CN1361197A - Polypropylene composition for hot water pipe and its prepn - Google Patents
Polypropylene composition for hot water pipe and its prepn Download PDFInfo
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- CN1361197A CN1361197A CN 00129469 CN00129469A CN1361197A CN 1361197 A CN1361197 A CN 1361197A CN 00129469 CN00129469 CN 00129469 CN 00129469 A CN00129469 A CN 00129469A CN 1361197 A CN1361197 A CN 1361197A
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Abstract
The present invention relates to polypropylene composite and its preparation. By using the material includes random polypropylene, antioxidant, assistant and pigment particle, the present invention can prepare polypropylene composite with excellent mechanical property, high temperature creeping property, heat aging property, extrusion processing property and low cost. It is used in producing hot water pipeline and pipe parts. One two-step process of preparing the said composite is also provided to ensure the homogeneous mixing of various components and the excellent property of the product.
Description
The present invention relates to polypropene composition and preparation method thereof.Specifically, the present invention relates to polypropylene (PP), oxidation inhibitor and auxiliary agent etc., preparation has the polypropene composition of good heat resistance energy and long-term aging performance, is used to prepare hot water pipeline system tubing and pipe fitting.
Acrylic resin has under density is low, temperature of fusion is high, good thermotolerance, chemical stability, the room temperature and is insoluble to common solvent, rigidity, hardness, the characteristics that weldability is good, thereby the PP pipe is usually used in hot water heater or heat exchanger in waterworks, the floor.
The sixties having occurred first-generation PP pipeline group compound, is to adopt homopolymerization PP to add an amount of impact modifier to form through blend, is called PP-H (I type); The seventies occurs s-generation PP pipeline group compound, adopted block copolymerization polypropylene, be called PP-B (II type); Bring into use the third generation polypropylene random copolymer pipeline composition nineties, be called PP-R (III type), be to adopt advanced gas-phase copolymerization technology, make propylene and ethene in heating, copolymerization obtains under pressure and the catalyst action, ethene embeds in the long-chain of propylene randomly among the PP-R, polyacrylic hardness and melt temperature have been reduced, improved the high temperature resistant creep properties of material, and the advantage with easy welding is under certain temperature and interior pressure long term, the PP-R pipe is managed than PP-H, the strength retrogression of PP-B pipe is slower, i.e. longer service life under identical temperature and inside casing spare, the PP-R pipeline is at the hot water of carrying 70 ℃, pressing in long-term can reach 50 years following work-ing life for the 1MPa condition, is comparatively ideal plastic hot water pipe composition.
European patent EP 0702056 is heat-resisting about preparing, the plastics of hot-water line particularly, this invents described hot-water line composition is polyethylene by 1～10% (weight), the blend polymer that the polybutene of the polypropylene of 5～75% (weight) and 5～75% (weight) is formed.This mixture has good high temperature creep property, good low-temperature impact-resistant performance, good moulding processability.But the not mentioned heatproof air aging performance of this patent, for hot-water line, the heat oxygen aging resistance of material is a very important index, it directly has influence on the work-ing life of tubing.And by several materials mixed material, cause the change of material long-term behaviour bad owing to the difference of material degree of crystallinity makes the blend phase interface can produce defective.
Russian patent SU 1808837 described hot-water line compositions are by 0.1～0.5% many (dithio purpurin), and 19.5～19.9% LDPE and rest part are that polypropylene is formed.The major advantage of this invention is to have improved the hot mechanical aging stability of co-mixing system.But same LDPE and PP degree of crystallinity differ bigger owing to there is a large amount of polyethylene to exist in the blend, and both are difficult to even blend, and the blend phase interface also can produce defective and cause the change of material long-term behaviour bad.
The object of the present invention is to provide a kind of polypropene composition, it is compared with existing this based composition, adopted single atactic copolymerized polypropene to do base resin, and sneak into specific antioxidant systems to improve its long-term heat resistance energy, make composition have excellent mechanical property, high temperature resistant creep property, heat aging property and extrude processing characteristics, and cost is lower.
