guarantees welding junction quality.
It is some in terms of engineer application that S.Wood et al. analyzes the strippable bimodal polyethylene pipeline of this protective layer
Advantage.Especially PP layers can provide protection to kernel PE pipeline in the welding processing and installation process of pipeline, while peelable
From PP layer can carry out kernel pipeline failure type analysis.Also studies have found that the high PE pipeline of long-term mechanical property, peace
Overall coefficient and service life are accordingly promoted.
Summary of the invention
In view of the deficiencies in the prior art, the purpose of the present invention is to provide one kind to have properties of infrared reflection, and barrier is outdoor
Ultraviolet light adjusts the crystals of calcium salts modified poly- third for improving the resistance to outdoor light-heat aging of bimodal polyethylene pipe of compound bond strength between layers
Alkene cortex preparation method, the compound PP cortex of calcium sulfate crystal whiskers can effectively improve the service life of PE pipeline, stability, riser
Weld installation effectiveness in road.
The technical solution adopted by the present invention to solve the technical problems is: a kind of crystals of calcium salts for bimodal polyethylene pipe
The preparation method of modified polypropene cortex, it is characterised in that the isotactic polypropylene (iPP) with metallocene catalysis synthesis is original
To expect to be blended with modified calcium sulfate crystal whiskers for filler and cortical material is prepared, the cortical material passes through coextrusion processes,
One layer of crystals of calcium salts modified polypropene cortex is coextruded on the bimodal polyethylene surface (BPE) that the metallocene catalysis of extrusion synthesizes.
According to the above scheme, the crystals of calcium salts modified polypropene cortex with a thickness of 0.4-0.8mm.
According to the above scheme, the calcium sulfate crystal whiskers are α-hemihydrate calcium sulfate crystal whisker, and diameter is in 5-10 μ m, major diameter
Than being no more than 10.
According to the above scheme, the α-hemihydrate calcium sulfate crystal whisker is prepared with the following method: preparation mass fraction is 20%-
30% heat stabilizer solution is added ardealite and crystal polymorph control agent and reacts 4-6 hours under the conditions of 95-115 DEG C of normal pressure, then
It filters while hot, it is α-hemihydrate calcium sulfate crystal whisker that filter cake, which is placed on after vacuum oven drying,；Wherein, ardealite and heat stabilizer
The solid-liquid mass ratio of solution is 1:(4~8)；The additional amount of crystal polymorph control agent is the 0.05-0.10% of phosphogypsum quality.
According to the above scheme, the whisker heat stabilizer solution be mass fraction be 20%-30% NaCl solution and
CaCl2Solution is by 1:(0.1-10) volume mixture is formulated.
According to the above scheme, the crystal polymorph control agent is the mixture of sodium citrate and sodium gluconate, sodium citrate and grape
Sour sodium quality proportioning scope control is in 1:(0.1~10).
A kind of preparation method of the crystals of calcium salts modified polypropene cortex for bimodal polyethylene pipe, preferred embodiment, including
Following steps:
1) calcium sulfate crystal whiskers are chosen, for diameter in 5-10 μ m, draw ratio is no more than 10；By mass percentage, claim
Take polypropylene 3-3.6%, calcium sulfate crystal whiskers 0.4-2%, polyethylene 95-96%；
2) the odium stearate ethanol solution for preparing mass fraction 3%-5% goes out after calcium sulfate crystal whiskers are added thereto mixing
Material, obtains modified calcium sulfate crystal whiskers solution；
3) by modified calcium sulfate crystal whiskers and polypropylene double screw extruder mixing extruding pelletization, modified polypropene is prepared
The pellet of cortex, then single screw extrusion machine barrel is added in the pellet of modified polypropene cortex, setting modified polypropene cortex
Pellet extruded tube temperature range, in a composite machine head co-extrusion for polyethylene pipe outer surface, is formed and is modified at 220 DEG C -240 DEG C
Polypropylene cortex.
According to the above scheme, the polyethylene is selected from the bimodal polyethylene that the metallocene catalysis of Borealis AG synthesizes；Institute
It states polypropylene and is selected from metallocene catalysis synthesis isotactic polypropylene.
