CN104592644A - Cold-cracking resistant PPR pipeline with controllable crystal form and preparation method of cold-cracking resistant PPR pipeline - Google Patents
Cold-cracking resistant PPR pipeline with controllable crystal form and preparation method of cold-cracking resistant PPR pipeline Download PDFInfo
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Abstract
The invention discloses a cold-cracking resistant PPR pipeline with a controllable crystal form, and belongs to the technical field of tubular product preparation. The cold-cracking resistant PPR pipeline comprises the following components in parts by weight: 100 parts of PPR, 4 parts of color master batches, 4-6 parts of a cold-cracking resistant modifier, 2-4 parts of a crystal form regulating agent, 1-3 parts of an antioxidant and 0.2-1 part of a light stabilizer, and is obtained by stirring evenly, extruding and pelletizing. The method comprises the following steps: by virtue of a melt extrusion reaction grafting technology, grafting a polyethylene molecule on a polypropylene molecule skeleton as a long-chain tie molecule to obtain a polyethylene cold-cracking resistant modifier; codoping into PPR resin together with the crystal form regulating agent; extruding a PPR modified tubular product; and carrying out internal stress removal treatment on the tubular product. The spherocrystal dimension and distribution of polyethylene in the molding and processing processes can be regulated and controlled by combination of two master batches; the brittleness and stress cracking character of the polyethylene can be significantly improved; and compared with a common PPR tubular product, the cold-cracking resistance can be improved by 20%.
Description
Technical field
The invention belongs to tubing preparing technical field, be specifically related to controlled low temperature resistant cracking PPR pipe road of a kind of crystal formation and preparation method thereof.
Background technology
Polypropylene random copolymer pipeline (PPR pipe road) introduced China from 1997 short 15 years so far, just with the resistance toheat of its excellence, shock resistance and green building material concept, more and more obtain the favor of people, give in building, water exhaust system is greatly developed.
Because PPR pipe low temperature (5-10 DEG C) fragility is large, very easily there is stress induced cracking phenomena, seriously have impact on the construction and installation in PPR pipe road for many years always, seriously have impact on PPR pipe road and carry the safety of water system and the daily production of people, living needs under cryogenic, solving in the urgent need to exerting.
In current industry, conventional improving one's methods is formula modification, and sum up compositional refinements technical scheme in industry, result is all undesirable, is all in conceptual phase, does not carry out product marketization application.Be analyzed as follows: 1) nano-particles filled modification: obvious to PPR pipe normal temperature impact effect, but little to low-temperature impact contribution; 2) elastomer-modified: impact is greatly improved, there is the problems such as poor compatibility, sacrifice the withstand voltage properties of pipeline, there is no using value; 3) PPB blending and modifying: the hot water withstand voltage properties that have impact on tubing, have impact on the life-span of tubing, inadvisable.
Summary of the invention
For problems of the prior art, low temperature resistant cracking PPR pipe road that the object of the present invention is to provide crystal formation controlled and preparation method thereof, it is by formula modification, improve the branch lengths in PPR pipe road, control PPR pipe road spherulite size and distribution, improve the defect existed in PPR pipe road construction process in the market.
The low temperature resistant cracking PPR pipe road that described a kind of crystal formation is controlled, is characterized in that the component comprising following parts by weight:
The anti-cold cracking properties-correcting agent 4-6 part of PPR 100 parts of Masterbatchs 4 parts
Crystal polymorph control agent 2-4 part oxidation inhibitor 1-3 part photostabilizer 0.2-1 part.
The low temperature resistant cracking PPR pipe road that described a kind of crystal formation is controlled, is characterized in that described anti-cold cracking properties-correcting agent is long chain branched polypropylene, is obtained by the micro-cross-linked graft of two steps.
The low temperature resistant cracking PPR pipe road that described a kind of crystal formation is controlled, it is characterized in that anti-cold cracking properties-correcting agent by LLDPE linking agent, oxidation inhibitor and acetone solvent exist under, micro-crosslinked polyethylene master batch is obtained through stirring, extruding, micro-crosslinked polyethylene master batch is again with under the existence of POE, PPH, linking agent, branching promotor, through twin screw granulation, obtain cold cracking properties-correcting agent master batch.