The present invention also aims to provide a kind of two-step approach to prepare the method for the present composition, this method can guarantee that various components mix, and the composition properties of preparing is good.
According to of the requirement of polypropylene thermal water pipe to use properties, should select the less atactic copolymerized polypropene of melt flow rate (MFR) as base resin, select for use specific antioxidant systems must reach the composition of the object of the invention simultaneously.
Composition provided by the invention comprises (parts by weight):
Atactic copolymerized polypropene: 100;
Oxidation inhibitor: 0.2～2.0, better be 0.3～1.5, preferably 0.3～0.9;
Photostabilizer: 0～1.0, preferably 0.1～0.5.
Colour batch: 0～6, preferably 0.5～4.
Atactic copolymerized polypropene: melt flow rate (MFR) (230 ℃, the 2.16Kg counterweight) 0.1～1.0g/10min better is 0.1～0.8g/10min, preferably 0.2～0.5g/10min; 130～150 ℃ of melt temperatures (DSC measures by difference formula scanning calorimeter) better are 135～145 ℃; Preferably 138～144 ℃; 731cm is arranged on infrared spectra
-1Or 733cm
-1Absorption peak, do not have tangible 721cm
-1And 719cm
-1Absorption peak; Ethylene content is 2.0～8.0 (wt) %, better is 2.5～6.5 (wt) %, and preferably 3.0～6.0 (wt) % does not contain alpha-olefin and other group in the polymkeric substance except that ethene and propylene.731cm
-1The place is the segmental absorption peak that ethene and propylene head-head join, 733cm
-1The place is the segmental absorption peak that ethene and propylene head-tail join, at 721cm
-1The place is the absorption peak of 5 carbon and above long-chain thereof, 719cm
-1Absorption peak be poly characteristic peak, be the absorption peak of ethene long-chain.731cm
-1Or 733cm
-1Absorption peak be the characteristic peak of atactic copolymerized polypropene, plant the tubing that atactic copolymerized polypropene makes thus and have better heat-resisting stability and high temperature resistant creep property.721cm
-1And 719cm
-1Absorption peak be the absorption peak of ethene long-chain because there is the weak link of long ethylene chain, when polypropylene contains tangible 721cm on infrared spectra
-1And 719cm
-1Absorption peak the time, plant the high temperature resistant creep properties variation of tubing that material is made thus.
Antioxidant systems of the present invention is selected from Hinered phenols antioxidant, phosphite ester kind antioxidant and thioesters kind antioxidant, the fusing point of Hinered phenols antioxidant is between 100 ℃～260 ℃ in the antioxidant systems, can from following material, choose: four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; (2,4,6-trioxy--1,3,5-triazines-1,3,5 (2H, 4H, 6H)-three base) trivinyl three [3-(3, the 5-di-tert-butyl-hydroxy phenyl) acrylate; 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyl benzyl) benzene; 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone; 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) triketone.In the above-mentioned oxidation inhibitor of the optional usefulness of Hinered phenols antioxidant 1～3 kind when selecting more than 2 kinds Hinered phenols antioxidant for use, can mix by arbitrary proportion.
The phosphite ester kind antioxidant fusing point can be chosen from following material greater than 160 ℃ in the antioxidant systems of the present invention: three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester; Tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester.
Thioesters kind antioxidant in the antioxidant systems can be chosen from following material: two (18) esters of thio-2 acid; Tyox B.
When with Hinered phenols antioxidant (fusing point is between 100 ℃～260 ℃) and phosphite ester kind antioxidant, Hinered phenols antioxidant is selected two kinds at least for use, available arbitrary proportion mixes, the weight ratio of Hinered phenols antioxidant and phosphite ester kind antioxidant is 1: (0.1～10), better be 1: (0.2～8), preferably 1: (0.3～5), can not use photostabilizer this moment, and the ratio of this antioxidant systems and photostabilizer is: 1: (0～0.5).
