CN102040757A - High-density polyethylene alloy pipe and manufacturing method thereof - Google Patents
High-density polyethylene alloy pipe and manufacturing method thereof Download PDFInfo
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- CN102040757A CN102040757A CN2009100445220A CN200910044522A CN102040757A CN 102040757 A CN102040757 A CN 102040757A CN 2009100445220 A CN2009100445220 A CN 2009100445220A CN 200910044522 A CN200910044522 A CN 200910044522A CN 102040757 A CN102040757 A CN 102040757A
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Abstract
The invention discloses a high-density polyethylene alloy pipe and a manufacturing method thereof. High-density polyethylene 100 (HDPE 100) is used as base resin, high-density polyethylene-g-maleic anhydride (HDPE-g-MAH) is used as a compatilizer, calcium carbonate (CaCO3) and low-density polyethylene (LDPE) are added into the base resin and the compatilizer, and the mixture is blended with modifier polyamide 6 (PA6) to form a modified polyethylene (PE) alloy product. The method comprises the main operation steps of: (I) preparing HDPE modified granules; and (II) adding the modifier PA6, performing high-speed mixing to form a modified PE mixture, and extruding the modified PE mixture into the product in an extruder. According to the technical scheme, the high-density polyethylene alloy pipe overcomes the defects the defects that the conventional polyethylene resin has low tensile strength, poor rigidity and poor abrasion resistance, chemical resistance, environmental stress cracking resistance and heat resistance, has insufficient blocking property on hydrocarbon solvents and fuel oil, is easily damaged by ultraviolet under the irradiation of sunlight, seriously affects the service life of the product and the like; and the high-density polyethylene alloy pipe is suitable to be used as various heat resistant, abrasion resistant and temperature resistant pipes, and is particularly suitable for pipeline transportation of special industries of drainage, fuel gas and fuel oil delivery, chemistry and chemical industry and the like.
Description
Technical field
The present invention relates to a kind of high density polyethylene(HDPE) compo pipe and manufacture method thereof.
Background technology
Existing polyvinyl resin, because it is low to have density, embrittlement temperature is low, good toughness, the erosion resisting insulation performance is good, is easy to characteristics such as construction and installation, and it is very fast to be widely used in making water service pipe, gas line and development.But because the softening temperature of polyethylene is low, the HDPE fusing point is 130 ℃, a little higher than 100 ℃ of LDPE fusing point, low, the poor rigidity of tensile strength, performances such as wear resistance, chemical proofing, environmental stress crack resistance and thermotolerance are not good, to varsol and oil fuel barrier deficiency, under sun exposure, easily destroyed by ultraviolet ray, have a strong impact on the work-ing life of product.
Summary of the invention
At above-mentioned situation, the purpose of this invention is to provide a kind of existing compatible preferably effect, can form elastic interface layer preferably again, and weave construction is tight, thermotolerance and shock resistance are obviously improved, also manufacturing process is simple and reliable, and the starting material wide material sources are abundant, and cost is low, environmental protection, energy-conservation, non-environmental-pollution is convenient to penetration and promotion.
For achieving the above object, a kind of high density polyethylene(HDPE) compo pipe, it selects for use high density polyethylene 100 to be base resin, uses HDPE-g-MAH to make compatilizer, adds ultra-fine micropowder lime carbonate CaCO
3With ldpe resin LDPE, carry out blend with properties-correcting agent PA6 again and make the modified PE alloy product.
A kind of method of high density polyethylene(HDPE) compo pipe is made in further measure for achieving the above object, and its operation steps is as follows:
(I) preparation HDPE modification pellet
1. select polythene PE raw material high-density polyethylene resin HDPE71-76% for use, ldpe resin LDPE8-12% and grafting compatilizer HDPE-g-MAH3-7%, filler CaCO
38-12%, oxidation inhibitor 0.3-0.5%, auxiliary antioxidant 0.3-0.5%, UV light absorber 0.3-0.5%, dispersion agent 0.3-0.5%;
2. above-mentioned raw materials is dropped into blender in proportion and carry out high-speed mixing, make blend composition;
3. blend composition is extruded into strip-shaped materials through duplex e Foerderanlage input extrusion machine through melting mixing;
4. strip-shaped materials exports dicing machine to, makes work in-process-granulation;
(II) extrusion molding
1. in above-mentioned work in-process-granulation, add properties-correcting agent PA6 high-speed mixing and become the modified PE compound;
2. product mold is installed on extrusion machine;
3. will be crushed to the modified PE alloy product in the modified PE compound input extruder mold.
