CN103360698A - Inflaming-retarding and antistatic high-strength polyvinyl chloride tube stock composition - Google Patents
Inflaming-retarding and antistatic high-strength polyvinyl chloride tube stock composition Download PDFInfo
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Abstract
The invention relates to an inflaming-retarding and antistatic high-strength polyvinyl chloride tube stock composition. According to the tube stock composition, due to addition of a high-fluidity modified resin, the use amount of a liquid auxiliary agent is greatly reduced under a condition of the same addition amount of a filling agent, the tensile strength of the tube stock composition is improved, and the improvement of the voltage endurance capability of a low-cost inflaming-retarding and antistatic polyvinyl chloride tube stock is guaranteed; after the inflaming-retarding and antistatic high-strength polyvinyl chloride tube stock composition can be prepared into a standard sample by the processing steps of two-roll slicing, mould-pressing flaking, cutting and profile modeling, and the prepared standard sample has the characteristics that the inflaming-retarding performance can meet a V-0-level requirement of a UL-94 standard, the surface resistance is less than or equal to 1.0*10<6> ohms, and the tensile strength is more than or equal to 42.0 MPa; and the inflaming-retarding and antistatic high-strength polyvinyl chloride tube stock produced in an extruding manner has excellent combination property which is superior to index requirements of a Coal Department Industry Standard MT558.2-2006.
Description
Technical field
High-strength polyvinyl chloride flame-retardant and anti-static pipe composition belongs to technical field of plastic.
Background technology
It is to add carbon black in polyvinyl chloride that polyvinyl chloride (PVC) RESINS is carried out the antistatic modified method of modifying of commonly using at present, the addition of superconductive carbon black is about 6%～10%, the addition of common acetylene method carbon black is about 15%～25%, just can reach the antistatic requirement of mining polychloroethylene pipes.But because polyvinyl chloride is relatively difficult to machine material of a kind of high melt viscosity, and the processing temperature scope is narrow, adds the carbon black of high filler loading capacity like this, thus the antistatic polyvinyl chloride pipe composition extrude processing difficulties, production unit is required height, and production energy consumption is higher.
In order to improve the processing characteristics of extruding of fire retarding antistatic polyvinyl chloride pipe composition, usual method is to add a certain amount of liquid adjuvants in composition, such as clorafin, white oil, epoxy soybean oil, dioctyl phthalate (DOP) etc., and addition is higher generally between 10～30 parts.And in order to reduce cost, often need in pipe composition, add a large amount of pearl fillers, and the viscosity of pipe composition is large like this, and fluidity of molten is poorer, causes the consumption of liquid adjuvants higher.Although these liquid adjuvants be added with the viscosity that helps reduce the composition melt, but also reduced the tensile strength of composition simultaneously, the voltage endurance capability of producing tubing can not be guaranteed, and not satisfying Ministry of Coal Industry's industry standard " plastic pipe for coal mine material part 2: polychloroethylene pipes " is the index request among the MT558.2-2006.Simultaneously, the interpolation of liquid adjuvants also can produce certain impact to the flame retardant properties of material.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, and the high-strength polyvinyl chloride flame-retardant and anti-static that a kind of cost is low, the liquid adjuvants addition is little, fluidity of molten is high pipe composition is provided.
The technical solution adopted for the present invention to solve the technical problems is: high-strength polyvinyl chloride flame-retardant and anti-static pipe composition; Specifically (the pressing mass fraction) composed as follows that it is characterized in that said composition: 100 parts of polyvinyl chloride (PVC) RESINS, 3～6 parts of thermo-stabilizers, 5～15 parts in softening agent, 1～5 part of sequestrant, 4～12 parts of impact modifiers, 0.5～3.0 part of lubricant, 8～15 parts in static inhibitor, 20～50 parts in calcium carbonate, 10～20 parts of modified resin; Wherein modified resin is (190 ℃/5kg) acrylonitritrile-styrene resin between 2.0～10.0g/10min (SAN) resin of melt flow rate (MFR)s.
The component of preferred weight part of described high-strength polyvinyl chloride flame-retardant and anti-static pipe composition is: 100 parts of polyvinyl chloride (PVC) RESINS, 4～5 parts of thermo-stabilizers, 8～12 parts in softening agent, 2～4 parts of sequestrants, 6～8 parts of impact modifiers, 1.0～2.0 parts of lubricants, 10～12 parts in static inhibitor, 25～35 parts in calcium carbonate, 10～15 parts of modified resin.
