CN115304867A - Special resin for toughened PPR (polypropylene random copolymer) pipe and preparation method thereof - Google Patents
Special resin for toughened PPR (polypropylene random copolymer) pipe and preparation method thereof Download PDFInfo
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- CN115304867A CN115304867A CN202110492665.9A CN202110492665A CN115304867A CN 115304867 A CN115304867 A CN 115304867A CN 202110492665 A CN202110492665 A CN 202110492665A CN 115304867 A CN115304867 A CN 115304867A
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Abstract
The invention discloses a special resin for a toughened PPR pipe and a preparation method thereof, wherein the special resin comprises the following components in parts by weight: 100 parts of random copolymerization polypropylene resin, 0.1 to 3 parts of antioxidant, 0.05 to 1 part of nucleating agent and 2 to 15 parts of toughening agent. The PPR pipe produced by the special resin has high strength and good low-temperature toughness, and the hydraulic resistance of the PPR pipe product is greatly improved.
Description
Technical Field
The invention belongs to the field of resin, and particularly relates to special resin for a toughened PPR (polypropylene random copolymer) pipe and a preparation method of the special resin for the toughened PPR pipe.
Background
Plastic pipes are increasingly favored in today's life and industrial fields due to their corrosion resistance, aging resistance, environmental protection and safety, and play an important and irreplaceable role. The random copolymerization polypropylene hot water pipe has the characteristics of energy conservation, sanitation, corrosion resistance, heat resistance, pressure resistance, long service life, convenient installation, reliable connection, material recycling and the like, and can be widely used for hot water pipes, pipes for hot water heating systems, industrial hot water pipes, hot spring water pipes, solar house hot water pipes and the like.
Random copolymer polypropylene pipes originated from europe, the 90 s of the 20 th century, and the first propylene copolymer pipe production line in the world, developed successfully by KRAVSSMAFFEI (kravsmamffei) in germany. The pipe has the advantages that the pipe is superior in performance and attracts people's attention, the German plastic pipe is repositioned in the format in short years, the random copolymerization polypropylene pipe jumps to the second place in competition with other pipes, and the random copolymerization polypropylene pipe is adopted in 80 percent of Germany indoor tap water and heating pipes. Then, polypropylene copolymer pipes are developed and produced in all countries in the world, and random copolymer polypropylene pipes are developed at a higher speed. In 1998, the government of China also sends out the stipulations about rapid popularization and application of chemical building materials, restriction and elimination of laggard products, the newly built buildings are forbidden to be galvanized and cast iron pipes from 6 months to 1 day in 2000, the environment-friendly random copolymerization polypropylene pipes are popularized and used, under the guidance of national policies, the random copolymerization polypropylene pipes show strong vitality in the market, the development prospect is very good, and merchants also invest in PPR pipe production lines at times, and until now, china has 130 introduced and domestic random copolymerization polypropylene production lines to form the production capacity of 6-7 ten thousand tons of random copolymerization polypropylene pipes. However, the domestic random copolymerization polypropylene pipe generally has the problems of poor processing performance, poor long-term aging resistance and the like.
The uneven pipe wall thickness or the shark skin phenomenon on the outer wall of the pipe and the unsmooth pipe inner wall caused by low melt strength and narrow molecular weight distribution can occur in the forming and processing process of the random copolymerization polypropylene resin, and in addition, the random copolymerization polypropylene hot water pipe needs to bear certain water pressure and environmental aging in the using process, so the random copolymerization polypropylene hot water pipe is required to have excellent long-term aging resistance and maintain certain ring stress, and therefore, when the random copolymerization polypropylene pipe is produced, a certain amount of special auxiliary agent needs to be added to improve the processing performance of the random copolymerization polypropylene, the pipe is endowed with excellent aging resistance and mechanical property, and the using requirement of the building industry on the random copolymerization polypropylene hot water pipe is met.
Disclosure of Invention
The invention mainly aims to provide a special resin for a toughened PPR pipe and a preparation method thereof, so as to overcome the defect that the special resin for the PPR pipe in the prior art is weak in impact resistance and processability.
