CN103172937A - Special material for silicane grafted PPR (polypropylene random) pipe and preparation method thereof - Google Patents
Special material for silicane grafted PPR (polypropylene random) pipe and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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Abstract
The invention discloses a special material for a silicane grafted PPR (polypropylene random) pipe. The special material for the silicane grafted PPR pipe is formed by a material A and a material B in ratio in parts by weight of 90:10-95:5, wherein the material A comprises 80-95 parts of PPR, 5-20 parts of high-density polyethylene, 1-3 parts of unsaturated silicane, 0.01-0.03 part of initiator, 0.1-0.5 part of antioxidant and 0.1-2 parts of auxiliary crosslinking agent; and the material B comprises 100 parts of PPR, 1-3 parts of catalyst, 0.1-0.5 part of antioxidant and 1-5 parts of auxiliary catalyst. The preparation method comprises that the material A and the material B are respectively independently extruded and pelletized, then the material A and the material B are mixed to be uniform in proportion, and a pipe can be directly extruded. The special material disclosed by the invention is good in impact strength and creep resistance and can be widely applied to various pipeline products such as a hot and cold water pipe; and the preparation method is simple, and a long-time high temperature poaching process is not required, so that the preparation method disclosed by the invention is convenient for industrial production.
Description
Technical field
The invention belongs to PPR tubing field, be specifically related to a kind of Silane Grafted PPR special material for tube and preparation method thereof.
Background technology
The PPR duct products is made by atactic copolymerized polypropene.It is after crosslinked polyethylene, polybutene tubing, the thermoplastic plastic pipe that another is novel.Pipeline by PPR production, have that quality is light, resistance toheat good, heat conductivility is lower, Young's modulus is less, the resistance of ducting is little, health, corrosion-resistant, long service life, easy for installation, connect the characteristics such as reliable and material recoverable, can be widely used in various hot water pipes.But existing PPR pipeline also comes with some shortcomings, and mainly contain: rigidity and erosion-resisting characteristics are poorer than metallic conduit, and coefficient of linear expansion is larger, and construction is easily broken, and creep properties is larger.Particularly because PPR tube material molecule is linear structure, the rigidity of PPR tubing and shock resistance are relatively poor comparatively speaking.For satisfying different goods to the different requirements of PPR performance, to overcome the existing deficiency of PPR tubing, someone has done a large amount of research work, but mainly concentrates on the aspects such as blending and modifying, whisker modified enhancing and thermal treatment.Such as:
Application number is the Chinese invention patent application of CN99119655.4 disclosed " polypropene composition and tubing thereof ", said composition is mixed in the proper ratio by polymer grade polypropylene, chemical degradation polypropylene, polypropylene, ethylene/alpha-olefin copolymer, adds appropriate amount of addition agent (as stablizer, flow ability modifying agent, dispersion agent, tinting material etc.) and forms.Adopt said composition by melt extruding the thin-walled property that can realize tubing, the wall thickness of this tubing is applicable to the tubing of all size of water-saving irrigation system between 0.1-10mm.
Application number is the Chinese invention patent application of CN200510017644.2 disclosed " polypropene composition and the method for producing modified polypropylene pipes with said composition ", this disclosure of the invention a kind of polypropene composition, and produce heat supply heating with the method for whisker modified fiberglass reinforced polypropylene pipe with said composition.Take weight part as unit, it is by 50～100 parts of polypropylene, 10～50 parts of whiskers, 0.5～5 part of lubricant, compound before the granulation of 0.5～10 part of composition of coupling agent, with compound high-speed mixer mixing, oven dry is placed on extruding pelletization formation combination pellet in dual-screw-stem machine, again add a certain amount of polypropylene, the polypropylene that again adds in the combination pellet: make up pellet=1: 0.5～3, again use the high-speed mixer mixing, be placed in single-screw machine, the heating extruding pipe material through Vacuum shaping, cooling and traction, forms the tubing of required specification.This invention is claimed and not only can be improved heat resisting temperature, but also can increase the service life in fields such as being fit to delivering hot water, geothermal heating.