It is base resin that the present invention adopts HDPE100, uses HDPE-g-MAH to make compatilizer, adds CaCO
3With LDPE, carry out the technical scheme that blend alloy is made modified PE alloy finished product with PA again, overcome low, the poor rigidity of existing polyvinyl resin tensile strength, performances such as wear resistance, chemical proofing, environmental stress crack resistance and thermotolerance are not good, to varsol and oil fuel barrier deficiency, under sun exposure, easily destroyed, have a strong impact on the defectives such as work-ing life of product by ultraviolet ray.
The present invention's producing effect compared to existing technology is:
(1) with HDPE is matrix resin, adds CaCO
3, LDPE, selecting HDPE-g-MAH for use is compatilizer, carry out the modification granulation, carry out blend alloy with properties-correcting agent PA again, improved the barrier property of HDPE, thereby comprehensive physicals such as the thermotolerance, wear resistance, temperature tolerance etc. that have improved HDPE has been expanded the range of application of HDPE tubing;
(2) simple and reliable process need not drop into valuable equipment, and utilizes existing installation just can implement, operation, easy to maintenance, production efficiency height;
(3) no waste water and dregs discharging, no dust, odorlessness, no sewage pollution, environmental protection, energy-conservation, be convenient to penetration and promotion;
(4) the starting material wide material sources are abundant, and cost performance is good, and cost is low;
(5) weave construction is tight, the interfacial layer good springiness, and compatible effect strengthens, thereby has expanded the Application Areas of HDPE tubing greatly, is convenient to penetration and promotion.
The present invention is fit to do the usefulness of the tubing of various heat-resisting, wear-resisting, heatproofs, is particularly suitable for plumbing, the pipe-line transportation of special industries such as combustion gas, fuel delivery and chemical.
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is the schema of high density polyethylene(HDPE) compo pipe of the present invention and manufacture method thereof.
Fig. 2 is the performance structure synoptic diagram of reaction process formula of the present invention.
Fig. 3 is HDPE-g-MAH of the present invention, CaCO
3Modification HDPE expressing technique parameter list.
Fig. 4 is 3% pair of effect of material performance table for HDPE-g-MAH consumption of the present invention.
Fig. 5 is 5% pair of effect of material performance table for HDPE-g-MAH consumption of the present invention.
Fig. 6 is 7% pair of effect of material performance table for HDPE-g-MAH consumption of the present invention.
Fig. 7 is CaCO of the present invention
3Consumption is 8.0% pair of effect of material performance table.
Fig. 8 is CaCO of the present invention
3Consumption is 12.0% pair of effect of material performance table.
Fig. 9 is 8.0% pair of effect of material performance table for LDPE consumption of the present invention.
Figure 10 is 12.0% pair of effect of material performance table for LDPE consumption of the present invention.
Figure 11 is a modification HDPE/PA6 extruding pipe material process parameter table of the present invention.
Figure 12 is modification HDPE/PA6 of the present invention and pure HDPE tubing organic solvent-resistant perviousness comparative test result table.
Figure 13 is a mechanical property detected result table of the present invention.
Figure 14 is pure HDPA tubing of the present invention and modification HDPE/PA compo pipe material performance comparison sheet.
Figure 15 is the SEM photo of HDPE/PA6 of the present invention (92.4/7) alloy pipe.
Figure 16 is the SEM photo of HDPE/PA6 of the present invention (90.4/9) alloy alloy pipe.
Figure 17 is the SEM photo of HDPE/PA6 of the present invention (88./11) alloy alloy pipe.
