CN105348690A - Modified coal ash PVC composite corrugated pipe and preparation method thereof - Google Patents
Modified coal ash PVC composite corrugated pipe and preparation method thereof Download PDFInfo
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Abstract
The invention relate to the field of pipelines, in particular to a modified coal ash PVC composite corrugated pipe and a preparation method thereof. Modified coal ash adopting water soluble phenol-formaldehyde resin and resin aqueous emulsion as a composite modifying agent is added to the inner layer and the outer layer of a corrugated pipe, a stabilizing agent, a melt strength increasing agent, a lubricant, plasticizer, flexibilizer and the like are in cooperation, and the product is obtained through independent manufacturing of an inner mixture layer and an outer mixture layer, extruding and melting, forming and cutting. The prepared modified coal ash PVC composite corrugated pipe is excellent in performance and low in cost, resin and coal ash are firm in contact, the preparation method is simple, operation is easy, and no pollution is caused to the environment.
Description
Technical field
The present invention relates to pipeline field, especially a kind of modified coal PVC compound bellows and preparation method thereof.
Background technology
China is the maximum country of world's producing coal amount, and be also the maximum country of consumption of coal amount, the annual coal ash producing enormous amount, takies a large amount of soils, increase the weight of environment and go from bad to worse.The major ingredient of coal ash is the materials such as silicon-dioxide, aluminium sesquioxide, ferric oxide, and is adsorbed with part free-water or chemically-bonded water, can carry out recycling.Present coal ash is mainly used in material of construction preparation, as low in value addeds such as aerated bricks, light wall material, coal-dust brick, cement, the field that state of the art content is low.Coal ash also has report gradually for macromolecular material padding field, but due to coal ash density large, the many wetting abilities of surface hydroxyl are strong, and cause free settling, layering in the material, the shortcomings such as poor compatibility, consumption is few.There are abundant coal resources in China, utilizes coal to generate electricity in a long time and remains a kind of a kind of mode of the main acquisition energy.Therefore, while the environmental pollution of minimizing coal ash, realize high-quality, the high value added utilization of coal ash, the weighting agent such as white carbon black, calcium carbonate, potter's clay, talcum powder substituting highly energy-consuming is the inevitable requirement of China's sustained economic development.
Chinese patent literature " flyash plastic material and tubing, production technique and system " (CN102660128B) adopts unmodified flyash filled plastics to prepare tubing; " a kind of method taking coal ash as major ingredient and manufacture tubing " (CN101168268B); " a kind of heat-shrinkable materials modified coal ash and preparation method thereof " (CN104119564A); " a kind of PVC containing modified coal ash and preparation method thereof " (application number CN103059457) discloses employing soaking with sodium hydroxide, and pull oven dry out, repeated hydrogenation aluminum oxide etc. are inorganic material-modified.
Existing public technology adopts the direct filled plastics material of unmodified flyash to prepare tubing, and the mechanical property sacrificing composite pipe while reducing costs is cost; Or adopt the method for highly corrosive bronsted lowry acids and bases bronsted lowry process, and very high to equipment requirements, also harm is greatly produced to person health; Coal ash modification is not for plastics simultaneously, not high with plastic bonding degree; In prior art, the system of coal ash modification is open type, is obvious to the dust pollution of Working environment; In existing public technology, also seldom utilize coal ash to fill on the other hand prepare tubing, the application particularly in the composite corrugated pipeline of PVC does not also have.
Summary of the invention
The present invention is directed to the problems referred to above and propose a kind of modified coal PVC compound bellows and preparation method thereof, adopt modified coal effectively to promote the performance of PVC compound bellows.
To achieve these goals, the present invention by the following technical solutions, a kind of modified coal PVC compound bellows comprises internal layer with outer, internal layer raw material comprises by weight: PVC resin powder 100 parts, modified coal 40 ~ 120 parts, outer raw material comprise by weight: PVC resin powder 100 parts, modified coal 20 ~ 40 parts, described modified coal carries out modification to coal ash with water soluble phenol resin, resin water miscible liquid for composite modifier.
Described composite modifier composition counts phenolic resin aqueous solution by weight: resin water miscible liquid=25 ~ 100:100, parts by weight, described composite modifier: coal ash is 10 ~ 50:100.