Application number is the Chinese invention patent application of CN200710030073.5 disclosed " special-purpose multifunctional modified random polypropylene material for pipe and preparation method thereof ", and this PP Pipe Compound is comprised of atactic copolymerized polypropene, environmental protection fire retarding agent, the pre-dispersed masterbatch of mineral filler, anti-impact modifier, oxidation inhibitor, composite antibiosis masterbatch and dispersion agent.This invention also discloses the application of special-purpose multifunctional modified random polypropylene material for pipe in the irrigation system in cold and hot water building pipe, tap water and foodstuffs industry tubing system, floor heating and traditional heat supply heating system, farmland.This invention claims that the special material for tube of preparation has the flame-proof antibiotic function, solve simultaneously atactic copolymerized polypropene and shunk large, the poor problem of low temperature impact properties, have higher resistance toheat and fabulous mechanical property, and have excellent thermostability, have good anti-contracility and low temperature resistance property.
Application number is the Chinese invention patent application of CN200810117477.2 disclosed " a kind of composite auxiliary agent for random copolymerized polypropylene pipe material ", this invention relates to a kind of composite auxiliary agent for random copolymerized polypropylene pipe material that is polymerized through the liquid phase noumenal method single loop reactors, forms by compound system is composite by weight: 10～30 parts of 10～40 parts of resisting ageing for long time performance auxiliary agents, 10～30 parts of processing aids, 20～50 parts of compound modifying agents and weather resisting agent; Resisting ageing for long time performance auxiliary agent is lactone stabilizer, Hinered phenols antioxidant and nontoxic amine antioxidants compound system; Processing aid is a kind of in fluoroelastomer or low-molecular(weight)polymer or mixture that any proportioning is several; Weather resisting agent is UV light absorber, organic nickel stablizer and the hindered amines compound stabilizer system in photostabilizer; Compound modifying agent is the compound modifying agent that alpha-crystal form is converted into beta crystal.This invention claims that processing characteristics, mechanical property and environmental stress cracking resistance and the resisting ageing for long time performance that can make the atactic copolymerized polypropene resin significantly improve.
Application number is a kind of Chinese invention patent application of CN201110335949.3 disclosed " method of improving low-temperature impact resistance of random copolymerization polypropylene pipe ", this invention comprises the processing of random copolymerization polypropylene pipe, random copolymerization polypropylene pipe puts into that baking car, thermal treatment, taking-up are cooling, check, thermal treatment was divided into for three steps: one at the uniform velocity rises to 90 ℃ by room temperature, and the heating-up time is 20min; Two at the uniform velocity rise to 105-110 ℃ by 90 ℃, and the heating-up time is 30min; Three under 105-110 ℃ of condition, thermal treatment 100-120min.This invention is claimed, by adopting above-mentioned technology, has improved random copolymerization polypropylene pipe low-temperature impact resistance qualification rate, has reduced production cost, has improved economic benefit.Improve more than five times through the heat treated random copolymerization polypropylene pipe falling ball impact test at low temperature serviceability rate of this invention, impact serviceability rate and reach 8/10～10/10, but also improved the compressive strength of tubing, effective unification of compatible toughness and intensity.
Application number is the Chinese invention patent application of CN201110439863.5 disclosed " a kind of polyacrylic special material for tube ", and this PP Pipe Compound is comprised of copolymerization grade polypropylene, water-ground limestone, glass microballon, oxidation inhibitor.This invention claims that the tubing of producing with this PP Pipe Compound compares with plain polypropylene tubing, in the situation that other performances are constant, its heat-drawn wire can improve 20-30 ℃, the rigidity of tubing improves greatly, its hardness can improve more than 1.5 times, linear expansivity reduces 30-40%, due to the raising of heat-drawn wire, has enlarged the range of application of polypropylene pipe; Due to the raising of hardness, can reduce the quantity of suspension and support built on stilts when laying, due to the reduction of the coefficient of expansion, the impact of in use being expanded with heat and contract with cold reduces simultaneously, can reduce the consumption of loop expansion pipe.
The inventor notices, the rigidity of PPR tubing is relative with shock resistance relatively poor, and its basic reason is that PPR tubing molecule is linear structure.Simultaneously, the inventor recognizes that after the molecular change of linear structure reticulates structure, the rigidity of polymer materials, resistance toheat, creep-resistant property and intensity all will obviously improve.The patent No. is the preparation method that the Chinese patent of ZL02151548.4 discloses a kind of Silane Grafted hdpe pipe.After polymkeric substance silane is crosslinked, improved the mechanical property of material.But the contriver finds: although PE and PP are under the effect of initiator, the Silane Grafted reaction mechanism is the same, but the chemical reaction that PPR and PE occur is different, PPR easily degrades under the initiator effect, and PE can not degrade, the degraded of PPR will have a negative impact to the mechanical property of tubing, and the technology that therefore can't directly adopt this patent to point out is improved the performance of PPR.