The present invention is set out with the calcium sulfate crystal whiskers of ideal dimensions, carries out hydrophobic place to the whisker with odium stearate ethanol solution
Then reason passes through coextrusion processes one layer of crystals of calcium salts modified polypropene cortex compound to PE pipeline.Compared with prior art, originally
Advantageous effect of the invention is:
1, the present invention makees the functional filler of PP exodermis using calcium sulfate crystal whiskers, and passes through the addition of control crystals of calcium salts
MODIFIED PP cortex is measured, the interfacial adhesion area of metallocene PE and metallocene PP are adjusted, so that the interface for adjusting the removing of PP cortex is viscous
Knotting strength realizes that PE inner tube and PP crust interlayer adhesion are adjustable, and process is environmentally protective, and processing performance is good, at low cost.
2, the present invention can be by being prepared into whisker for phosphorus ore association calcium resource, and raw material is phosphorous chemical industry solid waste, at low cost；Institute
The calcium sulphate-based whisker thermal decomposition temperature obtained is higher, efficiently solves the whisker dehydration under the hot conditions in coextrusion stage and disintegrates
The problem of；Whisker surface is effectively compound through hydrophobic modified PP, and the calcium sulfate whisker modified polypropylene cortex of formation can effectively drop
The heat for the infrared solar radiation transmitting that low pipeline absorbs when stacking outdoors, while PE kernel pipeline is obstructed under the conditions of the external world
Ultraviolet radiation aging, improve PE pipeline extraneous service life.
3, the present invention combines influence of the addition sodium ion to thermodynamic behavior in semi-hydrated gypsum whisker, utilizes phosphorus ore association calcium
Resource in the salting liquid containing sodium ion by add crystal polymorph control agent prepared under the conditions of constant pressure hydro-thermal thermal decomposition temperature compared with
Height, the lower short and thick shape α-hemihydrate calcium sulfate crystal whisker of draw ratio, can be carried out functionalization to the infrared heat reflectivity of PP exodermis and changes
Property, waste is subjected to higher value application, it can be achieved that inexpensive multifunction, reduces the modification cost of PE pipeline.
Specific embodiment
In order to better understand the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but summary of the invention
It is not limited only to the following examples.
Embodiment 1
A kind of crystals of calcium salts modified polypropene cortex preparation method for bimodal polyethylene pipe, is prepared with metallocene catalysis
Isotactic polypropylene (iPP) be raw material, wastewaters with modified calcium sulfate whiskers be filler be blended preparation cortical material.
α-hemihydrate calcium sulfate crystal whisker used by the present embodiment, diameter is at 5-10 μm, and draw ratio 1-6, preparation method is such as
Under:
The CaCl that NaCl solution, concentration that concentration is 20wt% are 20wt% is prepared respectively2The two is pressed volume by solution
Than being poured into reactor after 3:1 mixing；Then ardealite and crystal polymorph control agent (sodium citrate and grape acid are added into reactor
The mixture of sodium, sodium citrate and sodium gluconate quality proportioning scope control are in 2:1), reaction temperature is set as 95 DEG C, and water-bath adds
Heat filters while hot after isothermal reaction 5 hours, and filter cake is placed on vacuum oven drying, it is brilliant to be dried to obtain α-half-H 2 O calcium sulphate
Palpus.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:4；The additional amount of crystal polymorph control agent is phosphogypsum quality
0.10%.
The preparation method of the crystals of calcium salts modified polypropene cortex of the resistance to outdoor light-heat aging of above-mentioned raising bimodal polyethylene pipe,
Include the following steps:
(1) calcium sulfate crystal whiskers are chosen, for diameter in 5-10 μ m, draw ratio is no more than 10；By mass percentage, claim
Take polypropylene 3%, polyethylene 95%, calcium sulfate crystal whiskers 2%；
(2) the odium stearate ethanol solution for preparing mass fraction 3%-5% goes out after calcium sulfate crystal whiskers are added thereto mixing
Material, obtains modified calcium sulfate crystal whiskers solution；
(3) it by modified calcium sulfate crystal whiskers and polypropylene double screw extruder mixing extruding pelletization, prepares modified poly-
The pellet of propylene cortex, then single screw extrusion machine barrel is added in the pellet of modified polypropene cortex, modified polypropene skin is set
The pellet extruded tube temperature range of layer, in a composite machine head co-extrusion for polyethylene pipe outer surface, is formed at 220 DEG C -240 DEG C
Modified polypropene cortex, with a thickness of 0.4-0.8mm.
