CN105670079A - HDPE pipe material and preparing method thereof - Google Patents
HDPE pipe material and preparing method thereof Download PDFInfo
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- CN105670079A CN105670079A CN201610104639.3A CN201610104639A CN105670079A CN 105670079 A CN105670079 A CN 105670079A CN 201610104639 A CN201610104639 A CN 201610104639A CN 105670079 A CN105670079 A CN 105670079A
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- quaternary ammonium
- ammonium salt
- hindered phenol
- hdpe
- modified montmorillonoid
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
The invention relates to an HDPE pipe material and a preparing method thereof. A formula of the HDPE pipe material contains hindered phenol quaternary ammonium salt modified imvite, the mass of which is 1-10% of the total mass of all components of the HDPE pipe material. The invention further provides a preparing method of the HDPE pipe material. The HDPE pipe material has excellent processing stability and thermal resistance stability, durable weather resistance and well color.
Description
Technical field
The present invention relates to plastic pipe technical field, be specifically related to a kind of HDPE tubing and preparation method thereof.
Background technology
Almost all of macromolecule is all attended by catabiosis, and HDPE is no exception. For HDPE, inevitably there is unsaturated double-bond, side chain, terminal groups etc. inside it and cause aging weakness, in its storage, processing, use procedure, it is subject to the effects such as heat, oxygen, light, the structure that its result is HDPE changes, and relative molecular mass declines or produces crosslinking, so that the hydraulic performance decline of material even results in destruction, therefore HDPE material anti ageing property is most important. In order to suppress that HDPE is aging, keep material property, increase the service life, the most frequently used and most efficient method is to be added to antioxidant; Antioxidant mainly have amine, phenols, containing Phosphorus and sulfur-bearing class etc., in traditional antioxidant, some antioxidant poor stability, toxicity is big; Some antioxidant easily migrates, and action time is short, and these traditional antioxidant all cannot solve the aging problem of HDPE pipe and cannot obtain the HDPE tubing that a kind of antioxidant effect is good; Therefore, still need to by study the good antioxidant of a kind of antioxidant effect to prepare that antioxidant effect is good, the HDPE tubing of weatherability and good stability and preparation method thereof.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of HDPE tubing, the present invention has prepared a kind of HDPE tubing with excellent processing stability, heat-resistant stability and weathering durability by a kind of novel antioxidant of selection.
Another object of the present invention is to the preparation method that above-mentioned HDPE tubing is provided.
Another object of the present invention is to provide above-mentioned hindered phenol quaternary ammonium salt modified montmorillonoid as antioxidant application in HDPE tubing.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of HDPE tubing, containing hindered phenol quaternary ammonium salt modified montmorillonoid in the formula of described HDPE tubing, the quality of described hindered phenol quaternary ammonium salt modified montmorillonoid is the 1～10% of each component gross mass of described HDPE tubing.
The present invention selects hindered phenol quaternary ammonium salt modified montmorillonoid as antioxidant, applies it to the HDPE tubing prepared after in HDPE tubing and has excellent processing stability and heat-resistant stability, and weatherability persistently and has good color and luster.
Hindered phenol quaternary ammonium salt modified montmorillonoid antioxidant provided by the invention selects the quaternary ammonium salt containing hindered phenol group to carry out modified montmorillonoid, hydrogen atom is provided to stop the formation of chain free radical by hindered phenol group, the blocking effect that lamella montmorillonite simultaneously has, the feature of heat-resistant quality and restriction polymer molecule segment motion, the hindered phenol quaternary ammonium salt modified montmorillonoid prepared is made to have better antioxidant effect, and also make hindered phenol quaternary ammonium salt modified montmorillonoid have the advantages that not easily migrate, this makes to have good antioxidant effect when being applied in the preparation of HDPE tubing by hindered phenol quaternary ammonium salt modified montmorillonoid,Additionally, inventor selects hindered phenol quaternary ammonium salt to carry out modified montmorillonoid, significantly improve the dispersibility of montmorillonite, and making, between modified hindered phenol quaternary ammonium salt modified montmorillonoid and the HDPE matrix material resin obtained, there is good bond strength so that the HDPE tubing prepared has more excellent processing stability, heat-resistant stability and weathering durability.