When with Hinered phenols antioxidant (fusing point is between 100 ℃～200 ℃), phosphite ester kind antioxidant and thioesters kind antioxidant, used weight ratio is: Hinered phenols antioxidant: (phosphite ester kind antioxidant and thioesters kind antioxidant)=1: (0.1～15), better be 1: (0.3～10), preferably 1: (0.5～6), wherein the ratio of phosphite ester kind antioxidant and thioesters kind antioxidant is: 1: (0.1～5); During with this antioxidant systems, must use photostabilizer, the ratio of this antioxidant systems and photostabilizer is 1: (0.1～5) better is 1: (0.2～4), preferably 1: (0.3～3).
Select for use above-mentioned antioxidant systems in PP-R, can play good synergy, make composition have good long-term heatproof air aging performance and high temperature resistant creep property.
The used photostabilizer of the present invention can be selected hindered amine light stabilizer for use, can choose from following material: two (2,2,6,6-tetramethyl--4-piperidyl) sebate; Succinic Acid and (4-hydroxyl-2,2,6, the polymkeric substance of 6-tetramethyl--1-piperidines alcohol; Poly--[6-[(1,1,3,3-tetramethyl butyl)-imino-]-1,3,5 triazines-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6, the 6-tetramethyl-piperidyl)-imino-] }.Selected three kinds of photostabilizers are the high-molecular weight photostabilizer, have stability preferably, with above-mentioned said antioxidant systems synergistic effect are preferably arranged.
The used Masterbatch of the present invention is the commercially available prod, and its base-material is a polypropylene, can be grey, red-brown, blueness, black etc.
Preparation method of composition of the present invention comprises: adopt the two-step approach preparation to finish, the first step is to prepare aid master batches earlier, the PP-R powder in stirring, is mixed high mixing time 3～5 minutes, extruding pelletization with auxiliary agent, 180～240 ℃ of extrusion temperatures, better be 180～220 ℃, prepare masterbatch, then with aid master batches again with PP-R pellet and colour batch blend granulation, 180～250 ℃ of extrusion temperatures better are 180～230 ℃.Adopt two-step approach that various components are mixed.
Adopt the PP-R composition of above method preparation to have the good long term heat aging property, behind 150 ℃, 1000h thermal ageing the reserved elongation at break of material greater than 80%, the high temperature resistant creep property of material, welding property is good.
The present composition can be used as cold and hot water pipeline system in the buildings, comprises industry and civilian hot water or cold water, tap water and heating heating system.
With embodiment effect of the present invention is described below, the embodiment performance is as shown in table 1.Embodiment 1 (is parts by weight, as follows): 100 part of four [β-(3 of PP resin (MI=0.3g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.2 part 1 of pentaerythritol ester, 3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) triketone is 0.15 part three (2, the 4-di-tert-butyl-phenyl) 0.1 part of poly--{ [6-[(1 of 0.2 part of Tyox B of phosphorous acid ester, 1,3, the 3-tetramethyl butyl)-and imino-]-1,3,5 triazines-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6,6-tetramethyl-piperidyl)-imino-] 2 parts of 0.1 part of colour batches
100 part of four [β-(3 of embodiment 2PP resin (MI=0.3g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.2 part three (2 of pentaerythritol ester, the 4-di-tert-butyl-phenyl) 0.3 part of Tyox B of phosphorous acid ester is 0.1 part two (2,2,6,6-tetramethyl--4-piperidyl) 0.2 part of colour batch of sebate is 2 parts