Preferably, the preferred melt flow rate (MFR) of described acrylonitritrile-styrene resin resin is (190 ℃/5kg) resin between 3.0～6.0g/10min.
Described static inhibitor is the high electric conductivity carbon black, and performance is as follows: specific surface area＞500m
2/ g, iodine absorption value 500～1500mg/g, DBP absorption value 200～6000ml/100g, pH value 6.0～10, weight loss on drying＜1.0%, ash content＜2.5%, sulphur content＜0.8%, resistance＜100Ohm.cm, apparent density＞80g/l.Preferred Czech import high electric conductivity carbon black, its performance performance is as follows: specific surface area＞800m
2/ g, iodine absorption value 950～1250mg/g, DBP absorption value 380～460ml/100g, pH value 6.9～9.5, weight loss on drying＜0.8%, ash content＜1.7%, sulphur content＜0.6%, resistance＜15Ohm.cm, apparent density＞112g/l.
Described lubricant is two or more arbitrary proportion compound in paraffin, stearic acid, polyethylene wax, the oxidic polyethylene.
Described calcium carbonate is light calcium carbonate or water-ground limestone, the kind of the activated processing that preferred 800 orders are above.
Described softening agent is dioctyl phthalate (DOP) (DOP) or clorafin (No. 42, No. 52, No. 72 all can), considers preferred No. 52 clorafins of composite formula cost.
Described impact modifier is chlorinatedpolyethylene (CPE).The CPE135A of preferred Weifang AsiaSat limited-liability company, its indices is: Shao Er hardness 58 ± 4Shore A, tensile strength 〉=6.0MPa, elongation at break 〉=700%, thermal characteristics melting heat≤2.0J/g, other performance: cl content 35 ± 1%, volatile matter≤0.30%, screenings 0.9mm sieve≤2.0%, steady time 165 ℃ 〉=8min, apparent density 〉=0.50g/mL, chromoplastid subnumber≤40/(25cm * 60cm), the chlorinatedpolyethylene of calcium contents≤2.1%.
Described polyvinyl chloride (PVC) RESINS is that mean polymerisation degree is about 800～1100 suspension pvc resin.
Described thermo-stabilizer is compound plumbous thermo-stabilizer, and preferred lead content is greater than 20% stablizer.
Described sequestrant is epoxy soybean oil (ESBO), phosphorous acid esters or both arbitrary proportion compounds, and Main Function is the thermostability that improves polychloroethylene composition.
A kind of production method for preparing above-mentioned high-strength polyvinyl chloride flame-retardant and anti-static pipe composition, its processing step is:
1, in proportion weighing of ethenoid resin, thermo-stabilizer, softening agent, sequestrant, impact modifier, lubricant, calcium carbonate mixes in the adding high-speed mixer;
When 2, mixture temperature reaches 70～80 ℃ in the mixing machine, add graphitized carbon black, during continue to heat up;
Change low-speed mixer when 3, the material temperature degree reaches 100～110 ℃ over to, add modified resin, begin cooling, temperature of charge draws off material when dropping to 40 ℃, and get final product.
Compared with prior art, the beneficial effect that high-strength polyvinyl chloride flame-retardant and anti-static pipe composition of the present invention has is: the adding of modified resin greatly reduces the consumption of liquid adjuvants, and after adding a large amount of pearl fillers, still has good fluidity of molten, when having reduced cost, the tensile strength of the polyvinyl chloride flame-retardant and anti-static tubing of extrusion is far above the industry standard requirement, and withstand voltage properties satisfies the standard-required of MT558.2-2006.