The pellet of gained modified polypropene cortex and bimodal polyethylene pellet are separately added into two single screw rods and squeeze in the present invention
Machine barrel out, the bimodal polyethylene pellet extruded tube temperature range is at 190 DEG C -210 DEG C.
What this embodiment was prepared improves the crystals of calcium salts modified polypropene skin of the resistance to outdoor light-heat aging of bimodal polyethylene pipe
Layer makes bimodal polyethylene pipeline hemispherical reflectivity, emissivity >=80%, the heat-insulated temperature difference >=10 DEG C.
Embodiment 2
α-hemihydrate calcium sulfate crystal whisker used by the present embodiment, diameter is at 5-10 μm, and draw ratio 1-6, preparation method is such as
Under:
The CaCl that NaCl solution, concentration that concentration is 20wt% are 20wt% is prepared respectively2The two is pressed volume by solution
Than being poured into reactor after 3:1 mixing；Then ardealite and crystal polymorph control agent (sodium citrate and grape acid are added into reactor
The mixture of sodium, sodium citrate and sodium gluconate quality proportioning scope control are in 2:1), reaction temperature is set as 95 DEG C, and water-bath adds
Heat filters while hot after isothermal reaction 5 hours, and filter cake is placed on vacuum oven drying, it is brilliant to be dried to obtain α-half-H 2 O calcium sulphate
Palpus.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:4；The additional amount of crystal polymorph control agent is phosphogypsum quality
0.10%.
The preparation method of the crystals of calcium salts modified polypropene cortex of the resistance to outdoor light-heat aging of above-mentioned raising bimodal polyethylene pipe,
Include the following steps:
(1) calcium sulfate crystal whiskers are chosen, for diameter in 5-10 μ m, draw ratio is no more than 10；By mass percentage, claim
Take polypropylene 3.6%, polyethylene 96%, calcium sulfate crystal whiskers 0.4%；
(2) the odium stearate ethanol solution for preparing mass fraction 3%-5% goes out after calcium sulfate crystal whiskers are added thereto mixing
Material, obtains modified calcium sulfate crystal whiskers solution；
(3) it by modified calcium sulfate crystal whiskers and polypropylene double screw extruder mixing extruding pelletization, prepares modified poly-
The pellet of propylene cortex, then single screw extrusion machine barrel is added in the pellet of modified polypropene cortex, modified polypropene skin is set
The pellet extruded tube temperature range of layer, in a composite machine head co-extrusion for polyethylene pipe outer surface, is formed at 220 DEG C -240 DEG C
Modified polypropene cortex, with a thickness of 0.4-0.8mm.
The pellet of gained modified polypropene cortex and bimodal polyethylene pellet are separately added into two single screw rods and squeeze in the present invention
Machine barrel out, the bimodal polyethylene pellet extruded tube temperature range is at 190 DEG C -210 DEG C.
Embodiment 3
α-hemihydrate calcium sulfate crystal whisker used by the present embodiment, diameter is at 4-8 μm, and draw ratio 2-8, preparation method is such as
Under: the CaCl that NaCl solution, concentration that concentration is 25wt% are 25wt% is prepared respectively2Solution, by the two 3:1 by volume
It is poured into reactor after mixing；Then ardealite and crystal polymorph control agent are added into reactor, sets reaction temperature as 95 DEG C, water
Bath heating, after isothermal reaction 5 hours, filters while hot, and filter cake is placed on vacuum oven drying, is dried to obtain α-half-H 2 O calcium sulphate
Whisker.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:4；The additional amount of crystal polymorph control agent is ardealite matter
The 0.10% of amount.
The preparation method of the crystals of calcium salts modified polypropene cortex of the resistance to outdoor light-heat aging of above-mentioned raising bimodal polyethylene pipe,
Include the following steps:
(1) calcium sulfate crystal whiskers are chosen, diameter is in 4-8 μ m, draw ratio 2-8；By mass percentage, it weighs poly-
Propylene 3%, polyethylene 95%, calcium sulfate crystal whiskers 2%；
(2) the odium stearate ethanol solution for preparing mass fraction 3%-5% goes out after calcium sulfate crystal whiskers are added thereto mixing
Material, obtains modified calcium sulfate crystal whiskers solution；
(3) it by modified calcium sulfate crystal whiskers and polypropylene double screw extruder mixing extruding pelletization, prepares modified poly-
The pellet of propylene cortex, then single screw extrusion machine barrel is added in the pellet of modified polypropene cortex, modified polypropene skin is set
The pellet extruded tube temperature range of layer, in a composite machine head co-extrusion for polyethylene pipe outer surface, is formed at 220 DEG C -240 DEG C
Modified polypropene cortex, with a thickness of 0.4-0.8mm.
