CN103160055B - Outdoor ASA/PVC-M coextrusion pipe composition and preparation technology thereof - Google Patents
Outdoor ASA/PVC-M coextrusion pipe composition and preparation technology thereof Download PDFInfo
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- CN103160055B CN103160055B CN201110421712.7A CN201110421712A CN103160055B CN 103160055 B CN103160055 B CN 103160055B CN 201110421712 A CN201110421712 A CN 201110421712A CN 103160055 B CN103160055 B CN 103160055B
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Abstract
A kind of outdoor ASA/PVC-M coextrusion pipe composition and preparation technology thereof, belong to field of high-molecular polymeric material.By the internal layer component of PVC-M pipe composition as coextrusion tubing, ASA composition is as the outer component of ASA/PVC-M coextrusion tubing, and two kinds of compositions share a double-layer coextrusion by two extruders and go out compound mouth mould, once shaped.According to the present invention produce outdoor ASA/PVC-M coextrusion pipe composition there is good weather resistance, impact property and mechanical property, and out of doors life-time service time not easily there is metachromatism, there are wide market outlook.
Description
Technical field
The invention belongs to field of high-molecular polymeric material, 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, constantly make a breakthrough both at home and abroad to the research of novel material, impact-resistant modified polyvinyl chloride tube material, is called for short PVC-M and is widely used because of its good shock resistance, winter hardiness and processing fluidity.Compared with common PVC-U tubing, the shock resistance of PVC-M tubing significantly improves, and can resist the uneven decline of slight scuffing that tubing installs and produce in transportation, point load and ground better; PVC-M tubing effectively can resist water hammer, reduces the destruction of pipeline in operation, construction process; Resisting environmental stress and cracking ability significantly improves, and is highly resistant to the external impacts to tubing in installation and transportation, prevents the generation of rapid crack propagation phenomenon.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, mine pipeline etc.
ASA is a kind of ter-polymers succeeded in developing the seventies in last century be made up of vinyl cyanide, vinylbenzene, acrylic rubber, belongs to Resin Used As Impact Modifier, has splendid mechanical and physical performance.If containing double bond in macromolecular material, then double bond easily open by the ultraviolet in the larger sunlight of energy intensity, thus, cause macromolecular material to decompose.And ASA instead of the divinyl rubber containing unsaturated double-bond in ABS with the acrylic rubber not containing unsaturated double-bond just, therefore, not only can resist degraded that uviolizing causes, aging, fade, cause ASA decomposition or variable color to have strong guarantee to the high temperature in the oxidation course of processing in air simultaneously, improve the anti-aging of material and weathering performance thus greatly.
But, the outdoor ASA/PVC composite pipe weather resistance 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 are all subject to certain impact.When particularly white ASA/PVC composite pipe uses out of doors, work-ing life is short, easily produces variable color simultaneously, affects attractive in appearance.Be badly in need of the outdoor ASA/PVC-M coextrusion pipe composition that a kind of weathering resistance is better in the market.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, provides a kind of outdoor ASA/PVC-M coextrusion pipe composition and preparation technology thereof.The outdoor ASA/PVC-M coextrusion tubing using said composition and preparation technology thereof to produce both had maintained 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, is made up of tubing outer layer composition and Inner tubing layers composition, it is characterized in that,
Described tubing outer layer composition is made up of (weight part) following component: ASA100 part, ethylene bis stearamide 0.8 ~ 1.5 part, titanium dioxide 0 ~ 2 part, Hinered phenols antioxidant 0.6 ~ 0.8 part;
Described Inner tubing layers composition is made up of (weight part) following component:: PVC100 part, organotin stabilizer 1.5 ~ 2.5 parts, MBS impact modifier 10 ~ 12 parts, compounded lubricant 1.5 ~ 3.0 parts, weighting agent 5 ~ 10 parts.
In described tubing outer layer composition, ASA is acrylate rubber like body and vinyl cyanide, cinnamic graft copolymer, and the present invention selects extrusion grade ASA.
In described tubing outer layer composition, titanium dioxide selects 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 adding titanium dioxide in PVC can make its viscosity rise, mobility reduces, and moment of torsion increase causes processing difficulties.Therefore titanium dioxide is not added in Inner tubing layers composition of the present invention, thus under the prerequisite not affecting tubing weather resistance, greatly reduce the add-on of titanium dioxide in tubing, the flow characteristics difference processing range overcoming PVC is narrower, and particularly the PVC material of macromolecule is difficult to the problem of processing.
Ethylene bis stearamide selected by lubricant in described tubing outer layer composition.Ethylene bis stearamide is compared with the lubricants such as paraffin, polyethylene wax, stearate, not only there is good external lubrication effect, and there is good internal lubrication effect, the molten mobility every plastics and release property is improved in plastics processing, thus improve the output of plastic working, reduce energy consumption, make product obtain high surface smooth finish, smoothness.Simultaneously due in ethylene bis stearamide molecular structure containing two amide group-C-NH-, so after this product adds plastics, plastics also can have good static electricity resistance.
