CN101638500B - Composite auxiliary agent for random copolymerized polypropylene pipe material - Google Patents
Composite auxiliary agent for random copolymerized polypropylene pipe material Download PDFInfo
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Abstract
The invention relates to a composite auxiliary agent for a random copolymerized polypropylene pipe material, which is polymerized by a liquid phase bulk single-loop pipe reactor. The composite auxiliary agent is compounded by the following compound systems in portion by weight: 10 to 40 portions of long-term ageing resistant auxiliary agent, 10 to 30 portions of processing auxiliary agent, 20 to 50 portions of crystal shape transforming agent, and 10 to 30 portions of weather resisting agent, wherein the long-term ageing resistant auxiliary agent is a compound system of a lactone stabilizer, a hindered phenol antioxidant and a nontoxic amine antioxidant; the processing auxiliary agent is one or a mixture of several of fluorine elastomer or low-molecular polymers in random proportion; the weather resisting agent is a compound system of an ultraviolet absorbent in a light stabilizer, an organic nickel stabilizer and a hindered amine stabilizer; and the crystal shape transforming agent is a crystal shape transforming agent transformed from an alpha crystal shape to a beta crystal shape. Therefore, the processing property, the mechanical property, the environmental stress cracking resistance and the long-term ageing resistance of random copolymerized polypropylene resin are remarkably improved.
Description
Technical field:
The present 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.
Background technology:
Random copolymerization PPR hot-water line PP Pipe Compound is after crosslinked polyethylene (PEX), polybutene (PB) special material for tube, the thermoplastic plastic pipe PP Pipe Compound that another is novel, the PPR hot-water line that it is produced has energy-conservation, health, corrosion-resistant, heat-resisting, withstand voltage, long service life, easy for installation, characteristics such as connection is reliable, the recyclable utilization of material are widely used in hot-water line, hot water system pipe, industrial heat water pipe, thermal water tubing, solar house warm water tube etc.
PPR tubing is risen in Europe, and the nineties in 20th century, German Kroes agate phenanthrene (KRAVSSMAFFEI) company succeeds in developing article one propylene copolymer pipe production line in the world.Because pipe performance is superior, cause people's attention, in a few years, German plastic pipe general layout is reorientated, with the competition of other tubing in, PPR tubing leaps to second, adopts PPR tubing in the indoor tap water and the heating of Germany 80% with pipe.Countries in the world are all developed and are produced polypropylene copolymer tubing subsequently, and PPR tubing develops with fast speeds.1998, the Chinese government also sends " about applying the regulation of chemical building material and restriction, the eliminating of outmoded products fast ", require on June 1st, 2000 to rise, zinc-plated and the cast iron pipe of new building forbidding, promote the use of environment-friendly type PPR tubing, under the guiding of national policy, PPR tubing demonstrates powerful vitality on market, its development prospect is very good, businessman also invests one after another and introduces the PPR pipe production line, end up till now, China has and introduces and 130 of homemade PPR production lines, forms 6～70,000 tons PPR tubing throughput.But domestic PP-R tubing ubiquity problems such as poor processability, long-term loss of properties on aging.
Can occur in the PP-R resin forming course of processing because melt strength is low, the thickness of pipe that narrow molecular weight distribution causes is inhomogeneous or the shark skin phenomenon appears in the pipe outer wall and inside pipe wall is rough, in addition because the PP-R hot-water line in use will bear certain hydraulic pressure and environmental aging, so require the PP-R hot-water line to have excellent long-term ageing-resistant performance and the certain ring stress of maintenance, so when producing PP-R tubing, need to add a certain amount of special assistant, to improve the processing characteristics of PP-R, and give the ageing-resistant performance and the mechanical property of tubing excellence, satisfy the service requirements of building trade to PP-R hot water tubing.
--Qiu Xiangyu (" engineering plastics application " 30 (2), 2002, p28～30) having reported the PP-R hot water special material for tube of raising the exploitation of research institute of sub-petrochemical industry company limited is 1050 hours the test of 3.5Mpa by anti-static pressure, but because the degree of crystallinity height, the external force effect such as in use be hit of tubing welding zone easily produces fracture.