100 part of four [β-(3 of embodiment 3PP resin (MI=0.3g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.2 part three (2 of pentaerythritol ester, the 4-di-tert-butyl-phenyl) two (18) esters of 0.1 part of thio-2 acid of phosphorous acid ester are 0.4 part two (2,2,6,6-tetramethyl--4-piperidyl) 0.2 part of colour batch of sebate is 2 parts
100 part of four [β-(3 of embodiment 4PP resin (MI=0.3g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.2 part 1 of pentaerythritol ester, 3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyl benzyl) benzene is 0.25 part 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) triketone is 0.15 part three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.2 part of colour batch, 3 parts of embodiment 5PP resin (MI=0.37g/10min) is 100 part (2,4,6-trioxy--1,3,5-triazine-1,3,5 (2H, 4H, 6H)-three base) [3-(3 for trivinyl three, the 5-di-tert-butyl-hydroxy phenyl) acrylate is 0.2 part three (2, the 4-di-tert-butyl-phenyl) 0.1 part of Succinic Acid of 0.4 part of Tyox B of phosphorous acid ester and (4-hydroxyl-2,2,6, the polymkeric substance Succinic Acid of 6-tetramethyl--1-piperidines alcohol and (4-hydroxyl-2,2,6,2 parts of 0.1 part of colour batches of polymkeric substance of 6-tetramethyl--1-piperidines alcohol
100 part 1 of embodiment 6PP resin (MI=0.37g/10min), 3,5-three (the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-0.3 part of tetramethylolmethane diphosphite of triketone two (2,4-di-tert-butyl phenyl) 0.1 part of Succinic Acid of 0.4 part of Tyox B of ester and (4-hydroxyl-2,2,6, the polymkeric substance Succinic Acid of 6-tetramethyl--1-piperidines alcohol and (4-hydroxyl-2,2,6,1 part of 0.2 part of colour batch of polymkeric substance of 6-tetramethyl--1-piperidines alcohol
100 part (2 of embodiment 7PP resin (MI=0.37g/10min), 4,6-trioxy--1,3,5-triazine-1,3,5 (2H, 4H, 6H)-three base) [3-(3 for trivinyl three, the 5-di-tert-butyl-hydroxy phenyl) acrylate is 0.3 part three (2, the 4-di-tert-butyl-phenyl) 0.1 part of poly--{ [6-[(1 of 0.3 part of Tyox B of phosphorous acid ester, 1,3, the 3-tetramethyl butyl)-and imino-]-1,3,5 triazines-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6, the 6-tetramethyl-piperidyl)-imino-] 0.2 part of 100 part of four [β-(3 of 2 parts of embodiment 8PP of colour batch resin (MI=0.37g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.3 part three (2 of pentaerythritol ester, the 4-di-tert-butyl-phenyl) 0.4 part of Tyox B of phosphorous acid ester is 0.1 part two (2,2,6,6-tetramethyl--4-piperidyl) 0.2 part of colour batch of sebate is 2 parts
100 part 1 of embodiment 9PP resin (MI=0.25g/10min), 3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) 0.2 part of four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester of triketone is 0.2 part 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyl benzyl) 0.2 part of three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester of benzene is 0.2 part
100 part of four [β-(3 of embodiment 10PP resin (MI=0.25g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.3 part 1 of pentaerythritol ester, 3,5-three (the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-0.2 part of tetramethylolmethane diphosphite of triketone two (2,4-di-tert-butyl phenyl) 0.2 part of Succinic Acid of 0.3 part of Tyox B of ester and (4-hydroxyl-2,2,6, the polymkeric substance Succinic Acid of 6-tetramethyl--1-piperidines alcohol and (4-hydroxyl-2,2,6,4 parts of 0.5 part of colour batches of polymkeric substance of 6-tetramethyl--1-piperidines alcohol
