CN110591220A - High-modulus modified polypropylene krah pipe and production method thereof - Google Patents
High-modulus modified polypropylene krah pipe and production method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of krah pipes, and provides a high-modulus modified polypropylene krah pipe and a production method thereof. The high-modulus modified polypropylene Krah pipe comprises the following components in parts by weight: 100-150 parts of polypropylene, 5-15 parts of nano calcium carbonate, 5-10 parts of glass fiber powder, 10-20 parts of nano basic magnesium sulfate whisker, 3-10 parts of carboxylated silicon dioxide, 0.05-0.1 part of calcium stearate, 0.13-0.25 part of rosin amide, 2-5 parts of polyethylene, 0.02-0.05 part of cooling master batch, 0.5-2 parts of organic silicon tackifier, 5-10 parts of maleic anhydride grafted polypropylene, 2-5 parts of fully-vulcanized ultrafine powder nitrile rubber, 1-2 parts of trimethylolpropane trimethacrylate, 5-10 parts of metallocene polyolefin elastomer, 0.2-1 part of silane coupling agent, 0.5-2 parts of tetrabromobenzene anhydride ester, 0.5-1 part of antioxidant and 2-5 parts of heat stabilizer. The invention solves the problems that the rigidity of a high-density polyethylene carat pipe ring in the prior art is difficult to improve and a carat pipe cannot be formed by winding domestic polypropylene materials.
Description
Technical Field
The invention belongs to the technical field of krah pipes, and relates to a high-modulus modified polypropylene krah pipe and a production method thereof.
Background
The large-caliber pipe produced in China, namely the high-density polyethylene structural wall thermal-state winding pipe, is called Krah pipe for short, is a novel special-shaped structural wall pipe and is manufactured by adopting a high-density polyethylene thermal winding forming process. The Krah pipe is invented by German Krah company in the end of the eighties of the last century, China is introduced in the end of the 90 s, and the Krah pipe is widely used for urban municipal underground drainage and sewage pipelines and also used for pipeline systems for cables and optical cable sheaths and the like. Because the use environment is complex, the ring rigidity requirement of the Krah pipe is high.
The ring stiffness of the pipe is low due to the physical and chemical indexes of polyethylene, a large amount of raw materials are used for producing the Krah pipe so as to achieve the corresponding ring stiffness, the quality is heavier, the manufacturing cost is improved, the material waste is also caused, and the operable space for modification is small; certain properties of the polypropylene material are superior to those of high-density polyethylene, and the pure polypropylene material has some defects which can not be directly used for the production of the Krah pipe, particularly modulus and hot melt property, so that the polypropylene material is modified to improve the properties of the final Krah pipe product, and better meets the requirements of the actual market, particularly the high-end market. Meanwhile, the weight of the Krah pipe product is reduced, and the ring rigidity is improved. At present, the material capable of winding the polypropylene Krah pipe is monopolized abroad, and the localization of the high-performance pipeline material needs to be solved urgently.
Disclosure of Invention
The invention provides a high-modulus modified polypropylene Krah pipe and a production method thereof, and solves the problems that in the prior art, the ring stiffness of a high-density polyethylene Krah pipe is difficult to improve, and the Krah pipe cannot be formed by winding domestic polypropylene materials.
The technical scheme of the invention is realized as follows:
a high modulus modified polypropylene carat pipe is composed of the following components in parts by weight:
100-150 parts of polypropylene, 5-15 parts of nano calcium carbonate, 5-10 parts of glass fiber powder, 10-20 parts of nano basic magnesium sulfate whisker, 3-10 parts of carboxylated silicon dioxide, 0.05-0.1 part of calcium stearate, 0.13-0.25 part of rosin amide, 2-5 parts of polyethylene, 0.02-0.05 part of cooling master batch, 0.5-2 parts of organic silicon tackifier, 5-10 parts of maleic anhydride grafted polypropylene, 2-5 parts of fully-vulcanized ultrafine powder nitrile rubber, 1-2 parts of trimethylolpropane trimethacrylate, 5-10 parts of metallocene polyolefin elastomer, 0.2-1 part of silane coupling agent, 0.5-2 parts of tetrabromobenzene anhydride ester, 0.5-1 part of antioxidant and 2-5 parts of heat stabilizer.
As a further technical scheme, the paint comprises the following components in parts by weight:
130 parts of polypropylene, 10 parts of nano calcium carbonate, 7 parts of glass fiber powder, 15 parts of nano basic magnesium sulfate whisker, 6 parts of carboxylated silicon dioxide, 0.07 part of calcium stearate, 0.2 part of rosin amide, 3 parts of polyethylene, 0.04 part of cooling master batch, 1.5 parts of organic silicon tackifier, 7 parts of maleic anhydride grafted polypropylene, 3 parts of fully-vulcanized superfine powder nitrile rubber, 1.5 parts of trimethylolpropane trimethacrylate, 7 parts of metallocene polyolefin elastomer, 0.5 part of silane coupling agent, 1.2 parts of tetrabromobenzene anhydride ester, 0.7 part of antioxidant and 3 parts of heat stabilizer.