The low temperature resistant cracking PPR pipe road that described a kind of crystal formation is controlled, it is characterized in that preparing crosslinked LLDPE linking agent used is two-(t-butylperoxyisopropyl) benzene, preparing cold cracking properties-correcting agent master batch linking agent used is 2,5-dimethyl-2,5 di-t-butyl peroxy hexane and diacrylate-1, the mixture of 6 butanediol esters, described branching promotor is Thiuram dithioesters.
The low temperature resistant cracking PPR pipe road that described a kind of crystal formation is controlled, it is characterized in that described crystal polymorph control agent by PPR, Chain-shaped Nano-grade Calcium Carbonate, polyethylene wax, oxidation inhibitor and titanate coupling agent in homogenizer, with low speed, high-speed stirring to even, put into twin screw extruder extruding pelletization again, obtained crystal polymorph control agent master batch.
The low temperature resistant cracking PPR pipe road that described a kind of crystal formation is controlled, is characterized in that the chain diameter of described crystal polymorph control agent is 10nm.
The low temperature resistant cracking PPR pipe road that described a kind of crystal formation is controlled, is characterized in that described oxidation inhibitor is any one or more than one the mixture in antioxidant 1010, irgasfos 168 or antioxidant 330.
The low temperature resistant cracking PPR pipe road that described a kind of crystal formation is controlled, it is characterized in that described photostabilizer be photostabilizer 326, photostabilizer 770 or etc. the photostabilizer 326 of quality and photostabilizer 770 mixture.
The preparation method in the low temperature resistant cracking PPR pipe road that described crystal formation is controlled, is characterized in that described preparation method comprises the following steps:
1) preparation of anti-cold cracking properties-correcting agent master batch: pour LLDPE into stirrer, and the acetone being dissolved with linking agent and oxidation inhibitor is poured into stirrer stirring, stirring velocity is 70 revs/min, pour in twin screw extruder after stirring 300s and melt extrude, there is micro-crosslinking reaction, obtained micro-crosslinked polyethylene master batch; Then twin screw granulation after the micro-crosslinked polyethylene master batch in mass ratio for 30-40:30-35:30-45:0.15-0.17:0.008-0.01, POE, PPH, linking agent and branching promotor being stirred, obtained anti-cold cracking properties-correcting agent master batch;
2) preparation of crystal polymorph control agent: add PPR, Chain-shaped Nano-grade Calcium Carbonate polyethylene wax, oxidation inhibitor and titanate coupling agent in homogenizer surface treatment is carried out to Chain-shaped Nano-grade Calcium Carbonate, in homogenizer, with low speed, high-speed stirring to even, put into twin screw extruder extruding pelletization again, obtained crystal polymorph control agent master batch;
3) preparation in the low temperature resistant cracking PPR pipe road that crystal formation is controlled: anti-cold cracking properties-correcting agent master batch prepared by step 1), step 2) the crystal polymorph control agent master batch prepared, PPR, Masterbatch, after oxidation inhibitor and photostabilizer stir, carry out squeezing pipe with singe screw pipe extruder shaping, obtain low temperature resistant cracking PPR pipe road, described singe screw pipe extruder jacket temperature is 40-80 DEG C, barrel zone temperature is 190-220 DEG C, die head temperature is 200-220 DEG C, screw speed is 80-95rpm, moment of torsion is 40-60%, melt temperature is 185-210 DEG C, melt pressure is 140-175bar, vacuum tightness used is 0.010-0.020bar/Mpa,
4) the low temperature resistant cracking PPR pipe road that step 3) is obtained is positioned over baking oven 110 DEG C of thermal treatment 3h, eliminates pipeline internal stress, obtain the low temperature resistant cracking PPR pipe road that crystal formation is controlled.