100 part of four [β-(3 of embodiment 11PP resin (MI=0.25g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.2 part 1 of pentaerythritol ester, 3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyl benzyl) 0.3 part of colour batch of 0.25 part of three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester of benzene is 2 parts
100 part 1 of embodiment 12PP resin (MI=0.25g/10min), 3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) 0.20 part of four [β-(3 of triketone, 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.15 part 1 of pentaerythritol ester, 3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyl benzyl) 0.45 part of colour batch of 0.55 part of three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester of benzene is 2 parts
100 part of four [β-(3 of embodiment 13PP resin (MI=0.25g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.2 part three (2 of pentaerythritol ester, the 4-di-tert-butyl-phenyl) two 0.2 part of Succinic Acid of (18) ester of 0.6 part of thio-2 acid of phosphorous acid ester and (4-hydroxyl-2,2,6, the polymkeric substance Succinic Acid of 6-tetramethyl--1-piperidines alcohol and (4-hydroxyl-2,2,6,2.5 parts of 0.3 part of colour batches of polymkeric substance of 6-tetramethyl--1-piperidines alcohol
100 part 1 of embodiment 14PP resin (MI=0.25g/10min), 3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) 0.25 part of four [β-(3 of triketone, 5 di-tert-butyl-hydroxy phenyls) propionic acid] 2 parts of 0.2 part of colour batches of 0.3 part of three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester of pentaerythritol ester
100 part of four [β-(3 of embodiment 15PP resin (MI=0.25g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.25 part 1 of pentaerythritol ester, 3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyl benzyl) 0.25 part of colour batch of 0.25 part of three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester of benzene is 3 parts
100 part of four [β-(3 of embodiment 16PP resin (MI=0.40g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.2 part of tetramethylolmethane diphosphite of pentaerythritol ester two (2,4-di-tert-butyl phenyl) 0.2 part of poly--{ [6-[(1 of 0.2 part of Tyox B of ester, 1,3, the 3-tetramethyl butyl)-and imino-]-1,3,5 triazines-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6,6-tetramethyl-piperidyl)-imino-] 0.2 part
100 part of four [β-(3 of embodiment 17PP resin (MI=0.40g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.2 part three (2 of pentaerythritol ester, the 4-di-tert-butyl-phenyl) 0.1 part of Tyox B of phosphorous acid ester is 0.3 part two (2,2,6,6-tetramethyl--4-piperidyl) 0.2 part of colour batch of sebate is 2 parts
100 part of four [β-(3 of embodiment 18PP resin (MI=0.40g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.1 part (2 of pentaerythritol ester, 4,6-trioxy--1,3,5-triazine-1,3,5 (2H, 4H, 6H)-three base) [3-(3 for trivinyl three, the 5-di-tert-butyl-hydroxy phenyl) acrylate is 0.2 part three (2, the 4-di-tert-butyl-phenyl) 0.1 part of poly--{ [6-[(1 of 0.1 part of Tyox B of phosphorous acid ester, 1,3, the 3-tetramethyl butyl)-and imino-]-1,3,5 triazines-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6,6-tetramethyl-piperidyl)-imino-] 0.1 part
100 part of four [β-(3 of embodiment 19PP resin (MI=0.45g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.25 part of tetramethylolmethane diphosphite of pentaerythritol ester two (2,4-di-tert-butyl phenyl) 0.25 part of poly--{ [6-[(1 of 0.20 part of Tyox B of ester, 1,3, the 3-tetramethyl butyl)-and imino-]-1,3,5 triazines-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6,6-tetramethyl-piperidyl)-imino-] 1 part of 0.1 part of colour batch
