CN102863712A - High shock resistant PVC tubular product and preparation method thereof - Google Patents
High shock resistant PVC tubular product and preparation method thereof Download PDFInfo
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- CN102863712A CN102863712A CN2011101873162A CN201110187316A CN102863712A CN 102863712 A CN102863712 A CN 102863712A CN 2011101873162 A CN2011101873162 A CN 2011101873162A CN 201110187316 A CN201110187316 A CN 201110187316A CN 102863712 A CN102863712 A CN 102863712A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a high shock resistant PVC tubular product, comprising the following ingredients: 100 weight parts of PVC resin, 1.0-3.0 weight parts of heat stabilizer, 2.3-3.2 weight parts of lubricant, 0-8 weight parts of filling agent, 8-11.5 weight parts of toughening agent, 0.2-0.7 weight parts of coloring agent, and 2-4 weight parts of ASA resin. The tubular product disclosed herein has high strength of a PVC-U tubular product, has a tensile strength being 45-48 MPa and a yield strength being 45-48 MPa, has good shock resistance, has a simply-supported beam notch impact strength being 73-100kj/m<2>, has improved flexibility, has an elongation at break being 146.1-166.8%, and simultaneously has good pressure endurance and weather resistance. In hydraulic pressure tests, the PVC tubular product disclosed herein has no fracture and no leakage, if the PVC tubular product disclosed herein is used in pavement of water pipe networks, the leakage of the water pipe networks can be guaranteed to be less than 5%, thus the PVC tubular product disclosed herein is better than existing PVC tubular product.
Description
Technical field
A kind of impact polychloroethylene pipes and preparation method thereof belongs to polymeric material field, is specifically related to polychloroethylene pipes of a kind of high strength, high resistance momentum and preparation method thereof.
Background technology
At present, the PVC-U pipeline is the plastic conduit of market share maximum, accounts for the share of plastic conduit nearly 70%.The PVC-U water-feeding pipes is one of kind that is most widely used in the water-feeding pipes market segment, but because the fragility of PVC-U tubing is larger, easily breaks in the processes such as transportation, installation, construction.So recent year PVC manufacturing enterprise begins to produce the polychloroethylene pipes (being PVC-M tubing) of high-impact successively, PVC-M tubing is except the characteristics with common PVC-U tubing, also have excellent toughness and shock resistance, compare with common PVC-U tubing, the shock resistance of PVC-M tubing significantly improves, and can resist better the inhomogeneous decline of the slight scuffing, point load and the ground that produce in tubing installation and the transportation; PVC-M tubing can effectively be resisted water hammer, reduces the destruction of pipeline in the operation process; The resisting environmental stress and cracking ability significantly improves, be highly resistant to install and transportation in to the external impacts of tubing, prevent the generation of rapid crack propagation phenomenon; Conveyance power of water is strong, long service life, this kind tubing is existing more than ten years success use experience abroad, all be widely used in states such as Britain, Holland, South Africa, Australia, New Zealand, Germany, Japan, wherein in the plastic water supply pipe net of the states such as Australia, South Africa, polyvinyl chloride high-impact pipeline occupies 90% the market share at present.In China, government has also given great attention to the security of feedwater, requires to accelerate to promote new type plastic pipe and uses, and guarantees that the leak rate of water supply network is below 5%.This application for polyvinyl chloride high-impact tubing provides good opportunity.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, a kind of high strength that had both had PVC-U tubing is provided, have again good shock resistance, also have simultaneously impact polychloroethylene pipes of good withstand voltage properties and weathering resistance and preparation method thereof.
The present invention solves the technical scheme that its technical problem takes: this impact polychloroethylene pipes, it is characterized in that, comprise following component in parts by weight: 100 parts of polyvinyl chloride resins, 1.0～3.0 parts of thermo-stabilizers, 2.3～3.2 parts of lubricants, 0～8 part of weighting agent, 8～11.5 parts of toughner, 0.2～0.7 part of tinting material, 2～4 parts of ASA resins.
Preferably, calculate with parts by weight, above-mentioned impact polychloroethylene pipes component comprises 100 parts of polyvinyl chloride resins, 1.2～1.5 parts of organotin stabilizers, 2.7～3.2 parts of lubricants, 2～6 parts of weighting agents, 9～11.5 parts of toughner, 0.21～0.63 part of tinting material, 2～4 parts of ASA resins.