As a further technical scheme, the cooling master batch is a polypropylene cooling master batch PA-520.
As a further technical scheme, the silane coupling agent is a silane coupling agent KH 550.
As a further technical scheme, the antioxidant is antioxidant 1010.
As a further technical scheme, the heat stabilizer is a calcium zinc stabilizer.
A production method of a high modulus modified polypropylene Krah pipe comprises the following steps:
s1, weighing each component for later use according to the formula of the high-modulus modified polypropylene krat pipe;
s2, mixing the nano calcium carbonate, the glass fiber powder, the nano basic magnesium sulfate whisker and the silane coupling agent for 5min at the rotating speed of 200r/min of a high-speed mixer, and then mixing for 10min at the rotating speed of 2500r/min to obtain the nano calcium carbonate, the glass fiber powder and the nano basic magnesium sulfate whisker which are subjected to surface treatment;
s3, mixing polypropylene, polyethylene, fully-vulcanized ultrafine powder nitrile rubber, trimethylolpropane trimethacrylate and metallocene polyolefin elastomer for 10min at the rotating speed of 200r/min of a high-speed mixer to obtain a first premix;
s4, mixing the maleic anhydride grafted polypropylene with the surface-treated nano calcium carbonate, the glass fiber powder and the nano basic magnesium sulfate whisker obtained in the step S2 for 10min at the rotating speed of 200r/min of a high-speed mixer to obtain a second premix;
s5, mixing the premix I obtained in the step S3 and the premix II obtained in the step S4 for 5min at the rotating speed of 200r/min of a high-speed mixer, adding carboxylated silicon dioxide, cooling master batches, calcium stearate, rosin amide, tetrabromobenzene anhydride ester, an antioxidant and a heat stabilizer, and uniformly mixing at the rotating speed of 2000/min to obtain a mixed material;
s6, granulating the mixed material obtained in the step S5 through a double-screw granulator for later use;
s7, drying the granules granulated in the step S6, and processing the dried granules by a Krah pipe device to obtain a formed pipe;
s8, annealing the formed pipe obtained in the step S7 to obtain the high modulus modified polypropylene carat pipe.
As a further technical scheme, the moisture content of the dried particles in the step S7 is controlled to be less than or equal to 1 per thousand.
As a further technical proposal, the annealing treatment condition in the step S7 is heat preservation at 120 ℃ for 1 h.
The invention has the following using principle and beneficial effects:
in the invention, the raw materials with specific mixture ratio and the preparation method are obtained by a great deal of heart blood research of the inventor, and all the components in the whole formula are matched with each other to play a role in mutual synergism and synergy, so that the ring stiffness, the tensile strength, the bending elastic modulus and the like of the prepared modified polypropylene Krah pipe are obviously improved, the longitudinal retraction rate is low, the modified polypropylene Krah pipe is not cracked after a drop hammer impact test, the actual use requirement is met, and the modified polypropylene Krah pipe has a wide application prospect.
In the invention, polypropylene is taken as a basic raw material, and multiple auxiliary agents are adopted to modify polypropylene, so that the ring stiffness of the prepared modified polypropylene Krah pipe is obviously improved, the problem of low ring stiffness of polyethylene Krah pipes in the prior art is solved, the strength of the modified polypropylene Krah pipe is improved by matching nano calcium carbonate, nano basic magnesium sulfate whisker and glass fiber powder in the formula, the compatibility of polyethylene, carboxylated silicon dioxide and maleic anhydride grafted polypropylene is improved, the compatibility of the auxiliary agents in a polypropylene matrix is improved, the impact resistance of the modified polypropylene Krah pipe is improved by matching metallocene polyolefin elastomer, fully vulcanized ultrafine powder nitrile rubber and hydroxymethyl propane trimethacrylate, the impact resistance of the modified polypropylene Krah pipe is improved by matching calcium stearate and rosin amide, the ring stiffness and impact resistance of the modified polypropylene Krah pipe are improved, and the nano basic magnesium sulfate whisker and tetrabromobenzene anhydride ester are, the flame retardance of the modified polypropylene Krah pipe is improved, and the antioxidant and the calcium-zinc stabilizer are added, so that the performance of the modified polypropylene Krah pipe is more stable, and therefore, the prepared modified polypropylene Krah pipe is better in comprehensive performances such as ring stiffness, tensile strength, bending elastic modulus and impact resistance and high in practicability.