In order to achieve the purpose, the invention provides a special resin for a toughened PPR pipe, which comprises the following components in parts by weight: 100 parts of random copolymerization polypropylene resin, 0.1-3 parts of antioxidant, 0.05-1 part of nucleating agent and 2-15 parts of toughening agent.
The special resin for the toughened PPR pipe comprises a nucleating agent, a plasticizer and a plasticizer, wherein the nucleating agent is one or more of calcium octanedioate, calcium pimelate, calcium terephthalate, TMB-4, TMB-5, NA-85, NB-328, WBG-II and STARNU-100; the toughening agent is one or more of ethylene-octene copolymer, ethylene-propylene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, hydrogenated styrene-butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer and hydrogenated styrene-isoprene-styrene triblock copolymer.
The special resin for the toughened PPR pipe is characterized in that in the random copolymerization polypropylene resin, part of ethylene molecules are randomly distributed in a polypropylene chain segment, and the molar ratio of the randomly distributed ethylene molecules to the ethylene molecules is 70-100:100.
the special resin for the toughened PPR pipe, disclosed by the invention, has the advantages that the melt flow rate of the random copolymerization polypropylene resin is 0.2-0.5g/10min at 230 ℃ and under the load of 2.16Kg, the content of comonomer ethylene is 2-10 wt%, and the impact strength of a simply supported beam is more than 30KJ/m 2 。
The resin special for the toughened PPR pipe is characterized in that the antioxidant is one or more of a phenol antioxidant, an amine antioxidant, a phosphite antioxidant and a sulfur-containing ester antioxidant.
In order to achieve the purpose, the invention also provides a preparation method of the special resin for the toughened PPR pipe, the special resin for the PPR pipe comprises 100 parts by weight of random copolymerization polypropylene resin, 0.1-3 parts by weight of antioxidant, 0.05-1 part by weight of nucleating agent and 2-15 parts by weight of toughening agent, and the preparation method comprises the following steps: and uniformly stirring and mixing the random copolymerization polypropylene resin, the antioxidant, the nucleating agent and the toughening agent, and performing extrusion granulation to obtain the special resin for the PPR pipe.
The invention relates to a preparation method of special resin for a toughened PPR pipe, wherein the random copolymerized polypropylene resin is synthesized by adopting a Ziegler-Natta catalyst system through a one-step method, the Ziegler-Natta catalyst system comprises a main catalyst, and the preparation method of the main catalyst comprises the following steps:
step 1, adding a spherical magnesium alkoxide compound into a mixture containing a titanium compound and a vanadium compound at the temperature of-20-10 ℃ for reaction, wherein the molar ratio of titanium to magnesium is 1;
step 2, raising the temperature to 30-80 ℃, and adding an internal electron donor compound, wherein the molar ratio of magnesium to the internal electron donor compound is 2-15 l;
and 3, heating to 100-150 ℃ for reaction, filtering the reaction mixture, adding a titanium-vanadium-containing compound which is equal to the titanium-vanadium-containing compound in the step 1, reacting at 100-150 ℃, filtering, washing and drying to obtain the catalyst.
The invention relates to a preparation method of special resin for a toughened PPR (polypropylene random copolymer) pipe, wherein a titanium compound is at least one of chlorotrialkoxytitanium, dichlorodialkoxytitanium, trichloroalkoxytitanium, titanium tetrachloride and titanium tetrabromide; the vanadium compound is at least one of ammonium hexafluorovanadate, vanadium nitrate, vanadyl oxalate, ammonium metavanadate, vanadyl sulfate, vanadium (IV) oxide sulfate hydrate, vanadium (III) sulfate, vanadium oxide trichloride, sodium orthovanadate and sodium metavanadate.
The invention relates to a preparation method of special resin for a toughened PPR (polypropylene random) pipe, wherein an internal electron donor is selected from one or more of aliphatic carboxylic ester, aromatic carboxylic ester, phosphate ester, dihydric alcohol ester, aliphatic diether and aromatic ether.