--the Young's modulus that Chen Ronghua etc. (" plastics science and technology " 145 (5), 2001, p22～24) report the PP-R heat pipe material of its Development and Production is 800Mpa.
Summary of the invention:
The objective of the invention is to prepare a kind of at existing atactic copolymerized polypropene hot-water line composite assistant, only needing to add a small amount of this composite assistant just can improve melt strength, improve because vinyl monomer adds the irregular poor processability that causes of sequential building block distribution that causes in the macromole at random, the long-term ageing-resistant performance of raising atactic copolymerized polypropene resin makes random copolymerization polypropylene pipe reach rigidity and flexible is well balanced.
Atactic copolymerized polypropene hot-water line of the present invention be the composite of several compound systems with composite assistant: 10～30 parts (wherein said raw material umber is except that specified otherwise for 10～40 parts of long-term ageing-resistant performance auxiliary agents, 10～30 parts of processing aids, 20～50 parts of compound modifying agents and weather resisting agent, be parts by weight) add in the high-speed mixer and stir, mix, obtain atactic copolymerized polypropene hot-water line special compound additive.
Long-term ageing-resistant performance auxiliary agent of the present invention is to be 1: 0.1～10: 0.1～10 compound systems of preparing by lactone stabilizer, Hinered phenols antioxidant and nontoxic amine antioxidants by the quality proportioning, preferred 1: 0.2～5: 0.2～5, preferred 1: 0.5～2: 0.5～2.
Hinered phenols antioxidant of the present invention is that four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4-hydroxy phenyl-3, the 5-di-t-butyl) the positive octadecanol ester of propionic acid, β (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, N, N '-1, [3-(3 for 6-hexylidene-two, the 5-di-tert-butyl-hydroxy phenyl) propionic acid amide], N, [3-(3 for N '-two, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, 3-(3,5-di-t-butyl-4-hydroxyl) propionic acid octadecyl ester, 2,6-di-t-butyl-4-cresols, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2,6 di tert butyl 4 methyl phenol and 4,4 '-several mixture of a kind of or any proportioning in the methylene bis (2,6 di t butyl phenol).
Lactone stabilizer of the present invention is IrganoxHP-136 (benzofuranone derivatives), as a kind of carbon center free radical scavenger, can suppress the caused oxidation of processing in the initial stage.
Antioxidant effect is caused that by its special construction this special construction can produce bigger " steric effect ", makes α-H atom have high reactivity (bond energy of its c h bond is 336kJ/mol, and the bond energy of c h bond is 414kJ/mol usually).Therefore utilize its high reactivity α-H that provides to make the alkyl diradical (R) " quencher " of chain initiation stage generation, the oxidative degradation process of polymkeric substance can be suppressed at the budding stage like this, it catches one is the free radical (R) at center with " carbon ", equaling to have eliminated three is the center free radical with oxygen, thereby plays efficient effect.In stabilization process, this oxidation inhibitor with lactone structure can be caught two free polymer readicals, and the first step is as hydrogen donor, and second step combined with free polymer readical.Obviously, the free radical of the first step formation must just can be finished for second step than free polymer readical is stable.Theory thinks, the stability of this free radical is subjected to that it is sterically hindered, electron resonance structure and electrophilic and the influence of giving electron substituent group.In fact, the free radical that the first step forms is high stability, unbound electron can two adjacent phenyl ring and between move freely on the tertiary butyl etc. on the position, improved the stability of free radical greatly.This free radical is characterized by ESR (electron paramagnetic resonance spectrum (EPR)), can further accept a R free radical and form stable molecule, so its antioxygenation is strong.