100 part of four [β-(3 of embodiment 20PP resin (MI=0.45g/10min), 5 di-tert-butyl-hydroxy phenyls) propionic acid] 0.4 part three (2 of pentaerythritol ester, the 4-di-tert-butyl-phenyl) 0.2 part of poly--{ [6-[(1 of 0.1 part of Tyox B of phosphorous acid ester, 1,3, the 3-tetramethyl butyl)-and imino-]-1,3,5 triazines-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6,6-tetramethyl-piperidyl)-imino-] 1 part of 0.2 part of colour batch
Table 1. embodiment performance
Annotate 1:230 ℃, 2.16Kg; Annotate 2; 150 ℃, behind the 1000h thermo-oxidative ageing,
| Project | Melt flow rate (MFR) 1) | Yielding stress | Elongation at break | Reserved elongation at break 2) | Hydrostatic test 3) | Oxidation induction period (220 ℃, Al) |
| Unit | ??g/10min | ??MPa | ????％ | ????％ | By | ????Min |
| Testing standard | ??ISO?1133 | ?ISO?527 | ?ISO?527 | ??ISO?180 | By | ASTM?D3895 |
| Embodiment 1 | ????0.31 | ????27.0 | ????440 | ????80.2 | By | ????17.3 |
| Embodiment 2 | ????0.31 | ????26.9 | ????437 | ????80.0 | By | ????17.9 |
| Embodiment 3 | ????0.32 | ????27.0 | ????440 | ????81.3 | By | ????17.3 |
| Embodiment 4 | ????0.32 | ????26.3 | ????440 | ????84.5 | By | ????18.2 |
| Embodiment 5 | ????0.39 | ????28.1 | ????430 | ????80.6 | By | ????20.5 |
| Embodiment 6 | ????0.38 | ????27.9 | ????435 | ????80.3 | By | ????23.4 |
| Embodiment 7 | ????0.39 | ????28.3 | ????440 | ????81.6 | By | ????24.5 |
| Embodiment 8 | ????0.39 | ????27.9 | ????437 | ????82.1 | By | ????24.6 |
| Embodiment 9 | ????0.26 | ????25.8 | ????440 | ????84.5 | By | ????21.5 |
| Embodiment 10 | ????0.28 | ????26.0 | ????450 | ????83.1 | By | ????30.2 |
| Embodiment 11 | ????0.27 | ????25.3 | ????445 | ????83.4 | By | ????20.5 |
| Embodiment 12 | ????0.25 | ????25.6 | ????450 | ????85.8 | By | ????28.6 |
| Embodiment 13 | ????0.25 | ????26.0 | ????465 | ????82.4 | By | ????32.0 |
| Embodiment 14 | ????0.26 | ????26.1 | ????460 | ????84.7 | By | ????27.6 |
| Embodiment 15 | ????0.28 | ????25.8 | ????467 | ????85.3 | By | ????24.7 |
| Embodiment 16 | ????0.40 | ????28.3 | ????430 | ????81.0 | By | ????23.5 |
| Embodiment 17 | ????0.41 | ????28.2 | ????425 | ????80.0 | By | ????20.6 |
| Embodiment 18 | ????0.40 | ????27.9 | ????420 | ????80.6 | By | ????19.0 |
| Embodiment 19 | ????0.45 | ????28.6 | ????410 | ????81.0 | By | ????21.7 |
| Embodiment 20 | ????0.46 | ????28.8 | ????415 | ????80.2 | By | ????23.4 |
Reserved elongation at break=(elongation at break under the elongation at break/standard environment behind the thermo-oxidative ageing) * 100%; Annotate 3:95 ℃, ring stress 3.5MPa, 1000h, tubing is non-leakage, does not break.
Claims (20)
1. polypropylene composition for hot water pipe comprises:
(1) atactic copolymerized polypropene: 100;
(2) oxidation inhibitor: 0.2～2.0;
(3) photostabilizer: 0～1.0;
(4) colour batch: 0～6;
Said components is all in parts by weight.
2. polypropene composition according to claim 1 is characterized in that atactic copolymerized polypropene at 230 ℃, and the melt flow rate (MFR) under the 2.16Kg counterweight condition is: 0.1～1.0g/10min.
3. as polypropene composition as described in the claim 2, it is characterized in that atactic copolymerized polypropene at 230 ℃, the melt flow rate (MFR) under the 2.16Kg counterweight condition is: 0.1～0.8g/10min.
4. as polypropene composition as described in the claim 3, it is characterized in that atactic copolymerized polypropene at 230 ℃, the melt flow rate (MFR) under the 2.16Kg counterweight condition is: 0.2～0.5g/10min.