According to the invention, the strength of the modified polypropylene Krah pipe is obviously improved by adding the nano calcium carbonate and the nano basic magnesium sulfate whisker, the nano calcium carbonate, the nano basic magnesium sulfate whisker and the glass fiber powder are compatible with each other, the surface treatment is carried out by the silane coupling agent, the compatibility of the nano calcium carbonate, the nano basic magnesium sulfate whisker and the glass fiber powder with a polypropylene matrix is obviously improved, the glass fiber powder forms a three-dimensional framework structure in the polypropylene matrix, and the nano calcium carbonate and the nano basic magnesium sulfate whisker are distributed in the three-dimensional framework structure, so that the formed three-dimensional framework structure is more stable and plays a role in bearing stress, and the strength of the modified polypropylene Krah pipe is improved.
According to the invention, the strength of the modified polypropylene kraton pipe is obviously improved by adding the calcium stearate, the rosin amide and the hydroxymethyl propane trimethyl acrylate, the crystallization speed of polypropylene molecules can be accelerated by the cooperation of the calcium stearate and the rosin amide, so that the polypropylene molecules have a microcrystalline structure, the ring rigidity and the impact resistance of the modified polypropylene kraton pipe are improved, the hydroxymethyl propane trimethyl acrylate is matched with polyethylene, the dispersion of the calcium stearate and the rosin amide in a polypropylene matrix is promoted, and the crosslinking of the metallocene polyolefin elastomer and the fully-vulcanized ultrafine powder nitrile rubber in the melting and mixing process is promoted by adding the hydroxymethyl propane trimethyl acrylate, so that the strength of the modified polypropylene kraton pipe is improved.
According to the invention, the addition of polyethylene, carboxylated silicon dioxide and maleic anhydride grafted polypropylene obviously improves the strength of the modified polypropylene Kraft pipe, the melting point of polypropylene can be reduced by blending a small amount of polyethylene and polypropylene, hydroxyl on the surface of nano calcium carbonate and carboxyl on the surface of carboxylated silicon dioxide are combined through esterification and then are uniformly distributed in a three-dimensional framework structure formed by glass fiber powder, and the addition of maleic anhydride grafted polypropylene obviously improves the compatibility of the nano basic magnesium sulfate whisker and a polypropylene matrix, so that the polyethylene, carboxylated silicon dioxide and maleic anhydride grafted polypropylene are compatible with other components in the formula, and the strength of the modified polypropylene Kraft pipe is obviously improved.
The preparation method of the invention leads the modified polypropylene Clara tube to have better comprehensive properties such as ring stiffness, tensile strength, bending elastic modulus, impact resistance and the like, firstly, the raw materials are blended step by step and then melted, mixed and extruded, the components can be better mixed and dispersed, and the components in the raw materials are better compatible, thus the prepared modified polypropylene Clara tube has better comprehensive properties such as ring stiffness, tensile strength, bending elastic modulus, impact resistance and the like, in addition, the modified polypropylene Clara tube is annealed after being wound and formed, thus the local stress of a pipeline can be eliminated, and the overall performance of the modified polypropylene Clara tube is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A high modulus modified polypropylene carat pipe is composed of the following components in parts by weight:
100 parts of polypropylene, 5 parts of nano calcium carbonate, 5 parts of glass fiber powder, 10 parts of nano basic magnesium sulfate whisker, 3 parts of carboxylated silicon dioxide, 0.05 part of calcium stearate, 0.13 part of rosin amide, 2 parts of polyethylene, PA-5200.02 parts of polypropylene cooling master batch, 0.5 part of organic silicon tackifier, 5 parts of maleic anhydride grafted polypropylene, 2 parts of fully-vulcanized ultrafine powder nitrile rubber, 1 part of trimethylolpropane trimethacrylate, 5 parts of metallocene polyolefin elastomer, KH 5500.2 parts of silane coupling agent, 0.5 part of tetrabromobenzene anhydride ester, 10100.5 parts of antioxidant and 2 parts of calcium-zinc stabilizer.