Summary of the invention
The Silane Grafted PPR special material for tube that provides a kind of shock strength good is provided one of purpose of the present invention.
Two of purpose of the present invention is to provide a kind of preparation method of Silane Grafted PPR special material for tube.
Silane Grafted PPR special material for tube of the present invention expects that by A material and B the ratio in 90: 10～95: 5 forms in weight part; Wherein
The A material consists of: PPR80～95 weight parts, high density polyethylene(HDPE) 5～20 weight parts, unsaturated silane 1-3 weight part, initiator 0.01-0.03 weight part, oxidation inhibitor 0.1-0.5 weight part, auxiliary crosslinking agent 0.1-2 weight part; Described auxiliary crosslinking agent is stearic acid, oxystearic acid, PE-g-MAH(maleic anhydride grafted polyethylene), the PP-g-MHA(maleic anhydride inoculated polypropylene) or the mixture of at least two kinds in them;
The B material consists of: PPR100 weight part, catalyzer 1-3 weight part, oxidation inhibitor 0.1-0.5 weight part, cocatalyst 1-5 weight part; Wherein, described catalyzer is dibutyl tin laurate, two lauric acid dioctyl tins, Phenylsulfonic acid or the mixture of at least two kinds in them; Described cocatalyst is metal oxide.
Described metal oxide is zinc oxide, calcium oxide or their mixture.
The melt index of the PPR that uses in described A material less than 0.5g/10min (230 ℃, 2.16kg).
The melt index of the high density polyethylene(HDPE) that uses in described A material as 2-5g/10min (190 ℃, 2.16kg).
Described unsaturated silane is vinyltriethoxysilane, vinyltrimethoxy silane, vinyl front three Ethoxysilane or the mixture of at least two kinds in them.
Described initiator is peroxide initiator, as dicumyl peroxide, tert-butyl peroxide-3,5,5 Trimethylhexanoic acid ester or mixture both etc.
The oxidation inhibitor that uses in described A material is phosphite ester kind antioxidant, for example irgasfos 168.
The melt index of the PPR that uses in described B material less than 0.5g/10min (230 ℃, 2.16kg).
The oxidation inhibitor that uses in described B material is dihydroxyphenyl propane class, phosphite ester kind antioxidant or their mixture, as antioxidant 1010, irgasfos 168 etc. or their mixture.
The preparation method of Silane Grafted PPR special material for tube of the present invention, A material and B material be independent extruding pelletization separately, respectively comprises the following steps:
The preparation of A material:
Unsaturated silane and initiator in proportion after weighing, are fully mixed in airtight stainless steel mixing tank, and the temperature of mixing tank is controlled between 23-27 ℃, mixes rear standby;
Take in proportion PPR, high density polyethylene(HDPE), oxidation inhibitor and auxiliary crosslinking agent and put into mixing machine, stir fully; Then add gradually the unsaturated silane and the initiator mixture that mix, obtain initial formulation after stirring fully;
Initial formulation directly joins and carries out grafting granulation processing in parallel dual-screw extruding machine;
The forcing machine design temperature raises temperature 5-10 ℃ by charging opening successively gradually to a mouthful mould, and the processing temperature of whole forcing machine is controlled at 110-230 ℃;
It is 2-3 minute that the engine speed of forcing machine is controlled at the residence time of material in forcing machine;
The vacuum tightness of the vacuum extraction of forcing machine should be lower than-0.08MPa;
A material granulation final vacuum packed for standby use;
The preparation of B material:
Take in proportion PPR, catalyzer, oxidation inhibitor and cocatalyst, put into mixing machine, the temperature of mixing machine is controlled at 30-40 ℃, and the material after mixing fully directly enters the twin screw extruder granulation, and the temperature of forcing machine is controlled at 110-230 ℃;
B material granulation final vacuum packed for standby use;
After A material and B expect compounding in proportion evenly, namely can be used for direct extruding pipe material.