The invention relates to a preparation method of special resin for a toughened PPR pipe, wherein the preparation method of the spherical magnesium alkoxide compound comprises the following steps: under the protection of inert gas, anhydrous MgCl 2 And ethanol are added into a three-mouth bottle, then the temperature is raised to 110 to 140 ℃ to form a homogeneous solution, the homogeneous solution is stirred at a high speed for 0.5 to 2 hours and then transferred into n-hexane at the temperature of between 20 ℃ below zero and 10 ℃ below zero, the excessive n-hexane and ethanol are distilled out by slow heating and pressure reduction, magnesium chloride is cooled, crystallized and separated out to form spheres, and the spheres are dried in vacuum and stored under inert gas.
The invention relates to a preparation method of special resin for a toughened PPR pipe, wherein the preparation method of random copolymerized polypropylene resin comprises the following steps: and polymerizing propylene and ethylene in the presence of a main catalyst, a cocatalyst and an external electron donor to obtain the polypropylene random copolymer resin.
The invention relates to a preparation method of special resin for a toughened PPR pipe, wherein a cocatalyst is an organic aluminum compound, and an external electron donor is a silane compound.
The invention has the beneficial effects that:
the special resin for the PPR pipe provided by the invention has good impact resistance and processability, and solves the problem of weak toughness of polypropylene resin. Furthermore, the special resin for the PPR pipe can also have higher melt strength and rigidity, the technical indexes of the special material for the PPR pipe reach the level of foreign similar products, the defects that the processability is poor due to the fact that ethylene monomers are randomly added into polypropylene and the monomers are not uniformly dispersed, and the outer wall of the pipe is shark skin-shaped and the inner wall of the pipe is not smooth due to narrow molecular weight distribution are obviously improved, so that the processability, the mechanical property, the environmental stress cracking resistance and the long-term aging resistance of the random copolymerization polypropylene resin are obviously improved, and the special resin for the PPR pipe has good cost performance and popularization prospect.
Drawings
FIG. 1 is a schematic view showing the structure of a random copolymerized polypropylene resin of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are carried out on the premise of the technical solution of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are generally carried out under conventional conditions for the experimental methods not given specific conditions.
In the present invention, when a quality, concentration, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1 to 50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, and all fractional values between the above integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, specifically consider "nested sub-ranges" that extend from any endpoint within the range. For example, nested sub-ranges of exemplary range l-50 may include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction.
The invention provides a special resin for a toughened PPR pipe, which comprises the following components in parts by weight: 100 parts of random copolymerization polypropylene resin and 0.1-3 parts of antioxidant.
In one embodiment, in the random copolymerized polypropylene resin, a part of ethylene molecules are randomly distributed in the polypropylene segment, and the molar ratio of the randomly distributed ethylene molecules to the ethylene molecules is 70 to 100:100. it is generally considered that the structure in which a single ethylene molecule is inserted into a polypropylene segment is randomly distributed, and the structure in which two or more ethylene molecules are inserted into a polypropylene segment in succession is regularly distributed (i.e., non-randomly distributed). In the invention, part of ethylene molecules form a regular distribution structure, part of ethylene molecules form a random distribution structure, and the molar ratio of the randomly distributed ethylene molecules to all ethylene molecules (randomly distributed ethylene and regularly distributed ethylene) is 70-100:100. in another embodiment, the random copolymerized polypropylene resin has a melt flow rate of 0.2-0.5g/10min at 230 ℃ and a 2.16Kg load, a comonomer ethylene content of 2-10 wt%, and a simple beam impact strength of greater than 30KJ/m 2 。
In one embodiment, the present invention further provides a preparation method of the above random copolymerized polypropylene resin, which is synthesized by a one-step method using propylene as a raw material, ethylene as a comonomer, and a Ziegler-Natta catalyst system, wherein the Ziegler-Natta catalyst system includes a main catalyst, a cocatalyst, and an external electron donor, and the preparation method of the main catalyst includes the following steps:
step 1, adding a spherical magnesium alkoxide compound into a-20-10 ℃ mixture containing a titanium compound and a vanadium compound for reaction, wherein the molar ratio of titanium to magnesium is 1;
step 2, raising the temperature to 30-80 ℃, and adding an internal electron donor compound, wherein the molar ratio of magnesium to the internal electron donor compound is 2-15 l, namely the molar ratio of the spherical magnesium alkoxide compound to the internal electron donor compound is 2-15 l based on magnesium;
and 3, heating to 100-150 ℃ for reaction, filtering the reaction mixture, adding the titanium compound and the vanadium compound which are equal to those in the step 1, reacting at 100-150 ℃, filtering, washing and drying to obtain the catalyst.