Embodiment
Referring to accompanying drawing, principle of work of the present invention and technological process:
In order to improve poly over-all properties and its range of application of expansion.It is base resin that the present invention selects for use with HDPE100, selects for use HDPE-g-MAH as compatilizer, adds ultra-fine micropowder CaCO again
3, LDPE and properties-correcting agent PA6 carry out the mixed and modified modified PE compo pipe that becomes.
One, prescription
High-density polyethylene resin HDPE71-76%, ldpe resin LDPE8-12%, grafting compatilizer HDPE-g-MAH3-7%, filler CaCO
38-12%, oxidation inhibitor 0.3-0.5%, auxiliary antioxidant 0.3-0.5%, UV light absorber 0.3-0.5%, dispersion agent 0.3-0.5%.
Two, selection
1.HDPE100 model 041 Shanghai petrochemical industry
2.LDPE the Yanshan Mountain, Beijing
3.HDPE-g-MAH the liter of Shanghai day
4. ultra-fine micropowder CaCO
3Jiangxi occasion space powder Products Co., Ltd
5.PA6 German import
6. oxidation inhibitor Beijing addition auxiliary agent institute
7. auxiliary antioxidant Beijing addition auxiliary agent institute
8. UV light absorber Beijing addition auxiliary agent institute
9. dispersion agent Shanghai Da Chang chemical plant
Three, preparation method
Carry out in two steps, the first step prepares HDPE modification pellet, second step preparation HDPE/PA alloy pipe.
Its operation steps is as follows:
(I) preparation HDPE modification pellet:
1. select polythene PE raw material high-density polyethylene resin HDPE71-76% for use, ldpe resin LDPE8-12% and grafting compatilizer HDPE-g-MAH3-7%, filler CaCO
38-12%, oxidation inhibitor 0.3-0.5%, auxiliary antioxidant 0.3-0.5%, UV light absorber 0.3-0.5%, dispersion agent 0.3-0.5%;
2. above-mentioned raw materials is dropped into blender in proportion and carry out high-speed mixing, make blend composition;
3. blend composition is extruded into strip-shaped materials through duplex e Foerderanlage input extrusion machine through melting mixing;
4. strip-shaped materials exports dicing machine to, makes work in-process-granulation;
(II) extrusion molding:
1. in above-mentioned work in-process-granulation, add properties-correcting agent PA6 high-speed mixing and become the modified PE compound;
2. product mold is installed on extrusion machine;
3. will be crushed to the modified PE alloy product in the modified PE compound input extruder mold.
Four, formula test
(1) determines the optimum amount of HDPE-g-MAH in prescription.
Base resin and CaCO3 and other auxiliary dosage are constant, only change the consumption of compatilizer, observe it to effect of material performance
1. fill a prescription: HDPE 75%, and LDPE 10%, and HDPE-g-MAH 3%, CaCO
310%, oxidation inhibitor 0.4%, auxiliary antioxidant 0.4%, UV light absorber 0.4%, dispersion agent 0.4%.
2. technology: accurately take by weighing various weight of material by above-mentioned prescription, carry out extruding pelletization by Fig. 3 processing parameter.
3. injection moulding Performance Detection batten
Injection moulding batten processing parameter: baking material temperature: 85 ℃, injection temperature: 190 ℃ in 1 district, 210 ℃ in 2 districts, 220 ℃ in 3 districts; Injection pressure: 1 district 80MPa, 2 district 40MPa, 3 district 15MPa, inject time 15S, dwell time 10S, cooling time 15S.
4. Fig. 4 is seen in performance analysis.
1. fill a prescription: HDPE 73%, and LDPE 10%, and HDPE-g-MAH 5%, CaCO
310%, oxidation inhibitor 0.4% auxiliary antioxidant 0.4% UV light absorber 0.4%, dispersion agent 0.4%.
2. the processing parameter by embodiment 1 carries out extruding pelletization and injection moulding Performance Detection batten.
3. performance test results is seen Fig. 5.
1. fill a prescription: HDPE 71%, and LDPE 10%, and HDPE-g-MAH 7%, CaCO
310%, oxidation inhibitor 0.3%, auxiliary antioxidant 0.3%, UV light absorber 0.3%, dispersion agent 0.3%.