For improving the antioxidant property of PVC, avoid flavescence when outdoor life-time service, become fragile among the present invention, in prescription, also be added with 0.01～0.014 part oxidation inhibitor.
Concrete, described oxidation inhibitor is antioxidant 1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) and DLTP (the two lauryls of thio-2 acid).
Preferably, the mean polymerisation degree of described polyvinyl chloride resin is 1000.The QS-1050P type tubing speciality resin that preferred Qilu Petrochemical Company is produced.
Described thermo-stabilizer of the present invention is selected organotin stabilizer, and organotin stabilizer can be selected methyl tin, dibutyl tin laurate, sulfuric acid dibutyl tin or sulfuric acid dioctyl tin stablizer.
Lubricant choose in calcium stearate, paraffin, Microcrystalline Wax, polyethylene wax and the oxidized polyethlene wax any four or more.
Weighting agent is selected calcene or nano-calcium carbonate.
Toughner is selected MBS (methyl methacrylate, divinyl and cinnamic terpolymer) and/or anti-impact type ACR (acrylic ester impact-resisting modifier).
Tinting material is selected carbon black and/or titanium dioxide.
The invention also discloses a kind of preparation method of impact polychloroethylene pipes, it is characterized in that may further comprise the steps:
1, each furnish component is put in proportion gradually heat temperature raising of high-speed mixer, and under rotating speed 1000～2000r/min, fully stir, when the mixture temperature reaches 120～125 ℃, mixture is delivered in the low speed mixer, at room temperature continue to stir, rotating speed is 450～500r/min, discharging when temperature of charge to be mixed is down to 40～50 ℃;
2, with the extrusion moulding on screw extrusion press of step 1 gained mixture material, traction, cooling, Vacuum shaping namely get the impact polychloroethylene pipes, processing condition are 180～215 ℃ of head temperatures, 170～185 ℃ of body temperatures, engine speed 15rpm, feeding rotating speed 25rpm, main frame electric current 56.0～60A, pulling speed is 2.5～2.8m/min.
The present invention is that the ASA resin is as properties-correcting agent with general-purpose plastics PVC and the modification of engineering plastics ASA resin alloy, and admixture is 2～4 parts in 100 parts polyvinyl chloride resin, and consumption is little, plays the effect that improves rigidity of material, promotes plasticizing.By contrast experiment repeatedly, determine raw material, processing aid and optimum formula, select suitable complete processing and the PVC of novel weathering resistant, high impact resistance and the excellent machinability made is material modified.Used ASA resin is unformed terpolymer in the described technical scheme, it is the terpolymer of vinyl cyanide (A), vinylbenzene (S) and acrylate (A), be saturated backbone structure, do not contain two keys, the carbonyl in the macromolecular chain and itrile group possess stronger ultraviolet-resistant capacity, and phenyl ring is typical rock steady structure, be difficult to occur photochemical reaction, therefore, the ASA resin has extremely strong ultraviolet-resistant capacity, colour stable, excellent weather resistance and hard.Owing to having introduced acrylic elastomer in the ASA resin structure, make its multipolymer have fabulous shock resistance, especially low-temperature impact resistance is good; Contain itrile group in the ASA resin structure, therefore have extremely strong chemical resistance; Heat stability is good in the course of processing, heat-drawn wire can reach 92 ℃; The ASA resin has excellent weather resistance, and this material has good mechanical property simultaneously.And the solubility parameter δ of ASA resin is 9.6～9.8, and very approaching with the solubility parameter of PVC, both have good intermiscibility, and rheological property, thermal expansivity are more approaching, and the two consistency of theoretical analysis is fine.Adopt the ASA resin as PVC properties-correcting agent, rigidity that can the Effective Raise material, and less to the Toughness of material can be improved again the processing characteristics of composition simultaneously, the Effective Raise extruding pipe material withstand voltage properties and weathering resistance.Make tubing both have the high strength of PVC-U tubing, have again good shock resistance.