In one embodiment, the titanium compound is at least one of chlorotrialkoxytitanium, dichlorodialkoxytitanium, trichloroalkoxytitanium, titanium tetrachloride and titanium tetrabromide; the vanadium compound is at least one of ammonium hexafluorovanadate, vanadium nitrate, vanadyl oxalate, ammonium metavanadate, vanadyl sulfate, vanadium (IV) oxide sulfate hydrate, vanadium (III) sulfate, vanadium oxide trichloride, sodium orthovanadate and sodium metavanadate.
In one embodiment, the spherical magnesium alkoxide compound is prepared by: adding a magnesium compound and alcohol into a three-neck flask under the protection of inert gas, heating to 110-140 ℃ to form a homogeneous solution, stirring at a high speed for 0.5-2 hours, transferring into n-hexane at the temperature of-20 to-10 ℃, slowly heating and distilling under reduced pressure to remove excessive n-hexane and alcohol, cooling and crystallizing the magnesium compound to separate out a ball, drying in vacuum, and storing under inert gas. The magnesium compound is selected from one of anhydrous magnesium dichloride, magnesium dibromide, chloromethoxymagnesium and chloroethoxymagnesium; the alcohol is selected from one of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol.
In one embodiment, the internal electron donor is selected from one or more of aliphatic carboxylic acid esters, aromatic carboxylic acid esters, phosphoric acid esters, glycol esters, aliphatic diethers and aromatic ethers, such as diisobutyl phthalate, di-n-butyl phthalate, diethyl 2-methyl-2-isopropylmalonate, 9-bis (methoxymethyl) fluorene, phenetole, o-diethylether and 2-methoxymethyl dibenzofuran.
Therefore, the main catalyst obtained by the invention is a solid catalyst component taking magnesium, titanium, vanadium, halogen and an internal electron donor as main components, and contains a Ti active site and a V active site on the same spherical magnesium alkoxide compound.
In one embodiment, a method for preparing a random copolymerized polypropylene resin includes: propylene and ethylene are polymerized, such as liquid-phase bulk polymerization or gas-phase polymerization, in the presence of a main catalyst, a cocatalyst and an external electron donor to obtain the random copolymer polypropylene resin.
In another embodiment, the cocatalyst is an organoaluminum compound and the external electron donor is a silane-based compound. In a further embodiment, the cocatalyst is an alkylaluminum compound, more preferably a trialkylaluminum compound; the external electron donor is at least one of tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisobutyldimethoxysilane and di-tert-butyldimethoxysilane.
In the random copolymer polypropylene resin obtained by the method, a large number of long-chain tie molecules exist, so that the random copolymer polypropylene resin forms an aggregation structure similar to a reinforced bar-concrete type structure, has high strength and good creep resistance, greatly improves the hydraulic resistance of a PPR (polypropylene random copolymer) pipe product, and has a structure shown in figure 1.
In one embodiment, the special resin for the PPR pipe further comprises 2-15 parts by weight of polybutene so as to improve the creep resistance of the product. In another embodiment, the polybutene of the present invention is an extrusion grade poly l-butene having a melt flow rate of 0.2 to 0.8g/10min at 230 ℃ under a load of 2.16Kg and a tensile strength greater than 20MPa.
In one embodiment, the resin special for the PPR pipe further comprises 0.05-1 part by weight of nucleating agent and 2-15 parts by weight of toughening agent, so as to solve the problem of low-temperature toughness of the product.