5. polypropene composition according to claim 1 is characterized in that by the melt temperature that difference formula scanning calorimeter DSC measures being: 130～150 ℃; Weight ethylene content is 2.0～8.0% in the polypropylene; 731cm is arranged on infrared spectra
-1Or 733cm
-1Absorption peak, do not have tangible 721cm
-1And 719cm
-1Absorption peak.
6. as polypropene composition as described in the claim 5, it is characterized in that by the melt temperature that difference formula scanning calorimeter DSC measures being: 135～145 ℃; Weight ethylene content is 2.5～6.5% in the polypropylene.
7. as polypropene composition one of as described in the claim 6, it is characterized in that by the melt temperature that difference formula scanning calorimeter DSC measures being: 138～144 ℃; Weight ethylene content is 3.0～6.0% in the polypropylene.
8. polypropene composition according to claim 1, it is characterized in that antioxidant systems is made up of at least two kinds of Hinered phenols antioxidants and phosphite ester kind antioxidant, the weight ratio of Hinered phenols antioxidant and phosphite ester kind antioxidant is 1: 0.1～10, and the parts by weight of antioxidant systems in composition are: 0.3～1.5.
9. as polypropene composition as described in the claim 8, the weight ratio that it is characterized in that Hinered phenols antioxidant and phosphite ester kind antioxidant is 1: 0.2～8, and the parts by weight of antioxidant systems in composition are: 0.3～0.9.
10. as polypropene composition as described in the claim 9, it is characterized in that Hinered phenols antioxidant and phosphite ester kind antioxidant weight ratio are 1: 0.3～5.
11. polypropene composition according to claim 1, it is characterized in that used antioxidant systems is Hinered phenols antioxidant, phosphite ester kind antioxidant and thioesters kind antioxidant, Hinered phenols antioxidant: the ratio of phosphite ester kind antioxidant and thioesters kind antioxidant is 1: 0.1～15, wherein the ratio of phosphite ester kind antioxidant and thioesters kind antioxidant oxidation inhibitor is: 1: 0.1～5, and the parts by weight of antioxidant systems in composition are: 0.3～1.5.
12. as polypropene composition as described in the claim 11, it is characterized in that Hinered phenols antioxidant: the ratio of phosphite ester kind antioxidant and thioesters kind antioxidant is 1: 0.3～10, the parts by weight of antioxidant systems in composition are: 0.3～0.9.
13. as polypropene composition as described in the claim 12, it is characterized in that Hinered phenols antioxidant: the ratio of phosphite ester kind antioxidant and thioesters kind antioxidant is 1: 0.5～6.
14., it is characterized in that Hinered phenols antioxidant is selected from four [β-(3,5 di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester as polypropene composition one of as described in claim 1 and 8 to 13; (2,4,6-trioxy--1,3,5-triazines-1,3,5 (2H, 4H, 6H)-three base) trivinyl three [3-(3, the 5-di-tert-butyl-hydroxy phenyl) acrylate; 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyl benzyl) benzene; 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone; 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) triketone; Phosphite ester kind antioxidant is selected from three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester.
15., it is characterized in that the thioesters kind antioxidant is selected from two (18) esters of thio-2 acid, Tyox B as polypropene composition one of as described in the claim 11 to 13.
16. polypropene composition is characterized in that used photostabilizer is a hindered amine light stabilizer according to claim 1, the parts by weight in composition are: 0.1～0.5.
17., it is characterized in that used photostabilizer is selected from: two (2,2,6,6-tetramethyl--4-piperidyl) sebate as polypropene composition as described in the claim 16; Succinic Acid and (4-hydroxyl-2,2,6, the polymkeric substance of 6-tetramethyl--1-piperidines alcohol; Poly--[6-[(1,1,3,3-tetramethyl butyl)-imino-]-1,3,5 triazines-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-amino]-hexylidene-[4-(2,2,6, the 6-tetramethyl-piperidyl)-imino-] }.