By adopting above-mentioned technology, compared with prior art, beneficial effect of the present invention is as follows:
1) anti-cold cracking properties-correcting agent of the present invention adopts two step synthesis, improve polyacrylic branch lengths, LLDPE and the POE of interpolation is made to have good consistency, thus reduce the impact of toughness raising on pipe performance, compared with the increasing tougheness of common PPR, improve the prerequisite of equal proportion at low temperature resistant cracking performance under, the feature that the decline of rigidity is little, both ensure that the intensity of material, the tubing resistance to cracking simultaneously produced obtains obvious improvement;
2) the present invention is when preparing anti-cold cracking properties-correcting agent master batch, use Thiuram dithioesters as branching promotor, can obviously suppress because the uncle in superoxide attack polypropylene chains visits the β cleavage reaction that atom causes polypropylene chains, promote the growth of polypropylene long-chain branch, ensure polyacrylic melt strength;
3) the present invention is when preparing crystal polymorph control agent, is the ultra-fine Chain-shaped Nano-grade Calcium Carbonate of 10nm, plays nucleation, can accelerate crystalling propylene speed in crystalling propylene process by chain length, forms the tiny and spherocrystal of densification, improves the performance of product.Chain-shaped Nano-grade Calcium Carbonate length-to-diameter ratio is large simultaneously, add in polypropylene and not only can significantly improve polyacrylic mechanical property, it is made to obtain the thermotolerance of good bending elastic modulus, flexural strength and dimensional stability, raising product, and the processing characteristics in PPR pipe road can be improved, make surface, PPR pipe road brighter;
4) in the low temperature resistant cracking PPR pipe road preparation process that crystal formation of the present invention is controlled, thermal treatment process is used to eliminate the internal stress produced in pipeline manufacturing processed, the secondary crystal in short pipe inlet pipe road, thus promote the compressive strength of tubing, make up the intensity caused because of the raising of anti-toughness and reduce and the impact resistance of product can be improved;
5) the present invention adopts and melt extrudes reactive grafting technology, on polypropylene molecule skeleton, grafted polyethylene molecule is as long-chain tie molecule, obtain the anti-cold cracking properties-correcting agent of polypropylene, jointly support by the arm in PPR resin with crystal polymorph control agent, extrude PPR modification tubing, and this tubing is carried out internal stress Processing for removing.The combination of two kinds of master batches can not only regulate and control polypropylene spherulite size and distribution in molding process, and can significantly improve polyacrylic fragility and stress cracking, can improve 200% compared with the low temperature resistant cracking behavior of common PPR pipe.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1: the preparation in the low temperature resistant cracking PPR pipe road that crystal formation is controlled
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1: the preparation in the low temperature resistant cracking PPR pipe road that crystal formation is controlled
1) preparation of anti-cold cracking properties-correcting agent master batch
The preparation of the micro-crosslinked LLDPE master batch of a: 0.4 kilogram of antioxidant 1010,0.5 kilogram two-(t-butylperoxyisopropyl) benzene and 500ml acetone glass stick are stirred until all dissolve, then solute is poured in 40 kilograms of linear low density polyethylene LLDPE and stir, stirring velocity is 70 revs/min, blanking after stirring 300S, place 3 hours, after acetone volatilization, material is poured in twin screw and melt extrude the micro-crosslinking reaction of generation, the obtained LLDPE master batch having certain degree of crosslinking; Wherein each district temperature of twin screw extruder is set as: one section 100 DEG C, two sections 120 DEG C, three sections 150 DEG C, four sections 150 DEG C, five sections 150 DEG C, six sections 155 DEG C, seven sections 155 DEG C, eight sections 155 DEG C, nine sections 155 DEG C, ten sections 150 DEG C, head 150 DEG C, rotating speed 300rpm;
The preparation of b anti-cold cracking properties-correcting agent master batch: 0.1 kilogram of 2,5-dimethyl-2,5 di-t-butyl peroxy hexane and 0.05 kilogram of diacrylate-1,6 butanediol ester, 0.1 kilogram of antioxidant 1010 are dissolved in 500ml acetone; Micro-crosslinked LLDPE master batch 30 kilograms, POE POE30 kilogram, homo-polypropylene PPH40 kilogram, Thiuram dithioesters 0.01 kilogram are stirred 200S in stirrer, then the acetone after dissolving is poured in stirrer and stir 300S, place 3 hours, after acetone volatilization, material is poured into the granulation of tablets press twin screw, obtained anti-cold cracking properties-correcting agent master batch; Wherein each district temperature of twin screw extruder is set as: one section 150 DEG C, two sections 180 DEG C, three sections 180 DEG C, four sections 180 DEG C, five sections 180 DEG C, six sections 185 DEG C, seven sections 185 DEG C, eight sections 175 DEG C, nine sections 175 DEG C, ten sections 170 DEG C, head 170 DEG C, rotating speed 300rpm;
2) preparation of crystal polymorph control agent master batch
30 kilograms of Chain-shaped Nano-grade Calcium Carbonate, 0.5 kilogram of polyethylene wax, 0.4 kilogram of antioxidant 1010,0.2 kilogram of irgasfos 168,0.15 kilogram of antioxidant 330,0.45 kilogram of titanate coupling agent are added in homogenizer surface treatment is carried out to Chain-shaped Nano-grade Calcium Carbonate, reduce and reunite.Stirring at low speed 3 minutes, high-speed stirring 5 minutes, takes out after stirring and puts into twin screw extruder extruding pelletization, obtained crystal polymorph control agent;
3) preparation in the low temperature resistant cracking PPR pipe road that crystal formation is controlled
Anti-cold cracking properties-correcting agent master batch 4 kilograms, step 2 prepared by step 1)) after the crystal polymorph control agent master batch 2 kilograms prepared and RRR tubing special raw material double centner and Masterbatch 4 kilograms, 2 kilograms, oxidation inhibitor, photostabilizer 0.2 kilogram stir, carry out squeezing pipe with singe screw pipe extruder shaping, the tubing produced is positioned over baking oven 110 DEG C of thermal treatment 3h, eliminate pipeline internal stress, improve tubing intensity, obtain the low temperature resistant cracking PPR pipe road that crystal formation is controlled.