Preferably, the preparation method of described hindered phenol quaternary ammonium salt modified montmorillonoid is as follows: montmorillonite is stirred to obtain mixed liquor in 60～80 DEG C of water, dropwise dropping hindered phenol quaternary ammonium salt, reacts 8～24h under 60～80 DEG C of conditions, obtains hindered phenol quaternary ammonium salt modified montmorillonoid.
Preferably, described hindered phenol quaternary ammonium salt is containing one or more in the mono-quaternaries of hindered phenol group, bi-quaternary ammonium salt, three quaternary ammonium salts, multi-quaternary ammonium salt, hyperbranched quaternary ammonium salt.
Preferably, possibly together with phosphite ester kind antioxidant in the formula of described HDPE tubing; Not peroxide decomposition quietly can be become stable compound by phosphite ester kind antioxidant, to stop new free radical to be formed, by better with phosphite ester kind antioxidant antioxidant effect after composite for the hindered phenol quaternary ammonium salt modified montmorillonoid in the present invention.
Preferably, described hindered phenol quaternary ammonium salt modified montmorillonoid is 10～20:1～2 with the mass ratio of described phosphite ester kind antioxidant; It is further preferred that the mass ratio of described hindered phenol quaternary ammonium salt modified montmorillonoid and described phosphite ester kind antioxidant is 10:1.
Preferably, described phosphite ester kind antioxidant is one or more in irgasfos 168, pentaerythritol bis-phosphite, antioxidant 618.
Preferably, described HDPE tubing is made up of following raw material by mass fraction:
High density polyethylene (HDPE) 85～100 parts;
Hindered phenol quaternary ammonium salt modified montmorillonoid 1～10 part;
Phosphite ester kind antioxidant 0.05～2 part.
It is further preferred that described HDPE tubing is made up of following raw material by mass fraction:
High density polyethylene (HDPE) 85～98 parts;
Hindered phenol quaternary ammonium salt modified montmorillonoid 2～6 parts;
Phosphite ester kind antioxidant 0.05～1 part.
The preparation method of above-mentioned HDPE tubing, specifically includes following steps:
(1) preparation of hindered phenol quaternary ammonium salt modified montmorillonoid: montmorillonite is stirred to obtain in the water of 60～80 DEG C mixed liquor, the quaternary ammonium salt that dropwise dropping ethanol has dissolved in mixed liquor, at 60～80 DEG C, react 8～24h, obtain hindered phenol quaternary ammonium salt modified montmorillonoid;
(2) dispensing: weigh raw material by above-mentioned formula by high density polyethylene (HDPE), hindered phenol quaternary ammonium salt modified montmorillonoid, phosphite ester kind antioxidant;
(3) tubing is prepared: raw material step (2) prepared adds in double screw extruder, carries out blended molding, cooling, pelletizing, drying, injection mo(u)lding.
Preferably, the technological parameter of described double screw extruder is set to: 160 DEG C of a district, 165 DEG C of 2nd district, 170 DEG C of 3rd district, 175 DEG C of 4th district, 180 DEG C of 5th district, head 175 DEG C, screw speed 40r/min.
Preferably, described Hot Air Dying Technology Parameters is: oven temperature is set to 90 DEG C, and drying time is 180min.
Preferably, in extruding-out process, extrusion parameter is set to: 185 DEG C of a district, 190 DEG C of 2nd district, 195 DEG C of 3rd district, 195 DEG C of 4th district, 195 DEG C of 5th district, 195 DEG C of 6th district, 200 DEG C of 7th district, 207 DEG C of 8th district, head 200 DEG C, vacuum is 0.48MPa.
Hindered phenol quaternary ammonium salt modified montmorillonoid is as antioxidant application in HDPE tubing.
The hindered phenol quaternary ammonium salt modified montmorillonoid that the present invention prepares not only has good antioxidant effect, also has that pollution is little, not easy to change, persistency good, is not easily decomposed and the advantage such as migration.