Amine antioxidants of the present invention is the derivative of aromatic amine, mainly contains secondary diarylamine, Ursol D, ketoamine, aldehyde amine, naphthylamines, pentanoic, quinoline etc.Though this kind antioxidant antioxygen usefulness is good, variable fat pollutes, so they are used in the less demanding material of goods color more.Can be N; N '-di-sec-butyl-p-phenyl enediamine, secondary-butyl-p-phenylenediamine, 5-methoxyl group-1-indone; 5-chloro-2-methylbenzoxazole; 4-fluoroaniline (antioxidant 3114), dimethyl-two-[right-(2-naphthylamine base)-phenoxy group] silane, N; N-two-betanaphthyl Ursol D, N; N '-two-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, in several mixture of a kind of or any proportioning.
Processing aid of the present invention is several mixture of a kind of or any proportioning in fluoroelastomer, the low-molecular(weight)polymer.
Processing aid of the present invention is that fluoroelastomer is to be the processing aid series of foundation structure with the fluoro containing polymers polymkeric substance, can be several mixture of a kind of or any proportioning among FX-5911, FX-5924, FX-5916, the FPA-102.
Low-molecular(weight)polymer of the present invention can be several mixture of a kind of or any proportioning in low-molecular polypropylene, the low-molecular polyethylene wax.
Compound modifying agent of the present invention is to make alpha-crystal form in the PP-R macromole be converted into the compound modifying agent of beta crystal, it is beta crystal-type nucleater, mainly containing quinacridone red, heptan two metallic soap, some aryl diamide and derivatives class thereof, can be that TMB-4 (substituted aromatic amide class), TMB-5 (substituted benzene amides), new STARNU-100 (aromatic amine), the bright woods in Guangdong that releases of Japanese physics and chemistry company receive the brilliant nucleator WBG of rare earth compounding β that functional materials company produces etc.
Weather resisting agent of the present invention is that the quality proportioning in UV light absorber, organic nickel stablizer and the hindered amines in the photostabilizer is 1: 0.1～10: 0.1～10 compound systems of preparing, preferred 1: 0.2～5: 0.2～5, preferred 1: 0.5～2: 0.5～2.
UV light absorber of the present invention can be 2,4-dihydroxy benaophenonel (UV-0), 2-hydroxyl-4-methoxy benzophenone (UV-9), 2-hydroxyl-4-octyloxy benzophenone (UV-531), 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole (UV-327), 2-(2 '-hydroxyl-3 ', 5 '-the diamyl phenyl) benzotriazole (UV-328), 2-(2 ' hydroxyl-5 '-aminomethyl phenyl) benzotriazole (UV-P), 2-benzotriazole-4-tert-octylphenol (UV-329), 2-(2 '-hydroxyl-3 ' di-t-butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole (UV-328), 2-[2 '-hydroxyl-3 ', 5 ' two (α α-Er Jiajibianji) phenyl] benzotriazole (UV-234), several mixture of a kind of or any proportioning in 2-Phenylbenzimidazole-5-sulfonic acid (UV-T) and 2-(2H-benzotriazole-2-yl)-6-(dodecyl)-4-methylphenol (UV-571).
Organic nickel stablizer of the present invention can be two (3,5-di-t-butyl-4 hydroxybenzyl monoethyl phosphate) nickel, dimercapto isooctyl acetate, dioctyltin, 2,2 '-thiobis (uncle's 4-octyl phenol) n-Butyl Amine 99 nickel salt, two (right-three grades of octyl phenols)-2,2 '-thioether n-Butyl Amine 99 nickel salt and N, several mixture of a kind of or any proportioning in the N-second, n-butyl dithiocarbamate nickel salt.
Hindered amines of the present invention can be with 2,2,6, and 6-tetramethyl--4-piperidyl is the organic amine compound that parent one class has space steric effect.Can be poly--{ [6-[(1,1,3, the 3-tetramethyl butyl)-imino-]-1,3,5-triazine-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-inferior amino-hexa-methylene-[4-(2,2,6, the 6-tetramethyl-is sent the pyridine base)-inferior amino] photostabilizer 944, two (2,2,6, the 6-tetramethyl-piperidyl) sebate (Sanol LS-770), Succinic Acid and 4-hydroxyl-2,2,6, the polymer hindered amine as light stabilizer 622 of 6-tetramethyl-1-piperidines alcohol, two (1,2,2,6,6-pentamethyl--4-piperidyl) certain herbaceous plants with big flowers two acid esters TINUVIN 765, TINUVIN 1235, TINUVIN 744, TINUVIN 44, MarkLA57, MarkLA52, MarkLA67, MarkLA 68, CHIMASSORB 119, several mixture of a kind of or any proportioning among the CHIMASSORB 2020.