In described tubing outer layer composition, Hinered phenols antioxidant is the mixture of antioxidant 1076 and antioxidant 264, and antioxidant 1076 and antioxidant 264 are used in combination by weight 1: 1.
In described Inner tubing layers composition, compounded lubricant is the composition of Microcrystalline Wax and oxidized polyethlene wax.Conventional lubricant many employings stearic acid or calcium stearate, but stearic acid or calcium stearate contain into the organic impurity of split pole complexity in building-up process, these impurity are very easily oxidized under ultraviolet and heat effect, become the lipid oxidation thing of black, thus cause PVC to occur the phenomenon of serious discoloration and local blackspot; On the other hand, because sunlight under, humidity increase, temperature raise and anoxia condition under, pipe outer surface easily goes mouldy, generate a large amount of mould cause tubing become ash.Therefore, in Inner tubing layers composition of the present invention and outer layer composition, all do not adopt stearic acid or calcium stearate as lubricant.
In described Inner tubing layers composition, weighting agent is for being more than or equal to 1200 object super-fine active calcium carbides.Packing material size is thinner, on composite materials property impact less, super-fine active calcium carbide as a kind of mineral filler, suitable particle diameter be greater than 1200 orders for effect best.Super-fine active calcium carbide, because carrying out overactivation to its calcium carbonate microparticle, when using super-fine active calcium carbide as weighting agent, can increase the mechanical property of polymkeric substance, and not impact the shock resistance of polymkeric substance.
In the inner layer composition of described tubing, polyvinyl chloride resin is 1000 types, i.e. V-type polyvinyl chloride resin.The resin dedicated PVCQS-1050P of PVC that preferred Sinopec asphalt in Shenli Refinery produces.
Select MBS as impact modifying agent in described PVC-M inner layer composition, 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 the shock resistance that goods are higher; Its shell is the polymkeric substance with high glass transition temperature.MBS and polyvinyl chloride resin have good interface compatibility, keep particle shape complete again in PVC/MBS system.Improving impact simultaneously, MBS is to other performances of polyvinyl chloride resin, as very little in the impact such as tensile strength, elongation at break.
Traditional CPE is not adopted to make impact modifier in inner layer composition of the present invention.This is because CPE is non-predetermined elastomeric-type impact modifying agent, it belongs to network polymer, and its mechanism of modification carries out modification with plastification mechanism to plastics.Therefore, NPDE must form a resin-coated reticulated structure, and it and PVC are not very good compatible bodies.CPE creates hydrogenchloride (HCl) because there is chlorination reaction in its preparation process, causes CPE particles coat to have HCl, can volatilize HCl when temperature raises.These can not produce obviously impact to CPE at normal temperatures, but owing to there is the molecular structure identical with PVC in CPE molecule, can as catalytic decomposition PVC when temperature raises, degraded CPE.PVC is because of the reason of its structure, and decomposable asymmetric choice net discharges HCl under light illumination.When there being HCl to exist, PVC takes off HCl and becomes self-catalyzed reaction, and PVC takes off HCl speed obviously to be accelerated.When 175 DEG C, this self-catalyzed reaction is 1000 times of uncatalyzed reaction, and when causing the PVC using CPE to do impact modifier to use out of doors, degree of aging is obviously accelerated.
In described PVC-M inner layer composition, organotin stabilizer is organotin stabilizer 2903.
A preparation technology for the arbitrary described outdoor ASA/PVC-M coextrusion pipe composition of claim 1-5, is undertaken by following operation:
A) by ASA powder, ethylene bis stearamide, titanium dioxide, Hinered phenols antioxidant take according to the above ratio puts into high low speed mixer, fully be uniformly mixed and be fully uniformly mixed, mixing speed 1000 ~ 2000 revs/min, mixing time 10 ~ 15 minutes, is mixed to temperature 110 ~ 120 DEG C, is put into by material in low speed mixer, to be mixed to temperature 40 ~ 45 DEG C of dischargings, obtained tubing outer layer composition.
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 be uniformly mixed, mixing speed 1000 ~ 2000 revs/min, mixing time 10 ~ 15 minutes, when being mixed to temperature 110 ~ 120 DEG C, material is put in low speed mixer, to be mixed to temperature 40 ~ 45 DEG C of dischargings, obtained Inner tubing layers composition.