Described internal layer raw material also comprises by weight: stablizer 1.5 ~ 2.5 parts, lubricant 0.5 ~ 2 part, 0.5 ~ 1.2 part, softening agent, toughner 0.5 ~ 2 part, feed back 30 ~ 80 parts; Described skin also comprises by weight: stablizer 2 ~ 3 parts, lubricant 0.5 ~ 1.5 part, 0.5 ~ 1.2 part, softening agent, melt strength dose 0.5 ~ 2.5 part, toughner 3 ~ 6 parts.
Prepare a method for modified coal PVC compound bellows, comprise the following steps:
Prepared by a modified coal: coal ash by weight: coal ash and composite modifier are chosen in composite modifier=100:10 ~ 50, add kneader, mediates mixing 5 ~ 15min under normal temperature; And then while stirring in this kneader, be warmed up to 120 ~ 150 DEG C of dryings, reaction; Last cool to room temperature obtains modified coal;
The inside and outside layer compound preparation of b: weigh up material by internal layer and outer skin materials proportioning respectively and join in high temperature mixing machine, be heated to 100 ~ 120 DEG C while stirring, then control temperature mixes 5 ~ 20min at 100 ~ 120 DEG C; Above-mentioned hot mixture material is drained into mixing in low temperature low speed mixer by sealing-duct, stirs, is cooled, is finally cooled to 30 ~ 60 DEG C to stop stirring, obtains outer compound and internal layer compound;
C extrudes melting: by internal layer compound in the first extrusion equipment through melting, compression, homogenizing, molten tubing A is extruded into by forming mould, by the melting in the second extrusion equipment of outer compound, compression, homogenizing, be extruded into molten tubing B by forming mould;
D is shaping: move in ripple mould by molten tubing A and molten tubing B, and corrugated mould extrusion molten state tubular material B becomes bellows-shaped, and is welded together in outside and internal layer extruding, then moves into refrigerating unit, cooling, sizing;
E cuts: length is cut as required, obtains product.
Described resin water miscible liquid is vinyl chloride-vinyl acetate copolymer water miscible liquid, one or both in vinyl chloride-acrylate copolymer water miscible liquid, vinyl chloride-vinyl acetate-copolymer-maleic anhydride water miscible liquid, polyurethane aqueous emulsions; Described phenolic resin aqueous solution weight percent is 30% ~ 60%, described resin water miscible liquid weight percent is 10% ~ 50%.
Described PVC resin powder select in general suspension polymerization 8 type (SG-8) or 7 types (SG-7) resin one or both.
Described melt strength dose is one or both in benzoyl peroxide, two maleinamide, dithio tetra methylthiuram, iso-cyanuric acid triallyl ester, mercaptopropyi Trimethoxy silane, 5-Mercaptopropyltriethoxysilane, Y-aminopropyltriethoxywerene werene; Described stablizer select in unleaded environment-friendly PVC calcium-zinc composite stabilizing agent, rare-earth stabilizer one or both; Described lubricant select in polyethylene wax (PE-WAX), calcium stearate, chlorinatedpolyethylene wax, paraffin, fatty acid alcohol, fatty amide one or both; Softening agent select in epoxy soybean oil, peanut oil, dioctyl phthalate (DOP), dimixo-octyl phthalate, low-molecular-weight liquid polyester one or both; Special low-molecular-weight liquid polyester comes from the split product of polyester bottles as mineral water bottle, beverage bottle, food oil drum; Described toughner selects chlorinatedpolyethylene, paracril, carboxy nitrile rubber, chloroprene rubber, chlorinated butyl rubber, thermoplastic polyurethane, ethylene-vinyl acetate copolymer, one or both in esters of acrylic acid rubber.
The temperature parameter of described internal layer extrusion equipment is: 140 DEG C, transportation section, 180 DEG C, compression section, melt zone 220 DEG C, homogenizing zone 210 DEG C.
The temperature parameter of outer extrusion equipment is: 160 DEG C, transportation section, 200 DEG C, compression section, melt zone 220 DEG C, homogenizing zone 210 DEG C.
Described ripple die temperature is 120 ~ 180 DEG C.
The section of described forming mould is the one-piece construction containing two concentric(al) circles circumferential weld compositions, changes the mould of the annulus seam of the size that varies in size, can obtain the corrugated tube that diameter is different with wall thickness dimension.