18. polypropene composition is characterized in that the colour batch base-material is a polypropylene according to claim 1, the colour batch color is selected from grey, red-brown, blueness and black, and the parts by weight of colour batch in composition are 0.5～4.
19. the preparation method of the described polypropene composition of claim 1 is characterized in that may further comprise the steps:
(1) the PP-R powder is mixed in height stirs with auxiliary agent, mixing time 3～5 minutes,
Extruding pelletization again, 180～240 ℃ of extrusion temperatures are prepared masterbatch;
(2) with aid master batches again with PP-R pellet and colour batch blend granulation, extrusion temperature
180～250℃。
20., it is characterized in that as polypropene composition as described in the claim 19:
(1) the PP-R powder is mixed in height stirs with auxiliary agent, mixing time 3～5 minutes,
Extruding pelletization again, 180～220 ℃ of extrusion temperatures are prepared masterbatch;
(2) with aid master batches again with PP-R pellet and colour batch blend granulation, extrusion temperature
180～230℃。
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| Application Number | Priority Date | Filing Date | Title |
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| CNB001294695A CN1170878C (en) | 2000-12-29 | 2000-12-29 | Polypropylene composition for hot water pipe and its prepn |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001294695A CN1170878C (en) | 2000-12-29 | 2000-12-29 | Polypropylene composition for hot water pipe and its prepn |
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| CN1361197A true CN1361197A (en) | 2002-07-31 |
| CN1170878C CN1170878C (en) | 2004-10-13 |
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| CN101216132B (en) * | 2007-12-29 | 2010-12-15 | 姜晓兵 | Aging-resistant silver-plastic composite pipe |
| CN101638500B (en) * | 2008-07-31 | 2011-05-25 | 中国石油天然气股份有限公司 | Composite auxiliary agent for random copolymerized polypropylene pipe material |
| CN102286173A (en) * | 2011-07-15 | 2011-12-21 | 浙江伟星新型建材股份有限公司 | High weatherproof polypropylene random copolymer (PPR) pipe and preparation method thereof |
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| CN102952323A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | PE-RT (polyethylene of raised temperature resistance) composition and application thereof |
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| CN101638500B (en) * | 2008-07-31 | 2011-05-25 | 中国石油天然气股份有限公司 | Composite auxiliary agent for random copolymerized polypropylene pipe material |
| CN102286173B (en) * | 2011-07-15 | 2013-01-09 | 浙江伟星新型建材股份有限公司 | High weatherproof polypropylene random copolymer (PPR) pipe and preparation method thereof |
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| CN102399394A (en) * | 2011-11-24 | 2012-04-04 | 上海日之升新技术发展有限公司 | High-surface thermal oxidative ageing-resistant glass fiber reinforced polypropylene composite material and preparation method thereof |
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| CN103709520A (en) * | 2012-10-09 | 2014-04-09 | 浙江中德实业有限公司 | Beta PP-R tubular product, and manufacturing method thereof |
| CN102964690A (en) * | 2012-12-05 | 2013-03-13 | 上海日之升新技术发展有限公司 | High-strength corrosion resistance polypropylene composite material and preparation method thereof |
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| CN109517280A (en) * | 2017-09-18 | 2019-03-26 | 中国石化扬子石油化工有限公司 | A kind of hot water pipe as special material and preparation method thereof |
| CN110028751A (en) * | 2018-01-12 | 2019-07-19 | 天津利安隆新材料股份有限公司 | A kind of solid antioxidants composition for C5 Petropols |
| CN112679854A (en) * | 2020-12-28 | 2021-04-20 | 浙江普利特新材料有限公司 | High-heat-resistance and high-weather-resistance polypropylene composition and preparation method thereof |
| CN116063797A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Polypropylene composition, polypropylene material and polypropylene pressure pipe |
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