CN115926319B - Impact-resistant type Clar pipe and processing technology thereof - Google Patents
Impact-resistant type Clar pipe and processing technology thereof Download PDFInfo
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- 238000005516 engineering process Methods 0.000 title claims abstract description 8
- 238000012545 processing Methods 0.000 title claims abstract description 8
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 52
- -1 polypropylene Polymers 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 239000004743 Polypropylene Substances 0.000 claims abstract description 33
- 229920001155 polypropylene Polymers 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 31
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 18
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- HMPSHLKEYWJVJV-UHFFFAOYSA-N 4-(aminomethyl)-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(CN)=CC(C(C)(C)C)=C1O HMPSHLKEYWJVJV-UHFFFAOYSA-N 0.000 claims abstract description 17
- GWOLZNVIRIHJHB-UHFFFAOYSA-N 11-mercaptoundecanoic acid Chemical compound OC(=O)CCCCCCCCCCS GWOLZNVIRIHJHB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (e)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 claims abstract description 13
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 13
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 9
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000013329 compounding Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
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- 239000000126 substance Substances 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
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- 239000002655 kraft paper Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an impact-resistant type Clar pipe and a processing technology thereof. The method comprises the following steps: step 1: reacting 4-amino-2, 6-tetramethylpiperidine, 3, 5-di-tert-butyl-4-hydroxybenzylamine with fumaryl chloride to prepare an anti-aging agent; step 2: sequentially using 11-mercaptoundecanoic acid as an anti-aging agent, and modifying the anti-aging agent by using layered double hydroxide to obtain a composite reinforcing agent; step 3: pre-compounding the composite reinforcing agent with part of polypropylene to obtain a raw material A; step 4: and (3) drying and uniformly mixing the raw material A, the rest of polypropylene, high-density polyethylene, ethylene propylene diene monomer and a lubricant, granulating by a screw extruder, extruding by the screw extruder for molding, and annealing to obtain the impact-resistant type clara tube.
Description
Technical Field
The invention relates to the technical field of clara pipes, in particular to an impact-resistant clara pipe and a processing technology thereof.
Background
The traditional clarinet is a pipe formed by hot winding high-density polyethylene, but due to the characteristics of the polyethylene, the ring rigidity of the polyethylene type clarinet is lower, and the gram weight is higher, so that the application of the clarinet in drainage pipelines and cable pipelines in complex environments is greatly limited. The polypropylene material has the advantages of small relative density and good heat resistance, and besides the impact resistance, the mechanical properties of the polypropylene material are better than those of polyethylene, and the prepared clara pipe can improve the ring stiffness, reduce the requirement on the bearing capacity of a foundation and reduce the construction cost. However, polypropylene type clara pipe has the disadvantages of large brittleness and poor impact resistance due to the nature of the material, and cannot meet the requirements of the actual market.
On the other hand, polypropylene is easier to degrade than other olefins, and a tertiary carbon atom free radical can be generated by photo-thermal action, so that chain degradation is initiated, embrittlement occurs, and the mechanical properties of the polypropylene type Kraft pipe are reduced. Of course, antioxidants or ultraviolet absorbers are incorporated in the general process for improving aging defects; however, in the prior art, the ageing resistance is still lower, and substances such as antioxidants and the like have compatibility and dispersibility problems in the polypropylene main material, so that the mobility is high, the leaching loss is caused, the ageing resistance of the Kela pipe is reduced, and the service life of the Kela pipe is reduced.
In summary, to solve the above problems, it is necessary to prepare an impact-resistant type of claret by using polypropylene as a main material.
Disclosure of Invention
The invention aims to provide an impact-resistant type Clar pipe and a processing technology thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a processing technology of an impact-resistant type clarinet comprises the following steps:
step 1: reacting 4-amino-2, 6-tetramethylpiperidine, 3, 5-di-tert-butyl-4-hydroxybenzylamine with fumaryl chloride to prepare an anti-aging agent;
step 2: sequentially using 11-mercaptoundecanoic acid as an anti-aging agent, and modifying the anti-aging agent by using layered double hydroxide to obtain a composite reinforcing agent;
step 3: pre-compounding the composite reinforcing agent with part of polypropylene to obtain a raw material A;
step 4: and (3) drying and uniformly mixing the raw material A, the rest of polypropylene, high-density polyethylene, ethylene propylene diene monomer and a lubricant, granulating by a screw extruder, extruding by the screw extruder for molding, and annealing to obtain the impact-resistant type clara tube.
Further, the preparation method of the anti-aging agent comprises the following steps: sequentially dispersing fumaryl chloride and triethylamine in dichloromethane to obtain a reaction solution A; dispersing 4-amino-2, 6-tetramethyl piperidine and 3, 5-di-tert-butyl-4-hydroxybenzylamine in methylene dichloride in sequence, keeping the temperature at 0-5 ℃ in nitrogen atmosphere, dropwise adding a reaction solution A for 30-40 minutes, and reacting for 2-3 hours; and (3) continuing to react for 20-24 hours at room temperature, adding sodium hydroxide for neutralization, washing and drying to obtain the anti-aging agent.