The pellet of gained modified polypropene cortex and bimodal polyethylene pellet are separately added into two single screw rods and squeeze in the present invention
Machine barrel out, the bimodal polyethylene pellet extruded tube temperature range is at 190 DEG C -210 DEG C.
Embodiment 4
α-hemihydrate calcium sulfate crystal whisker used by the present embodiment, diameter is at 4-8 μm, and draw ratio 2-8, preparation method is such as
Under: the CaCl that NaCl solution, concentration that concentration is 25wt% are 25wt% is prepared respectively2Solution, by the two 3:1 by volume
It is poured into reactor after mixing；Then ardealite and crystal polymorph control agent are added into reactor, sets reaction temperature as 95 DEG C, water
Bath heating, after isothermal reaction 5 hours, filters while hot, and filter cake is placed on vacuum oven drying, is dried to obtain α-half-H 2 O calcium sulphate
Whisker.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:4；The additional amount of crystal polymorph control agent is ardealite matter
The 0.10% of amount.
The preparation method of the crystals of calcium salts modified polypropene cortex of the resistance to outdoor light-heat aging of above-mentioned raising bimodal polyethylene pipe,
Include the following steps:
(1) calcium sulfate crystal whiskers are chosen, diameter is in 4-8 μ m, draw ratio 2-8；By mass percentage, it weighs poly-
Propylene 3%, polyethylene 95%, calcium sulfate crystal whiskers 2%；
(2) the odium stearate ethanol solution for preparing mass fraction 3%-5% goes out after calcium sulfate crystal whiskers are added thereto mixing
Material, obtains modified calcium sulfate crystal whiskers solution；
(3) it by modified calcium sulfate crystal whiskers and polypropylene double screw extruder mixing extruding pelletization, prepares modified poly-
The pellet of propylene cortex, then single screw extrusion machine barrel is added in the pellet of modified polypropene cortex, modified polypropene skin is set
The pellet extruded tube temperature range of layer, in a composite machine head co-extrusion for polyethylene pipe outer surface, is formed at 220 DEG C -240 DEG C
Modified polypropene cortex, with a thickness of 0.4-0.8mm.
The pellet of gained modified polypropene cortex and bimodal polyethylene pellet are separately added into two single screw rods and squeeze in the present invention
Machine barrel out, the bimodal polyethylene pellet extruded tube temperature range is at 190 DEG C -210 DEG C.
Embodiment 5
α-hemihydrate calcium sulfate crystal whisker used by the present embodiment, diameter is at 3-6 μm, and draw ratio 1-9, preparation method is such as
Under: the CaCl that NaCl solution, concentration that concentration is 20wt% are 20wt% is prepared respectively2Solution, by the two 1:1 by volume
It is poured into reactor after mixing；Then ardealite and crystal polymorph control agent are added into reactor, sets reaction temperature as 95 DEG C, water
Bath heating, after isothermal reaction 4 hours, filters while hot, and filter cake is placed on vacuum oven drying, is dried to obtain α-half-H 2 O calcium sulphate
Whisker.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:8；The additional amount of crystal polymorph control agent is ardealite matter
The 0.10% of amount.
The preparation method of the crystals of calcium salts modified polypropene cortex of the resistance to outdoor light-heat aging of above-mentioned raising bimodal polyethylene pipe,
Include the following steps:
(1) calcium sulfate crystal whiskers are chosen, diameter is in 3-6 μ m, draw ratio 1-9；By mass percentage, it weighs poly-
Propylene 3.6%, polyethylene 96%, calcium sulfate crystal whiskers 0.4%；
(2) the odium stearate ethanol solution for preparing mass fraction 3%-5% goes out after calcium sulfate crystal whiskers are added thereto mixing
Material, obtains modified calcium sulfate crystal whiskers solution；
(3) it by modified calcium sulfate crystal whiskers and polypropylene double screw extruder mixing extruding pelletization, prepares modified poly-
The pellet of propylene cortex, then single screw extrusion machine barrel is added in the pellet of modified polypropene cortex, modified polypropene skin is set
The pellet extruded tube temperature range of layer, in a composite machine head co-extrusion for polyethylene pipe outer surface, is formed at 220 DEG C -240 DEG C
Modified polypropene cortex, with a thickness of 0.4-0.8mm.