The preparation method of special compound additive of the present invention is with in 10～40 parts of long-term ageing-resistant performance auxiliary agents, 10～30 parts of processing aids, 20～50 parts of compound modifying agents and 10～30 parts of adding high-speed mixers of weather resisting agent, about 20 ℃～80 ℃, stir, mixed 5～30 minutes, obtain atactic copolymerized polypropene hot-water line special compound additive.
The application of special compound additive of the present invention is characterized in that: at 200 ℃～250 ℃ melting mixings, the pipe moulding is squeezed in plasticizing evenly back with this composite assistant and atactic copolymerized polypropene resin.
This composite assistant system can significantly improve through the polymerization of liquid phase noumenal method single loop reactors produce monomer disperses the uneven poor in processability that causes among the PP because of vinyl monomer adds at random, and narrow molecular weight distribution occurs making the pipe outer wall to present shark skin shape, the rough shortcoming of inwall, the processing characteristics of atactic copolymerized polypropene resin and mechanical property and environmental stress cracking resistance and long-term ageing-resistant performance are significantly improved, and the PP-R hot water tubing of producing with this composite assistant is the long-term resistance to hydrostatic pressure test by 8760 hours.
Embodiment:
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further detailed; can not be interpreted as limiting the scope of the invention, the person skilled in art can make more corresponding nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1～6th, the preparation of composite assistant
Embodiment 1
70 gram lactone stabilizer IrganoxHP-136,300 gram bisphenols antioxidant 1010s, 150 Ke Naihou agent (are restrained N by 100 gram UV-531 and 50, N-second, n-butyl dithiocarbamate nickel salt composition), 1500 gram crystal formation changing agent TMB-5,1000 gram fluoroelastomer FX-5911 join in the mixing machine, after 50 ℃ of middling speeds are mixed 10min, take out, make composite auxiliary for processing (SY-1).
Embodiment 2
80 gram lactone stabilizer IrganoxHP-136,200 gram bisphenols antioxidant 1010s, 3114, the 150 Ke Naihou agent of 100 donaxine kind antioxidants (are restrained two (right-three grades of octyl phenols)-2 by 50 gram UV-327 and 50,2 '-thioether n-Butyl Amine 99 nickel salt and 50 gram photostabilizers 944 form), 1500 gram crystal formation changing agent TMB-4,800 gram fluoroelastomer FX-5916 join in the mixing machine, after 50 ℃ of middling speeds are mixed 20min, take out, make composite auxiliary for processing (SY-2).
Embodiment 3
90 gram lactone stabilizer IrganoxHP-136,168, the 150 Ke Naihou agent of 300 gram bisphenols oxidation inhibitor (are restrained two (right-three grades of octyl phenols)-2 by 50 gram UV-328 and 50,2 '-thioether n-Butyl Amine 99 nickel salt and 50 gram S anolLS-770 form), 1500 gram crystal formation changing agent WBG, 800 gram fluoroelastomer FPA-102 join in the mixing machine, after 50 ℃ of middling speeds are mixed 20min, take out, make composite auxiliary for processing (SY-3).
Embodiment 4
90 gram lactone stabilizer IrganoxHP-136,150 gram bisphenols oxidation inhibitor, 168,150 donaxine kind antioxidant dimethyl-two-[right-(2-naphthylamine base)-phenoxy group] silane, 150 Ke Naihou agent S ano l LS-770,1500 gram crystal formation changing agent TMB-5,1000 gram fluoroelastomer FX-5924 are joined in the mixing machine, after 50 ℃ of middling speeds are mixed 20min, take out, make composite auxiliary for processing (SY-4).