In another embodiment, the nucleating agent of the present invention is one or more of calcium suberate, calcium pimelate, calcium terephthalate, TMB-4 (N, N ' -tetrakis (4-methylphenyl) [1,1' -biphenyl ] -3,3' -diamine), TMB-5 (N, N ' -dicyclohexyl-2, 6-naphthalenedicarboxamide), NA-85, NB-328 (arylamide compounds), WBG-II (rare earth nucleating agent), STARNU-100 (N, N ' -dicyclohexylamine-2, 6-naphthalenedicarboxamide); the toughening agent is one or more of ethylene-octene copolymer, ethylene-propylene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, hydrogenated styrene-butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer and hydrogenated styrene-isoprene-styrene triblock copolymer.
In one embodiment, the antioxidant of the present invention may be one or more of a phenol type antioxidant, an amine type antioxidant, a phosphite type antioxidant, and a sulfur-containing ester type antioxidant, such as 2, 6-di-t-butyl-4-methylphenol, 2, 6-di-t-butyl-4-N-butylphenol, 4-hydroxymethyl-2, 6-di-t-butylphenol, N-phenyl- α -naphthylamine, butylated hydroxyaldehyde- α -naphthylamine, N '-diphenyl-p-phenylenediamine, pentaerythritol diisodecyl diphosphite, triisodecyl phosphite, diisodecyl phosphite, distearyl thiodipropionate, and dioctadecyl β, β' -thiodibutyrate.
The special resin for the PPR pipe can also comprise other auxiliary agents, such as processing aids, acid-absorbing agents and coupling agents, wherein the processing aids are organic silicon and organic fluorine polymer processing aids, such as PDMS (polydimethylsiloxane) of Doe Coning, fluoroelastomer FX-5920, FX-5911, FX-5924, FX-5916 and FPA-102 of 3M company, one or a mixture of a plurality of low molecular polypropylene and low molecular polyethylene wax in any proportion, the acid-absorbing agents are one or a plurality of calcium stearate, zinc stearate, magnesium stearate, hydrotalcite and the like, and the coupling agents are one or a plurality of silanes, phthalate esters, aluminate esters and rare earth coupling agents.
The special resin for the PPR pipe is prepared by uniformly mixing the polypropylene resin and various additives according to the proportion by a common method, and granulating by an extruder.
In order to improve the long-term hydrostatic pressure resistance problem of the PPR pipe, improve the creep property of the PPR pipe and keep the strength of the PPR pipe, the poly-1-butylene is added into the atactic polypropylene and is extruded after being mixed, so that the creep property of the pipe is improved.
The invention aims to improve the defect of insufficient low-temperature impact performance of the PPR pipe, and the phenomenon of brittle fracture easily occurs when external force is applied in the construction or transportation process in winter, particularly in the north, so that the normal use is influenced. The nucleating agent and the toughening agent are added into the atactic polypropylene, and the mixture is mixed and extruded out of the pipe, so that the low-temperature resistance of the pipe is improved.
According to the invention, the poly-1-butene, the nucleating agent and the toughening agent can also be added into the atactic polypropylene at the same time, and the pipes are extruded after being mixed, so that the creep property and the low temperature resistance of the pipes are improved at the same time.
In conclusion, the special resin for the PPR pipe has higher melt strength and rigidity, and simultaneously has good impact resistance and processability, and solves the problem that the polypropylene needs to improve the rigidity and the toughness. The technical indexes of the special resin for the PPR pipe reach the level of foreign like products, the defects that the processability is poor due to the fact that monomers are not uniformly dispersed when ethylene monomers are randomly added into polypropylene and the outer wall of the pipe is shark skin-shaped and the inner wall of the pipe is not smooth due to narrow molecular weight distribution are obviously improved, the processability, the mechanical property, the environmental stress cracking resistance and the long-term aging resistance of the random copolymerization polypropylene resin are obviously improved, and the special resin has good cost performance and popularization prospect.
The technical solution of the present invention is further described in detail by specific examples below.
(1) Preparing a main catalyst:
cat1# (1) adding spherical magnesium alkoxide compound into TiCl at-20-10 deg.C 4 And VCl 3 In a molar ratio of titanium to magnesium of 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) After filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃,and filtering, washing and drying to obtain the catalyst Cat1#.