2. extrude by the processing parameter of embodiment 1 and make material and injection moulding Performance Detection batten.
3. performance test results is seen Fig. 6.
4. performance analysis
Adopt macromolecule interfacial compatilizer HDPE-g-MAH to PE/CaCO
3Infill system has tangible compatible effect, after adding interfacial compatibilizer HDPE-g-MAH in the system, bigger variation takes place in impact property, its reason is that interfacial compatibilizer HDPE-g-MAH brings into play central role therein, it is as the interface modification material, in system, mainly brought into play three effects: the one, coupled action, HDPE-g-MAH has the polar macromolecular material, its polar group can be rich in " end carboxyl " with the inorganic fillings surface and produces stronger interaction, its nonpolar flexible chain can tangle with polyvinyl resin again, improve two alternate surface propertieies thus, improved the phase interface bonding, promoted CaCO
3Dispersion.Its reaction process as shown in Figure 2.The 2nd, the interfacial layer effect, HDPE-g-MAH becomes an elastic interface layer, can transmit stress with the elastic layer of mineral filler good " grafting ", brings out the matrix surrender, stops further expanding of crackle; The 3rd, coordinative role, though HDPE-g-MAH is identical with the backbone structure of polyvinyl resin, behind the introducing polar group, variation has to a certain degree all taken place in its melt viscosity, crystal property, mechanical property, reduce as degree of crystallinity, toughness improves can make the system yield strength increase.Moreover, the maleic anhydride group on the grafted polyethylene macromolecular chain in the fusion filling process with CaCO
3Filling surface has formed certain Chemical bond, has improved the interface affinity between resin and the filler, has improved stretching, impact and resistance toheat.Through its optimum amount of Performance Detection is 5%.
(2) determine CaCO
3Optimum amount in prescription.
Base resin, compatilizer and other auxiliary dosage are constant, change CaCO
3Consumption, observe it to effect of material performance.
Embodiment 4
1. fill a prescription: HDPE 75%LDPE 10%, HDPE-g-MAH 5%, CaCO
38%, oxidation inhibitor 0.5%, auxiliary antioxidant 0.5%, UV light absorber 0.5%, dispersion agent 0.5%.
2. its extruding and pelletizing process parameter and injection moulding Performance Detection batten processing parameter are with reference to embodiment 1.
3. performance test results is seen Fig. 7.
1. the HDPE 71.5% that fills a prescription, LDPE 10%, and HDPE-g-MAH 5%, CaCO
312%, oxidation inhibitor 0.45%, auxiliary antioxidant 0.45%, UV light absorber 0.45%, dispersion agent 0.45%.
2. its extruding and pelletizing process parameter and injection moulding Performance Detection batten processing parameter are with reference to embodiment 1.
3. performance test results is seen Fig. 8.
From accompanying drawing 5,7,8 CaCO as can be seen
3Consumption is to effect of material performance.When add-on is 12%, flexural strength, notched Izod impact strength and elongation at break all descend to some extent.Especially the elongation at break reduction is more, but tensile strength and flexural strength change not quite.Take all factors into consideration CaCO from material property and cost
3Optimum amount be 10%.
(3) determine the optimum amount of LDPE in prescription.
1. fill a prescription: HDPE 76%, and LDPE 8%, and HDPE-g-MAH 5%, CaCO
310%, oxidation inhibitor 0.5%, auxiliary antioxidant 0.5%, UV light absorber 0.5%, dispersion agent 0.5%.
2. its extruding and pelletizing process parameter and injection moulding Performance Detection batten processing parameter are with reference to embodiment 1
3.. performance test results is seen Fig. 9.
1. the .:HDPE 71% that fills a prescription, LDPE 12%, and HDPE-g-MAH 5%, CaCO
310%, oxidation inhibitor 0.5%, auxiliary antioxidant 0.5%, UV light absorber 0.5%, dispersion agent 0.5%.
2. its extruding and pelletizing process parameter and injection moulding Performance Detection batten processing parameter are with reference to embodiment 1.