Further, the mass ratio of the fumaroyl chloride to the 4-amino-2, 6-tetramethylpiperidine to the 3, 5-di-tert-butyl-4-hydroxybenzylamine is 1: (1.2-1.5): (0.8-1).
Further, in step 2, the preparation method of the composite reinforcing agent comprises the following steps: (1) Dispersing the anti-aging agent in methylene dichloride, keeping the temperature at 0-5 ℃, adding dimethyl aluminum chloride, adding 11-mercaptoundecanoic acid, stirring for 30-40 minutes, reacting for 20-24 hours at room temperature, washing and drying to obtain the modified anti-aging agent; (2) Dispersing the modified anti-aging agent in deionized water to obtain a solution A; dissolving aluminum nitrate and magnesium nitrate in deionized water to obtain a metal solution; dispersing sodium hydroxide in deionized water to obtain a solution B; and (3) dropwise adding the solution B into the solution A, adjusting the pH value to be 9.5-10, dropwise adding a metal solution, keeping the pH value unchanged in the process, aging for 4-5 hours, washing and drying to obtain the composite reinforcing agent.
Further, the mass ratio of the anti-aging agent to 11-mercaptoundecanoic acid is 1: (0.5 to 0.6); the concentration of the solution A is 2wt%, the concentration of the metal solution is 1.6wt%, and the volume ratio of the solution A to the metal solution is 1:1, the concentration of the solution B is 8-10wt%.
Further, in step 3, the preparation method of the raw material a comprises the following steps: the mass ratio is 1:2, sequentially dispersing the composite reinforcing agent and the polypropylene in the dimethylbenzene, carrying out reflux reaction for 3-4 hours at 137-142 ℃, adding n-hexane, cooling, washing and drying to obtain the raw material A.
Further, the raw materials of the impact-resistant type clara pipe comprise the following components: 65-75 parts of polypropylene, 15-20 parts of high-density polyethylene, 10-12 parts of ethylene propylene diene monomer rubber, 8-10 parts of composite reinforcing agent and 1-2 parts of lubricant.
Further, in the step 4, the granulating temperature is 185-210 ℃; the extrusion temperature is 180-210 ℃, the extrusion pressure is 5-10 MPa, the traction speed is 3-5 m/min, and the screw rotating speed is 10-20 rpm; the annealing temperature is 110-120 ℃, and the annealing time is 1-1.5 hours.
Further, the impact-resistant type clara pipe is prepared by the processing technology of the impact-resistant type clara pipe.
The beneficial effects in this technical scheme:
(1) In the scheme, polypropylene is used as a main body to prepare the clarinet with high ring rigidity and light gram weight. While introducing high density polyethylene due to enhanced toughness and ductility. Although polyethylene and polypropylene are similar thermoplastic materials, the two substances have different melting temperature and crystallization temperature, so that the compatibility is reduced, the phase separation form is present, and the mechanical property is reduced, therefore, ethylene propylene diene monomer, a copolymer formed by ethylene, propylene and diene, is further introduced in the scheme, and the two substances are connected in a diffusion area formed by the similar structure between the ethylene propylene diene monomer and the polypropylene and the polyethylene, so that good interfacial acting force is established, and the impact resistance is enhanced. However, the ethylene propylene diene monomer is limited in the amount to be introduced, and is not as good as the amount to be introduced, and when the amount to be introduced is too large, the performance is rather deteriorated.
(2) In the scheme, in order to further enhance the shock resistance, the ageing resistance is increased. In the scheme, the prepared anti-aging agent is compounded with the layered double hydroxide compound to form a compound reinforcing agent, and the performance of the Kela tube is improved.
(3) Wherein the anti-aging agent is prepared by utilizing nucleophilic substitution reaction between acyl chloride and amino, and 4-amino-2, 6-tetramethylpiperidine containing hindered ammonia structure and 3, 5-di-tert-butyl-4-hydroxybenzylamine containing hindered phenol structure are grafted by reacting with two ends of fumaryl chloride, thereby obtaining the anti-aging agent which has the functions of inhibiting thermal oxidation aging and inhibiting photo-oxidation aging. Compared with the separately introduced anti-aging agent, the anti-aging agent prepared in the scheme has the advantages that the compatibility with matrix resin is improved due to the fact that the anti-aging agent contains carbon chains; secondly, the molecular weight is higher, so that the migration is inhibited; and thirdly, the two are introduced in a combined way, so that the synergistic capability is higher, and the two are introduced separately. Thus, the anti-aging performance of the Clar pipe is remarkably improved. In addition, the introduced amount of the two substances needs to be limited, and when the hindered ammonia structure is more, the anti-aging performance is better.