The pellet of gained modified polypropene cortex and bimodal polyethylene pellet are separately added into two single screw rods and squeeze in the present invention
Machine barrel out, the bimodal polyethylene pellet extruded tube temperature range is at 190 DEG C -210 DEG C.
Embodiment 6
α-hemihydrate calcium sulfate crystal whisker used by the present embodiment, diameter is at 3-6 μm, and draw ratio 1-9, preparation method is such as
Under: the CaCl that NaCl solution, concentration that concentration is 20wt% are 20wt% is prepared respectively2Solution, by the two 1:1 by volume
It is poured into reactor after mixing；Then ardealite and crystal polymorph control agent are added into reactor, sets reaction temperature as 95 DEG C, water
Bath heating, after isothermal reaction 4 hours, filters while hot, and filter cake is placed on vacuum oven drying, is dried to obtain α-half-H 2 O calcium sulphate
Whisker.Wherein, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:8；The additional amount of crystal polymorph control agent is ardealite matter
The 0.10% of amount.
The preparation method of the crystals of calcium salts modified polypropene cortex of the resistance to outdoor light-heat aging of above-mentioned raising bimodal polyethylene pipe,
Include the following steps:
(1) calcium sulfate crystal whiskers are chosen, diameter is in 3-6 μ m, draw ratio 1-9；By mass percentage, it weighs poly-
Propylene 3%, polyethylene 95%, calcium sulfate crystal whiskers 2%；
(2) the odium stearate ethanol solution for preparing mass fraction 3%-5% goes out after calcium sulfate crystal whiskers are added thereto mixing
Material, obtains modified calcium sulfate crystal whiskers solution；
(3) it by modified calcium sulfate crystal whiskers and polypropylene double screw extruder mixing extruding pelletization, prepares modified poly-
The pellet of propylene cortex, then single screw extrusion machine barrel is added in the pellet of modified polypropene cortex, modified polypropene skin is set
The pellet extruded tube temperature range of layer, in a composite machine head co-extrusion for polyethylene pipe outer surface, is formed at 220 DEG C -240 DEG C
Modified polypropene cortex, with a thickness of 0.4-0.8mm.
The pellet of gained modified polypropene cortex and bimodal polyethylene pellet are separately added into two single screw rods and squeeze in the present invention
Machine barrel out, the bimodal polyethylene pellet extruded tube temperature range is at 190 DEG C -210 DEG C.
Claims (6)
1. a kind of preparation method of the bimodal polyethylene pipe comprising crystals of calcium salts modified polypropene cortex, it is characterised in that Yi Maojin
It is that filler is blended cortical material is prepared that belong to the isotactic polypropylene that catalyzes and synthesizes, which be raw material with the calcium sulfate crystal whiskers of modification,
The cortical material is by coextrusion processes, in the bimodal polyethylene pipe surface coextrusion one that the metallocene catalysis of extrusion synthesizes
Layer crystals of calcium salts modified polypropene cortex, the calcium sulfate crystal whiskers are α-hemihydrate calcium sulfate crystal whisker, and diameter is in 5-10 μ m
Interior, draw ratio is no more than 10, and the calcium sulfate crystal whiskers of the modification are prepared with the following method: preparation mass fraction is 20%-
30% heat stabilizer solution is added ardealite and crystal polymorph control agent and reacts 4-6 hours under the conditions of 95-115 DEG C of normal pressure, then
It filters while hot, filter cake is placed on after vacuum oven drying up to α-hemihydrate calcium sulfate crystal whisker, prepares mass fraction 3%-5%'s
Odium stearate ethanol solution discharges after gained calcium sulfate crystal whiskers are added thereto mixing, obtains modified calcium sulfate crystal whiskers；Its
In, the solid-liquid mass ratio of ardealite and heat stabilizer solution is 1:(4~8)；The additional amount of crystal polymorph control agent is phosphogypsum quality
0.05-0.10%.
2. a kind of preparation side of bimodal polyethylene pipe comprising crystals of calcium salts modified polypropene cortex according to claim 1
Method, it is characterised in that the crystals of calcium salts modified polypropene cortex with a thickness of 0.4-0.8mm.