PPR is the macromolecular material of ethene, propylene random copolymerization, and molecular structure is linear structure.The macromolecular material of linear structure is subject under external load, and the relative slippage of molecule meeting causes the mechanical property of material to reduce.And existing a large amount of tertiary carbons and a small amount of unsaturated double-bond in the PPR molecule, the two keys of the H on the polymer molecule tertiary carbon atom or a small amount of C=C issue biochemical reaction in the effect of peroxide initiator, produce free radical.The free radical that the two keys of this free radical and insatiable hunger silane produce reacts, and has obtained Silane Grafted PPR material.
But under the effect of peroxide initiator, PPR can generating portion degrade, and the mechanical property of PPR material is reduced.In order to overcome this problem, the present invention has introduced a small amount of high density polyethylene(HDPE) in composition, is used for making up PPR because of the defective of degraded mechanical properties decrease, has improved macro property and the working (machining) efficiency of PPR pipe.The introducing of high density polyethylene(HDPE) has also improved the percentage of grafting of material, thereby improves the degree of crosslinking of PPR tubing.The present invention simultaneously except having used aforesaid catalyzer, has also introduced auxiliary crosslinking agent in grafting A material, be conducive to improve the percentage of grafting of PPR material.In catalysis B material, introduced cocatalyst, be conducive to improve the rate of crosslinking of PPR material.Because the present invention has adopted aforesaid these technology, Silane Grafted PPR at room temperature just can be occured crosslinked, for Chinese patent CN02151548.4, the poach process that does not need the long-term time, just reach the degree of crosslinking that needs within very short time, thereby make the technology of the present invention greatly reduce the material preparation cost and simplify technique.
And after the molecular change of linear structure reticulated structure, the rigidity of polymer materials, resistance toheat, creep-resistant property and intensity all obviously improved.After polymkeric substance silane is crosslinked, improved the mechanical property of material, thus adopt the Silane Grafted technology to make PPR tube material generating network structure, thus can improve the macro property of PPR tubing, reduce its coefficient of linear expansion.
Embodiment
The invention will be further described by the following examples.
In the embodiment of the present invention, the preparation method of each embodiment is as follows:
All adopt the preparation were established of two-step approach.Namely adopt two-step approach to prepare respectively Silane Grafted PPR material (A material) and crosslinked with silicane catalysis PPR material (B material).
The preparation method of A material:
Unsaturated silane and initiator in proportion after weighing, are fully mixed approximately 5-10 minute in airtight stainless steel mixing tank, the temperature of mixing tank is controlled between 23-27 ℃, mixes rear standby.
Take in proportion PPR, high density polyethylene(HDPE), oxidation inhibitor and auxiliary crosslinking agent and put into high-speed mixer, the rotating speed of high-speed mixer is controlled at 50-100 rev/min, stirs 8-10 minute.Then add gradually the unsaturated silane and the initiator mixture that mix, this moment, the rotating speed of mixing machine was controlled at 200-300 rev/min, stirred and obtained initial formulation after 3-5 minute.
Initial formulation directly joins and carries out grafting granulation processing in parallel dual-screw extruding machine.The technical parameter of parallel dual-screw extruding machine:
The length-to-diameter ratio of forcing machine (L/D) is at (40-52): between 1.
The heating zone number of forcing machine should be between the 12-16 section.
Open the vacuum extraction mouth in the 9-10 heating zone.
The working process parameter of parallel dual-screw extruding machine:
The forcing machine design temperature raises temperature 5-10 ℃ by charging opening successively gradually to a mouthful mould, and the processing temperature of whole forcing machine is controlled at 110-230 ℃.
It is 2-3 minute that the engine speed of forcing machine is controlled at the residence time of material in forcing machine.
The vacuum tightness of the vacuum extraction of forcing machine should be lower than-0.08MPa.
A material adopts the water cooling granulation in granulation process, after granulation after 50-70 ℃ of vacuum-drying 30-60 minute, the aluminium plastic bag vacuum packaging.
The preparation method of B material:
Take in proportion PPR, catalyzer, oxidation inhibitor and cocatalyst, put into high-speed mixer, the rotating speed of mixing machine is controlled at 200-300 rev/min.The temperature of mixing machine is controlled at 30-40 ℃.Mixing time is 10-15 minute.Mixed material directly enters twin screw extruder, and the temperature of forcing machine is controlled at 110-230 ℃.
B material adopts the water cooling granulation in granulation process, after granulation after 50-70 ℃ of vacuum-drying 30-60 minute, the aluminium plastic bag vacuum packaging.
After A material and B expect compounding in proportion evenly, direct extruding pipe material.