3. performance test results is seen Figure 10.
4. performance analysis
From accompanying drawing 4,9,10 as can be seen the matrix material based on the matrix resin of HDPE, LDPE can increase material percentage elongation, but can influence the crystal property of HDPE, and the strength of materials is reduced, be tending towards soft, flexural strength, tensile strength and notched Izod impact strength decrease.Therefore the optimum amount of taking all factors into consideration LDPE is 10%.
Five, modified PE pellet and PA alloy
A, principle:, because HDPE is poor to the oozing property of resistance of hydrocarbon polymer and organic solvent, limited its application in important industries such as chemical pipeline, fuel delivery line though pure HDPE tubing has many good qualities.For barrier and its over-all properties that improves HDPE, carry out the over-all properties that blend further improves HDPE with modified PE pellet and PA6.Because PA is a polar polymer, and HDPE is a non-polar polymer, because both molecular polarity chain structure, viscoelastic ratio differ greatly, can be poor during blend because of reactive force between the co-mixing system, phase interface is smooth and serious being separated takes place, cause dispersion particle thick, thereby be difficult to form layers sheet dispersion when mixing.In order to improve the consistency of HDPE and PA, the present invention adds the HDPE-g-MAH compatilizer in advance in HDPE, carry out fusion high speed mixing granulator, again with the PE pellet and the PA6 blend of this modification, improved the biphase consistency so greatly, increased the avidity of two-phase interface, the particle of disperse phase is reduced, thus form layers sheet structure when mixing easily.As accompanying drawing 15, Figure 16, Figure 17.
B, preparation method
Embodiment 8
1. fill a prescription:
HDPE modification pellet 92.4%, PA6 7%, oxidation inhibitor 0.3%, auxiliary antioxidant 0.3%.
2. preparation technology
Accurately take by weighing various weight of material by last prescription, extrude ￠ 63 * 5.8mm by Figure 11 processing parameter, pressure rating is the tubing of 1.0MPa.
3. barrier test
Get ￠ 63 * 5.8mm tubing, long 100mm, sealed at both ends good, to put in the organic solvent that benzene,toluene,xylene is housed, normal temperature was placed 24 days down, recorded its rate of permeation and saw Figure 12.
1. fill a prescription: HDPE modification pellet 90.4%, PA6 9%, oxidation inhibitor 0.3%, auxiliary antioxidant 0.3%.
2. preparation technology
Accurately take by weighing various weight of material by last prescription, extrude ￠ 63 * 5.8mm by embodiment 8 processing parameters, pressure rating is the tubing of 1.0MPa.
3. barrier test
Get ￠ 63 * 5.8mm tubing, long 100mm, sealed at both ends good, to put in the organic solvent that benzene,toluene,xylene is housed, normal temperature was placed 24 days down, recorded its rate of permeation and saw Figure 12.
Embodiment 10
1. fill a prescription: HDPE modification pellet 88.4%, PA6 11%, oxidation inhibitor 0.3%, auxiliary antioxidant 0.3%.
2. preparation technology: accurately take by weighing various weight of material by last prescription, extrude ￠ 63 * 5.8mm by embodiment 8 processing parameters, pressure rating is the tubing of 1.0MPa.
3. barrier test
Get ￠ 63 * 5.8mm tubing, long 100mm, sealed at both ends good, to put in the organic solvent that benzene,toluene,xylene is housed, normal temperature was placed 24 days down, recorded its rate of permeation and saw Figure 12.
C, mechanical and physical performance test
1. injection moulding Performance Detection batten
Carry out physicals respectively and detect, it the results are shown in Figure 13.
(4) modification HDPE/PA alloy pipe optimum formula determines
Modification HDPE and PA blend alloy as can be seen from Figure 13, the consumption of PA in prescription is many more, and barrier and physicals are good more, but consider that the PA cost is too high, so the consumption of PA is defined as 9%.
Six, pure HDPA tubing and modification HDPE/PA compo pipe material performance relatively reach conclusion and see Figure 14.
