CN103160055A - Outdoor ASA / PVC-M co-extrusion pipe compositions and preparation technology thereof - Google Patents
Outdoor ASA / PVC-M co-extrusion pipe compositions and preparation technology thereof Download PDFInfo
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- CN103160055A CN103160055A CN2011104217127A CN201110421712A CN103160055A CN 103160055 A CN103160055 A CN 103160055A CN 2011104217127 A CN2011104217127 A CN 2011104217127A CN 201110421712 A CN201110421712 A CN 201110421712A CN 103160055 A CN103160055 A CN 103160055A
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Abstract
The invention provides an outdoor ASA / PVC-M co-extrusion pipe compositions and a preparation technology thereof, belonging to a field of high-molecular polymeric material. PVC-M pipe compositions are used as inner-layer components of the co-extrusion pipe compositions, ASA compositions are used as outer-layer components of the ASA / PVC-M co-extrusion pipe compositions, and the twp compositions are molded for one time by two extruders sharing a double-layer co-extrusion composite die. The outdoor ASA / PVC-M co-extrusion pipe compositions provided by the invention are good in weather resistance, impact resistance and mechanical properties, is not easy to discolor, and has a wide market prospect.
Description
Technical field
The invention belongs to the macromolecule polymeric material field, relate generally to a kind of outdoor ASA/PVC-M coextrusion pipe composition and preparation technology thereof.
Background technology
Along with development and the raising of material synthesis technology, both at home and abroad the research of novel material constantly made a breakthrough, impact-resistant modified polyvinyl chloride tube material is called for short PVC-M and is extensively used because of its good shock resistance, winter hardiness and processing fluidity.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 transportation; PVC-M tubing can effectively be resisted water hammer, reduces the destruction of pipeline in operation, construction 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.The PVC-M pipe is produced in a large number in many countries, is widely used in town and country and building water supply and drainage, and the mine is with pipeline etc.
ASA is a kind of ter-polymers of succeeding in developing the seventies in last century that is comprised of vinyl cyanide, vinylbenzene, acrylic rubber, belongs to Resin Used As Impact Modifier, has splendid mechanical and physical performance.If contain two keys in macromolecular material, two keys are easily opened by the ultraviolet ray in the larger sunlight of energy intensity, thus, cause macromolecular material to decompose.And ASA has substituted with the acrylic rubber that does not contain unsaturated double-bond the divinyl rubber that contains unsaturated double-bond in ABS just, therefore, not only can resist degraded that uviolizing causes, aging, fade, simultaneously the high temperature in the oxidation course of processing in atmosphere is caused that ASA decomposes or variable color has had strong guarantee, promoted greatly thus the anti-aging of material and weather resisteant energy.
Yet, the outdoor ASA/PVC composite pipe weather resistance that has occurred in the market is unsatisfactory, because formulating of recipe for pipes, raw material and complete processing in preparation process are reasonable not, the weathering resistance of ASA/PVC composite pipe, shock-resistance and toughness all are subject to certain impact.When particularly white ASA/PVC composite pipe used out of doors, work-ing life was short, easily produced simultaneously variable color, affected attractive in appearance.Be badly in need of in the market the better outdoor ASA/PVC-M coextrusion pipe composition of a kind of weathering resistance.
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 outdoor ASA/PVC-M coextrusion pipe composition and preparation technology thereof are provided.The outdoor ASA/PVC-M coextrusion tubing that uses said composition and preparation technology thereof to produce had both kept the mechanical property of PVC-M, possessed again high-weatherability and the antistatic property of ASA tubing.
The technical solution adopted for the present invention to solve the technical problems is: this outdoor ASA/PVC-M coextrusion pipe composition, formed by layer composition in the outer layer composition of tubing and tubing, and it is characterized in that,
The outer layer composition of described tubing forms 100 parts of (weight part): ASA by following component, 0.8～1.5 part of ethylene bis stearamide, 0～2 part of titanium dioxide, 0.6～0.8 part of Hinered phenols antioxidant;
In described tubing, layer composition forms (weight part) by following component:: PVC100 part, 1.5～2.5 parts of organotin stabilizers, 10～12 parts of MBS impact modifiers, 1.5～3.0 parts of compounded lubricants, 5～10 parts of weighting agents.
In the outer layer composition of described tubing, ASA is acrylate rubber like body and vinyl cyanide, cinnamic graft copolymer, and the present invention selects extrusion grade ASA.
In the outer layer composition of described tubing, titanium dioxide is selected the rutile-type structure titanium dioxide.Weathering resistance and the tinting strength of rutile-type structure titanium dioxide are better, can improve the weathering resistance of tubing of the present invention.But add titanium dioxide can make its viscosity rise in PVC, mobility reduces, and the moment of torsion increase causes processing difficulties.Therefore do not add titanium dioxide in layer composition in tubing of the present invention, thereby greatly reduced the add-on of titanium dioxide in tubing under the prerequisite that does not affect the tubing weather resistance, the poor processing range of flow characteristics that has overcome PVC is narrower, particularly the PVC material of the macromolecule problem that is difficult to process.