Embodiment 5
100 gram lactone stabilizer IrganoxHP-136,168, the 250 Ke Naihou agent of 400 gram bisphenols oxidation inhibitor (are restrained 2 by 150 gram UV-329 and 50,2 '-thiobis (uncle's 4-octyl phenol) n-Butyl Amine 99 nickel salt and 50 gram TINUVIN 744 form), 1500 gram crystal formation changing agent STARNU-100,1000 gram low-molecular polyethylene waxs join in the mixing machine, after 50 ℃ of middling speeds are mixed 20min, take out, make composite auxiliary for processing (SY-5).
Embodiment 6
125 gram lactone stabilizer IrganoxHP-136,400 gram bisphenols oxidation inhibitor, 168,150 donaxine kind antioxidants, 300 Ke Naihou agent (are restrained 2 by 100 gram UV-571 and 100,2 '-thiobis (uncle's 4-octyl phenol) n-Butyl Amine 99 nickel salt and 100 gram TI NUVIN 765 form), 1800 gram crystal formation changing agent TMB-4,1000 gram low-molecular polypropylene waxes join in the mixing machine, after 50 ℃ of middling speeds are mixed 20min, take out, make composite auxiliary for processing (SY-6).
Application example 1～6th, the application of composite assistant in the Co-polypropylene resin of preparation
Application example 1:
SY-110 gram and atactic copolymerized polypropene resin (trade mark EP1D30P) are mixed with high-speed mixer for 5 kilograms, squeeze down in 220 ℃ in 230 ℃ of extruding pelletizations, with single screw extrusion machine at twin screw extruder and manage moulding, smooth, the even tube wall of tubing inside and outside wall; The oxidation induction period of tube material is that 60min, modulus in flexure are that 813Mpa, shock strength are 67.4KJ/m
2, see table 1PP-R special material for tube and PP-R base resin basis Physical Property Analysis for details.
Application example 2:
SY-215 gram and atactic copolymerized polypropene resin (trade mark EP1D30P) are mixed with high-speed mixer for 7 kilograms, squeeze down in 220 ℃ in 230 ℃ of extruding pelletizations, with single screw extrusion machine at twin screw extruder and manage moulding, smooth, the even tube wall of outer pipe wall; The oxidation induction period of tube material is that 68min, modulus in flexure are that 817Mpa, shock strength are 67.4KJ/m
2, see table 2PP-R special material for tube and PP-R base resin basis Physical Property Analysis for details.
Application example 3:
SY-325 gram and atactic copolymerized polypropene resin (trade mark EP1D30P) are mixed with high-speed mixer for 10 kilograms, squeeze down in 220 ℃ in 230 ℃ of extruding pelletizations, with single screw extrusion machine at twin screw extruder and manage moulding, smooth, the even tube wall of outer pipe wall; The oxidation induction period of tube material is that 70min, modulus in flexure are that 860Mpa, shock strength are 69.4KJ/m
2, see table 3PP-R special material for tube and PP-R base resin basis Physical Property Analysis for details.
Application example 4:
SY-430 gram and atactic copolymerized polypropene resin (trade mark EP1D30P) are mixed with high-speed mixer for 10 kilograms, squeeze down in 220 ℃ in 230 ℃ of extruding pelletizations, with single screw extrusion machine at twin screw extruder and manage moulding, smooth, the even tube wall of outer pipe wall; The oxidation induction period of tube material is that 75min, modulus in flexure are that 880Mpa, shock strength are 70.4KJ/m
2, see table 4PP-R special material for tube and PP-R base resin basis Physical Property Analysis for details.
Application example 5:
SY-535 gram and atactic copolymerized polypropene resin (trade mark EP1D30P) are mixed with high-speed mixer for 10 kilograms, squeeze down in 220 ℃ in 230 ℃ of extruding pelletizations, with single screw extrusion machine at twin screw extruder and manage moulding, smooth, the even tube wall of outer pipe wall; The oxidation induction period of tube material is that 78min, modulus in flexure are that 890Mpa, shock strength are 72.4KJ/m
2, see table 5PP-R special material for tube and PP-R base resin basis Physical Property Analysis for details.