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 high-weatherability material, and has higher shock resistance and weathering performance.Extrude high durable PVC-M tubing with not double bond containing, that ageing resistance is excellent ASA compound composition 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.The internal layer PVC being ASA, ASA extruding pipe material together due to the outer field main component of coextrusion pipe composition is completely compatible material, has good cohesive strength, there will not be the phenomenons such as interlayer delamination, separation in use procedure between the tubing interface of coextrusion.The outdoor ASA/PVC-M pipe composition that the present invention produces, its shock resistance is apparently higher than common ASA/PVC pipe composition, simultaneously tensile strength and simple beam impact strength value all higher, wherein tensile strength can reach 47.9MPa, and simple beam impact strength value can reach 85.6MPa.The production method that the present invention goes out owing to adopting double-layer coextrusion, 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 (with parts by weight)
Comparative example 1 ~ 3
Comparative example 1 ~ 3 is for comparing the contrast double-deck ASA/PVC-M coextrusion composite pipe composition of the properties design of the inside and outside layer composition of outdoor ASA/PVC-M coextrusion tubing of the present invention, and the proportioning component of the inside and outside layer composition of comparative example 1 ~ 3 is as shown in table 2.
The component (with parts by weight) of table 2 comparative example 1 ~ 3 pipe composition
Performance test is tested:
Preparation technology according to pipe composition of the present invention prepares sample:
The inside and outside layer composition raw material of tubing is taken respectively by component concentration described in embodiment 1 ~ 6 and comparative example 1 ~ 3, and raw material is put into respectively high low speed mixer and be fully uniformly mixed, mixing speed 1000 ~ 2000 revs/min, mixing time 10 ~ 15 minutes, when being mixed to temperature 110 ~ 120 DEG C, material is put in low speed mixer, to be mixed to temperature 40 ~ 45 DEG C of dischargings, the obtained inside and outside layer composition of tubing.
The composition prepared is plastified on the double roller plastic-making device of 180 DEG C and hacks, compressing tablet on the press of 180 DEG C, print preheating 5 minutes, pressurize 5 minutes, wherein the internal layer of embodiment 1,2,3 is 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 DEG C also, print preheating 5 minutes, and pressurize 5 minutes, is pressed into 4mm sheet material.Be made into standard batten by copying cutting, carry out performance test, the results are shown in Table 3.Wherein weathering resistance tests print thickness used is 1mm.Ultraviolet illumination intensity 0.67 watt/m
2, weathering resistance ultraviolet illumination 1000 hours, the yellow index variation difference of sample represents, yellow index variation difference larger expression weathering resistance 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 example 1 | 44.9 | 102 | 25.3 | 1.3 |
| Comparative example 2 | 39.5 | 98 | 75 | 0.55 |
| Comparative example 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 excellent, and after ultraviolet light and aging, yellow index variation is less, can use for a long time out of doors and metachromatism does not occur; Although and comparative example 2 after using ASA yellow index variation difference also less, but still excellent not as embodiment 1 ~ 6, 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 example 2 is found out, comparative example 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 example 3 in Inner tubing layers component, use chlorinatedpolyethylene as the impact modifier of tubing, compared with embodiment 2, in comparative example 3, the weathering resistance of tubing and shock resistance are subject to obvious impact, and the impact property selecting MBS561 to be conducive to improving ASA/PVC-M pipe composition of the present invention as impact modifier is described.
The above is only preferred embodiment of the present invention, and be not restriction invention being made to other form, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the Equivalent embodiments of equivalent variations.But everyly do not depart from technical solution of the present invention content, any simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (3)
1. an outdoor ASA/PVC-M coextrusion pipe composition, is characterized in that, the inside and outside layer composition of tubing is made up of the component of following weight part respectively:
Tubing outer layer composition: ASA100 part, ethylene bis stearamide 0.8 ~ 1.5 part, titanium dioxide 0 ~ 2 part, Hinered phenols antioxidant 0.6 ~ 0.8 part;
Inner tubing layers composition: PVC100 part, organotin stabilizer 1.5 ~ 2.5 parts, MBS impact modifier 10 ~ 12 parts, compounded lubricant 1.5 ~ 3.0 parts, weighting agent 5 ~ 10 parts;
Described titanium dioxide is Rutile type Titanium Dioxide;
Described Hinered phenols antioxidant is antioxidant 1076 and the antioxidant 264 mixture by weight 1:1 proportioning;
Described compounded lubricant is that Microcrystalline Wax and oxidized polyethlene wax are mixed by any ratio.
2. outdoor ASA/PVC-M coextrusion pipe composition according to claim 1, is characterized in that: described weighting agent is for being more than or equal to 1200 object super-fine active calcium carbides.
3., according to the preparation technology of the arbitrary described outdoor ASA/PVC-M coextrusion pipe composition of claim 1-2, it is characterized in that, comprise following processing step:
Take the inside and outside layer composition raw material of tubing, put into high low speed mixer respectively to be fully uniformly mixed, mixing speed 1000 ~ 2000 revs/min, mixing time 10 ~ 15 minutes, when being mixed to temperature 110 ~ 120 DEG C, material is put in low speed mixer, to be mixed to temperature 40 ~ 45 DEG C of dischargings, the obtained inside and outside layer composition of tubing.
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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 |
| CN104530600B (en) * | 2014-12-26 | 2016-08-31 | 辽宁程威塑料型材有限公司 | A kind of color coextrusion plastic pipe |
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