3. a kind of preparation side of bimodal polyethylene pipe comprising crystals of calcium salts modified polypropene cortex according to claim 1
Method, it is characterised in that the whisker heat stabilizer solution is the NaCl solution and CaCl that mass fraction is 20%-30%2Solution
By 1:(0.1-10) volume mixture is formulated.
4. a kind of preparation side of bimodal polyethylene pipe comprising crystals of calcium salts modified polypropene cortex according to claim 1
Method, it is characterised in that the crystal polymorph control agent is the mixture of sodium citrate and sodium gluconate, sodium citrate and sodium gluconate matter
Ratio range control is measured in 1:(0.1~10).
5. a kind of preparation side of bimodal polyethylene pipe comprising crystals of calcium salts modified polypropene cortex according to claim 1
Method, which comprises the following steps:
1) the heat stabilizer solution that mass fraction is 20%-30% is prepared, ardealite and crystal polymorph control agent is added in normal pressure 95-
It reacts 4-6 hours under the conditions of 115 DEG C, then filters while hot, obtain α-sulfate hemihydrate after filter cake is placed on vacuum oven drying
Calcium pyroborate, for diameter of whiskers in 5-10 μ m, draw ratio is no more than 10；
2) isotactic polypropylene 3-3.6%, the calcium sulfate crystal whiskers 0.4- of metallocene catalysis synthesis by mass percentage, are weighed
2%, the bimodal polyethylene 95-96% of metallocene catalysis synthesis；
3) the odium stearate ethanol solution for preparing mass fraction 3%-5%, discharges after calcium sulfate crystal whiskers are added thereto mixing, obtains
To modified calcium sulfate crystal whiskers；
4) by modified calcium sulfate crystal whiskers and isotactic polypropylene double screw extruder mixing extruding pelletization, preparation changes
Property polypropylene cortex pellet, then single screw extrusion machine barrel, setting modified poly- third is added in the pellet of modified polypropene cortex
The pellet extruded tube temperature range of alkene cortex is at 220 DEG C -240 DEG C, in a composite machine head co-extrusion for the bimodal polyethylene pipe
Road outer surface forms modified polypropene cortex.
6. a kind of preparation side of bimodal polyethylene pipe comprising crystals of calcium salts modified polypropene cortex according to claim 5
Method, it is characterised in that the bimodal polyethylene is selected from the bimodal polyethylene that the metallocene catalysis of Borealis AG synthesizes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611056171.1A CN106750897B (en) | 2016-11-25 | 2016-11-25 | The preparation method of crystals of calcium salts modified polypropene cortex for bimodal polyethylene pipe |
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| CN201611056171.1A CN106750897B (en) | 2016-11-25 | 2016-11-25 | The preparation method of crystals of calcium salts modified polypropene cortex for bimodal polyethylene pipe |
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| Publication Number | Publication Date |
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| CN106750897A CN106750897A (en) | 2017-05-31 |
| CN106750897B true CN106750897B (en) | 2019-06-28 |
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| CN201611056171.1A Active CN106750897B (en) | 2016-11-25 | 2016-11-25 | The preparation method of crystals of calcium salts modified polypropene cortex for bimodal polyethylene pipe |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4842951A (en) * | 1985-06-05 | 1989-06-27 | Idemitsu Petrochemical Company Limited | Thermoforming resin laminate sheet |
| CN101476651A (en) * | 2009-01-14 | 2009-07-08 | 佛山高明顾地塑胶有限公司 | Reinforced polypropylene industrial pipes and method for producing the same |
| CN103497425A (en) * | 2013-10-22 | 2014-01-08 | 四川万润非金属矿物材料有限公司 | High-strength and high-tenacity polypropylene composite materials and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4842951A (en) * | 1985-06-05 | 1989-06-27 | Idemitsu Petrochemical Company Limited | Thermoforming resin laminate sheet |
| CN101476651A (en) * | 2009-01-14 | 2009-07-08 | 佛山高明顾地塑胶有限公司 | Reinforced polypropylene industrial pipes and method for producing the same |
| CN103497425A (en) * | 2013-10-22 | 2014-01-08 | 四川万润非金属矿物材料有限公司 | High-strength and high-tenacity polypropylene composite materials and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 硫酸钙晶须的制备及其在塑料中的应用;田浩等;《塑料》;20120218;第41卷(第1期);第47-49,112页 |
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