CN105860342A - Low-cost polyvinyl chloride plastic pipe and preparation method thereof - Google Patents
Low-cost polyvinyl chloride plastic pipe and preparation method thereof Download PDFInfo
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- CN105860342A CN105860342A CN201610266566.8A CN201610266566A CN105860342A CN 105860342 A CN105860342 A CN 105860342A CN 201610266566 A CN201610266566 A CN 201610266566A CN 105860342 A CN105860342 A CN 105860342A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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Abstract
The invention discloses a low-cost polyvinyl chloride plastic pipe which is composed of the following raw materials in parts by weight: 1-2 parts of sodium silicate, 0.4-1 part of tetrahydrofurfuryl alcohol, 13-20 parts of fly ash, 1-2 parts of magnesium aluminum silicate, 3-4 parts of carbon nanotube, 40-60 parts of 90-93% sulfuric acid, 60-70 parts of 95-97% nitric acid, 1-2 parts of acryloyl chloride, 0.01-0.02 part of 1,4-dioxane, 0.2-0.3 part of azodiisobutyronitrile, 6-10 parts of 2-hydroxyethyl acrylate, 7-8 parts of triethylamine, 10-14 parts of liquid ethylene propylene diene monomer rubber, 1-1.2 parts of dicumyl peroxide, 100-120 parts of polyvinyl chloride, 0.8-2 parts of ammonium octamolybdate, 0.4-1 part of hexamethyl phosphoryl triamide, 0.2-0.3 part of dimethylformamide, 3-4 parts of dibutyl maleate and 0.8-1 part of sodium myristate. The method effectively lowers the processing cost of the finished product, and enhances the surface strength and impact resistance of the finished product.
Description
Technical field
The present invention relates to tubing technical field, particularly relate to a kind of low cost pvc tube and preparation method thereof.
Background technology
CNT has the strongest axial strength, toughness and elastic modelling quantity, draws through Theoretical Calculation: the Young's modulus of CNT can reach 5TPa, higher an order of magnitude than general fibre;Its Theoretical Tensile Strength is 50-20OGPa, for steel 100 times, but density only has 1/6th of steel, in addition, the cage structure of CNT hollow can occur certain volume deformation when by external force strong effect, and then show as out good pliability, it can be regarded as the most excellent fiber " and the tensile strain that CNT is born, brittle fracture will not be presented, plastic deformation fracture or bond fission, therefore, the structure of CNT than common high molecular materials firm much, at present, the compound composite prepared is carried out with other engineering material with CNT as filler, show surprising intensity, elastic, toughness and fatigue resistance etc., this just provides the widely scope of application for CNT；
The specific surface area huge due to CNT and surface can, CNT is made to be very easy to reunite, this can limit its dispersion in various matrixes virtually, effectively improve CNT dispersion in the base, it is made can more efficiently to transmit load, having become as CNT and apply institute's urgent problem, therefore, the surface modification of CNT is particularly important；
nullAnd owing to CNT can improve the mechanical property of composite、Electrical property and other performances，So CNT/rubber composite causes increasing concern，In order to realize the purpose strengthened，Two problems are had to need to solve: one is the scattering problem of CNT、Another is the interface problem of CNT and matrix，Owing to carbon nano tube surface compares relatively inert，And specific surface area easily causes more greatly reunion，So the effect of carbon nanotubes reinforced polymer is not clearly，Based on this reason，A lot of people start CNT is carried out physical or chemical treatment，In the middle of these methods，It is a kind of conventional and efficient that acid treatment produces the method for oxy radical，Because it can be provided with the reflecting point of effect，Thus realize chemical bond with matrix resin and be connected，But，In most cases,The group that this method produces is the most little，The connection that can not provide enough is bonded with matrix；
CNT has the performance of every excellence due to it, the most extremely concern of various countries' research worker, especially carbon nanotube composite materials is owing to it can possess function that more original CNT do not possesses or strengthens CNT and possesses but more weak function, the present invention is just to provide a kind of functionalization and strengthens CNT, and its composite is applied in life production field on conventional tubing, the effect reaching to improve pipe performance with this.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of low cost pvc tube and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of low cost pvc tube, it is made up of the raw material of following weight parts:
Sodium silicate 1-2, tetrahydrofurfuryl alcohol 0.4-1, flyash 13-20, aluminium-magnesium silicate 1-2, the nitric acid 60-70 of sulphuric acid 40-60,95-97% of CNT 3-4,90-93%, acryloyl chloride 1-2, Isosorbide-5-Nitrae-dioxane 0.01-0.02, azodiisobutyronitrile 0.2-0.3,2-(Acryloyloxy)ethanol 6-10, triethylamine 7-8, liquid ethylene-propylene-diene rubber 10-14, cumyl peroxide 1-1.2, polrvinyl chloride 100-120, ammonium octamolybdate 0.8-2, HMPA 0.4-1, dimethylformamide 0.2-0.3, dibutyl maleate 3-4, myristic acid soda soap 0.8-1.