Lubricant in the outer layer composition of described tubing is selected ethylene bis stearamide.Ethylene bis stearamide is compared with lubricants such as paraffin, polyethylene wax, stearate, not only has good external lubrication effect, and has a good internal lubrication effect, improve molten mobility and release property every plastics in plastics processing, thereby improved the output of plastic working, reduced energy consumption, made product obtain high any surface finish, smoothness.Simultaneously owing to containing two amide group-C-NH-in the ethylene bis stearamide molecular structure, so after this product added plastics, plastics also can have static electricity resistance preferably.
In the outer layer composition of described tubing, Hinered phenols antioxidant was the mixture of antioxidant 1076 and antioxidant 264, and antioxidant 1076 and antioxidant 264 mixed use by weight 1: 1.
In the interior layer composition of described tubing, compounded lubricant is the composition of Microcrystalline Wax and oxidized polyethlene wax.Conventional lubricant adopts stearic acid or calcium stearate more, but stearic acid or calcium stearate contain into the organic impurity of split pole complexity in building-up process, the very easily oxidation under ultraviolet ray and heat effect of these impurity, become the lipid oxidation thing of black, thereby cause the pvc pipe material phenomenon of serious discoloration and local blackspot to occur; On the other hand, because under sunlight, humidity increases, temperature raises and anoxia condition under, pipe outer surface easily goes mouldy, and generates a large amount of moulds and causes the tubing change grey.Therefore, in layer composition and outer layer composition, all do not adopt stearic acid or calcium stearate as lubricant in tubing of the present invention.
In the interior layer composition of described tubing, weighting agent is more than or equal to 1200 purpose super-fine active calcium carbides.Packing material size is thinner, and is less on composite materials property impact, and super-fine active calcium carbide is as a kind of mineral filler, suitable particle diameter take greater than 1200 orders as effect best.Super-fine active calcium carbide, can increase the mechanical property of polymkeric substance, and the shock resistance of polymkeric substance not impacted when using super-fine active calcium carbide as weighting agent because its calcium carbonate microparticle is carried out overactivation.
In the interior layer composition of described tubing, polyvinyl chloride resin is 1000 types, i.e. V-type polyvinyl chloride resin.The resin dedicated PVC QS-1050P of pvc pipe material that preferred Sinopec asphalt in Shenli Refinery is produced.
Select MBS as impact modifying agent in layer composition in described PVC-M, MBS is MBS, and the preferred trade mark is MBS561.
MBS is a kind of predetermined elasticity build impact modifying agent, and it belongs to the polymkeric substance of nucleocapsid structure, and its core is that styrene-butadiene rubber(SBR) core belongs to soft shape elastomerics, can give goods higher shock resistance; Its shell is the polymkeric substance with high glass transition temperature.MBS and polyvinyl chloride resin have interface compatibility preferably, keep again particle shape complete in the PVC/MBS system.Improving impact simultaneously, MBS other performances to polyvinyl chloride resin are as very little in impacts such as tensile strength, elongation at breaks.
Do not adopt traditional CPE to make impact modifier in layer composition in the present invention.This is that it belongs to network polymer because CPE is non-predetermined elasticity build impact modifying agent, and its mechanism of modification is with plastification mechanism, plastics to be carried out modification.Therefore, NPDE must form a resin-coated reticulated structure, and it and PVC are not very good compatible bodies.CPE has produced hydrogenchloride (HCl) because the chlorination reaction occurs in its preparation process, causes the CPE particle to be coated with HCl, can volatilize HCl when temperature raises.These can not produce obviously impact to CPE at normal temperatures, but owing to there being the molecular structure identical with PVC in the CPE molecule, can be as catalytic decomposition PVC when temperature raises, degraded CPE.PVC can decompose release HCl because of the reason of its structure under illumination.When having HCl to exist, PVC takes off HCl and becomes self-catalyzed reaction, and PVC takes off HCl speed obviously to be accelerated.In the time of 175 ℃, this self-catalyzed reaction is 1000 times of uncatalyzed reaction, and when causing the PVC that uses CPE to do impact modifier to use out of doors, degree of aging is obviously accelerated.
In the interior layer composition of described PVC-M, organotin stabilizer is organotin stabilizer 2903.