Embodiment 2: the preparation in the low temperature resistant cracking PPR pipe road that crystal formation is controlled
1) preparation of anti-cold cracking properties-correcting agent master batch
0.42 kilogram of antioxidant 1010,0.55 kilogram two-(t-butylperoxyisopropyl) benzene and 500ml acetone glass stick stir until all dissolve by a, then solute is poured in 40 kilograms of linear low density polyethylene LLDPE and stir, stirring velocity is 70 revs/min, blanking after stirring 300S, place 3 hours, after acetone volatilization, material is poured in twin screw and melt extrude the micro-crosslinking reaction of generation, the obtained LLDPE master batch having certain degree of crosslinking.Each district temperature of twin screw extruder is set as: one section 100 DEG C, two sections 120 DEG C, three sections 145 DEG C, four sections 145 DEG C, five sections 150 DEG C, six sections 150 DEG C, seven sections 150 DEG C, eight sections 150 DEG C, nine sections 150 DEG C, ten sections 145 DEG C, head 150 DEG C, rotating speed 300rpm;
The preparation of b anti-cold cracking properties-correcting agent master batch: 0.09 kilogram of 2,5-dimethyl-2,5 di-t-butyl peroxy hexane and 0.08 kilogram of diacrylate-1,6 butanediol ester, 0.09 kilogram of antioxidant 1010 are dissolved in 500ml acetone; Micro-crosslinked LLDPE master batch 20 kilograms, POE POE 35 kilograms, homo-polypropylene PPH 45 kilograms, Thiuram dithioesters 0.008 kilogram are stirred 200S in stirrer; then the acetone after dissolving is poured in stirrer and stir 300S; place 3 hours; after acetone volatilization; material is poured into the granulation of tablets press twin screw, obtained anti-cold cracking properties-correcting agent master batch.Each district temperature of twin screw extruder is set as: one section 150 DEG C, two sections 185 DEG C, three sections 185 DEG C, four sections 185 DEG C, five sections 185 DEG C, six sections 185 DEG C, seven sections 185 DEG C, eight sections 185 DEG C, nine sections 185 DEG C, ten sections 180 DEG C, head 170 DEG C, rotating speed 300rpm;
2) preparation of crystal polymorph control agent master batch
30 kilograms of Chain-shaped Nano-grade Calcium Carbonate, 0.42 kilogram of polyethylene wax, 0.40 kilogram of antioxidant 1010,0.40 kilogram of irgasfos 168,0.20 kilogram of antioxidant 330,0.50 kilogram of titanate coupling agent are added in homogenizer surface treatment is carried out to Chain-shaped Nano-grade Calcium Carbonate, reduce and reunite.Stirring at low speed 3 minutes, high-speed stirring 5 minutes, takes out after stirring and puts into twin screw extruder extruding pelletization, obtained crystal polymorph control agent;
3) preparation in the low temperature resistant cracking PPR pipe road that crystal formation is controlled
Anti-cold cracking properties-correcting agent master batch 5 kilograms, step 2 prepared by step 1)) after the crystal polymorph control agent 2.5 kilograms prepared and RRR tubing special raw material double centner and Masterbatch 4 kilograms, 2 kilograms, oxidation inhibitor, photostabilizer 0.6 kilogram stir, carry out squeezing pipe with singe screw pipe extruder shaping, the tubing produced is positioned over baking oven 110 DEG C of thermal treatment 3h, eliminate pipeline internal stress, improve tubing intensity.