The preparation method of a kind of described low cost pvc tube, comprises the following steps:
(1) above-mentioned CNT is joined in the mixed solution of nitric acid of the sulphuric acid of above-mentioned 90-93%, 95-97%, ultrasonic agitation 20-24 hour, at 136-140 DEG C, it is incubated 50-60 minute, sucking filtration, wash 3-4 time, be dried 20-30 minute at 70-80 DEG C, obtain acidifying CNT；
(2) above-mentioned flyash is calcined 1-2 hour at 800-870 DEG C, it is cooled to room temperature, send in the hydrochloric acid of 10-13mol/l and soak 40-50 minute, filter discharging, wash 2-3 time, mix with above-mentioned sodium silicate, add aluminium-magnesium silicate, heat 10-20 minute at 160-200 DEG C, be cooled to room temperature, obtain modified coal ash；
(3) above-mentioned azodiisobutyronitrile is joined in the dehydrated alcohol of its weight 20-30 times, stirs, with aforesaid propylene acyl chlorides, 1; 4-dioxane mixes, magnetic agitation 2-3 minute, rises high-temperature and is 60-65 DEG C; insulation reaction 47-50 hour under the protection of nitrogen, obtains grafting auxiliary agent；
(4) 20-30% of above-mentioned modified coal ash weight is taken; mix with above-mentioned acidifying CNT; join in the dehydrated alcohol of its weight 100-130 times, magnetic agitation 2-3 minute, add above-mentioned grafting auxiliary agent; rise high-temperature and be 80-85 DEG C; stirring reaction 40-50 hour, centrifugal under nitrogen protection, by solid content successively with oxolane, dehydrated alcohol, deionized water wash 2-3 time; normal temperature drying, obtains grafted modified carbon nano tube；
(5) take above-mentioned myristic acid soda soap, join in the dehydrated alcohol of its weight 10-13 times, stir, obtain soap alcohol liquid；
(6) being joined by above-mentioned remaining modified coal ash in the deionized water of its weight 4-6 times, stir, add tetrahydrofurfuryl alcohol, rise high-temperature and be 60-67 DEG C, add above-mentioned soap alcohol liquid, 100-200 rev/min is stirred 10-15 minute, obtains flyash dispersion liquid；
(7) above-mentioned grafted modified carbon nano tube is joined in the dehydrated alcohol of its weight 100-120 times; add aforesaid propylene acid hydroxyl ethyl ester, triethylamine; rise high-temperature and be 60-65 DEG C; insulated and stirred 20-30 hour under the protection of nitrogen, adds above-mentioned HMPA, stirs; centrifugal; solid content is used oxolane, deionized water wash 3-4 time successively, normal temperature drying, obtain vinyl CNT；
(8) above-mentioned vinyl CNT is joined in the oxolane of its weight 30-47 times, add aforesaid liquid ethylene propylene diene rubber, cumyl peroxide, it is stirred at room temperature 10-13 hour, mix with above-mentioned flyash dispersion liquid, send in vacuum drying oven, be dried 1-2 hour at 76-80 DEG C, place at normal temperatures 2-3 days after discharging, sucking filtration, is vacuum dried filter cake 20-30 minute at 90-100 DEG C, obtains modified composite material；
(9) above-mentioned modified composite material is mixed with remaining each raw material, using twin screw pelletize, prilling temperature is 120-150 DEG C, and by pellet extruding pipe material on the twin screw extruder, extruder temperature is 170-190 DEG C, and tubing is cooled, cutting, expanding, packaging are pipe finished.