Described phenolic resin aqueous solution, employing phenol, formaldehyde are raw material, and with sodium hydroxide, potassium hydroxide, hydrated barta etc. obtain for catalyzer synthesizes.
Described resin water miscible liquid is vinyl chloride-vinyl acetate copolymer water miscible liquid, one or both in vinyl chloride-acrylate copolymer water miscible liquid, vinyl chloride-vinyl acetate-copolymer-maleic anhydride water miscible liquid, polyurethane aqueous emulsions.
Described phenolic resin aqueous solution weight percent is 30%-60%; Described resin water miscible liquid weight percent is 10%-50%.
Resin water miscible liquid is with OP-10, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, Soxylat A 25-7 be tensio-active agent formed emulsion, then add resin monomer and initiator polymerization obtain.
The PVC of recovery selected by feed back, or the waste material produced in production process and tankage, and through coarse breaking, then abrasive dust obtains.
The present invention has the following advantages:
1. adopted coal ash adopts water soluble phenol resin, water solubility copolymer as modification agent, and cost is low, avoids adopting expensive coupling agent; Organic solvent is not obtained containing poisonous and harmful, and the strong acid and strong base that corrodibility is extremely strong.Conveying between raw material adopts sealing-duct, improves Working environment, reduces environmental pollution;
2. adopt resin solution and the consumption of higher concentration, and adopt kneader to carry out the method for mediating again dry reaction, make mixing more even, surface-coated is better, and the contact of resin and coal ash is more firm, and the flow process of modification simultaneously shortens, efficiency improves;
3. low-molecular-weight liquid polyester selected by softening agent, and low-molecular-weight liquid polyester comes from the split product of polyester bottles as mineral water bottle, beverage bottle, food oil drum, and products material is cheap;
4. can improve the loading level in polyvinyl chloride resin through modified coal ash, performance is more excellent; Adopt from the low-molecular-weight polyester of waste polyester cracking and PVC, or the waste material produced in production process and tankage are as feed back, have and turn waste into wealth, realize the recycle of resource, and can effectively reduce costs;
5. form compounding machine by two extrusion equipments, internal layer and outer field bi-material are carried out melting compound, effectively improves production efficiency;
6. the section of forming mould is the one-piece construction containing two concentric(al) circles circumferential weld compositions, changes the mould of the annulus seam of the size that varies in size, can obtain the corrugated tube that diameter is different with wall thickness dimension.
Embodiment
For setting forth the predetermined object and technique means and effect that the present invention reaches further, below in conjunction with embodiment, specific embodiment of the invention scheme is described in detail.
Embodiment 1: a kind of modified coal PVC compound bellows comprises ectonexine, internal layer raw material comprises by weight: suspension polymerization 8 type PVC resin powder 100 parts, modified coal 100 parts, stablizer 2 parts, lubricant 1.5 parts, 0.8 part, softening agent, chlorinatedpolyethylene 0.4 part, paracril 0.8 part, feed back 55 parts; Outer raw material comprises by weight: suspension polymerization 8 type PVC resin powder 100 parts, modified coal 30 parts, stablizer 2.5 parts, lubricant 1 part, 0.7 part, softening agent, benzoyl peroxide 0.8 part, two maleinamide 0.7 part, toughner 5 parts; Modified coal carries out modification to coal ash with water soluble phenol resin, resin water miscible liquid for composite modifier, coal ash by weight: composite modifier=100:30, described resin water miscible liquid is vinyl chloride-vinyl acetate copolymer water miscible liquid, its weight percent is 30%, phenolic resin aqueous solution weight percent is 45%, by weight, vinyl chloride-vinyl acetate copolymer water miscible liquid: phenolic resin aqueous solution=1:1.