Embodiment
Below in conjunction with embodiment and Comparative Examples (see Table 1, table 2, table 3), the present invention is further illustrated:
Table 1: each component of the embodiment of the invention and Comparative Examples forms (mass parts)
| Starting material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 |
| Polyvinyl chloride QS-1050P | 100 | 100 | 100 | 100 | 100 | 100 |
| Compound plumbous thermo-stabilizer | 3 | 4 | 5 | 6 | 4 | 4 |
| ESBO | 1 | 2 | 2 | 2 | - | 2 |
| The phosphorous acid ethyl ester | - | - | 1 | 2 | - | 1 |
| No. 52 clorafins | 5 | 8 | 10 | 10 | 10 | 10 |
| CPE135A | 4 | 6 | 8 | 10 | 6 | 6 |
| Paraffin | 0.2 | 0.2 | 1.0 | 1.2 | 1.0 | 1.2 |
| Stearic acid | 0.3 | 0.4 | 1.0 | 0.8 | 0.6 | 0.8 |
| Polyethylene wax | - | 0.2 | 0.5 | 0.2 | - | 0.2 |
| The high electric conductivity carbon black | 8 | 11 | 12 | 15 | 10 | 12 |
| Active water-ground limestone 1000 orders | 20 | 35 | 40 | 50 | 30 | 40 |
| The SAN resin | 10 | 14 | 18 | 20 | - | - |
Annotate: the MFR of SAN resin is 5.0g/10min.
Table 2: each component of the embodiment of the invention and Comparative Examples forms (mass parts)
| Starting material | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative Examples 3 | Comparative Examples 4 |
| Polyvinyl chloride QS-1050P | 100 | 100 | 100 | 100 | 100 | 100 |
| Compound plumbous thermo-stabilizer | 5 | 5 | 5 | 5 | 5 | 5 |
| ESBO | 5 | 3 | 3 | 3 | 3 | 3 |
| No. 52 clorafins | 8 | 10 | 12 | 15 | 15 | 15 |
| CPE135A | 12 | 5 | 5 | 5 | 6 | 6 |
| Paraffin | 0.3 | 0.8 | 1.5 | 1.2 | 1.0 | 1.2 |
| Stearic acid | 0.5 | 0.6 | 1.2 | 1.8 | 1.5 | 3.0 |
| The high electric conductivity carbon black | 10 | 12 | 13 | 14 | 12 | 14 |
| Active water-ground limestone 1000 orders | 30 | 35 | 40 | 45 | 30 | 35 |
| The SAN resin | 10 | 12 | 15 | 18 | - | - |
Annotate: the MFR of SAN resin is 5.0g/10min.
Table 3: each component of the embodiment of the invention and Comparative Examples forms (mass parts)
| Starting material | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 |
| Polyvinyl chloride QS-1050P | 100 | 100 | 100 | 100 | 100 |
| Compound lead | 5 | 5 | 5 | 5 | 5 |
| ESBO | 3 | 3 | 3 | 3 | 3 |
| No. 52 clorafins | 10 | 10 | 10 | 10 | 10 |
| CPE135A | 5 | 5 | 5 | 5 | 5 |
| Paraffin | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Stearic acid | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 |
| Preferred high electric conductivity carbon black | 10 | 10 | 10 | 10 | 10 |
| Active water-ground limestone 1000 orders | 30 | 30 | 30 | 30 | 30 |
| SAN resin (MFR is 2.0g/10min) | 12 | - | - | - | - |
| SAN resin (MFR is 3.0g/10min) | - | 12 | - | - | - |
| SAN resin (MFR is 5.7g/10min) | - | - | 12 | - | - |
| SAN resin (MFR is 8.0g/10min) | - | - | - | 12 | - |
| SAN resin (MFR is 10.0g/10min) | -- | - | - | - | 12 |
Annotate: the performance of the preferred high electric conductivity carbon black of table 1～table 3 is: specific surface area 1080m
2/ g, iodine absorption value 1100mg/g, DBP absorption value 426ml/100g, pH value 8.5, weight loss on drying 0.6%, ash content 1.5%, resistance 10 Ohm.cm.
The preparation method of embodiments of the invention and Comparative Examples is:
The preparation method of embodiment: first with the in proportion weighing of polyvinyl chloride (PVC) RESINS, thermo-stabilizer, softening agent, sequestrant, impact modifier, lubricant, calcium carbonate, add in the high-speed mixer, during 70～80 ℃ of mixture temperatures, add graphitized carbon black, about mixing time 10min, put into low-speed mixer when temperature of charge reaches 100～110 ℃, then add modified resin, temperature of charge draws off material when dropping to 40 ℃, is high-strength polyvinyl chloride flame-retardant and anti-static pipe composition of the present invention.
The preparation method of Comparative Examples: first with the in proportion weighing of polyvinyl chloride (PVC) RESINS, thermo-stabilizer, softening agent, sequestrant, impact modifier, lubricant, calcium carbonate, add in the high-speed mixer, after stirring 5min, add the clorafin liquid ingredient, when mixture temperature reaches 70～80 ℃, add graphitized carbon black, about stir mixing time 10min, put into low-speed mixer when temperature of charge reaches 100～110 ℃, temperature of charge draws off material when dropping to 40 ℃, is the Comparative Examples pipe composition.