The preparation method of the spherical magnesium alkoxide compound comprises the following steps: under the protection of nitrogen, anhydrous MgCl with certain quality is added 2 Adding ethanol into a three-neck flask, heating to 130 ℃ to obtain a homogeneous solution, stirring at a high speed for 1 hour, transferring into n-hexane at the temperature of-15 ℃, slowly heating and distilling under reduced pressure to remove excessive n-hexane and ethanol, cooling magnesium chloride, crystallizing, separating out balls, drying in vacuum, and storing under nitrogen.
The following preparation method of the magnesium alkoxide compound in Cat2# to Cat12# is the same as that in Cat1#, and the mixture of titanium and vanadium is TiCl 4 And VCl 3 A mixture of (a).
Cat2# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat2#.
Cat3# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat3#.
Cat4# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat4#.
Cat5# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound, namely diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding titanium compound and vanadium compound in the same amount as that in the step (1), reacting at 120 ℃ for 3 hours, filtering, washing and drying to obtain a catalyst Cat5#.
Cat6# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding titanium compound and vanadium compound in the same amount as that in the step (1), reacting at 120 ℃ for 3 hours, filtering, washing and drying to obtain a catalyst Cat6#.
Cat7# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound, namely diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain a catalyst Cat7#.
Cat8# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat8#.
Cat9# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat9#.
Cat10# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat10#.
Cat11# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat11#.
Cat12# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding titanium compound and vanadium compound which are equal to those in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain a catalyst Cat12#.
(2) Preparation of random copolymerized polypropylene
Resin # 1: the main catalyst is Cat1#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin No. 1 is obtained.
Resin # 2: the main catalyst is Cat2#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin No. 2 is obtained.
Resin # 3: the main catalyst is Cat3#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin 3#.
Resin 4#: the main catalyst is Cat4#, the cocatalyst is triethylaluminum, the external electron donor is cyclohexyl methyldimethoxysilane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymer polypropylene resin No. 4 is obtained.
Resin # 5: the main catalyst is Cat5#, the cocatalyst is triethylaluminum, the external electron donor is cyclohexyl methyldimethoxysilane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymer polypropylene resin 5#.
Resin 6#: the main catalyst is Cat6#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin 6#.
Resin 7#: the main catalyst is Cat7#, the cocatalyst is triethylaluminum, the external electron donor is cyclohexyl methyldimethoxysilane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymer polypropylene resin 7#.
Resin # 8: the main catalyst is Cat8#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin 8#.
Resin 9#: the main catalyst is Cat9#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin 9#.
Resin 10#: the main catalyst is Cat10#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin 10#.
Resin 11#: the main catalyst is Cat10#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin No. 11 is obtained.
Resin 12#: the main catalyst is Cat12#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin 12#.
(3) Preparation of special material for PPR pipe (the following materials are calculated by weight portion)
Example 1:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 2:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 3:
weighing polypropylene, antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes at a stirring speed of 500r/min to obtain uniform mixture;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 4:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 5:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 6:
weighing polypropylene, antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes at a stirring speed of 500r/min to obtain uniform mixture;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 7:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 8:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 9:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 10:
weighing polypropylene, antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes at a stirring speed of 500r/min to obtain uniform mixture;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 11:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 12:
weighing polypropylene, antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes at a stirring speed of 500r/min to obtain uniform mixture;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
(4) Preparation of creep-resistant PPR pipe special resin (the following substances are calculated by weight portion)
Example 13:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 14:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 15:
weighing polypropylene, polybutene, antioxidant and other assistants according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 16:
weighing polypropylene, polybutene, antioxidant and other assistants according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 17:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 18:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 19:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 20:
weighing polypropylene, polybutene, antioxidant and other assistants according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 21:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 22:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 23:
weighing polypropylene, polybutene, antioxidant and other assistants according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 24:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
(5) Preparation of resin special for toughening PPR pipe (the following substances are calculated by weight portion)
Example 25:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 26:
weighing polypropylene, nucleating agent, toughening agent, antioxidant and other auxiliary agents according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to ensure that the components are uniform;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 27:
weighing polypropylene, nucleating agent, toughening agent, antioxidant and other auxiliary agents according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to ensure that the components are uniform;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 28:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 29:
weighing polypropylene, nucleating agent, toughening agent, antioxidant and other auxiliary agents according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to ensure that the components are uniform;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 30:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 31:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 32:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 33:
weighing polypropylene, nucleating agent, toughening agent, antioxidant and other auxiliary agents according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to ensure that the components are uniform;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 34:
weighing polypropylene, nucleating agent, toughening agent, antioxidant and other auxiliary agents according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to ensure that the components are uniform;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 35:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 36:
weighing polypropylene, nucleating agent, toughening agent, antioxidant and other auxiliary agents according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to ensure that the components are uniform;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Comparative example:
the special material for foreign imported pipes is selected as the comparative example of the invention.