Prepare modified coal PVC compound bellows as above, comprise the following steps:
Prepared by a modified coal: coal ash by weight: composite modifier=100:30 chooses coal ash and composite modifier, modification recombiner weight percent to be 30% vinyl chloride-vinyl acetate copolymer water miscible liquid and weight percent be 45% phenolic resin aqueous solution form, by weight, vinyl chloride-vinyl acetate copolymer water miscible liquid: phenolic resin aqueous solution=1:1, add kneader, under normal temperature, mediate mixing 10min; And then while stirring in this kneader, be warmed up to 140 DEG C of dryings, reaction; Last cool to room temperature obtains modified coal;
The inside and outside layer compound preparation of b: weigh up material by internal layer and outer skin materials proportioning respectively and join in high temperature mixing machine, be heated to 100 ~ 120 DEG C while stirring, then control temperature mixes 15min at 100 ~ 120 DEG C; Above-mentioned hot mixture material is drained into mixing in low temperature low speed mixer by sealing-duct, stirs, is cooled, is finally cooled to 35 DEG C to stop stirring, obtains outer compound and internal layer compound;
C extrudes melting: by internal layer compound in the first extrusion equipment through melting, compression, homogenizing, be extruded into molten tubing A, by the melting in the second extrusion equipment of outer compound, compression, homogenizing, be extruded into molten tubing B;
D is shaping: molten tubing A and molten tubing B is moved into temperature in the ripple mould of 150 DEG C, and corrugated mould extrusion molten state tubular material B becomes bellows-shaped, and is welded together in outside and internal layer extruding, then moves into refrigerating unit, cooling, sizing.
E cuts: length is cut as required, obtains product.
Product is carried out detection obtain:
| Sequence number | Project | Unit | Detected result |
| 1 | Blasting experiment | Pressure rises to 0.90MPa, breaks | |
| 2 | Vicat softening point | ℃ | 82 |
| 3 | Ring stiffness | KN/m 2 | 18.6 |
| 4 | Static pressure test | Do not break, non-seepage | |
| 5 | Squeezing test | Impact 10 times, broken 0, ring | |
| 6 | Drop hammer test | Do not break | |
| 7 | Surface smoothness | Smooth surface, zero defect | |
| 8 | Internal layer and outer stripping strength | N/cm 2 | 21 |
By upper Biao Ke get, these product performance are excellent, resistance to compression, cracking resistance, and ectonexine combines firm.
Embodiment 2: a kind of modified coal PVC compound bellows comprises ectonexine, and internal layer raw material comprises by weight: suspension polymerization 7 type PVC resin powder 100 parts, modified coal 40 parts, stablizer 1.5 parts, lubricant 2 parts, 1.2 parts, softening agent, toughner 2 parts, feed back 80 parts; Outer raw material comprises by weight: suspension polymerization 8 type PVC resin powder 100 parts, modified coal 40 parts, stablizer 3 parts, lubricant 1.5 parts, 1.2 parts, softening agent, dithio tetra methylthiuram 1 part, iso-cyanuric acid triallyl ester 1.5 parts, toughner 6 parts; Modified coal carries out modification to coal ash with water soluble phenol resin, resin water miscible liquid for composite modifier, coal ash by weight: composite modifier=100:10, described resin water miscible liquid is vinyl chloride-acrylate water miscible liquid and vinyl chloride-vinyl acetate-copolymer-maleic anhydride water miscible liquid, its weight percent is 50%, phenolic resin aqueous solution weight percent is 60%, phenolic resin aqueous solution by weight: resin water miscible liquid=25:100.
Prepare modified coal PVC compound bellows as above, comprise the following steps:
Prepared by a modified coal: coal ash by weight: composite modifier=100:10 chooses coal ash and composite modifier, modification recombiner by weight percent be 50% vinyl chloride-acrylate copolymer water miscible liquid and vinyl chloride-vinyl acetate-copolymer-maleic anhydride water miscible liquid and weight percent be 60% phenolic resin aqueous solution form, phenolic resin aqueous solution by weight: resin water miscible liquid=25:100, add kneader, under normal temperature, mediate mixing 5min; And then while stirring in this kneader, be warmed up to 150 DEG C of dryings, reaction; Last cool to room temperature obtains modified coal;
The inside and outside layer compound preparation of b: weigh up material by internal layer and outer skin materials proportioning respectively and join in high temperature mixing machine, be heated to 100 ~ 120 DEG C while stirring, then control temperature mixes 20min at 100 ~ 120 DEG C; Above-mentioned hot mixture material is drained into mixing in low temperature low speed mixer by sealing-duct, stirs, is cooled, is finally cooled to 60 DEG C to stop stirring, obtains outer compound and internal layer compound;
C extrudes melting: by internal layer compound in the first extrusion equipment through melting, compression, homogenizing, be extruded into molten tubing A, by the melting in the second extrusion equipment of outer compound, compression, homogenizing, be extruded into molten tubing B;
D is shaping: move in ripple mould by molten tubing A and molten tubing B, and corrugated mould extrusion molten state tubular material B becomes bellows-shaped, and is welded together in outside and internal layer extruding, then moves into refrigerating unit, cooling, sizing;
E cuts: length is cut as required, obtains product.