The two rollers of the above-mentioned material that mixes at 180 ℃ are hacked, compressing tablet on 180 ℃ press, print preheating 5min, pressurize 5min is cooled to normal temperature.Sample is made the standard batten by copying cutting, carries out performance test, the results are shown in Table 4, table 5, table 6.
The performance test results of table 4: embodiment and Comparative Examples
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 |
| Flame retardant properties | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Tensile strength, MPa | 43.5 | 44.8 | 44.2 | 45.0 | 32.7 | 29.8 |
| Surface resistivity, Ω | 3.3×10 4 | 5.1×10 4 | 1.8×10 4 | 2.6×10 4 | 1.8×10 4 | 2.9×10 4 |
The performance test results of table 5: embodiment and Comparative Examples
| Project | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative Examples 3 | Comparative Examples 4 |
| Flame retardant properties | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Tensile strength, MPa | 42.8 | 44.7 | 45.2 | 45.5 | 31.6 | 29.5 |
| Surface resistivity, Ω | 4.3×10 4 | 4.2×10 4 | 1.1×10 4 | 5.9×10 3 | 2.8×10 4 | 3.4×10 4 |
The performance test results of table 6: embodiment and Comparative Examples
Can find out that from the performance test of table 4 and table 5 flame retardant properties of embodiment and Comparative Examples and antistatic property all can satisfy standard-required.The embodiment tensile strength of high-strength polyvinyl chloride flame-retardant and anti-static pipe composition of the present invention can guarantee that far above Comparative Examples the withstand voltage properties of extruding pipe material is improved.Can find out from the detected result of table 6, along with mobile speed (2.0～10.0g/10min) the increase of SAN resin melt, the plasticizing moment of torsion of pipe composition reduces gradually, and shock strength also descends to some extent, and the mobile speed of SAN resin melt then can affect when too small extrudes processing characteristics.When the SAN resin melt speed that flows can guarantee to draw high intensity and withstand voltage properties 3.0～6.0 the time, the good processing characteristics of extruding is arranged again.
High-strength polyvinyl chloride flame-retardant and anti-static pipe composition of the present invention is used for tube extrusion, it is lower to extrude electric current, extrude smoothly, can produce continuously, the tubing surfaces externally and internally of extruding is smooth smooth, flawless, decomposition variable color line or obvious groove, depression, impurity and cut, pipe performance can be applied in the drainage gas pipe of colliery far above the standard-required of MT558.2-2006.The contrast of Φ 110 * 6.5 pipe performance detected results of present composition embodiment 2 and Comparative Examples 1 pipe composition extrusion sees Table 7, table 8 and table 9, the result shows that the tubing all properties of high-strength polyvinyl chloride flame-retardant and anti-static pipe composition embodiment 2 extrusions of the present invention is better than standard-required, and particularly the tensile strength of tubing of the present invention is far above standard value and Comparative Examples tubing.
Table 7: alcohol blast burner combustionproperty
Annotate: A tubing is the tubing that present composition embodiment 2 extrudes; B tubing is the tubing that Comparative Examples 1 composition is extruded
Table 8: physical property test
Annotate: A tubing is the tubing that the embodiment of the invention 2 is extruded; B tubing is the tubing that Comparative Examples 1 is extruded
Table 9: conductivity test
Annotate: A tubing is the tubing that the embodiment of the invention 2 is extruded; B tubing is the tubing that Comparative Examples 1 is extruded
Above-described embodiment, it only is preferred embodiment of the present invention, be not to be the restriction of the present invention being made 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 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 (8)
1. high-strength polyvinyl chloride flame-retardant and anti-static pipe composition, it is characterized in that, component by following weight part is made: 100 parts of polyvinyl chloride (PVC) RESINS, 3～6 parts of thermo-stabilizers, 5～15 parts in softening agent, 1～5 part of sequestrant, 4～12 parts of impact modifiers, 0.5～3.0 part of lubricant, 8～15 parts in static inhibitor, 20～50 parts in calcium carbonate, 10～20 parts of modified resin; Wherein modified resin be melt flow rate (MFR) (190 ℃/5kg) be the acrylonitritrile-styrene resin resin of 2.0～10.0g/10min.