Application example 6:
SY-640 gram and atactic copolymerized polypropene resin (trade mark EP1D30P) are mixed with high-speed mixer for 10 kilograms, squeeze down in 220 ℃ in 230 ℃ of extruding pelletizations, with single screw extrusion machine at twin screw extruder and manage moulding, smooth, the even tube wall of outer pipe wall; The oxidation induction period of tube material is that 78min, modulus in flexure are that 890Mpa, shock strength are 72.4KJ/m
2, Φ 32 * 4.8 hot water tubing physicalies and the table 9 grand celebration PPR PP Pipe Compound that see table 6PP-R special material for tube and PP-R base resin basis Physical Property Analysis, table 7PPR PP Pipe Compound physical property measurement result, the production of table 8PPR hot-water line PP Pipe Compound for details prepare the test of Φ 32 * 4.8 hot-water line resistance to hydrostatic pressure.
PP-R hot-water line special compound additive can improve the processing characteristics of the atactic copolymerized polypropene base resin that is generated by the polymerization of liquid phase noumenal method single loop reactors, increase the ring stress intensity of tubing, its oxidation induction period surpasses 100min, rigidity and tough performance reach balance preferably, shock strength reaches 600J/m, modulus in flexure is 900Mpa, with the PP-R hot water tubing of its production by hydrostatic test in 8760 hours.
From table 1～9 as can be seen, composite assistant system of the present invention can significantly improve through the polymerization of liquid phase noumenal method single loop reactors produce monomer disperses the uneven poor in processability that causes among the PP because of vinyl monomer adds at random, and narrow molecular weight distribution occurs making the pipe outer wall to present shark skin shape, the rough shortcoming of inwall, the processing characteristics of atactic copolymerized polypropene resin and mechanical property and environmental stress cracking resistance and long-term ageing-resistant performance are significantly improved, and the PP-R hot water tubing of producing with this composite assistant is the long-term resistance to hydrostatic pressure test by 8760 hours.
Table 1
| MFR g/10min | D g/cm 3 | Tensile yield MPa | Modulus in flexure MPa | Oxidation induction period min | Shock strength KJ/ m 2 | Softening account for ℃ | |
| The PP-R PP Pipe Compound | 0.257 | 0.8975 | 24.16 | 813 | 60.0 | 67.4 | 125 |
| The PP-R base resin | 0.251 | 0.8967 | 23.12 | 801 | 6.0 | 40.1 | 125 |
Table 2
| MFR g/10min | D g/cm3 | Tensile yield MPa | Modulus in flexure MPa | Oxidation induction period min | Shock strength KJ/ m 2 | Softening account for ℃ | |
| The PP-R PP Pipe Compound | 0.257 | 0.8975 | 24.16 | 813 | 68.0 | 674 | 125 |
| The PP-R base resin | 0.251 | 0.8967 | 23.12 | 801 | 6.0 | 40.1 | 125 |
Table 3
| MFR g/10min | D g/cm3 | Tensile yield MPa | Modulus in flexure MPa | Oxidation induction period min | Shock strength KJ/ m 2 | Softening account for ℃ | |
| The PP-R PP Pipe Compound | 0.257 | 0.8975 | 24.16 | 860 | 78.0 | 69.4 | 125 |
| The PP-R base resin | 0.251 | 0.8967 | 23.12 | 801 | 6.0 | 40.1 | 125 |
Table 4
| MFR g/10min | D g/cm3 | Tensile yield MPa | Modulus in flexure MPa | Oxidation induction period min | Shock strength KJ/ m 2 | Softening account for ℃ | |
| The PP-R PP Pipe Compound | 0.257 | 0.8975 | 24.16 | 880 | 79.0 | 69.4 | 125 |
| The PP-R base resin | 0.251 | 0.8967 | 23.12 | 801 | 6.0 | 40.1 | 125 |
Table 5
| MFR g/10min | D g/cm3 | Tensile yield MPa | Modulus in flexure MPa | Oxidation induction period min | Shock strength KJ/ m 2 | Softening account for ℃ | |