Compared with prior art, the beneficial effect that a kind of impact polychloroethylene pipes of the present invention and preparation method thereof has is: this tubing had both had the high strength of PVC-U tubing, tensile strength can reach 45～48MPa, and yield strength can reach 45～48MPa and have again good shock resistance: the simply supported beam notched Izod impact strength is at 73～100kJ/m
2Between, its snappiness also is improved: elongation at break reaches 146.1～166.8%, also have simultaneously good withstand voltage properties and weathering resistance, experimental results show that pvc pipe material of the present invention all has outstanding representation in falling weight impact test and high speed impact test, product is all qualified, especially (20 ℃ of hydro-tests, ring stress 38MPa, 1h), pvc pipe material crack-free of the present invention, ne-leakage, and the pvc pipe material commonly used in the simultaneous test under test conditions, show break, seepage, do not satisfy tubing, particularly grid is with the service requirements of tubing.Therefore PVC modification pipe performance of the present invention is excellent, as being used for the laying of grid, can guarantee the leak rate of water supply network below 5%, be better than existing pvc pipe material.
Embodiment
Embodiment 1
Impact polychloroethylene pipes composition component prescription and tubing preparation method are as follows:
Join by following weight part and to get each material component: 2 parts of the antioxidant 1010 of 100 parts of QS-1050p type pVC resins, 1.2 parts of organotin stabilizers (methyl tin), 8.0 parts of MBS toughner, 1.0 parts of ACR toughner, 2 parts of ASA resins, 0.2 part of calcium stearate, 0.6 part of polyethylene wax, 0.9 part in paraffin, 1.0 parts of Microcrystalline Waxes, 0.2 part of titanium dioxide, 0.01 part, 0.005 part of carbon black and 0.005 part DLTP, nano-calcium carbonates.
Above-mentioned material is put into high-speed mixer by proportioning raw materials heat up gradually, and under rotating speed 1000～1200r/min, fully stir 10～15min.When mixture temperature reaches 120～125 ℃, mixture is delivered at room temperature continuation stirring in the low speed mixer, rotating speed is 450～500r/min, discharging got mixture when mixture temperature to be stirred to was 40～50 ℃.
Then this mixture is extruded at twin screw extruder, obtained the impact polychloroethylene pipes that specification is Φ 110mm * 3.4mm * 1.0MPa through the vacuum sizing cooling forming, the concrete technology condition is:
Body temperature (℃) 180～185,180～185,175～180,170～175,173～178
Head temperature (℃) 180～185,190～195,195～205,205～215
Engine speed 15rpm; Feeding rotating speed 25rpm; Main frame electric current 56.0～60A; Pulling speed 2.5～2.8m/min.
Embodiment 2
Impact polychloroethylene pipes composition component prescription and tubing preparation method are as follows:
Join by following weight part and to get each material component: 5 parts of the antioxidant 1010 of 100 parts of QS-1050P type polyvinyl chloride resins, 1.5 parts of organotin stabilizers (dibutyl tin laurate), 3 parts of ASA resins, 9 parts of MBS toughner, 1.2 parts of ACR toughner, 0.4 part of calcium stearate, 0.8 part of polyethylene wax, 0.9 part in paraffin, 0.6 part of Microcrystalline Wax, 0.4 part of titanium dioxide, 0.02 part, 0.007 part of carbon black and 0.005 part DLTP, nano-calcium carbonates.
Above-mentioned material is put into high-speed mixer heat up gradually, and under rotating speed 1000～1200r/min, fully stir 10～15min.When mixture temperature reaches 120～125 ℃, mixture is delivered to continuation stirring under rotating speed 450～500r/min, room temperature in the low speed mixer, discharging got mixture when mixture temperature to be stirred to was 40～50 ℃.
Then this mixture is extruded at twin screw extruder, obtained the impact polychloroethylene pipes through the vacuum sizing cooling forming, the concrete technology condition is:
Body temperature (℃) 180～185,180～185,175～180,170～175,173～178
Head temperature (℃) 180～185,190～195,195～205,205～215
Engine speed 15rpm; Feeding rotating speed 25rpm; Main frame electric current 53.0～56.0A; Pulling speed 2.5～2.8m/min.
Embodiment 3
Impact polychloroethylene pipes composition component prescription and tubing preparation method are as follows:
Join by following weight part and to get each material component: 8 parts of the antioxidant 1010 of 100 parts of QS-1050P type polyvinyl chloride resins, 2.0 parts of organotin stabilizers (sulfuric acid dibutyl tin), 4 parts of ASA resins, 10 parts of MBS toughner, 1.5 parts of ACR toughner, 0.6 part of calcium stearate, 1.0 parts of polyethylene waxs, 0.9 part in paraffin, 0.7 part of Microcrystalline Wax, 0.6 part of titanium dioxide, 0.03 part, 0.007 part of carbon black and 0.005 part DLTP and nano-calcium carbonates.