Chemical constitution and the performance of the embodiment of the present invention tubing of preparation see Table 1 as stated above.
The testing method explanation:
1. gel content: ASTM D2655-1995;
2. shock strength: GB/T1843-1996;
3. drop impact experiment: GB/T11548-1989.
Typical starting material are:
The A material:
PPR:R4220 Sinopec yanshan petrochemical limited-liability company.
High density polyethylene(HDPE): 5000S Sinopec yanshan petrochemical limited-liability company.
Vinyltriethoxysilane: KBM-1003 Japan XINYUE.
Initiator: dicumyl peroxide (DCP) auxiliary reagent factory, Lanzhou.
Oxidation inhibitor: 168 Linyi City three Feng Huagong company limiteds.
Auxiliary crosslinking agent: the polite company of stearic acid SA1810 Indonesia.
The B material:
PPR:R4220 Sinopec yanshan petrochemical limited-liability company.
Catalyzer: linear alkyl benzene sulphonic acid LABSA Henan emerging inferior tensio-active agent limited-liability company.
Oxidation inhibitor: 1010 Linyi City three Feng Huagong company limiteds.
Cocatalyst: nano zine oxide Linan precious letter zinc industry company limited.
As can be seen from Table 1, the excellent property of PPR special material for tube of the present invention.The shock strength of tubing prepared therefrom obviously improves, and ageing-resistant performance obviously improves, and low temperature resistant drop impact performance also is significantly improved.
The composition and performance of table 1 embodiment of the present invention and Comparative Examples (in table 1, material consists of weight part)
The composition and performance of table 1 embodiment of the present invention and Comparative Examples (continuous 1)
The composition and performance of table 1 embodiment of the present invention and Comparative Examples (continuous 2)
The composition and performance of table 1 embodiment of the present invention and Comparative Examples (continuous 3)
The composition and performance of table 1 embodiment of the present invention and Comparative Examples (continuous 4)
The composition and performance of table 1 embodiment of the present invention and Comparative Examples (continuous 5)
The composition and performance of table 1 embodiment of the present invention and Comparative Examples (continuous 6)
Claims (10)
1. a Silane Grafted PPR special material for tube, is characterized in that expecting that by A material and B the ratio in 90: 10～95: 5 forms in weight part; Wherein
The A material consists of: PPR80～95 weight parts, high density polyethylene(HDPE) 5～20 weight parts, unsaturated silane 1-3 weight part, initiator 0.01-0.03 weight part, oxidation inhibitor 0.1-0.5 weight part, auxiliary crosslinking agent 0.1-2 weight part; Described auxiliary crosslinking agent is stearic acid, oxystearic acid, PE-g-MAH, PP-g-MHA or the mixture of at least two kinds in them;
The B material consists of: PPR100 weight part, catalyzer 1-3 weight part, oxidation inhibitor 0.1-0.5 weight part, cocatalyst 1-5 weight part; Wherein, described catalyzer is dibutyl tin laurate, two lauric acid dioctyl tins, Phenylsulfonic acid or the mixture of at least two kinds in them; Described cocatalyst is metal oxide.
2. Silane Grafted PPR special material for tube according to claim 1, is characterized in that described metal oxide is zinc oxide, calcium oxide or their mixture.
3. Silane Grafted PPR special material for tube according to claim 1 and 2, the melt index that it is characterized in that the PPR that uses in described A material less than 0.5g/10min (230 ℃, 2.16kg).
4. Silane Grafted PPR special material for tube according to claim 1 and 2, the melt index that it is characterized in that the high density polyethylene(HDPE) that uses in described A material as 2-5g/10min (190 ℃, 2.16kg).
5. Silane Grafted PPR special material for tube according to claim 1 and 2 is characterized in that described unsaturated silane is vinyltriethoxysilane, vinyltrimethoxy silane, vinyl front three Ethoxysilane or the mixture of at least two kinds in them.
6. Silane Grafted PPR special material for tube according to claim 1 and 2, is characterized in that described initiator is peroxide initiator.
7. Silane Grafted PPR special material for tube according to claim 1 and 2, is characterized in that the oxidation inhibitor that uses in described A material is phosphite ester kind antioxidant.
8. Silane Grafted PPR special material for tube according to claim 1 and 2, the melt index that it is characterized in that the PPR that uses in described B material less than 0.5g/10min (230 ℃, 2.16kg).