Embodiment 3: a kind of modified coal PVC compound bellows comprises ectonexine, and internal layer raw material comprises by weight: suspension polymerization 7 type PVC resin powder 100 parts, modified coal 120 parts, stablizer 2.5 parts, lubricant 0.5 part, 0.5 part, softening agent, toughner 0.5 part, feed back 30 parts; Outer raw material comprises by weight: suspension polymerization 7 type PVC resin powder 100 parts, modified coal 20 parts, stablizer 2 parts, lubricant 0.5 part, 0.5 part, softening agent, mercaptopropyi Trimethoxy silane 0.5 part, toughner 6 parts; Modified coal carries out modification to coal ash with water soluble phenol resin, resin water miscible liquid for composite modifier, coal ash by weight: composite modifier=100:50, described resin water miscible liquid is polyurethane aqueous emulsions, its weight percent is 10%, phenolic resin aqueous solution weight percent is 30%, by weight, phenolic resin aqueous solution: resin water miscible liquid=50:100.
Prepare modified coal PVC compound bellows as above, comprise the following steps:
Prepared by a modified coal: coal ash by weight: composite modifier=100:30, choose coal ash and composite modifier, modification recombiner by weight percent to be 10% polyurethane aqueous emulsions and weight percent be 30% phenolic resin aqueous solution form, phenolic resin aqueous solution by weight: resin water miscible liquid=25:100, add kneader, under normal temperature, mediate mixing 15min; And then while stirring in this kneader, be warmed up to 120 DEG C of dryings, reaction; Last cool to room temperature obtains modified coal;
The inside and outside layer compound preparation of b: weigh up material by internal layer and outer skin materials proportioning respectively and join in high temperature mixing machine, be heated to 100 ~ 120 DEG C while stirring, then control temperature mixes 5min at 100 ~ 120 DEG C; Above-mentioned hot mixture material is drained into mixing in low temperature low speed mixer by sealing-duct, stirs, is cooled, is finally cooled to 30 DEG C to stop stirring, obtains outer compound and internal layer compound;
C extrudes melting: by internal layer compound in the first extrusion equipment through melting, compression, homogenizing, be extruded into molten tubing A, by the melting in the second extrusion equipment of outer compound, compression, homogenizing, be extruded into molten tubing B;
D is shaping: molten tubing A and molten tubing B is moved into temperature in the ripple mould of 180 DEG C, and corrugated mould extrusion molten state tubular material B becomes bellows-shaped, and is welded together in outside and internal layer extruding, then moves into refrigerating unit, cooling, sizing;
E cuts: length is cut as required, obtains product.
Embodiment 4: with embodiment 1 basic simlarity, its difference is: the resin that internal layer and skin adopt is suspension polymerization 7 type polyvinyl chloride resin and mixes according to 1:1 with suspension polymerization 8 type polyvinyl chloride resin, by weight, vinyl chloride-vinyl acetate copolymer water miscible liquid: phenolic resin aqueous solution=100:75, ripple die temperature is 120 DEG C.
As mentioned above, be only present pre-ferred embodiments, therefore appoint and allly do not depart from this programme technology contents, according to technical spirit of the present invention, any simple change, equivalent variations and modification are made to above embodiment, all still belong to the scope of technical solution of the present invention.
Claims (10)
1. a modified coal PVC compound bellows comprises internal layer with outer, it is characterized in that: internal layer raw material comprises by weight: PVC resin powder 100 parts, modified coal 40 ~ 120 parts, outer raw material comprise by weight: PVC resin powder 100 parts, modified coal 20 ~ 40 parts, described modified coal carries out modification to coal ash with phenolic resin aqueous solution, resin water miscible liquid for composite modifier.
2. a kind of modified coal PVC compound bellows according to claim 1, it is characterized in that: composite modifier composition counts phenolic resin aqueous solution by weight: resin water miscible liquid=25 ~ 100:100, parts by weight, described composite modifier: coal ash is 10 ~ 50:100.