Above-mentioned material is put into high-speed mixer heat up gradually, and under rotating speed 1000～1200r/min, fully stir 10～15min.When mixture temperature reaches 120～125 ℃, mixture is delivered to continuation stirring under rotating speed 450～500r/min, room temperature in the low speed mixer, discharging got mixture when mixture temperature to be stirred to was 40～50 ℃.
Then this mixture is extruded at twin screw extruder, obtained the impact polychloroethylene pipes through the vacuum sizing cooling forming, the concrete technology condition is:
Body temperature (℃) 180～185,180～185,175～180,170～175,173～178;
Head temperature (℃) 180～185,190～195,195～205,205～215;
Engine speed 15rpm; Feeding rotating speed 25rpm; Main frame electric current 53.0～56.0A; Pulling speed 2.5～2.8m/min.
Embodiment 4～7
The impact polychloroethylene pipes composition component of embodiment 4～7 sees Table 1, and the preparation method of tubing is with embodiment 1.Wherein the organotin stabilizer described in the embodiment 4～7 is all the sulfuric acid dioctyl tin.
The tubing component (weight part) of table 1 embodiment 4～7
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Polyvinyl chloride resin | 100 | 100 | 100 | 100 |
| Organotin stabilizer | 1 | 1.5 | 2 | 3 |
| MBS toughner | 8 | 7 | 10 | 10 |
| ACR toughner | 2 | 1 | 0 | 1.5 |
| The ASA resin | 3 | 3 | 3 | 3 |
| Calcium stearate | 0.4 | 0.4 | 0.6 | 0.6 |
| Polyethylene wax | 0.6 | 0.9 | 0.3 | 0.5 |
| Paraffin | 0.7 | 1.0 | 0.6 | 0.9 |
| Microcrystalline Wax | 0.3 | 0 | 1.0 | 1.0 |
| Oxidized polyethlene wax | 0.3 | 0.4 | 0 | 0 |
| Titanium dioxide | 0 | 0.40 | 0.06 | 0.60 |
| Carbon black | 0.2 | 0.02 | 0.64 | 0.04 |
| Antioxidant 1010 | 0.007 | 0.006 | 0.006 | 0 |
| Anti-oxidant DLTP | 0.007 | 0.005 | 0.006 | 0 |
| Nano-calcium carbonate | 0 | 1 | 2 | 4 |
| Calcene | 0 | 2 | 4 | 2 |
Comparative Examples 1～3
Do not contain the ASA resin in the tubing component of Comparative Examples 1～3, concrete component sees Table 2.
The preparation method of Comparative Examples 1～3 described tubing is: first polyvinyl chloride resin, lubricant, thermo-stabilizer, impact modifier, tinting material and filler are put into super mixer by proportioning raw materials and mix, put into slow-speed mixer when reaching 120～125 ℃ and mix when material is stable, be conveyed into feed bin when reaching 40～50 ℃ when material is stable, the admixtion that takes a morsel is used for twin-roll mixing, compressing tablet profiling, sample preparation, the mechanical property of carrying out composition detects.
Use the twin screw extruder extruding pipe material, the processing condition of extruding pipe material are: 180 ℃, one section 190 ℃ of head temperatures, two sections 195 ℃, three sections 205 ℃.Engine speed 15rpm; Feeding rotating speed 25rpm; Main frame electric current 60.0～63A; Pulling speed 2.5～2.8m/min.
The tubing component (weight part) of table 2 Comparative Examples 1～3
| Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | |
| Polyvinyl chloride resin | 100 | 100 | 100 |
| Organotin stabilizer | 1.2 | 1.5 | 2.0 |
| MBS toughner | 8 | 9 | 10 |
| ACR toughner | 1.0 | 1.2 | 1.5 |
| Calcium stearate | 0.2 | 0.4 | 0.6 |
| Polyethylene wax | 0.6 | 0.8 | 1.0 |
| Paraffin | 0.9 | 0.9 | 0.9 |
| Microcrystalline Wax | 1.0 | 0.6 | 0.7 |
| Titanium dioxide | 0.2 | 0.4 | 0.6 |
| Carbon black | 0.01 | 0.02 | 0.03 |
| Antioxidant 1010 | 0.005 | 0.007 | 0.009 |
| Anti-oxidant DLTP | 0.005 | 0.005 | 0.005 |
| Nano-calcium carbonate | 2 | 5 | 8 |
Performance test is carried out in sampling on extruding pipe material, profiling, sample preparation, and embodiment 1～3 and Comparative Examples comparative result see Table 3.