| The PP-R PP Pipe Compound | 0.257 | 0.8975 | 24.16 | 890 | 82.0 | 72.4 | 125 |
| The PP-R base resin | 0.251 | 0.8967 | 23.12 | 801 | 5.8 | 40.1 | 125 |
Table 6
| MFR g/10min | D g/cm3 | Tensile yield MPa | Modulus in flexure MPa | Oxidation induction period min | Shock strength KJ/ m 2 | Softening account for ℃ | |
| The PP-R PP Pipe Compound | 0.257 | 0.8975 | 24.16 | 900 | 850 | 72.4 | 125 |
| The PP-R base resin | 0.251 | 0.8967 | 23.12 | 801 | 6.6 | 40.1 | 125 |
Table 7
| Project | Unit | Design load | Test value |
| MI | g/10min | 0.20-0.50 | 0.25 |
| D | g/cm 3 | 0.9±0.005 | 0.8979 |
| Tensile yield | Mpa | ≥23 | 24 |
| Elongation at break | ％ | ≥500 | 620 |
| Modulus in flexure | Mpa | ≥800 | 900 |
| The socle girder notched Izod impact strength | KJ/m 2 | ≥20 | 62 |
| Vicat softening point | ℃ | ≥126 | 128 |
| Oxidation induction period | min | ≥20 | 84 |
Table 8
| Project | The GBT18742 standard-required | Grand celebration PPR hot-water line |
| Outward appearance | The tubing inside and outside wall is smooth, smooth, and crackle, bubble, decomposition color or obvious groove, depression, impurity, cut mustn't be arranged, and otch is basically perpendicular to the tubing axis | By |
| Longitudinal extension rate % | ≤2.0 | 0.62 pass through |
| Tubing impact experiment ℃ | Maximum impact energy 15J, impact velocity 3.8m/s, destructive rate should be less than 10% of tested sample | By, all do not destroy |
| Melt flow rate (MFR) (230 ℃ of 2.16Kg) | ≤ 0.5g/10min, the difference of tubing and raw material is no more than 30% | 0.28g/ the difference of/10min tubing and raw material is no more than 30%, and is qualified |
Table 9
| 20℃ | 1h | Ring stress 16Mpa | Ne-leakage, by |
| 95℃ | 22h | Ring stress 4.2Mpa | Ne-leakage, by |
| 95℃ | 165h | Ring stress 3.8Mpa | Ne-leakage, by |
| 95℃ | 1000h | Ring stress 3.5Mpa | Ne-leakage, by |
Claims (7)
1. composite auxiliary agent for random copolymerized polypropylene pipe material is characterized in that: form by following compound system is composite by weight: 10～30 parts of 10～40 parts of long-term ageing-resistant performance auxiliary agents, 10～30 parts of processing aids, 20～50 parts of compound modifying agents and weather resisting agent;
Wherein: long-term ageing-resistant performance auxiliary agent is IrganoxHP-136 stablizer, Hinered phenols antioxidant and the nontoxic amine antioxidants compound system by mass ratio 1: 0.1～10: 0.1～10 preparations;
Processing aid is a fluoroelastomer;
Weather resisting agent is the compound system that UV light absorber, organic nickel stablizer and the hindered amines stablizer in the photostabilizer prepared by mass ratio 1: 0.1～10: 0.1～10;
Compound modifying agent is the compound modifying agent that alpha-crystal form is converted into beta crystal.
2. composite auxiliary agent for random copolymerized polypropylene pipe material according to claim 1, it is characterized in that: described Hinered phenols antioxidant is that four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4-hydroxy phenyl-3, the 5-di-t-butyl) the positive octadecanol ester of propionic acid, β (3, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, N, N '-1, [3-(3 for 6-inferior hexyl-two, the 5-di-tert-butyl-hydroxy phenyl) propionic acid amide], N, [3-(3 for N '-two, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, 2,6-di-t-butyl-4-cresols, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2,6 di tert butyl 4 methyl phenol, 4,4 '-several mixture of a kind of or any proportioning in the methylene bis (2,6 di t butyl phenol).