The production method comprises the following steps:
s1, weighing the components according to the formula for later use;
s2, mixing the nano calcium carbonate, the glass fiber powder, the nano basic magnesium sulfate whisker and the silane coupling agent for 5min at the rotating speed of 200r/min of a high-speed mixer, and then mixing for 10min at the rotating speed of 2500r/min to obtain the nano calcium carbonate, the glass fiber powder and the nano basic magnesium sulfate whisker which are subjected to surface treatment;
s3, mixing polypropylene, polyethylene, fully-vulcanized ultrafine powder nitrile rubber, trimethylolpropane trimethacrylate and metallocene polyolefin elastomer for 10min at the rotating speed of 200r/min of a high-speed mixer to obtain a first premix;
s4, mixing the maleic anhydride grafted polypropylene with the surface-treated nano calcium carbonate, the glass fiber powder and the nano basic magnesium sulfate whisker obtained in the step S2 for 10min at the rotating speed of 200r/min of a high-speed mixer to obtain a second premix;
s5, mixing the premix I obtained in the step S3 and the premix II obtained in the step S4 for 5min at the rotating speed of 200r/min of a high-speed mixer, adding carboxylated silicon dioxide, polypropylene cooling master batches PA-520, calcium stearate, rosin amide, tetrabromophthalic anhydride ester, antioxidant 1010 and a calcium-zinc stabilizer, and uniformly mixing at the rotating speed of 2000/min to obtain a mixed material;
s6, granulating the mixed material obtained in the step S5 through a double-screw granulator for later use;
s7, drying the granules granulated in the step S6, controlling the moisture of the dried granules to be less than or equal to 1 per thousand, and processing the granules by a Krah pipe device to obtain a formed pipe;
s8, carrying out annealing treatment on the formed pipe obtained in the step S7 at the temperature of 120 ℃ for 0.5-1 h to obtain the high-modulus modified polypropylene Krah pipe.
Example 2
A high modulus modified polypropylene carat pipe is composed of the following components in parts by weight:
120 parts of polypropylene, 8 parts of nano calcium carbonate, 6 parts of glass fiber powder, 14 parts of nano basic magnesium sulfate whisker, 5 parts of carboxylated silicon dioxide, 0.06 part of calcium stearate, 0.18 part of rosin amide, 2.5 parts of polyethylene, PA-5200.03 parts of polypropylene cooling master batch, 1.2 parts of organic silicon tackifier, 6 parts of maleic anhydride grafted polypropylene, 2.5 parts of fully vulcanized ultrafine powder nitrile rubber, 1.3 parts of trimethylolpropane trimethacrylate, 6 parts of metallocene polyolefin elastomer, KH 5500.4 parts of silane coupling agent, 1 part of tetrabromophthalic anhydride ester, 10100.6 parts of antioxidant and 2.5 parts of calcium zinc stabilizer.
The production method is the same as example 1.
Example 3
A high modulus modified polypropylene carat pipe is composed of the following components in parts by weight:
130 parts of polypropylene, 10 parts of nano calcium carbonate, 7 parts of glass fiber powder, 15 parts of nano basic magnesium sulfate whisker, 6 parts of carboxylated silicon dioxide, 0.07 part of calcium stearate, 0.2 part of rosin amide, 3 parts of polyethylene, PA-5200.04 parts of polypropylene cooling master batch, 1.5 parts of organic silicon tackifier, 7 parts of maleic anhydride grafted polypropylene, 3 parts of fully-vulcanized ultrafine powder nitrile rubber, 1.5 parts of trimethylolpropane trimethacrylate, 7 parts of metallocene polyolefin elastomer, KH 5500.5 parts of silane coupling agent, 1.2 parts of tetrabromobenzoate ester, 10100.7 parts of antioxidant and 3 parts of calcium zinc stabilizer.
The production method is the same as example 1.
Example 4
A high modulus modified polypropylene carat pipe is composed of the following components in parts by weight:
140 parts of polypropylene, 12 parts of nano calcium carbonate, 8 parts of glass fiber powder, 16 parts of nano basic magnesium sulfate whisker, 7 parts of carboxylated silicon dioxide, 0.08 part of calcium stearate, 0.22 part of rosin amide, 4 parts of polyethylene, PA-5200.04 parts of polypropylene cooling master batch, 1.6 parts of organic silicon tackifier, 8 parts of maleic anhydride grafted polypropylene, 4 parts of fully-vulcanized ultrafine powder nitrile rubber, 1.7 parts of trimethylolpropane trimethacrylate, 8 parts of metallocene polyolefin elastomer, KH 5500.6 parts of silane coupling agent, 1.5 parts of tetrabromobenzoate ester, 10100.8 parts of antioxidant and 4 parts of calcium zinc stabilizer.
The production method is the same as example 1.
Example 5
A high modulus modified polypropylene carat pipe is composed of the following components in parts by weight:
150 parts of polypropylene, 15 parts of nano calcium carbonate, 10 parts of glass fiber powder, 20 parts of nano basic magnesium sulfate whisker, 0.1 part of calcium stearate, 10 parts of carboxylated silicon dioxide, 0.25 part of rosin amide, 5 parts of polyethylene, PA-5200.05 parts of polypropylene cooling master batch, 2 parts of organic silicon tackifier, 10 parts of maleic anhydride grafted polypropylene, 5 parts of fully-vulcanized ultrafine powder nitrile rubber, 2 parts of trimethylolpropane trimethacrylate, 10 parts of metallocene polyolefin elastomer, 1 part of silane coupling agent KH 5501, 2 parts of tetrabromobenzene anhydride ester, 10101 parts of antioxidant and 5 parts of calcium zinc stabilizer.