Embodiment 3: the preparation in the low temperature resistant cracking PPR pipe road that crystal formation is controlled
1) preparation of anti-cold cracking properties-correcting agent master batch
0.38 kilogram of antioxidant 1010,0.45 kilogram two-(t-butylperoxyisopropyl) benzene and 450ml acetone glass stick stir until all dissolve by a, then solute is poured in 40 kilograms of linear low density polyethylene LLDPE and stir, stirring velocity is 70 revs/min, blanking after stirring 280S, place 3 hours, after acetone volatilization, material is poured in twin screw and melt extrude the micro-crosslinking reaction of generation, the obtained LLDPE master batch having certain degree of crosslinking.Each district temperature of twin screw extruder is set as: one section 100 DEG C, two sections 125 DEG C, three sections 155 DEG C, four sections 155 DEG C, five sections 155 DEG C, six sections 160 DEG C, seven sections 160 DEG C, eight sections 160 DEG C, nine sections 160 DEG C, ten sections 155 DEG C, head 155 DEG C, rotating speed 300rpm;
0.12 kilogram of 2,5-dimethyl-2,5 di-t-butyl peroxy hexane and 0.04 kilogram of diacrylate-1,6 butanediol ester, 0.11 kilogram of antioxidant 1010 are dissolved in 500ml acetone by b; Micro-crosslinked LLDPE master batch 40 kilograms, POE POE30 kilogram, homo-polypropylene PPH30 kilogram, Thiuram dithioesters 0.008 kilogram are stirred 200S in stirrer; then the acetone after dissolving is poured in stirrer and stir 300S; place 3 hours; after acetone volatilization; material is poured into the granulation of tablets press twin screw, obtained anti-cold cracking properties-correcting agent master batch.Each district temperature of twin screw extruder is set as: one section 148 DEG C, two sections 175 DEG C, three sections 175 DEG C, four sections 175 DEG C, five sections 175 DEG C, six sections 180 DEG C, seven sections 180 DEG C, eight sections 170 DEG C, nine sections 170 DEG C, ten sections 170 DEG C, head 170 DEG C, rotating speed 280rpm;
2) preparation of crystal polymorph control agent master batch
30 kilograms of Chain-shaped Nano-grade Calcium Carbonate, 0.55 kilogram of polyethylene wax, 0.4 kilogram of antioxidant 1010,0.4 kilogram of irgasfos 168,0.20 kilogram of antioxidant 330,0.53 kilogram of titanate coupling agent are added in homogenizer surface treatment is carried out to Chain-shaped Nano-grade Calcium Carbonate, reduce and reunite.Stirring at low speed 3 minutes, high-speed stirring 5 minutes, takes out after stirring and puts into twin screw extruder extruding pelletization, obtained crystal polymorph control agent;
3) preparation in the low temperature resistant cracking PPR pipe road that crystal formation is controlled
Anti-cold cracking properties-correcting agent master batch 6 kilograms, step 2 prepared by step 1)) after the crystal polymorph control agent 3 kilograms prepared and RRR tubing special raw material double centner and Masterbatch 4 kilograms, 1 kilogram, oxidation inhibitor, photostabilizer 1 kilogram stir, carry out squeezing pipe with singe screw pipe extruder shaping, the tubing produced is positioned over baking oven 110 DEG C of thermal treatment 3h, eliminate pipeline internal stress, improve tubing intensity.
The present invention's tubing inside and outside wall produced of filling a prescription is smooth, zero defect, and product meets the related request in national standard, and compared with the tubing produced with regular convention formula, pipeline hydraulic intensity is without decline, solves raising anti-impact in industry and reduces the difficult point of product strength.The impact strength of tubing improves 200%, effectively improves the low temperature resistant cracking behavior of tubing.Serviceability rate reaches 80% ~ 100% to modified PPR pipe falling ball impact test at low temperature (0 DEG C, 1.5kg, 1.0m), and unmodified common PPR pipe serviceability rate is lower than 20%.The hydraulic performance of tubing meets standard-required.