The invention have the advantage that
The molecular weight of traditional Liquid Ethylene Propylene Methylene presoma is relatively low, the mechanical property causing the EP rubbers after solidification is relatively low, the present invention first by the strand containing vinyl-functional by covalence graft to carbon nano tube surface, then mix with ethylene propylene diene rubber, the vinyl of vinyl carbon nano tube surface take part in the solidification of ethylene propylene diene rubber, make to be connected with each other between CNT and the strand of ethylene propylene diene rubber, thus result in the raising of gel content and mechanical property, composite after finally solidification being stablized joins in polrvinyl chloride base material, the purpose strengthened is reached through extrusion molding；
First the present invention has synthesized the grafting auxiliary agent with acid chloride groups, then it has consumed a part of acid chloride groups reacting with acidifying CNT when, but most of group is left behind, they can react with 2-(Acryloyloxy)ethanol, thus surface at CNT obtains a lot of vinyls indirectly；
The pvc tube of the present invention has higher mechanical strength: the present invention adds the preferable Liquid Ethylene Propylene Methylene of dispersibility in PVC base system, and Liquid Ethylene Propylene Methylene is effectively combined by the CNT after double bond and modification, thus loading stress can be passed to CNT by chemical bond by matrix, thus improve its mechanical strength；The present invention uses flyash etc. as filler, effectively reduces the processing cost of finished product, and flyash can also effectively improve surface strength and the shock resistance of finished product after treatment.
Detailed description of the invention
A kind of low cost pvc tube, it is made up of the raw material of following weight parts:
Sodium silicate 1, tetrahydrofurfuryl alcohol 0.4, flyash 13, aluminium-magnesium silicate 1, the nitric acid 60 of sulphuric acid 40,95% of CNT 3,90%, acryloyl chloride 1, Isosorbide-5-Nitrae dioxane 0.01, azodiisobutyronitrile 0.2,2-(Acryloyloxy)ethanol 6, triethylamine 7, liquid ethylene-propylene-diene rubber 10, cumyl peroxide 1, polrvinyl chloride 100, ammonium octamolybdate 0.8, HMPA 0.4, dimethylformamide 0.2, dibutyl maleate 3, myristic acid soda soap 0.8.
The preparation method of a kind of described low cost pvc tube, comprises the following steps:
(1) above-mentioned CNT is joined in the mixed solution of the sulphuric acid of above-mentioned 90%, the nitric acid of 95%, ultrasonic agitation 20 hours, at 136 DEG C, it is incubated 50 minutes, sucking filtration, wash 3 times, be dried 20 minutes at 70 DEG C, obtain acidifying CNT；
(2) above-mentioned flyash is calcined 1 hour at 800 DEG C, be cooled to room temperature, send in the hydrochloric acid of 10mol/l and soak 40 minutes, filter discharging, wash 2 times, mix with above-mentioned sodium silicate, add aluminium-magnesium silicate, heat 10 minutes at 160 DEG C, be cooled to room temperature, obtain modified coal ash；
(3) above-mentioned azodiisobutyronitrile is joined in the dehydrated alcohol of its weight 20 times, stirs, with aforesaid propylene acyl chlorides, 1; 4 dioxane mixing, magnetic agitation 2 minutes, rising high-temperature is 60 DEG C; insulation reaction 47 hours under the protection of nitrogen, obtain grafting auxiliary agent；