The production method is the same as example 1.
Comparative example 1
A high modulus modified polypropylene carat pipe is composed of the following components in parts by weight:
130 parts of polypropylene, 7 parts of glass fiber powder, 6 parts of carboxylated silicon dioxide, 0.07 part of calcium stearate, 0.2 part of rosin amide, 3 parts of polyethylene, 3 parts of polypropylene cooling master batch PA-5204, 1.5 parts of organic silicon tackifier, 7 parts of maleic anhydride grafted polypropylene, 3 parts of fully vulcanized ultrafine powder nitrile rubber, 1.5 parts of trimethylolpropane trimethacrylate, 7 parts of metallocene polyolefin elastomer, KH 5500.5 parts of silane coupling agent, 1.2 parts of tetrabromobenzene anhydride ester, 10100.7 parts of antioxidant and 3 parts of calcium-zinc stabilizer.
The production method is the same as the example 1 except that the nano calcium carbonate and the nano basic magnesium sulfate whiskers in the steps S2 and S4 are deleted correspondingly.
Comparative example 2
A high modulus modified polypropylene carat pipe is composed of the following components in parts by weight:
130 parts of polypropylene, 10 parts of nano calcium carbonate, 7 parts of glass fiber powder, 15 parts of nano basic magnesium sulfate whisker, 6 parts of carboxylated silicon dioxide, 0.07 part of calcium stearate, 0.2 part of rosin amide, 3 parts of polyethylene, 7 parts of polypropylene cooling master batch PA-5204, 1.5 parts of organic silicon tackifier, 7 parts of maleic anhydride grafted polypropylene, 3 parts of fully-vulcanized ultrafine powder nitrile rubber, 1.5 parts of trimethylolpropane trimethacrylate, 7 parts of metallocene polyolefin elastomer, KH 5500.5 parts of silane coupling agent, 1.2 parts of tetrabromobenzene anhydride ester, 10100.7 parts of antioxidant and 3 parts of calcium-zinc stabilizer.
The production method is the same as that of example 1 except that polyethylene in step S3, maleic anhydride-grafted polypropylene in step S4, and carboxylated silica in step S5 are removed.
Comparative example 3
A high modulus modified polypropylene carat pipe is composed of the following components in parts by weight:
130 parts of polypropylene, 10 parts of nano calcium carbonate, 7 parts of glass fiber powder, 15 parts of nano basic magnesium sulfate whisker, 6 parts of carboxylated silicon dioxide, 0.07 part of calcium stearate, 0.2 part of rosin amide, 3 parts of polyethylene, 7 parts of polypropylene cooling master batch PA-5204, 1.5 parts of organic silicon tackifier, 7 parts of maleic anhydride grafted polypropylene, 3 parts of fully-vulcanized ultrafine powder nitrile rubber, 1.5 parts of trimethylolpropane trimethacrylate, 7 parts of metallocene polyolefin elastomer, KH 5500.5 parts of silane coupling agent, 1.2 parts of tetrabromobenzene anhydride ester, 10100.7 parts of antioxidant and 3 parts of calcium-zinc stabilizer.
The production method is the same as that of example 1 except that trimethylolpropane trimethacrylate in step S3 is removed, calcium stearate and rosin amide in step S5 are removed.
Comparative example 4
A high modulus modified polypropylene carat pipe is composed of the following components in parts by weight:
130 parts of polypropylene, 10 parts of nano calcium carbonate, 7 parts of glass fiber powder, 15 parts of nano basic magnesium sulfate whisker, 6 parts of carboxylated silicon dioxide, 0.07 part of calcium stearate, 0.2 part of rosin amide, 3 parts of polyethylene, 7 parts of polypropylene cooling master batch PA-5204, 1.5 parts of organic silicon tackifier, 7 parts of maleic anhydride grafted polypropylene, 3 parts of fully-vulcanized ultrafine powder nitrile rubber, 1.5 parts of trimethylolpropane trimethacrylate, 7 parts of metallocene polyolefin elastomer, KH 5500.5 parts of silane coupling agent, 1.2 parts of tetrabromobenzene anhydride ester, 10100.7 parts of antioxidant and 3 parts of calcium-zinc stabilizer.