Table 1: low temperature resistant cracking PPR batten performance table
Table 2: low temperature resistant cracking tubing drop impact performance table
Table 3: low temperature resistant cracking tubing hydraulic performance table
Claims (9)
1. the low temperature resistant cracking PPR pipe road that crystal formation is controlled, is characterized in that the component comprising following parts by weight:
The anti-cold cracking properties-correcting agent 4-6 part of PPR 100 parts of Masterbatchs 4 parts
Crystal polymorph control agent 2-4 part oxidation inhibitor 1-3 part photostabilizer 0.2-1 part.
2. the low temperature resistant cracking PPR pipe road that a kind of crystal formation according to claim 1 is controlled, is characterized in that described anti-cold cracking properties-correcting agent is long chain branched polypropylene, is obtained by the micro-cross-linked graft of two steps.
3. the low temperature resistant cracking PPR pipe road that a kind of crystal formation according to claim 2 is controlled, it is characterized in that anti-cold cracking properties-correcting agent by LLDPE linking agent, oxidation inhibitor and acetone solvent exist under, micro-crosslinked polyethylene master batch is obtained through stirring, extruding, micro-crosslinked polyethylene master batch is again with under the existence of POE, PPH, linking agent, branching promotor, through twin screw granulation, obtain cold cracking properties-correcting agent master batch.
4. the low temperature resistant cracking PPR pipe road that a kind of crystal formation according to claim 2 is controlled, it is characterized in that preparing crosslinked LLDPE linking agent used is two-(t-butylperoxyisopropyl) benzene, preparing cold cracking properties-correcting agent master batch linking agent used is 2,5-dimethyl-2,5 di-t-butyl peroxy hexane and diacrylate-1, the mixture of 6 butanediol esters, described branching promotor is Thiuram dithioesters.
5. the low temperature resistant cracking PPR pipe road that a kind of crystal formation according to claim 1 is controlled, it is characterized in that described crystal polymorph control agent by PPR, Chain-shaped Nano-grade Calcium Carbonate, polyethylene wax, oxidation inhibitor and titanate coupling agent in homogenizer, with low speed, high-speed stirring to even, put into twin screw extruder extruding pelletization again, obtained crystal polymorph control agent master batch.
6. the low temperature resistant cracking PPR pipe road that a kind of crystal formation according to claim 1 is controlled, is characterized in that the chain diameter of described crystal polymorph control agent is 10nm.
7. the low temperature resistant cracking PPR pipe road that a kind of crystal formation according to claim 1 is controlled, is characterized in that described oxidation inhibitor is any one or more than one the mixture in antioxidant 1010, irgasfos 168 or antioxidant 330.
8. the low temperature resistant cracking PPR pipe road that a kind of crystal formation according to claim 1 is controlled, it is characterized in that described photostabilizer be photostabilizer 326, photostabilizer 770 or etc. the photostabilizer 326 of quality and photostabilizer 770 mixture.
9. the preparation method in the low temperature resistant cracking PPR pipe road that crystal formation according to claim 1 is controlled, is characterized in that described preparation method comprises the following steps:
1) preparation of anti-cold cracking properties-correcting agent master batch: pour LLDPE into stirrer, and the acetone being dissolved with linking agent and oxidation inhibitor is poured into stirrer stirring, stirring velocity is 70 revs/min, pour in twin screw extruder after stirring 300s and melt extrude, there is micro-crosslinking reaction, obtained micro-crosslinked polyethylene master batch; Then twin screw granulation after the micro-crosslinked polyethylene master batch in mass ratio for 30-40:30-35:30-45:0.15-0.17:0.008-0.01, POE, PPH, linking agent and branching promotor being stirred, obtained anti-cold cracking properties-correcting agent master batch;