3. composite auxiliary agent for random copolymerized polypropylene pipe material according to claim 1; it is characterized in that: described amine antioxidants is N; N '-di-sec-butyl-p-phenyl enediamine, secondary-butyl-p-phenylenediamine, 5-chloro-2-methylbenzoxazole; 4-fluoroaniline, dimethyl-two-[right-(2-naphthylamine base)-phenoxy group] silane, N; N-two-betanaphthyl Ursol D, N; several mixture of a kind of or any proportioning in N '-two-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine.
4. composite auxiliary agent for random copolymerized polypropylene pipe material according to claim 1 is characterized in that: described compound modifying agent is any one among the brilliant nucleator WBG of TMB-4, TMB-5, STARNU-100, rare earth compounding β.
5. composite auxiliary agent for random copolymerized polypropylene pipe material according to claim 1, it is characterized in that: described UV light absorber is 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-octyloxy benzophenone, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-the diamyl phenyl) benzotriazole, 2-(2 ' hydroxyl-5_ aminomethyl phenyl) benzotriazole, 2-benzotriazole-4-tert-octylphenol, 2-(2 '-hydroxyl-3 ' di-t-butyl-5 '-aminomethyl phenyl)-the 5-chlorinated benzotriazole, 2-[2 '-hydroxyl-3 ', 5 ' two (α α-Er Jiajibianji) phenyl] benzotriazole, several mixture of a kind of or any proportioning in 2-Phenylbenzimidazole-5-sulfonic acid and 2-(2H-benzotriazole-2-yl)-6-(dodecyl)-4-methylphenol.
6. composite auxiliary agent for random copolymerized polypropylene pipe material according to claim 1, it is characterized in that: the organic nickel stablizer is two (3,5-di-t-butyl-4 hydroxybenzyl monoethyl phosphate) nickel, dioctyltin, 2,2 '-thiobis (uncle's 4-octyl phenol) n-Butyl Amine 99 nickel salt, two (right-three grades of octyl phenols)-2,2 '-thioether n-Butyl Amine 99 nickel salt, N, several mixture of a kind of or any proportioning in the N-second, n-butyl dithiocarbamate nickel salt.
7. composite auxiliary agent for random copolymerized polypropylene pipe material according to claim 1, it is characterized in that: described hindered amines is poly--{ [6-[(1,1,3, the 3-tetramethyl butyl)-and imino-]-1,3,5-triazine-2,4-two bases] [2-(2,2,6, the 6-tetramethyl-piperidyl)-inferior amino-hexa-methylene-[4-(2,2,6, the 6-tetramethyl-is sent the pyridine base)-inferior amino], two (2,2,6, the 6-tetramethyl-piperidyl) sebate, Succinic Acid and 4-hydroxyl-2,2,6, the polymer of 6-tetramethyl-1-piperidines alcohol, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, TINUVIN 1235, TINUVIN 744, TINUVIN 44, MarkLA57, MarkLA52, MarkLA67, MarkLA 68, CHIMASSORB 119, several mixture of a kind of or any proportioning among the CHIMASSORB 2020.
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| CN103469559A (en) * | 2013-08-21 | 2013-12-25 | 昆山铁牛衬衫厂 | UV-resistant composite finishing agent and preparation method thereof |
| CN104151712B (en) * | 2014-07-25 | 2016-08-24 | 贵州师范大学 | A kind of PP-R pipe material of low-temperature impact resistance toughness 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 |
| CN108003479B (en) * | 2017-12-07 | 2020-12-18 | 广州赫尔普化工有限公司 | Composite additive for random copolymerization polypropylene pipe |
| CN109796867A (en) * | 2019-01-29 | 2019-05-24 | 法尔泰氪(苏州)安全科技有限公司 | A kind of preparation method of high temperature resistant type high-molecular coating |
| CN110003788B (en) * | 2019-03-28 | 2021-03-02 | 广东绿色大地化工有限公司 | Water-based single-component nano-modified self-crosslinking weather-resistant finish paint |
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