CN1865337A - High heat-durable resin dedicated to PP-R tube and its preparation method - Google Patents
High heat-durable resin dedicated to PP-R tube and its preparation method Download PDFInfo
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- CN1865337A CN1865337A CN 200610020942 CN200610020942A CN1865337A CN 1865337 A CN1865337 A CN 1865337A CN 200610020942 CN200610020942 CN 200610020942 CN 200610020942 A CN200610020942 A CN 200610020942A CN 1865337 A CN1865337 A CN 1865337A
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Abstract
The invention discloses a making method of nanometer whisker and inorganic nanometer particle compound, which is characterized by the following: adapting random copolymerization polypropylene (PP-R) as base material; improving the heat-durability for PP-R pipe specific resin and breakage extension rate and anti-bent strength through layer-shaped mica and modified nanometer whisker and inorganic nanometer particle compound; forming hollow network structure for nanometer whisker in the base; making the layer-shaped mica compound with plug-layer; combining distribution property of nanometer dimension for zero-dimension nanometer particle in the base with layer-shaped mica to improve heat property and mechanic property of PP-R pipe resin.
Description
One, technical field
The present invention relates to the material technology field of building plastic pipe, particularly relating to atactic copolymerized polypropene (PP-R) is the hot water pipe material for building of material of main part
Two, technical background
The PP-R pipe is a kind of building pipe that recent development is got up on the present international tubing development history, and it has outstanding high pressure resistant, high and low temperature resistance.Development is very fast abroad, has particularly surpassed aluminum-plastic laminated tube in the application of water-supply pipe.
The PP-R material has better heat-resisting, and its Vicat softening point is 131.5 ℃.Maximum operating temperature with the plastics tubing of PP-R resin treatment can reach 95 ℃, and long-term (under 50 years 1.0Mpa) use temperature generally can reach 70 ℃, can satisfy the water delivery requirement under the general condition fully.
At present, cold and hot water is mainly the import material with PP-R tubing materials on the domestic market, but import PP-R tubing materials price height, and most of tubing manufacturer is difficult to bear.In recent years, Overseas Company at home the raw-material sales volume of PP-R be more than 20,000 t/y; Homemade PP-R starting material exploitation is mainly Yanshan Petrochemical, raises sub-petrochemical industry with the enterprise that produces, and estimates about 5000t/y.PP-R special material for tube market demand was between 30,000～40,000 t in 2005.
PP-R in use mainly exists the problem of poor heat resistance, in some in particular cases (as the conveying of the hot water of northern area in winter, heating installation etc.), when the temperature of delivery medium surpasses 100 ℃, then must carry out modification to the PP-R material, improve its thermotolerance, could satisfy service requirements.In addition, its mechanical property is also not ideal enough.Dispersion agents such as nanoclay that patent 01129106.0 organises by interpolation (montmorillonite) and paraffin carry out compound to Co-polypropylene, obtained the special material for nano polypropylene tubing material of better performances.
Three, summary of the invention
Manage the deficiency of resin dedicated performance at existing PP-R, the purpose of this invention is to provide a kind of is body material with atactic copolymerized polypropene (PP-R), by with the compound resistance toheat that improves the effective resin of PP-R of stratiform mica, modified Nano whisker and nano particle, improve the preparation method of the mechanical property such as elongation at break, bending strength of resin simultaneously.
Content of the present invention is mainly:
High heat-durable resin dedicated to PP-R tube provided by the present invention mainly is made up of PP-R resin, stratiform mica, modified Nano whisker, inorganic antiaging agent, dispersion agent, and the mass percent of each component in modified resin dedicated to PP-R tube is:
PP-R resin 85～97%
Modified Nano whisker 1～5%
Stratiform mica 1～7%
Inorganic antiaging agent 0.5～3%
Dispersion agent 0.5～1%
Above-mentioned said PP-R resin preferably melt flow rate is the PP-R resin of 0.35 ± 0.1g/10min.
Modified Nano whisker in the above-mentioned prescription is that inorganic nano whisker is carried out the surface modification gained by coupling agent.Used whisker can be the nano-calcium carbonate calcium pyroborate, also the mixture of two kinds of nano zinc oxide crystal whisker or they; Used whisker length is 2～100 μ m, and diameter is 10～400m; The used coupling agent of modification can be silane coupling agent, also KH560 coupling agent or stearic acid.
Stratiform mica used in the above-mentioned prescription is mainly sericite, its granularity 〉=600 orders, radius-thickness ratio＞5: 1.
Used dispersion agent can be polyethylene wax, paraffin or polyacrylamide in the above-mentioned prescription.
Used inorganic antiaging agent can be the gold redrock nano-titanium dioxide with ultraviolet-resistent property in the above-mentioned prescription, also can be nano zine oxide, or both composite powders; The particle diameter of nanometer rutile nano titanium oxide and nano zine oxide is less than 50nm.