(4) the 20% of above-mentioned modified coal ash weight is taken; mix with above-mentioned acidifying CNT; join in the dehydrated alcohol of its weight 100 times, magnetic agitation 2 minutes, add above-mentioned grafting auxiliary agent; rising high-temperature is 80 DEG C; stirring reaction 40 hours, centrifugal under nitrogen protection, by solid content successively with oxolane, dehydrated alcohol, deionized water wash 2 times; normal temperature drying, obtains grafted modified carbon nano tube；
(5) take above-mentioned myristic acid soda soap, join in the dehydrated alcohol of its weight 10 times, stir, obtain soap alcohol liquid；
(6) being joined by above-mentioned remaining modified coal ash in the deionized water of its weight 4 times, stir, add tetrahydrofurfuryl alcohol, rising high-temperature is 60 DEG C, adds above-mentioned soap alcohol liquid, and 100 revs/min are stirred 10 minutes, obtain flyash dispersion liquid；
(7) being joined by above-mentioned grafted modified carbon nano tube in the dehydrated alcohol of its weight 100 times, add aforesaid propylene acid hydroxyl ethyl ester, triethylamine, rising high-temperature is 60 DEG C; insulated and stirred 20 hours under the protection of nitrogen; add above-mentioned HMPA, stir
Centrifugal, solid content is used oxolane, deionized water wash 3 times successively, normal temperature drying, obtain vinyl CNT；
(8) above-mentioned vinyl CNT is joined in the oxolane of its weight 30 times, add aforesaid liquid ethylene propylene diene rubber, cumyl peroxide, it is stirred at room temperature 10 hours, mixes with above-mentioned flyash dispersion liquid, send in vacuum drying oven, it is dried 1 hour at 80 DEG C, place at normal temperatures 2-3 days after discharging, sucking filtration, filter cake is vacuum dried 20 minutes at 100 DEG C, discharging cools down, and obtains modified composite material；
(9) above-mentioned modified composite material is mixed with remaining each raw material, using twin screw pelletize, prilling temperature is 120 DEG C, and by pellet extruding pipe material on the twin screw extruder, extruder temperature is 170 DEG C, and tubing is cooled, cutting, expanding, packaging are pipe finished.
Performance test:
Vicat softening temperature: 86.9 DEG C；
Dichloromethane impregnating experiment (15 DEG C): surfaces externally and internally change is 0N；
Longitudinal welds (150 DEG C, 1h): 3.0%；
Tensile yield strength: 49MPa；
Drop impact experiment (0 DEG C): TIR≤10%.
Claims (2)
1. a low cost pvc tube, it is characterised in that it is made up of the raw material of following weight parts:
Sodium silicate 1-2, tetrahydrofurfuryl alcohol 0.4-1, flyash 13-20, aluminium-magnesium silicate 1-2, the nitric acid 60-70 of sulphuric acid 40-60,95-97% of CNT 3-4,90-93%, acryloyl chloride 1-2, Isosorbide-5-Nitrae-dioxane 0.01-0.02, azodiisobutyronitrile 0.2-0.3,2-(Acryloyloxy)ethanol 6-10, triethylamine 7-8, liquid ethylene-propylene-diene rubber 10-14, cumyl peroxide 1-1.2, polrvinyl chloride 100-120, ammonium octamolybdate 0.8-2, HMPA 0.4-1, dimethylformamide 0.2-0.3, dibutyl maleate 3-4, myristic acid soda soap 0.8-1.