The production method comprises the following steps:
s1, weighing the components according to the formula for later use;
s2, mixing the nano calcium carbonate, the glass fiber powder, the nano basic magnesium sulfate whisker and the silane coupling agent for 5min at the rotating speed of 200r/min of a high-speed mixer, and then mixing for 10min at the rotating speed of 2500r/min to obtain the nano calcium carbonate, the glass fiber powder and the nano basic magnesium sulfate whisker which are subjected to surface treatment;
s3, mixing the surface-treated nano calcium carbonate, glass fiber powder, nano basic magnesium sulfate whisker, polypropylene, polyethylene, fully-vulcanized ultrafine powder nitrile rubber, trimethylolpropane trimethacrylate, metallocene polyolefin elastomer and maleic anhydride grafted polypropylene obtained in the step S2 for 20min at the rotating speed of 200r/min of a high-speed mixer, adding carboxylated silicon dioxide, cooling master batches, calcium stearate, rosin amide, tetrabromophthalic anhydride ester, an antioxidant and a heat stabilizer, and uniformly mixing to obtain a mixed material;
s4, granulating the mixed material obtained in the step S3 through a double-screw granulator for later use;
s5, drying the granules granulated in the step S4, controlling the moisture of the dried granules to be less than or equal to 1 per thousand, and processing the granules by a Krah pipe device to obtain a formed pipe;
s6, keeping the temperature of the formed pipe obtained in the step S5 at 120 ℃ for 1h, and annealing to obtain the high-modulus modified polypropylene Krah pipe.
The following performance tests were performed on pellets pelletized by a twin-screw pelletizer in the above examples and comparative examples, using a high density polyethylene carat pipe raw material made by the Kilin petrochemical industry under the designation JHCC 100S as a control:
1. melt index: testing the melt index of the material according to the specification in GB/T3682-2000 determination of the melt mass flow rate and the melt volume flow rate of the thermoplastic plastics;
2. oxidation induction time: according to GB/T19466.6-2009 part 6 of Differential Scanning Calorimetry (DSC) of plastics: determination of oxidation induction time (isothermal OIT) and oxidation induction temperature (dynamic OIT), testing the oxidation induction time of the material;
3. tensile property: testing the tensile strength and the elongation at break of the material according to the regulation in GB/T8804.3-2003 polyolefin pipe for testing the tensile property of thermoplastic plastic pipes;
the test results are given in the following table:
TABLE 1 results of particle Performance test after granulation in twin-screw granulator in examples and comparative examples
As can be seen from the data in Table 1, the melt indexes of the granules granulated by the twin-screw granulator in the examples and the comparative examples are similar, but the oxidation induction time of the granules granulated in the examples 1 to 5 is longer, the tensile strength and the elongation at break are higher, and the granules granulated in the examples 1 to 5 are more suitable for being used as the raw material of the Krah pipe.
The following performance tests were performed on the modified polypropylene cral pipe prepared in the above examples and comparative examples using cral pipe produced from gillin petrochemical high density polyethylene jhcc 100S as a control:
1. ring stiffness: the ring stiffness of the sample was tested as specified in GB 9647-;
2. longitudinal retraction rate: testing the longitudinal shrinkage rate of the sample according to the regulation in GB/T6671-2001' determination of the longitudinal shrinkage rate of the thermoplastic plastic pipe);
3. tensile strength: according to the regulation in GB/T8804.3-2003 polyolefin pipe for measuring the tensile property of thermoplastic plastic pipes, the tensile property of the sample is tested;
4. bending property: testing the bending strength and the bending elastic modulus of the sample according to the regulations in GB/T9341-2008 & ltPlastic bending Performance test method';
5. drop hammer impact: according to the regulations in GB/T6112-1985 method for testing the impact resistance of thermoplastic plastic pipes and pipe fittings, the sample is subjected to impact resistance test, and during the test, the sample is stored at the temperature of minus 5 ℃ for 8 hours, the diameter of a hammer head is 20mm, the mass of a drop hammer is 10kg, and the height of the drop hammer is 2 m;
the test results are given in the following table:
TABLE 2 results of performance test of modified polypropylene Krah pipes prepared in examples 1-5 and comparative examples 1-4
As can be seen from the data in Table 2, compared with comparative examples 1 to 4 and a comparison group, the modified polypropylene Kraft pipe prepared in examples 1 to 5 of the invention has the advantages of obviously improved ring stiffness, tensile strength, bending elastic modulus and the like, low longitudinal shrinkage rate and no cracking after a drop hammer impact test, and the modified polypropylene Kraft pipe prepared in the invention has high strength and ring stiffness, meets the actual use requirement and has wide application prospect.