Compared with prior art, there is advantages that
HDPE tubing provided by the invention has excellent processing stability and heat-resistant stability, and weatherability persistently and has good color pool; Hindered phenol quaternary ammonium salt modified montmorillonoid provided by the invention not only has that antioxidant effect is good, it is little to pollute, not allochroic feature, also has the feature that persistency is good, not easily migrate, and it is excellent to the thermo oxidative aging performance of HDPE, and usefulness is high.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described. These embodiments are only the typical case's descriptions to the present invention, but the invention is not restricted to this. Test method used in following embodiment if no special instructions, is conventional method, the raw material used, reagent etc., except quaternary ammonium salt self-control of being obstructed, if no special instructions, is the raw material and reagent that can obtain from commercial sources such as routine are commercial.
Embodiment 1
(1) preparation of hindered phenol quaternary ammonium salt modified montmorillonoid: to be furnished with magnetic agitation, condensing tube, thermometer 500mL there-necked flask in add 400mL deionized water, 5 parts of montmorillonites, 60 DEG C of heating in water bath 4h, 5 parts of hindered phenol quaternary ammonium salts that dropping has been dissolved with solvent, continue reaction 8h, sucking filtration, use deionized water wash filter cake, 50% alcoholic solution is washed till without chloride ion, and 100 DEG C dry, and ground 200 mesh sieves are standby.
(2) application that hindered phenol quaternary ammonium salt modified montmorillonoid antioxidant and phosphite ester kind antioxidant are composite: raw material by weight: add the hindered phenol quaternary ammonium salt modified montmorillonoid antioxidant of the above-mentioned synthesis of 3 parts to the HDPE of 96.7 parts, irgasfos 168 0.3 part, after extruding 1,2,3,4,5 times on the twin screw extruder, survey its melt index, then cool down, pelletizing, drying, standby; Finally select Single screw extrusion shaping pipe, investigate the heat resistance of tubing, weather resistance etc.
Wherein, double screw extruder temperature: 160 DEG C of a district, 165 DEG C of 2nd district, 170 DEG C of 3rd district, 175 DEG C of 4th district, 180 DEG C of 5th district, head 175 DEG C, screw speed 40r/min; Hot Air Dying Technology Parameters is: oven temperature is set to 90 DEG C, and drying time is 180min; Single screw extrusion molding technique parameter: 185 DEG C of a district, 190 DEG C of 2nd district, 195 DEG C of 3rd district, 195 DEG C of 4th district, 195 DEG C of 5th district, 195 DEG C of 6th district, 200 DEG C of 7th district, 207 DEG C of 8th district, head 200 DEG C, vacuum is 0.48MPa.
Embodiment 2
The preparation method of the present embodiment, with embodiment 1, is different in that, in the formula of the present embodiment step (2), the mass fraction of HDPE is 95.7 parts, and hindered phenol quaternary ammonium salt modified montmorillonoid is 4 parts, and pentaerythritol bis-phosphite is 0.3 part.
Embodiment 3
The preparation method of the present embodiment, with embodiment 1, is different in that, in the formula of the present embodiment step (2), the mass fraction of HDPE is 97 parts, and hindered phenol quaternary ammonium salt modified montmorillonoid is 3 parts.
Embodiment 4
The preparation method of the present embodiment, with embodiment 1, is different in that, in the formula of the present embodiment step (2), the mass fraction of HDPE is 97.5 parts, and hindered phenol quaternary ammonium salt modified montmorillonoid is 2 parts, and the mass fraction of antioxidant 618 is 0.5 part.
Reference examples 1
The preparation method of this reference examples, with embodiment 1, is different in that, containing only there being 100 parts of HDPE in the formula of this reference examples step (2), does not comprise any antioxidant.
Reference examples 2
The preparation method of this reference examples, with embodiment 1, is different in that, in the formula of this reference examples step (2), the mass fraction of HDPE is 97 parts, and the mass fraction of pentaerythritol bis-phosphite is 3 parts.
Reference examples 3
The preparation method of this reference examples, with embodiment 1, is different in that, in the formula of this reference examples step (2), the mass fraction of HDPE is 99.5 parts, and the mass fraction of hindered phenol quaternary ammonium salt modified montmorillonoid is 0.5 part.
After the HDPE that embodiment 1～4 and reference examples 1～3 are prepared extrudes 1,2,3,4,5 times on the twin screw extruder respectively, measure its melt index to judge the antioxygenic property of HDPE resin; And measuring final each embodiment and the outward appearance of HDPE tubing, heat resistance and weather resistance that reference examples prepares, concrete method of testing is as follows, and measurement result is shown in table 1 below and table 2.