9. Silane Grafted PPR special material for tube according to claim 1 and 2, is characterized in that the oxidation inhibitor that uses in described B material is dihydroxyphenyl propane class, phosphite ester kind antioxidant or their mixture.
10. the preparation method of a Silane Grafted PPR special material for tube, is characterized in that A material and B material independent extruding pelletization separately, respectively comprises the following steps:
The preparation of A material:
Unsaturated silane and initiator in proportion after weighing, are fully mixed in airtight stainless steel mixing tank, and the temperature of mixing tank is controlled between 23-27 ℃, mixes rear standby;
Take in proportion PPR, high density polyethylene(HDPE), oxidation inhibitor and auxiliary crosslinking agent and put into mixing machine, stir fully; Then add gradually the unsaturated silane and the initiator mixture that mix, obtain initial formulation after stirring fully;
Initial formulation directly joins and carries out grafting granulation processing in parallel dual-screw extruding machine;
The forcing machine design temperature raises temperature 5-10 ℃ by charging opening successively gradually to a mouthful mould, and the processing temperature of whole forcing machine is controlled at 110-230 ℃;
It is 2-3 minute that the engine speed of forcing machine is controlled at the residence time of material in forcing machine;
The vacuum tightness of the vacuum extraction of forcing machine should be lower than-0.08MPa;
A material granulation final vacuum packed for standby use;
The preparation of B material:
Take in proportion PPR, catalyzer, oxidation inhibitor and cocatalyst, put into mixing machine, the temperature of mixing machine is controlled at 30-40 ℃, and the material after mixing fully directly enters the twin screw extruder granulation, and the temperature of forcing machine is controlled at 110-230 ℃;
B material granulation final vacuum packed for standby use;
After A material and B expect compounding in proportion evenly, namely can be used for direct extruding pipe material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310125917.XA CN103172937B (en) | 2013-04-11 | 2013-04-11 | A kind of Silane Grafted PPR pipe PP Pipe Compound and preparation method thereof |
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| CN201310125917.XA CN103172937B (en) | 2013-04-11 | 2013-04-11 | A kind of Silane Grafted PPR pipe PP Pipe Compound and preparation method thereof |
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| CN112390996A (en) * | 2020-10-29 | 2021-02-23 | 江西格林美资源循环有限公司 | Modified regenerated polyethylene plastic for plastic pipeline and preparation method thereof |
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| CN116003912A (en) * | 2023-02-10 | 2023-04-25 | 创合新材料科技江苏有限公司 | Special polypropylene reinforcing material for micro-crosslinked high-pressure-resistant water pump and preparation method and application thereof |
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| CN106633379A (en) * | 2016-10-12 | 2017-05-10 | 重庆金山洋生管道有限公司 | Special large-diameter crosslinked polypropylene spirally enwound structure-wall pipeline for sewage drainage of underground pipe gallery |
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| CN112390996A (en) * | 2020-10-29 | 2021-02-23 | 江西格林美资源循环有限公司 | Modified regenerated polyethylene plastic for plastic pipeline and preparation method thereof |
| WO2022088230A1 (en) * | 2020-10-29 | 2022-05-05 | 江西格林美资源循环有限公司 | Modified recycled polyethylene plastic for plastic pipeline and preparation method therefor |
| CN115011058A (en) * | 2022-07-11 | 2022-09-06 | 青岛科技大学 | Reinforced polypropylene composite material and preparation method thereof |
| CN115011058B (en) * | 2022-07-11 | 2024-04-16 | 青岛科技大学 | Reinforced polypropylene composite material and preparation method thereof |
| CN116003912A (en) * | 2023-02-10 | 2023-04-25 | 创合新材料科技江苏有限公司 | Special polypropylene reinforcing material for micro-crosslinked high-pressure-resistant water pump and preparation method and application thereof |
| CN116003912B (en) * | 2023-02-10 | 2024-01-09 | 创合新材料科技江苏有限公司 | Special polypropylene reinforcing material for micro-crosslinked high-pressure-resistant water pump and preparation method and application thereof |
| CN117624789A (en) * | 2023-12-01 | 2024-03-01 | 杭州佳磊环保科技有限公司 | Modified polypropylene composite pipe and preparation process thereof |
| CN117624789B (en) * | 2023-12-01 | 2024-04-16 | 杭州佳磊环保科技有限公司 | Modified polypropylene composite pipe and preparation process thereof |
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