2. the preparation method of a low cost pvc tube as claimed in claim 1, it is characterised in that comprise the following steps:
(1) above-mentioned CNT is joined in the mixed solution of nitric acid of the sulphuric acid of above-mentioned 90-93%, 95-97%, ultrasonic agitation 20-24 hour, at 136-140 DEG C, it is incubated 50-60 minute, sucking filtration, wash 3-4 time, be dried 20-30 minute at 70-80 DEG C, obtain acidifying CNT；
(2) above-mentioned flyash is calcined 1-2 hour at 800-870 DEG C, it is cooled to room temperature, send in the hydrochloric acid of 10-13mol/l and soak 40-50 minute, filter discharging, wash 2-3 time, mix with above-mentioned sodium silicate, add aluminium-magnesium silicate, heat 10-20 minute at 160-200 DEG C, be cooled to room temperature, obtain modified coal ash；
(3) above-mentioned azodiisobutyronitrile is joined in the dehydrated alcohol of its weight 20-30 times, stirs, with aforesaid propylene acyl chlorides, 1; 4-dioxane mixes, magnetic agitation 2-3 minute, rises high-temperature and is 60-65 DEG C; insulation reaction 47-50 hour under the protection of nitrogen, obtains grafting auxiliary agent；
(4) 20-30% of above-mentioned modified coal ash weight is taken; mix with above-mentioned acidifying CNT; join in the dehydrated alcohol of its weight 100-130 times, magnetic agitation 2-3 minute, add above-mentioned grafting auxiliary agent; rise high-temperature and be 80-85 DEG C; stirring reaction 40-50 hour, centrifugal under nitrogen protection, by solid content successively with oxolane, dehydrated alcohol, deionized water wash 2-3 time; normal temperature drying, obtains grafted modified carbon nano tube；
(5) take above-mentioned myristic acid soda soap, join in the dehydrated alcohol of its weight 10-13 times, stir, obtain soap alcohol liquid；
(6) being joined by above-mentioned remaining modified coal ash in the deionized water of its weight 4-6 times, stir, add tetrahydrofurfuryl alcohol, rise high-temperature and be 60-67 DEG C, add above-mentioned soap alcohol liquid, 100-200 rev/min is stirred 10-15 minute, obtains flyash dispersion liquid；
(7) above-mentioned grafted modified carbon nano tube is joined in the dehydrated alcohol of its weight 100-120 times; add aforesaid propylene acid hydroxyl ethyl ester, triethylamine; rise high-temperature and be 60-65 DEG C; insulated and stirred 20-30 hour under the protection of nitrogen, adds above-mentioned HMPA, stirs; centrifugal; solid content is used oxolane, deionized water wash 3-4 time successively, normal temperature drying, obtain vinyl CNT；
(8) above-mentioned vinyl CNT is joined in the oxolane of its weight 30-47 times, add aforesaid liquid ethylene propylene diene rubber, cumyl peroxide, it is stirred at room temperature 10-13 hour, mix with above-mentioned flyash dispersion liquid, send in vacuum drying oven, be dried 1-2 hour at 76-80 DEG C, place at normal temperatures 2-3 days after discharging, sucking filtration, is vacuum dried filter cake 20-30 minute at 90-100 DEG C, obtains modified composite material；
(9) above-mentioned modified composite material is mixed with remaining each raw material, using twin screw pelletize, prilling temperature is 120-150 DEG C, and by pellet extruding pipe material on the twin screw extruder, extruder temperature is 170-190 DEG C, and tubing is cooled, cutting, expanding, packaging are pipe finished.
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| CN201610266566.8A CN105860342A (en) | 2016-04-26 | 2016-04-26 | Low-cost polyvinyl chloride plastic pipe and preparation method thereof |
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| CN201610266566.8A CN105860342A (en) | 2016-04-26 | 2016-04-26 | Low-cost polyvinyl chloride plastic pipe and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864591A (en) * | 2018-05-31 | 2018-11-23 | 安徽玉发塑业有限公司 | A kind of foam polyvinyl chloride plastic tube and preparation method thereof |
| CN115710398A (en) * | 2022-10-27 | 2023-02-24 | 万华化学（宁波）有限公司 | Low-odor anti-aging flame-retardant regenerated polypropylene material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508812A (en) * | 2009-03-24 | 2009-08-19 | 同济大学 | Process for producing high-strength high-ductility hard polyvinyl chloride |
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2016
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508812A (en) * | 2009-03-24 | 2009-08-19 | 同济大学 | Process for producing high-strength high-ductility hard polyvinyl chloride |
Non-Patent Citations (1)
| Title |
|---|
| 周洪福: ""碳纳米管表面有机高分子改性及其纳米复合材料的制备与表征"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864591A (en) * | 2018-05-31 | 2018-11-23 | 安徽玉发塑业有限公司 | A kind of foam polyvinyl chloride plastic tube and preparation method thereof |
| CN115710398A (en) * | 2022-10-27 | 2023-02-24 | 万华化学（宁波）有限公司 | Low-odor anti-aging flame-retardant regenerated polypropylene material and preparation method thereof |
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