(1) mensuration of melt flow rate (MFR) (MFR):
According to GB/T3682-2000, at 190 DEG C, when load is 21.6kg, fusion index instrument is used to measure the MFR of resin material, HDPE resin is extruded by double screw extruder, and extrusion number of times is more many, and melt index is more low, and to represent the antioxygenic property of resin more good;
(2) outward appearance:
According to the regulation of GB/T13663-2000, whether its color of perusal and outward appearance meet GB/T13663-2000 standard-required;
(3) heat resistance:
According to the regulation of GB/T1634-2004, adopt heat distortion temperature instrument, test its dimension card when 0.45MPa;
(4) melt index
The melt index of the HDPE tubing that single screw extrusion machine prepares is measured, and melt index herein represents mobile performance and the processing characteristics of material; Assay method is according to GB/T3682-2000, at 190 DEG C, when load is 21.6kg, uses fusion index instrument to measure;
(5) weather resistance:
Adopt the tubing of nominal outside diameter 32mm, SDR11. Being exposed to the sun according to the regulation of GB/T3681-2011, the time of being exposed to the sun is 1 year, specifies according to GB/T17391, takes its oxidation induction time of the sample test (OIT) after the aged surface scraping 0.4mm of the tubing that is exposed to the sun.
Melt flow rate (MFR) (MFR) (g/10min) after table 1HDPE thermo-oxidative ageing
Be can be seen that by the experimental data in upper table 1, it is added with the HDPE resin of hindered phenol quaternary ammonium salt modified montmorillonoid antioxidant after extrusion 5 times, melt flow rate (MFR) is up to 9.24, minimum is 8.25, showing that the palliating degradation degree of resin is relatively low, the hindered phenol quaternary ammonium salt modified montmorillonoid of the present invention has good antioxygenic property; By contrast, being not added with the HDPE resin of any antioxidant in reference examples 1 after extrusion 5 times, melt flow rate (MFR) is up to 18.94, and antioxidant effect is worst; Selecting the pentaerythritol bis-phosphite of routine as antioxidant in reference examples 2, antioxidant effect is poor; Though reference examples 3 has also selected hindered phenol quaternary ammonium salt modified montmorillonoid, but owing to its addition is less, antioxidant effect is inconspicuous.
Table 2: the performance parameter of the HDPE that embodiment 1～4 and reference examples 1～3 prepare
。
By upper table 2 it can be seen that the present invention tubing outward appearance that with the addition of hindered phenol quaternary ammonium salt modified montmorillonoid antioxidant is qualified, vicat temperature is higher, it was shown that the antioxidant of the present invention has good heat resistance, and not easy to change; The a little higher than each reference examples of melt index of the tubing that various embodiments of the present invention prepare, it was shown that the HDPE resin of the present invention has good mobile performance and processing characteristics after with the addition of hindered phenol quaternary ammonium salt modified montmorillonoid;The oxidation induction time of the HDPE tubing that embodiment 1～4 prepares is considerably longer than each reference examples, it was shown that hindered phenol quaternary ammonium salt modified montmorillonoid provided by the invention has good weather resistance.
Claims (10)
1. a HDPE tubing, it is characterised in that containing hindered phenol quaternary ammonium salt modified montmorillonoid in the formula of described HDPE tubing, the quality of described hindered phenol quaternary ammonium salt modified montmorillonoid is the 1～10% of each component gross mass of described HDPE tubing.
2. HDPE tubing according to claim 1, it is characterized in that, the preparation method of described hindered phenol quaternary ammonium salt modified montmorillonoid is as follows: montmorillonite is stirred to obtain mixed liquor in 60～80 DEG C of water, dropwise dropping hindered phenol quaternary ammonium salt, under 60～80 DEG C of conditions, react 8～24h, obtain hindered phenol quaternary ammonium salt modified montmorillonoid.
3. HDPE tubing according to claim 2, it is characterised in that described hindered phenol quaternary ammonium salt is containing one or more in the mono-quaternaries of hindered phenol group, bi-quaternary ammonium salt, three quaternary ammonium salts, multi-quaternary ammonium salt, hyperbranched quaternary ammonium salt.