It can be seen from the data of examples 1 to 5 and comparative example 1 in table 2 that the strength of the modified polypropylene clarinet is significantly improved by adding the nano calcium carbonate and the nano basic magnesium sulfate whisker, the nano calcium carbonate, the nano basic magnesium sulfate whisker and the glass fiber powder are compatible with each other, and the compatibility of the nano calcium carbonate, the nano basic magnesium sulfate whisker and the glass fiber powder with a polypropylene matrix is significantly improved by performing surface treatment through a silane coupling agent, so that the glass fiber powder forms a three-dimensional framework structure in the polypropylene matrix, and the nano-sized calcium carbonate and the nano basic magnesium sulfate whisker are distributed in the three-dimensional framework structure, so that the formed three-dimensional framework structure is more stable, and plays a role in bearing stress, and the strength of the modified polypropylene clarinet is improved.
It can be seen from the data of examples 1 to 5 and comparative example 2 in table 2 that the addition of polyethylene, carboxylated silica, and maleic anhydride grafted polypropylene significantly improves the strength of the modified polypropylene krait, the blending of a small amount of polyethylene and polypropylene can reduce the melting point of polypropylene, the hydroxyl on the surface of nano calcium carbonate and the carboxyl on the surface of carboxylated silica are combined by esterification and then uniformly distributed in the three-dimensional framework structure formed by glass fiber powder, and the addition of maleic anhydride grafted polypropylene significantly improves the compatibility of the nano basic magnesium sulfate whisker and the polypropylene matrix, so that the polyethylene, carboxylated silica, and maleic anhydride grafted polypropylene are compatible with other components in the formula, and the strength of the modified polypropylene krait is significantly improved.
It can be seen from the data of examples 1 to 5 and comparative example 3 in table 2 that the addition of calcium stearate, rosin amide, and hydroxymethyl propane trimethacrylate significantly improves the strength of the modified polypropylene kraut tube, the calcium stearate and the rosin amide cooperate to accelerate the crystallization rate of polypropylene molecules, so that the polypropylene molecules have a microcrystalline structure, thereby improving the ring stiffness and impact resistance of the modified polypropylene kraut tube, the hydroxymethyl propane trimethacrylate and polyethylene cooperate to promote the dispersion of the calcium stearate and the rosin amide in the polypropylene matrix, and the addition of the hydroxymethyl propane trimethacrylate also promotes the crosslinking of the metallocene polyolefin elastomer and the fully-vulcanized ultrafine powder nitrile rubber during the melting and mixing process, thereby improving the strength of the modified polypropylene kraut tube.
As can be seen from the data of examples 1 to 5 and comparative example 4 in Table 2, the preparation method of the present invention enables the modified polypropylene Kraft pipe to have better comprehensive properties such as ring stiffness, tensile strength, bending elastic modulus, impact resistance, etc., compared with the preparation method of comparative example 4 in which the silane coupling agent is used to perform surface treatment on the nano calcium carbonate, nano basic magnesium sulfate whisker and glass fiber powder and then directly mix with other components in the formula and then perform melt-kneading extrusion, the preparation method of the present invention firstly performs stepwise blending of the raw materials and then performs melt-kneading extrusion, the components can be better mixed and dispersed, the compatibility of the components in the raw materials is better, so that the prepared modified polypropylene Kraft pipe has better comprehensive properties such as ring stiffness, tensile strength, bending elastic modulus, impact resistance, etc., and in addition, the modified polypropylene Kraft pipe is annealed after winding formation, the local stress of the pipeline can be eliminated, and the overall performance of the modified polypropylene Krah pipe is further improved.
In examples 1 to 5, the parameters of the krah pipe apparatus in step S7 are set as 110kg/h of extrusion amount of the flat belt, 120kg/h of extrusion amount of the belting, and 125mm of winding pitch, the diameter of the produced modified polypropylene krah pipe is 800mm, and the reinforcing rib is 54mm, compared with the high density polyethylene krah pipe with the same specification, the modified polypropylene krah pipe produced in examples 1 to 5 has higher ring stiffness, so that the modified polypropylene krah pipe produced by the invention has higher ring stiffness grade under the condition of the same mass, and similarly, under the same ring stiffness grade, the modified polypropylene krah pipe produced by the invention has lighter mass, thereby reducing the cost and having strong practicability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The high-modulus modified polypropylene krah pipe is characterized by comprising the following components in parts by weight:
100-150 parts of polypropylene, 5-15 parts of nano calcium carbonate, 5-10 parts of glass fiber powder, 10-20 parts of nano basic magnesium sulfate whisker, 3-10 parts of carboxylated silicon dioxide, 0.05-0.1 part of calcium stearate, 0.13-0.25 part of rosin amide, 2-5 parts of polyethylene, 0.02-0.05 part of cooling master batch, 0.5-2 parts of organic silicon tackifier, 5-10 parts of maleic anhydride grafted polypropylene, 2-5 parts of fully-vulcanized ultrafine powder nitrile rubber, 1-2 parts of trimethylolpropane trimethacrylate, 5-10 parts of metallocene polyolefin elastomer, 0.2-1 part of silane coupling agent, 0.5-2 parts of tetrabromobenzene anhydride ester, 0.5-1 part of antioxidant and 2-5 parts of heat stabilizer.