The preparation technology of the arbitrary described outdoor ASA/PVC-M coextrusion pipe composition of a kind of claim 1-5, undertaken by following operation:
A) with the ASA powder, ethylene bis stearamide, titanium dioxide, Hinered phenols antioxidant take according to the above ratio puts into high low speed mixer, fully mix fully and mix, 1000～2000 rev/mins of mixing speed, mixing time 10～15 minutes is mixed to 110～120 ℃ of temperature, and material is put in low speed mixer, to be mixed to 40～45 ℃ of dischargings of temperature, make the outer layer composition of tubing.
B) polyvinyl chloride resin, organotin stabilizer, MBS, compounded lubricant, weighting agent are taken according to the above ratio put into high low speed mixer, fully mix, 1000～2000 rev/mins of mixing speed, mixing time 10～15 minutes, when being mixed to 110～120 ℃ of temperature, material is put in low speed mixer, to be mixed to 40～45 ℃ of dischargings of temperature, make layer composition in tubing.
Compared with prior art, the invention has the beneficial effects as follows: the outdoor ASA/PVC-M tubing that two kinds of dedicated set compound coextrusion of the present invention are produced is the high-weatherability material, and has higher shock resistance and weather resisteant energy.Extrude high weather-proof PVC-M tubing with the ASA compound composition not double bond containing, that ageing resistance is excellent outer, make ASA/PVC-M coextrusion tubing have good weather resistance, life-time service can not produce metachromatism out of doors, its yellow index variation difference.Because the outer field main component of coextrusion pipe composition is ASA, the ASA internal layer PVC of extruding pipe material together is complete compatible material, has good cohesive strength between the tubing interface of coextrusion, the phenomenons such as interlayer delamination, separation can not occur in use procedure.The outdoor ASA/PVC-M pipe composition that the present invention produces, its shock resistance is apparently higher than common ASA/PVC pipe composition, tensile strength and simple beam impact strength value are all higher simultaneously, and wherein tensile strength can reach 47.9MPa, and the simple beam impact strength value can reach 85.6MPa.The present invention is due to the production method that adopts double-layer coextrusion to go out, and the interface of bi-material can be good at welding and bonding, can not cause the layering of tubing and come off, and has good market application foreground.
Embodiment
Embodiment 1～6
Table 1 embodiment 1～6ASA/PVC-M pipe composition (in weight part)
Comparative Examples 1～3
The double-deck ASA/PVC-M coextrusion of the contrast composite pipe composition that Comparative Examples 1～3 designs for the properties that compares the inside and outside layer composition of outdoor ASA/PVC-M coextrusion tubing of the present invention, the proportioning component of Comparative Examples 1～3 inside and outside layer composition is as shown in table 2.
The component (in weight part) of table 2 Comparative Examples 1～3 pipe composition
The performance test experiment:
Prepare sample according to the preparation technology of pipe composition of the present invention:
Take respectively the inside and outside layer composition raw material of tubing by embodiment 1～6 and the described component concentration of Comparative Examples 1～3, and raw material is put into respectively high low speed mixer fully mix, 1000～2000 rev/mins of mixing speed, mixing time 10～15 minutes, when being mixed to 110～120 ℃ of temperature, material is put in low speed mixer, to be mixed to 40～45 ℃ of dischargings of temperature, make the inside and outside layer composition of tubing.
The composition for preparing is plastified on the double roller plastic-making device of 180 ℃ hack, compressing tablet on the press of 180 ℃, print preheating 5 minutes, pressurize 5 minutes, wherein embodiment 1,2,3 internal layer are pressed into the sheet material of 3mm, skin is pressed into the sheet material that thickness is 1mm, then the ectonexine secondary mould pressing of correspondence formula is gone out two layers of composite sheet; Comparative example is compressing tablet on the press of 180 ℃ also, print preheating 5 minutes, and pressurize 5 minutes is pressed into the 4mm sheet material.Be made into the standard batten by copying cutting, carry out performance test, the results are shown in Table 3.Wherein weathering resistance test print thickness used is 1mm.0.67 watt/m of ultraviolet illumination intensity
2, weathering resistance represents with ultraviolet illumination 1000 hours, the yellow index variation difference of sample, the larger expression weathering resistance of yellow index variation difference is poorer.