The extruding pipe material mechanical performance compare of table 3 embodiment 1～3 and Comparative Examples 1～3
Carry out the detection of the physical and mechanical properties of extruding pipe material according to feedwater with impact-resistant modified polyvinyl chloride (PVC-M) tubing and pipe fitting CJ/T 272-2008 standard, the results are shown in Table 4 and table 5.
Table 4 embodiment 1～3 tubing physical and mechanical properties
Table 5 Comparative Examples 1～3 tubing physical and mechanical properties
From the performance test results of table 3～5 because ASA resin rigidity is strong, the adding of this component, Effective Raise the tensile strength of extruding pipe material, improved the rigidity of tubing, less to the Toughness of material, guaranteed that therefore the hydro-test of tubing can pass through.Reached purpose of the present invention.
The above only is preferred embodiment of the present invention, is not to be the restriction of invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away to any simple modification, equivalent variations and remodeling that above embodiment does, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (10)
1. an impact polychloroethylene pipes is characterized in that it comprises following component in parts by weight: 100 parts of polyvinyl chloride resins, 1.0～3.0 parts of thermo-stabilizers, 2.3～3.2 parts of lubricants, 0～8 part of weighting agent, 8～11.5 parts of toughner, 0.2～0.7 part of tinting material, 2～4 parts of ASA resins.
2. a kind of impact polychloroethylene pipes according to claim 1, it is characterized in that it comprises following component in parts by weight: 100 parts of polyvinyl chloride resins, 1.2～1.5 parts of thermo-stabilizers, 2.7～3.2 parts of lubricants, 2～6 parts of weighting agents, 9～11.5 parts of toughner, 0.21～0.63 part of tinting material, 2～4 parts of ASA resins.
3. a kind of impact polychloroethylene pipes according to claim 1 and 2, it is characterized in that: it also comprises 0.01～0.014 part oxidation inhibitor.
4. a kind of impact polychloroethylene pipes according to claim 3, it is characterized in that: described oxidation inhibitor is antioxidant 1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) and DLTP (the two lauryls of thio-2 acid).
5. a kind of impact polychloroethylene pipes according to claim 1 and 2, it is characterized in that: the mean polymerisation degree of described polyvinyl chloride resin is 1000.
6. a kind of impact polychloroethylene pipes according to claim 1 and 2, it is characterized in that: described thermo-stabilizer is organotin stabilizer, selects in methyl tin, dibutyl tin laurate, sulfuric acid dibutyl tin or the sulfuric acid dioctyl tin any; Lubricant choose in calcium stearate, paraffin, Microcrystalline Wax, polyethylene wax and the oxidized polyethlene wax any four or more.
7. a kind of impact polychloroethylene pipes according to claim 1 and 2, it is characterized in that: described weighting agent is calcene or nano-calcium carbonate.
8. a kind of impact polychloroethylene pipes according to claim 1 and 2, it is characterized in that: described toughner is MBS (methyl methacrylate, divinyl and cinnamic terpolymer) and/or anti-impact type ACR (acrylic ester impact-resisting modifier).
9. a kind of impact polychloroethylene pipes according to claim 1 and 2, it is characterized in that: described tinting material is carbon black and/or titanium dioxide.
10. the preparation method of a kind of impact polychloroethylene pipes according to claim 1 is characterized in that may further comprise the steps:
10.1, each furnish component is put into gradually heat temperature raising of high-speed mixer in proportion, and under rotating speed 1000～2000r/min, fully stir, when the mixture temperature reaches 120～125 ℃, mixture is delivered in the low speed mixer, at room temperature continue to stir, rotating speed is 450～500r/min, discharging when temperature of charge to be mixed is down to 40～50 ℃;
10.2, with the extrusion moulding on screw extrusion press of step 10.1 gained mixture material, traction, cooling, Vacuum shaping namely get the impact polychloroethylene pipes, processing condition are 180～215 ℃ of head temperatures, 170～185 ℃ of body temperatures, engine speed 15rpm, feeding rotating speed 25rpm, main frame electric current 56.0～60A, pulling speed is 2.5～2.8m/min.
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