2. a kind of high-strength polyvinyl chloride flame-retardant and anti-static pipe composition according to claim 1, it is characterized in that, component by following weight part is made: 100 parts of polyvinyl chloride (PVC) RESINS, 4～5 parts of thermo-stabilizers, 8～12 parts in softening agent, 2～4 parts of sequestrants, 6～8 parts of impact modifiers, 1.0～2.0 parts of lubricants, 10～12 parts in static inhibitor, 25～35 parts in calcium carbonate, 10～15 parts of modified resin.
3. a kind of high-strength polyvinyl chloride flame-retardant and anti-static pipe composition according to claim 1 is characterized in that: described acrylonitritrile-styrene resin resin be melt flow rate (MFR) (190 ℃/5kg) be the resin of 3.0～6.0g/10min.
4. a kind of high-strength polyvinyl chloride flame-retardant and anti-static pipe composition according to claim 1, it is characterized in that: described static inhibitor is specific surface area＞500m
2/ g, iodine absorption value 500～1500mg/g, DBP absorption value 200～6000ml/100g, pH value 6.0～10, weight loss on drying＜1.0%, ash content＜2.5%, sulphur content＜0.8%, resistance＜100Ohm.cm, the high electric conductivity carbon black of apparent density＞80g/l.
5. a kind of high-strength polyvinyl chloride flame-retardant and anti-static pipe composition according to claim 1, it is characterized in that: described lubricant is two or more arbitrary proportion compound in paraffin, stearic acid, polyethylene wax, the oxidic polyethylene.
6. a kind of high-strength polyvinyl chloride flame-retardant and anti-static pipe composition according to claim 1 is characterized in that: described calcium carbonate is light calcium carbonate or the water-ground limestone of the above activated processing of 800 orders.
7. a kind of high-strength polyvinyl chloride flame-retardant and anti-static pipe composition according to claim 1 is characterized in that: described thermo-stabilizer is lead content greater than 20% compound plumbous thermo-stabilizer; Described softening agent is dioctyl phthalate (DOP) or clorafin; Described sequestrant is epoxy soybean oil (ESBO), phosphorous acid esters or the arbitrary proportion compound of the two; Described impact modifier is chlorinatedpolyethylene.
8. plant the method for producing such as each described a kind of high-strength polyvinyl chloride flame-retardant and anti-static pipe composition of claim 1～7, it is characterized in that processing step is:
8.1, ethenoid resin, thermo-stabilizer, softening agent, sequestrant, impact modifier, lubricant, in proportion weighing of calcium carbonate, add in the high-speed mixer and mix;
8.2, when mixture temperature reaches 70～80 ℃ in the mixing machine, add graphitized carbon black, during continue to heat up;
8.3, the material temperature degree changes low-speed mixer over to when reaching 100～110 ℃, add modified resin, begins cooling, temperature of charge draws off material when dropping to 40 ℃, and get final product.
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| CN104109304A (en) * | 2014-06-23 | 2014-10-22 | 安徽荣玖光纤通信科技有限公司 | High-fluidity PVC cable material and preparation method thereof |
| CN104744849A (en) * | 2013-12-26 | 2015-07-01 | 上海凯波特种电缆料厂有限公司 | Environment-friendly antistatic high-flame retardation PVC sheath material and preparation method thereof |
| CN105273325A (en) * | 2014-06-11 | 2016-01-27 | 中国石油化工股份有限公司 | Cold-resistant wear-resistant polyvinyl chloride composition and preparation method thereof |
| CN105419149A (en) * | 2015-11-29 | 2016-03-23 | 贵州开磷集团股份有限公司 | PVC rigid tube and preparation method thereof |
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| CN103571102A (en) * | 2013-10-25 | 2014-02-12 | 安徽工贸职业技术学院 | Preparation method of inflaming retardant type PVC (polyvinyl chloride) pipe |
| CN104744849A (en) * | 2013-12-26 | 2015-07-01 | 上海凯波特种电缆料厂有限公司 | Environment-friendly antistatic high-flame retardation PVC sheath material and preparation method thereof |
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| CN104109304A (en) * | 2014-06-23 | 2014-10-22 | 安徽荣玖光纤通信科技有限公司 | High-fluidity PVC cable material and preparation method thereof |
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