The performance test results of table 3 embodiment and comparative example
| Project | Tensile strength | Elongation at break | Simple beam impact strength | Yellow index variation difference |
| Unit | MPa | ％ | kJ/m 2 | |
| Embodiment 1 | 47.2 | 165 | 74.2 | 0.3 |
| Embodiment 2 | 46.5 | 174 | 80.5 | 0.35 |
| Embodiment 3 | 45.3 | 161 | 85.6 | 0.5 |
| Embodiment 4 | 46.3 | 178 | 81.2 | 0.33 |
| Embodiment 5 | 47.9 | 181 | 83.5 | 0.32 |
| Embodiment 6 | 48.5 | 191 | 82.4 | 0.39 |
| Comparative Examples 1 | 44.9 | 102 | 25.3 | 1.3 |
| Comparative Examples 2 | 39.5 | 98 | 75 | 0.55 |
| Comparative Examples 3 | 42.3 | 159 | 67.5 | 0.59 |
As can be seen from the table, the embodiment of the present invention 1～6 has higher impact mechanical performance and tensile property, and comprehensive mechanical property is good, after ultraviolet light and aging yellow index variation less, can use for a long time out of doors and metachromatism not occur; Although and after Comparative Examples 2 use ASA, yellow index variation difference is also less, but still not as embodiment 1～6 excellence, illustrate that the anti-light aging performance of Hinered phenols antioxidant system in embodiment 1～6 is significantly better than comparative example 1 anti UV agent B-129 used; The contrast of embodiment 1～6 and Comparative Examples 2 finds out, Comparative Examples 2 does not all add super-fine active calcium carbide due to outer layer component and interior layer component, therefore its shock resistance obviously reduces; In Comparative Examples 3 in tubing in layer component, use chlorinatedpolyethylene as the impact modifier of tubing, compare with embodiment 2, in Comparative Examples 3, the weathering resistance of tubing and shock resistance are subject to obvious impact, illustrate to select MBS561 to be conducive to improve the impact property of ASA/PVC-M pipe composition of the present invention as impact modifier.
The above is only preferred embodiment of the present invention, is not to be invention to be done the restriction of 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 (6)
1. an outdoor ASA/PVC-M coextrusion pipe composition, is characterized in that, the inside and outside layer composition of tubing is made by the component of following weight part respectively:
100 parts of outer layer composition: the ASA of tubing, 0.8～1.5 part of ethylene bis stearamide, 0～2 part of titanium dioxide, 0.6～0.8 part of Hinered phenols antioxidant;
In tubing, layer composition: PVC is 100 parts, 1.5～2.5 parts of organotin stabilizers, 10～12 parts of MBS impact modifiers, 1.5～3.0 parts of compounded lubricants, 5～10 parts of weighting agents.
2. outdoor ASA/PVC-M coextrusion pipe composition according to claim 1, it is characterized in that: described titanium dioxide is Rutile type Titanium Dioxide.
3. outdoor ASA/PVC-M coextrusion pipe composition according to claim 1 is characterized in that: described Hinered phenols antioxidant is that antioxidant 1076 and antioxidant 264 are by weight the mixture of 1: 1 proportioning.
4. outdoor ASA/PVC-M coextrusion pipe composition according to claim 1, it is characterized in that: described compounded lubricant is that Microcrystalline Wax and oxidized polyethlene wax are mixed by any ratio.
5. outdoor ASA/PVC-M coextrusion pipe composition according to claim 1 is characterized in that: described weighting agent is for more than or equal to 1200 purpose super-fine active calcium carbides.
6. the preparation technology of according to claim 1-5 arbitrary described outdoor ASA/PVC-M coextrusion pipe compositions, is characterized in that, comprises following processing step:
Take the inside and outside layer composition raw material of tubing, putting into respectively high low speed mixer fully mixes, 1000～2000 rev/mins of mixing speed, mixing time 10～15 minutes, when being mixed to 110～120 ℃ of temperature, material is put in low speed mixer, to be mixed to 40～45 ℃ of dischargings of temperature, make the inside and outside layer composition of tubing.
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Cited By (10)
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| CN104151734A (en) * | 2014-06-30 | 2014-11-19 | 安徽国风塑料建材有限公司 | Metal cold pigment modified infrared reflection type colorful co-extruded profile and production process thereof |
| CN104479256A (en) * | 2014-12-31 | 2015-04-01 | 江阴市向阳科技有限公司 | Preparation method of high-performance composite decorative film |
| CN104530600A (en) * | 2014-12-26 | 2015-04-22 | 辽宁程威塑料型材有限公司 | Colorful co-extruded plastic pipeline |
| CN104987625A (en) * | 2015-07-24 | 2015-10-21 | 杨纪超 | PVC (polyvinyl chloride) composite water drainage tube |
| CN105924851A (en) * | 2016-06-23 | 2016-09-07 | 苏州亚科塑胶有限公司 | Preparation process for heat-resistant modified PVC (polyvinyl chloride) plastic pipe |
| CN109318560A (en) * | 2018-08-15 | 2019-02-12 | 广东联塑科技实业有限公司 | A kind of pressure resistance two-layer compound pipe fitting and its preparation process |
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| CN112812703A (en) * | 2021-01-04 | 2021-05-18 | 苏州中来光伏新材股份有限公司 | Photovoltaic adhesive film resisting mechanical impact, preparation process and photovoltaic module |
| CN112961442A (en) * | 2021-02-07 | 2021-06-15 | 河南绿色快车橡塑制品有限公司 | High-flexibility charging roller foaming sleeve, preparation method thereof and high-flexibility charging roller |
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