2. The high modulus modified polypropylene carat pipe of claim 1, consisting of the following components in parts by weight:
130 parts of polypropylene, 10 parts of nano calcium carbonate, 7 parts of glass fiber powder, 15 parts of nano basic magnesium sulfate whisker, 6 parts of carboxylated silicon dioxide, 0.07 part of calcium stearate, 0.2 part of rosin amide, 3 parts of polyethylene, 0.04 part of cooling master batch, 1.5 parts of organic silicon tackifier, 7 parts of maleic anhydride grafted polypropylene, 3 parts of fully-vulcanized superfine powder nitrile rubber, 1.5 parts of trimethylolpropane trimethacrylate, 7 parts of metallocene polyolefin elastomer, 0.5 part of silane coupling agent, 1.2 parts of tetrabromobenzene anhydride ester, 0.7 part of antioxidant and 3 parts of heat stabilizer.
3. The high modulus modified polypropylene krah pipe of claim 1 wherein the temperature reducing masterbatch is polypropylene temperature reducing masterbatch PA-520.
4. The high modulus modified polypropylene carat pipe of claim 1, wherein the silane coupling agent is silane coupling agent KH 550.
5. The high modulus modified polypropylene carat pipe of claim 1, wherein the antioxidant is antioxidant 1010.
6. The high modulus modified polypropylene carat pipe of claim 1, wherein the heat stabilizer is a calcium zinc stabilizer.
7. A production method of a high modulus modified polypropylene Krah pipe is characterized by comprising the following steps:
s1, weighing each component for later use according to the formula of the high-modulus modified polypropylene krat pipe as claimed in any one of claims 1-6;
s2, mixing the nano calcium carbonate, the glass fiber powder, the nano basic magnesium sulfate whisker and the silane coupling agent for 5min at the rotating speed of 200r/min of a high-speed mixer, and then mixing for 10min at the rotating speed of 2500r/min to obtain the nano calcium carbonate, the glass fiber powder and the nano basic magnesium sulfate whisker which are subjected to surface treatment;
s3, mixing polypropylene, polyethylene, fully-vulcanized ultrafine powder nitrile rubber, trimethylolpropane trimethacrylate and metallocene polyolefin elastomer for 10min at the rotating speed of 200r/min of a high-speed mixer to obtain a first premix;
s4, mixing the maleic anhydride grafted polypropylene with the surface-treated nano calcium carbonate, the glass fiber powder and the nano basic magnesium sulfate whisker obtained in the step S2 for 10min at the rotating speed of 200r/min of a high-speed mixer to obtain a second premix;
s5, mixing the premix I obtained in the step S3 and the premix II obtained in the step S4 for 5min at the rotating speed of 200/min of a high-speed mixer, adding carboxylated silicon dioxide, cooling master batches, calcium stearate, rosin amide, tetrabromobenzene anhydride ester, an antioxidant and a heat stabilizer, and uniformly mixing at the rotating speed of 2000/min to obtain a mixed material;
s6, granulating the mixed material obtained in the step S5 through a double-screw granulator for later use;
s7, drying the granules granulated in the step S6, and processing the dried granules by a Krah pipe device to obtain a formed pipe;
s8, annealing the formed pipe obtained in the step S7 to obtain the high modulus modified polypropylene carat pipe.
8. The method as claimed in claim 7, wherein the moisture content of the dried particles in step S7 is controlled to 1 ‰.
9. The method as claimed in claim 7, wherein the annealing condition in step S7 is 120 ℃ for 1 h.
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| CN111763377A (en) * | 2020-07-09 | 2020-10-13 | 福建结诚塑业科技有限公司 | Krah pipe and preparation process thereof |
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| CN112679847A (en) * | 2020-12-22 | 2021-04-20 | 青岛正大环保科技有限公司 | High-toughness heat-resistant polypropylene packaging bag and preparation method thereof |
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| CN115627026A (en) * | 2022-09-30 | 2023-01-20 | 福建晟扬管道科技有限公司 | Modified polypropylene Krah pipe and demolding process for producing same |
| CN115627026B (en) * | 2022-09-30 | 2023-10-20 | 福建晟扬管道科技有限公司 | Modified polypropylene clara pipe and demolding process for production thereof |
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Application publication date: 20191220 |