With HDPE is basic matrix resin, adds CaCO
3LDPE, selecting HDPE-g-MAH for use is compatilizer, carries out the modification granulation, carries out blend alloy with PA again, not only changed the barrier property of HDPE, and improved the comprehensive physicals of HDPE greatly, thereby expand the application neck of HDPE tubing, modification HDPE/PA compo pipe material greatly, not only can be used as water service pipe, gas line, also can be used for important special industries such as Chemicals, fuel delivery line.
Claims (2)
1. a high density polyethylene(HDPE) compo pipe is characterized in that it selects high density polyethylene 100 for use is base resin, uses HDPE-g-MAH to make compatilizer, adds ultra-fine micropowder lime carbonate CaCO
3With ldpe resin LDPE, carry out blend with properties-correcting agent PA6 again and make the modified PE alloy product.
2. make the method for the described high density polyethylene(HDPE) compo pipe of claim 1, it is characterized in that its operation steps is as follows:
(I) preparation HDPE modification pellet
1. select polythene PE raw material high-density polyethylene resin HDPE71-76% for use, ldpe resin LDPE8-12% and grafting compatilizer HDPE-g-MAH3-7%, filler CaCO
38-12%, oxidation inhibitor 0.3-0.5%, auxiliary antioxidant 0.3-0.5%, UV light absorber 0.3-0.5%, dispersion agent 0.3-0.5%;
2. above-mentioned raw materials is dropped into blender in proportion and carry out high-speed mixing, make blend composition;
3. blend composition is extruded into strip-shaped materials through duplex e Foerderanlage input extrusion machine through melting mixing;
4. strip-shaped materials exports dicing machine to, makes work in-process-granulation;
(II) extrusion molding
1. in above-mentioned work in-process-granulation, add properties-correcting agent PA6 high-speed mixing and become the modified PE compound;
2. product mold is installed on extrusion machine;
3. will be crushed to the modified PE alloy product in the modified PE compound input extruder mold.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993543A (en) * | 2012-12-10 | 2013-03-27 | 南京聚锋新材料有限公司 | Composition for preparing nylon-containing polyolefin and preparation process of composition |
| CN109593249A (en) * | 2018-11-12 | 2019-04-09 | 张桂芬 | A kind of rub resistance PE alloy |
| CN110628111A (en) * | 2019-09-20 | 2019-12-31 | 安徽滁州德威新材料有限公司 | Physical termite-proof high-hardness polyethylene sheath material and preparation method thereof |
| CN110938247A (en) * | 2019-12-16 | 2020-03-31 | 良和包装(浙江)有限公司 | High-strength PE plastic barrel and preparation process thereof |
| CN114573897A (en) * | 2022-03-04 | 2022-06-03 | 四川仁智新材料科技有限责任公司 | Special material for polyethylene mute drain pipe and preparation method |
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| CN101358005A (en) * | 2008-09-06 | 2009-02-04 | 广东三凌塑料管材有限公司 | Preparation method of high density polyethylene hollow wrapped pipe |
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| CN101358005A (en) * | 2008-09-06 | 2009-02-04 | 广东三凌塑料管材有限公司 | Preparation method of high density polyethylene hollow wrapped pipe |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993543A (en) * | 2012-12-10 | 2013-03-27 | 南京聚锋新材料有限公司 | Composition for preparing nylon-containing polyolefin and preparation process of composition |
| CN109593249A (en) * | 2018-11-12 | 2019-04-09 | 张桂芬 | A kind of rub resistance PE alloy |
| CN110628111A (en) * | 2019-09-20 | 2019-12-31 | 安徽滁州德威新材料有限公司 | Physical termite-proof high-hardness polyethylene sheath material and preparation method thereof |
| CN110938247A (en) * | 2019-12-16 | 2020-03-31 | 良和包装(浙江)有限公司 | High-strength PE plastic barrel and preparation process thereof |
| CN114573897A (en) * | 2022-03-04 | 2022-06-03 | 四川仁智新材料科技有限责任公司 | Special material for polyethylene mute drain pipe and preparation method |
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Application publication date: 20110504 |