The preparation method of nano whisker modified resin dedicated to PP-R tube is:
1. coupling agent is dissolved in the organic solvent (as ethanol), carry out ultra-sonic dispersion after again whisker being put into, filter and after oven dry under 100 ℃, promptly get the nano whisker of modification;
2. with the evenly pre-mixing in homogenizer of the nano whisker of PP-R resin, stratiform mica, modification, inorganic antiaging agent and dispersion agent;
3. solid mixture fully blend melting under molten state;
With the material after the blend melting with screw rod extrude, granulation.
The invention has the advantages that:
1. used stratiform mica is the flaky texture of two dimension, and radius-thickness ratio reaches, can and the PP-R melt between to carry out intercalation compound; The mica powder granularity is less, greater than 600 orders, can realize the dispersion of submicron order; The stratiform mica has stronger heat-proof quality simultaneously.
2. nano whisker is an one-dimensional material, and its length is 2～100 μ m, is fibrous on length, helps forming in matrix the spatial network structure; The nano whisker diameter is 10～400nm, is nano-scale on diameter, does not influence the continuity of PP-R resin matrix; Used nano whisker is after coupling agent modified, and the surface is the lipophilicity structure, can have dispersed preferably in matrix.
3. gold redrock nano-titanium dioxide and nano zine oxide have ultraviolet-resistent property, can make resin have ageing resistance preferably; Simultaneously the two be particle diameter less than 50nm, be the zero dimension material.
4. therefore, intercalation by stratiform mica two-dimensional slice shape structure is compound, nano crystal whisker material forms the spatial network structure in matrix, the dispersiveness of zero-dimension nano titanium dioxide and the nano zine oxide nanoscale in matrix, and the stratiform mica has the combined action of stronger heat-proof quality, improved the thermal property and the mechanical property of PP-R resin greatly.
After the present invention finished, every after testing performance all was better than unmodified PP-R resin, and concrete technical feature parameter sees attached list 1.
Four, subordinate list explanation
Subordinate list 1 is that the performance of the PP-R resin of the prepared high heat-durable resin dedicated to PP-R tube of the present invention and coventional type PP-R resin and import compares.
Five, embodiment
Be several embodiments of the present invention below, it may be noted that embodiment further specifies of the present invention, rather than limitation of the present invention, in following examples, each percentages of ingredients all is weight percentage.
Embodiment 1:
Common PP-R resin (melt flow rate is 0.30g/10min) 93%
Modified nano calcium carbonate whisker 2.5%
Stratiform mica 3%
Gold redrock nano-titanium dioxide (d
50=20nm) 1%
Polyacrylamide 0.5%
Wherein used modified nano calcium carbonate whisker is through silane coupler modified, and the length of used nano-calcium carbonate calcium pyroborate is 0.5 μ m, and diameter is 10～50nm; Stratiform micaceous granularity is 600 orders, and radius-thickness ratio is 6: 1.
Nano-calcium carbonate calcium pyroborate, gold redrock nano-titanium dioxide, PP-R resin and dispersion agent evenly pre-mixing in homogenizer with stratiform mica, modification; Solid mixture is fully blend melting under molten state; With the material after the blend melting with screw rod extrude, granulation.
Embodiment 2:
Common PP-R resin (melt flow rate is 0.35g/10min) 91%
Modified nano zinc oxide whisker 2.5%
Stratiform mica 4%
Gold redrock nano-titanium dioxide (d
50=40nm) 2%
Polyacrylamide 0.5%
Wherein used stratiform micaceous granularity is 800 orders, and radius-thickness ratio is 6: 1; The modified nano zinc oxide whisker is coupling agent modified through KH560, and used nano zinc oxide crystal whisker is three-dimensional four needle-likes, the centrosome diameter 300nm of whisker, and needles length is 15 μ m.
Nano zinc oxide crystal whisker, gold redrock nano-titanium dioxide, PP-R resin and dispersion agent evenly pre-mixing in homogenizer with stratiform mica, modification; Solid mixture is fully blend melting under molten state; With the material after the blend melting with screw rod extrude, granulation.
Subordinate list 1:
Claims (6)
1. the PP-R of high heat resistance pipe is resin dedicated, it is characterized in that it is made up of the raw material of weight ratio:
PP-R resin 85～97%
Modified Nano whisker 1～5%
Stratiform mica 1～7%
Inorganic antiaging agent 0.5～3%
Dispersion agent 0.5～1%
2. the PP-R of high heat resistance according to claim 1 pipe is resin dedicated, it is characterized in that used stratiform mica is mainly sericite, its granularity 〉=600 orders, radius-thickness ratio＞5: 1.
3. the PP-R of high heat resistance according to claim 1 pipe is resin dedicated, it is characterized in that used whisker can be the nano-calcium carbonate calcium pyroborate in the described modified Nano whisker, also the mixture of two kinds of nano zinc oxide crystal whisker or they; Whisker length is 2～100 μ m, and diameter of whiskers is 10～400nm.
4. the PP-R of high heat resistance according to claim 1 pipe is resin dedicated, it is characterized in that the melt flow rate of described PP-R resin is 0.35 ± 0.1g/10min.