4. HDPE tubing according to claim 1, it is characterised in that possibly together with phosphite ester kind antioxidant in the formula of described HDPE tubing.
5. HDPE tubing according to claim 4, it is characterised in that the mass ratio of described hindered phenol quaternary ammonium salt modified montmorillonoid and described phosphite ester kind antioxidant is 10～20:1～2.
6. HDPE tubing according to claim 5, it is characterised in that the mass ratio of described hindered phenol quaternary ammonium salt modified montmorillonoid and described phosphite ester kind antioxidant is 10:1.
7. HDPE tubing according to claim 4, it is characterised in that described phosphite ester kind antioxidant is one or more in irgasfos 168, pentaerythritol bis-phosphite, antioxidant 618.
8. HDPE tubing according to claim 1, it is characterised in that described HDPE tubing is made up of following raw material by mass fraction:
High density polyethylene (HDPE) 85～100 parts;
Hindered phenol quaternary ammonium salt modified montmorillonoid 1～10 part;
Phosphite ester kind antioxidant 0.05～2 part.
9. the preparation method of HDPE tubing described in claim 1～8 any claim, it is characterised in that the preparation method of described HDPE tubing is as follows:
S1: the preparation of hindered phenol quaternary ammonium salt modified montmorillonoid
Montmorillonite is stirred to obtain in the water of 60～80 DEG C mixed liquor, the quaternary ammonium salt that dropwise dropping ethanol has dissolved in mixed liquor, at 60～80 DEG C, reacts 8～24h, obtain hindered phenol quaternary ammonium salt modified montmorillonoid;
S2: dispensing
Each raw material is weighed by above-mentioned formula;
S3: prepare tubing
The raw material prepared by step S2 adds in double screw extruder, carries out blended molding, cooling, pelletizing, drying, injection mo(u)lding.
10. hindered phenol quaternary ammonium salt modified montmorillonoid is as antioxidant application in HDPE tubing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610104639.3A CN105670079A (en) | 2016-02-25 | 2016-02-25 | HDPE pipe material and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610104639.3A CN105670079A (en) | 2016-02-25 | 2016-02-25 | HDPE pipe material and preparing method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106700269A (en) * | 2016-11-22 | 2017-05-24 | 联塑科技发展(贵阳)有限公司 | Hindered-phenol-quaternary-ammonium-salt-modified-imvite-modified PP-R pipe |
| CN111171455A (en) * | 2020-03-09 | 2020-05-19 | 广东圆融新材料有限公司 | Thermal-aging-resistant polypropylene composite material and preparation method thereof |
| CN113429673A (en) * | 2021-07-15 | 2021-09-24 | 安徽瑞丰管业有限公司 | Corrosion-resistant water supply pipe and preparation method thereof |
| CN115785552A (en) * | 2022-12-07 | 2023-03-14 | 天津泰达滨海清洁能源集团有限公司 | Polyethylene pipe for conveying hydrogen and preparation method thereof |
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| CN101020776A (en) * | 2006-12-11 | 2007-08-22 | 杭州鸿雁电器有限公司 | Nanometer random olefin copolymer/montmorillonite composite material and its prepn |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700269A (en) * | 2016-11-22 | 2017-05-24 | 联塑科技发展(贵阳)有限公司 | Hindered-phenol-quaternary-ammonium-salt-modified-imvite-modified PP-R pipe |
| CN111171455A (en) * | 2020-03-09 | 2020-05-19 | 广东圆融新材料有限公司 | Thermal-aging-resistant polypropylene composite material and preparation method thereof |
| CN111171455B (en) * | 2020-03-09 | 2022-06-03 | 广东圆融新材料有限公司 | Thermal-aging-resistant polypropylene composite material and preparation method thereof |
| CN113429673A (en) * | 2021-07-15 | 2021-09-24 | 安徽瑞丰管业有限公司 | Corrosion-resistant water supply pipe and preparation method thereof |
| CN115785552A (en) * | 2022-12-07 | 2023-03-14 | 天津泰达滨海清洁能源集团有限公司 | Polyethylene pipe for conveying hydrogen and preparation method thereof |
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Application publication date: 20160615 |