Table 1 shows the results of the performance analyses of examples and comparative examples
TABLE 1
As can be seen from Table 1, the special material for PPR pipes provided by the invention has excellent rigidity and toughness balance.
Testing the performance of the pipe:
the special pipe materials prepared in the examples 1 to 36 are extruded to prepare pipes 1 to 36, the hydrostatic performance of the pipes is tested, the imported material is also selected as a comparative example, and the test results are shown in the following table 2:
TABLE 2 hydrostatic test of pipes
Note: the time in the table is the tube blasting time of the hydrostatic test, and the standard is met when the ring stress is 16MPa and 17MPa and exceeds 1 hour; when tested at a high temperature of 95 ℃, the hydrostatic pressure of the pipe exceeds the standard time, but the pipe is not burst, so the specific time is not listed.
As shown in Table 2, the PPR pipe obtained by the invention has high rigidity and toughness to meet various performance requirements of indexes, and completely meets the requirements of users.
As shown in tables 1 and 2, the special material for the PPR pipe has higher melt strength and rigidity, and simultaneously has good impact resistance and processability, solves the problem that the polypropylene needs to improve the rigidity and the toughness, obviously improves the processability, the mechanical property, the environmental stress cracking resistance and the long-term aging resistance of the random copolymerization polypropylene resin, and has good cost performance and popularization prospect.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (12)
1. The special resin for the toughened PPR pipe is characterized by comprising the following components in parts by weight: 100 parts of random copolymerization polypropylene resin, 0.1-3 parts of antioxidant, 0.05-1 part of nucleating agent and 2-15 parts of toughening agent.
2. The special resin for the toughened PPR pipe material as claimed in claim 1, wherein the nucleating agent is one or more of calcium octanedioate, calcium heptanedioate, calcium terephthalate, TMB-4, TMB-5, NA-85, NB-328, WBG-II, STARNU-100; the toughening agent is one or more of ethylene-octene copolymer, ethylene-propylene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, hydrogenated styrene-butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer and hydrogenated styrene-isoprene-styrene triblock copolymer.
3. The resin special for the toughened PPR pipe as claimed in claim 1, wherein in the random copolymerized polypropylene resin, part of ethylene molecules are randomly distributed in the polypropylene chain segment, and the molar ratio of the randomly distributed ethylene molecules to the ethylene molecules is 70-100:100.
4. the special resin for the toughened PPR pipe material as claimed in claim 1, wherein the melt flow rate of the random copolymerized polypropylene resin is 0.2-0.5g/10min at 230 ℃ and under a load of 2.16Kg, the comonomer ethylene content is 2-10 wt%, and the impact strength of the simply supported beam is more than 30KJ/m 2 。
5. The resin special for the toughened PPR pipe as claimed in claim 1, wherein the antioxidant is one or more of phenolic antioxidant, amine antioxidant, phosphite antioxidant and sulfur-containing ester antioxidant.
6. A preparation method of special resin for a toughened PPR pipe is characterized by comprising 100 parts by weight of random copolymerization polypropylene resin, 0.1-3 parts by weight of antioxidant, 0.05-1 part by weight of nucleating agent and 2-15 parts by weight of toughening agent, and the preparation method comprises the following steps: and uniformly stirring and mixing the random copolymerization polypropylene resin, the antioxidant, the nucleating agent and the toughening agent, and performing extrusion granulation to obtain the special resin for the PPR pipe.