5. the PP-R of high heat resistance according to claim 1 pipe is resin dedicated, it is characterized in that described inorganic antiaging agent can be the gold redrock nano-titanium dioxide with ultraviolet-resistent property, also can be nano oxidized 1 zinc, or both composite powders; The particle diameter of nanometer rutile nano titanium oxide and nano zine oxide is less than 50nm.
6. the PP-R of a high heat resistance manages resin dedicated preparation method, it is characterized in that described preparation method is as follows:
(1) coupling agent is dissolved in the organic solvent (as ethanol), carry out ultra-sonic dispersion after again whisker being put into, filter and after oven dry under 100 ℃, promptly get the nano whisker of modification;
(2) with the evenly pre-mixing in homogenizer of nano whisker, stratiform mica, inorganic antiaging agent, PP-R resin and the dispersion agent of modification;
(3) solid mixture fully blend melting under molten state;
(4) with the material after the blend melting with screw rod extrude, granulation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200610020942 CN1865337A (en) | 2006-04-30 | 2006-04-30 | High heat-durable resin dedicated to PP-R tube and its preparation method |
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| CN 200610020942 CN1865337A (en) | 2006-04-30 | 2006-04-30 | High heat-durable resin dedicated to PP-R tube and its preparation method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130000734A1 (en) * | 2010-02-09 | 2013-01-03 | Tronc Frederic | Flexible underwater pipe including a layer including a polymer resin including surface-modified titanium nanoparticles |
| CN103383023A (en) * | 2013-07-29 | 2013-11-06 | 刘忠斌 | Antibiosis polypropylene random (PPR) drinking water pipe |
| CN103951889A (en) * | 2014-04-29 | 2014-07-30 | 浙江普耐姆塑业股份有限公司 | Composite particle modified polypropylene material and preparation method thereof |
| CN104151703A (en) * | 2014-08-08 | 2014-11-19 | 嘉兴市金阳塑胶管业有限公司 | MPP (modified polypropylene) electric power tube with high heat resistance |
| CN104725725A (en) * | 2015-03-26 | 2015-06-24 | 湖州科达化工燃料有限公司 | Novel modified polypropylene (PP) pipe and preparation method thereof |
| CN106009288A (en) * | 2016-07-14 | 2016-10-12 | 瑞安市智造科技有限公司 | Polypropylene composite material for high-pressure resistant water supply pipe and preparation method of polypropylene composite material |
| CN110818925A (en) * | 2019-10-14 | 2020-02-21 | 深圳市峰泳科技有限公司 | High-voltage-resistant polymer-based dielectric material and preparation method thereof |
| CN111154171A (en) * | 2019-12-31 | 2020-05-15 | 安徽蒙特尔电缆集团有限公司 | Aging-resistant and cracking-resistant sheath material for mineral insulated cable and preparation method thereof |
-
2006
- 2006-04-30 CN CN 200610020942 patent/CN1865337A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130000734A1 (en) * | 2010-02-09 | 2013-01-03 | Tronc Frederic | Flexible underwater pipe including a layer including a polymer resin including surface-modified titanium nanoparticles |
| US9266302B2 (en) | 2010-02-09 | 2016-02-23 | Technip France | Flexible underwater pipe including a layer including a polymer resin including surface-modified titanium nanoparticles |
| CN103383023A (en) * | 2013-07-29 | 2013-11-06 | 刘忠斌 | Antibiosis polypropylene random (PPR) drinking water pipe |
| CN103951889A (en) * | 2014-04-29 | 2014-07-30 | 浙江普耐姆塑业股份有限公司 | Composite particle modified polypropylene material and preparation method thereof |
| CN103951889B (en) * | 2014-04-29 | 2015-04-01 | 浙江普耐姆塑业股份有限公司 | Composite particle modified polypropylene material and preparation method thereof |
| CN104151703A (en) * | 2014-08-08 | 2014-11-19 | 嘉兴市金阳塑胶管业有限公司 | MPP (modified polypropylene) electric power tube with high heat resistance |
| CN104725725A (en) * | 2015-03-26 | 2015-06-24 | 湖州科达化工燃料有限公司 | Novel modified polypropylene (PP) pipe and preparation method thereof |
| CN106009288A (en) * | 2016-07-14 | 2016-10-12 | 瑞安市智造科技有限公司 | Polypropylene composite material for high-pressure resistant water supply pipe and preparation method of polypropylene composite material |
| CN110818925A (en) * | 2019-10-14 | 2020-02-21 | 深圳市峰泳科技有限公司 | High-voltage-resistant polymer-based dielectric material and preparation method thereof |
| CN110818925B (en) * | 2019-10-14 | 2020-11-24 | 深圳市峰泳科技有限公司 | High-voltage-resistant polymer-based dielectric material and preparation method thereof |
| CN111154171A (en) * | 2019-12-31 | 2020-05-15 | 安徽蒙特尔电缆集团有限公司 | Aging-resistant and cracking-resistant sheath material for mineral insulated cable and preparation method thereof |
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