2) preparation of crystal polymorph control agent: add PPR, Chain-shaped Nano-grade Calcium Carbonate polyethylene wax, oxidation inhibitor and titanate coupling agent in homogenizer surface treatment is carried out to Chain-shaped Nano-grade Calcium Carbonate, in homogenizer, with low speed, high-speed stirring to even, put into twin screw extruder extruding pelletization again, obtained crystal polymorph control agent master batch;
3) preparation in the low temperature resistant cracking PPR pipe road that crystal formation is controlled: anti-cold cracking properties-correcting agent master batch prepared by step 1), step 2) the crystal polymorph control agent master batch prepared, PPR, Masterbatch, after oxidation inhibitor and photostabilizer stir, carry out squeezing pipe with singe screw pipe extruder shaping, obtain low temperature resistant cracking PPR pipe road, described singe screw pipe extruder jacket temperature is 40-80 DEG C, barrel zone temperature is 190-220 DEG C, die head temperature is 200-220 DEG C, screw speed is 80-95rpm, moment of torsion is 40-60%, melt temperature is 185-210 DEG C, melt pressure is 140-175bar, vacuum tightness used is 0.010-0.020bar/Mpa,
4) the low temperature resistant cracking PPR pipe road that step 3) is obtained is positioned over baking oven 110 DEG C of thermal treatment 3h, eliminates pipeline internal stress, obtain the low temperature resistant cracking PPR pipe road that crystal formation is controlled.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945742A (en) * | 2015-07-07 | 2015-09-30 | 天津市伟星新型建材有限公司 | Copolymer enhanced PPR tube and preparation method thereof |
| CN105542294A (en) * | 2016-01-05 | 2016-05-04 | 广东联塑科技实业有限公司 | High-performance polyolefin pipe fitting and preparing method thereof |
| CN105778296A (en) * | 2016-03-17 | 2016-07-20 | 海南联塑科技实业有限公司 | Cold-resistant PP-R (polypropylene random) pipe and preparation method thereof |
| CN106750989A (en) * | 2016-11-22 | 2017-05-31 | 广东联塑科技实业有限公司 | A kind of low temperature resistant high rigidity PPR pipe and preparation method thereof |
| CN109438853A (en) * | 2018-09-27 | 2019-03-08 | 湖北永晟塑料管业有限责任公司 | A kind of PPR pipe road with long service life and preparation method thereof |
| CN110406065A (en) * | 2018-04-28 | 2019-11-05 | 上海伟星新型建材有限公司 | A kind of β-PPR pipe and its processing method |
| CN111029155A (en) * | 2019-12-24 | 2020-04-17 | 中南大学 | Solid-state aluminum electrolytic capacitor with good mechanical property and preparation method thereof |
| CN113061304A (en) * | 2021-03-31 | 2021-07-02 | 长春联塑实业有限公司 | Low-temperature-cracking-resistant PPR pipe material, preparation method thereof and prepared PPR pipe product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870784A (en) * | 2010-03-29 | 2010-10-27 | 金发科技股份有限公司 | Impact resisting weather-proof polypropylene and preparation method thereof |
| 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 |
| CN102977456A (en) * | 2012-12-07 | 2013-03-20 | 湖北工业大学 | Polypropylene toughening modifying agent and polypropylene modified product thereof |
-
2015
- 2015-01-08 CN CN201510007465.4A patent/CN104592644B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870784A (en) * | 2010-03-29 | 2010-10-27 | 金发科技股份有限公司 | Impact resisting weather-proof polypropylene and preparation method thereof |
| 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 |
| CN102977456A (en) * | 2012-12-07 | 2013-03-20 | 湖北工业大学 | Polypropylene toughening modifying agent and polypropylene modified product thereof |
Non-Patent Citations (1)
| Title |
|---|
| 余绍火、王雪丽总编，吴宏富主编: "《中国粉体工业通鉴》", 31 May 2005, 西安：西安地图出版社 * |
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| CN105542294B (en) * | 2016-01-05 | 2018-12-07 | 广东联塑科技实业有限公司 | A kind of High performance polyolefin pipe fitting and preparation method thereof |
| CN105542294A (en) * | 2016-01-05 | 2016-05-04 | 广东联塑科技实业有限公司 | High-performance polyolefin pipe fitting and preparing method thereof |
| CN105778296A (en) * | 2016-03-17 | 2016-07-20 | 海南联塑科技实业有限公司 | Cold-resistant PP-R (polypropylene random) pipe and preparation method thereof |
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Denomination of invention: The invention relates to a low temperature cracking resistant PPR pipeline with controllable crystal form and a preparation method thereof Effective date of registration: 20210917 Granted publication date: 20170721 Pledgee: Industrial and Commercial Bank of China Limited Linhai Branch Pledgor: ZHEJIANG WEIXING NEW BUILDING MATERIALS Co.,Ltd. Registration number: Y2021330001688 |