3. a kind of modified coal PVC compound bellows according to claim 1, it is characterized in that, described internal layer raw material also comprises by weight: stablizer 1.5 ~ 2.5 parts, lubricant 0.5 ~ 2 part, 0.5 ~ 1.2 part, softening agent, toughner 0.5 ~ 2 part, feed back 30 ~ 80 parts; Described skin also comprises by weight: stablizer 2 ~ 3 parts, lubricant 0.5 ~ 1.5 part, 0.5 ~ 1.2 part, softening agent, melt strength dose 0.5 ~ 2.5 part, toughner 3 ~ 6 parts.
4. a kind of modified coal PVC compound bellows according to claim 2, it is characterized in that: described resin water miscible liquid is vinyl chloride-vinyl acetate copolymer water miscible liquid, one or both in vinyl chloride-acrylate copolymer water miscible liquid, vinyl chloride-vinyl acetate-copolymer-maleic anhydride water miscible liquid, polyurethane aqueous emulsions; Described phenolic resin aqueous solution weight percent is 30% ~ 60%, described resin water miscible liquid weight percent is 10% ~ 50%.
5. require described a kind of modified coal PVC compound bellows according to claim 1, it is characterized in that: described PVC resin powder select in general suspension polymerization 8 type (SG-8) or 7 types (SG-7) resin one or both.
6. prepare a method for the arbitrary described modified coal PVC compound bellows of claim 1 to 5, it is characterized in that, comprise the following steps:
Prepared by a modified coal: coal ash by weight: coal ash and composite modifier are chosen in composite modifier=100:10 ~ 50, add kneader, mediates mixing 5 ~ 15min under normal temperature; And then while stirring in this kneader, be warmed up to 120 ~ 150 DEG C of dryings, reaction; Last cool to room temperature obtains modified coal;
The inside and outside layer compound preparation of b: weigh up material by internal layer and outer skin materials proportioning respectively and join in high temperature mixing machine, be heated to 100 ~ 120 DEG C while stirring, then control temperature mixes 5 ~ 20min at 100 ~ 120 DEG C; Above-mentioned hot mixture material is drained into mixing in low temperature low speed mixer by sealing-duct, stirs, is cooled, is finally cooled to 30 ~ 60 DEG C to stop stirring, obtains outer compound and internal layer compound;
C extrudes melting: by internal layer compound in the first extrusion equipment through melting, compression, homogenizing, molten tubing A is extruded into by forming mould, by the melting in the second extrusion equipment of outer compound, compression, homogenizing, become molten tubing B by forming mould;
D is shaping: move in ripple mould by molten tubing A and molten tubing B, and corrugated mould extrusion molten state tubular material B becomes bellows-shaped, and is welded together in outside and internal layer extruding, then moves into refrigerating unit, cooling, sizing;
E cuts: length is cut as required, obtains product.
7. the preparation method of a kind of modified coal PVC compound bellows according to claim 6, is characterized in that: the temperature parameter of described internal layer extrusion equipment is: 140 DEG C, transportation section, 180 DEG C, compression section, melt zone 220 DEG C, homogenizing zone 210 DEG C.
8. the preparation method of a kind of modified coal PVC compound bellows according to claim 6, is characterized in that: the temperature parameter of outer extrusion equipment is: 160 DEG C, transportation section, 200 DEG C, compression section, melt zone 220 DEG C, homogenizing zone 210 DEG C.
9. the preparation method of a kind of modified coal PVC compound bellows according to claim 6, is characterized in that: ripple die temperature is 120 ~ 180 DEG C.
10. the preparation method of a kind of modified coal PVC compound bellows according to claim 6, is characterized in that: the section of described forming mould is the one-piece construction containing two concentric(al) circles circumferential weld compositions.
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| CN107355605A (en) * | 2016-11-18 | 2017-11-17 | 王靖崇 | The stainless steel thin-wall bellows and its preparation technology of a kind of waste or used plastics cylinder-packing |
| CN110157116A (en) * | 2019-05-29 | 2019-08-23 | 福建亚通新材料科技股份有限公司 | A kind of unleaded drainage pipe of novel hard polyvinyl chloride and preparation method thereof |
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| CN105348690B (en) | 2017-08-08 |
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