7. The method for preparing the special resin for the toughened PPR pipe as claimed in claim 6, wherein the random copolymerized polypropylene resin is synthesized by a one-step method by using a Ziegler-Natta catalyst system, the Ziegler-Natta catalyst system comprises a main catalyst, and the preparation method of the main catalyst comprises the following steps:
step 1, adding a spherical magnesium alkoxide compound into a mixture containing a titanium compound and a vanadium compound at the temperature of-20-10 ℃ for reaction, wherein the molar ratio of titanium to magnesium is 1-1;
step 2, raising the temperature to 30-80 ℃, and adding an internal electron donor compound, wherein the molar ratio of magnesium to the internal electron donor compound is 2-15 l;
and step 3, heating to 100-150 ℃ for reaction, filtering the reaction mixture, adding the titanium compound and the vanadium compound which are equal to those in the step 1, reacting at 100-150 ℃, filtering, washing and drying to obtain the catalyst.
8. The method for preparing the special resin for the toughened PPR pipe as claimed in claim 7, wherein said titanium compound is at least one of chlorotrialkoxytitanium, dichlorodialkoxytitanium, trichloroalkoxytitanium, titanium tetrachloride and titanium tetrabromide; the vanadium compound is at least one of ammonium hexafluorovanadate, vanadium nitrate, vanadyl oxalate, ammonium metavanadate, vanadyl sulfate, vanadium (IV) oxide sulfate hydrate, vanadium (III) sulfate, vanadium oxide trichloride, sodium orthovanadate and sodium metavanadate.
9. The preparation method of the special resin for the toughened PPR pipe as claimed in claim 7, wherein the internal electron donor is selected from one or more of aliphatic carboxylic acid ester, aromatic carboxylic acid ester, phosphoric acid ester, glycol ester, aliphatic diether and aromatic ether.
10. The preparation method of the special resin for the toughened PPR pipe material as claimed in claim 7, wherein the preparation method of the spherical magnesium alkoxide compound comprises the following steps: under the protection of inert gas, anhydrous MgCl 2 Adding ethanol into a three-neck flask, heating to 110-140 ℃ to obtain a homogeneous solution, stirring at a high speed for 0.5-2 hours, transferring into n-hexane at the temperature of-20 to-10 ℃, slowly heating, decompressing and distilling out excessive n-hexane and ethanol, cooling magnesium chloride, crystallizing, separating out balls, drying in vacuum, and storing under inert gas.
11. The preparation method of the special resin for the toughened PPR pipe as claimed in claim 7, wherein the preparation method of the random copolymerized polypropylene resin comprises: and polymerizing propylene and ethylene in the presence of a main catalyst, a cocatalyst and an external electron donor to obtain the random copolymerization polypropylene resin.
12. The preparation method of the special resin for the toughened PPR pipe as claimed in claim 11, wherein the cocatalyst is an organic aluminum compound, and the external electron donor is a silane compound.
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| CN106750988A (en) * | 2016-11-22 | 2017-05-31 | 广东联塑科技实业有限公司 | A kind of PPR pipe with excellent low temperature toughness and preparation method thereof |
| CN106832069A (en) * | 2017-02-22 | 2017-06-13 | 营口市风光化工有限公司 | A kind of catalyst for olefinic polymerization and preparation method thereof |
| CN108864347A (en) * | 2018-06-22 | 2018-11-23 | 云南云天化石化有限公司 | The production method of PPR pipe PP Pipe Compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106750988A (en) * | 2016-11-22 | 2017-05-31 | 广东联塑科技实业有限公司 | A kind of PPR pipe with excellent low temperature toughness and preparation method thereof |
| CN106832069A (en) * | 2017-02-22 | 2017-06-13 | 营口市风光化工有限公司 | A kind of catalyst for olefinic polymerization and preparation method thereof |
| CN108864347A (en) * | 2018-06-22 | 2018-11-23 | 云南云天化石化有限公司 | The production method of PPR pipe PP Pipe Compound |
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