Further, the anti-aging agent is modified by using 11-mercaptoundecanoic acid, the modified anti-aging agent is obtained by grafting through Michael addition reaction between unsaturated double bond and mercapto, and then the modified anti-aging agent is introduced into a precursor of layered double hydroxide compound and combined through coprecipitation, so that the composite reinforcing agent is obtained. Since the modified aging inhibitor is intercalated in the layered double hydroxide, the mobility of the aging inhibitor is further suppressed; meanwhile, the layered double hydroxide compound cooperates with the anti-aging agent, so that the oxidative degradation of the Clar pipe is further slowed down, and the anti-aging performance is improved. The modified long-chain alkyl increases the compatibility with matrix substances, improves the ductility, improves the entanglement with the polymer, reduces the mobility and improves the ageing resistance. In addition, the introduction of the layered double hydroxide compound further improves the heat stability of the Kela tube, and simultaneously improves heterogeneous nucleation and crystallization rate, thereby cooperating with ethylene propylene diene monomer rubber and further improving the shock resistance.
(4) In the scheme, the composite reinforcing agent is compounded with part of polypropylene in advance, so that the dispersibility in the integral Kraft pipe is improved. Different from common pre-screw compounding, the scheme adopts a solvent method for compounding, and the compatibility is increased due to the chemical modification of an organic solvent, so that the interface effect between a compound reinforcing agent and polypropylene is increased, and the shock resistance is enhanced.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, the polypropylene model was PPT4401 and the high density polyethylene model was QHM22F, both from China petrochemical Co., ltd; the ethylene propylene diene monomer rubber model is DuPont 764P and is derived from Dongshuo plastic raw materials; fumaryl chloride is derived from Shanghai Ala Biochemical technology Co., ltd; 4-amino-2, 6-tetramethylpiperidine, 11-mercaptoundecanoic acid, all derived from Zhengzhou alpha chemical Co., ltd; 3, 5-di-tert-butyl-4-hydroxybenzylamine is derived from Nanjing Ailikede chemical Co.
Example 1:
step 1: sequentially dispersing 10g of fumaryl chloride and 8g of triethylamine in 40g of dichloromethane to obtain a reaction liquid A; 13g of 4-amino-2, 6-tetramethylpiperidine and 10g of 3, 5-di-tert-butyl-4-hydroxybenzylamine are dispersed in 60g of dichloromethane in sequence, the temperature is kept at 0 ℃ under the nitrogen atmosphere, the reaction solution A is dropwise added for 30 minutes, and the reaction is carried out for 3 hours; and (3) continuing the reaction for 24 hours at room temperature, adding sodium hydroxide for neutralization, washing and drying to obtain the anti-aging agent.
Step 2: (1) Dispersing 10g of an anti-aging agent in 50g of dichloromethane, maintaining the temperature at 0 ℃, adding 0.5g of dimethyl aluminum chloride, adding 0.6g of 11-mercaptoundecanoic acid, stirring for 30 minutes, reacting for 24 hours at room temperature, washing and drying to obtain a modified anti-aging agent; (2) 10g of modified anti-aging agent is dispersed in 490g of deionized water to obtain solution A; 3g of aluminum nitrate and 5g of magnesium nitrate were dissolved in 492g of deionized water to obtain a metal solution; dispersing sodium hydroxide in deionized water to obtain a solution B with the weight percent of 10; dropwise adding the solution B into the solution A, adjusting the pH=9.7, and dropwise adding a metal solution, wherein the volume ratio of the solution A to the metal solution is 1:1, maintaining the pH unchanged in the process, aging for 4 hours, washing and drying to obtain the composite reinforcing agent.
Step 3: dispersing 9 parts of a composite reinforcing agent and 18 parts of polypropylene in 60 parts of dimethylbenzene according to parts by weight, carrying out reflux reaction for 4 hours at 140 ℃, adding 60 parts of n-hexane, cooling, washing and drying to obtain a raw material A;
step 4: drying and uniformly mixing the raw materials A, 52 parts of polypropylene, 16 parts of high-density polyethylene, 11 parts of ethylene propylene diene monomer and 1 part of polyethylene wax, granulating by a double-screw extruder, wherein the temperature of a first zone 185 ℃, a second zone 190 ℃, a third zone 200 ℃, a fourth zone 205 ℃ and a mould is 210 ℃, and the rotating speed of a screw is 10rpm; extrusion molding by a screw extruder, a machine barrel: 180 ℃ in the first region, 185 ℃ in the second region, 190 ℃ in the third region and 195 ℃ in the fourth region, and die: 185 ℃ in the first area, 190 ℃ in the second area, 195 ℃ in the third area, 210 ℃ in the die temperature, 15rpm in the screw speed, 5MPa in the pressure and 4m/min in the traction speed; annealing at 120 ℃ for 1 hour to obtain the impact-resistant type Kela tube.
Example 2:
step 1: sequentially dispersing 10g of fumaryl chloride and 8g of triethylamine in 40g of dichloromethane to obtain a reaction liquid A; 12g of 4-amino-2, 6-tetramethylpiperidine and 10g of 3, 5-di-tert-butyl-4-hydroxybenzylamine are dispersed in 60g of dichloromethane in turn, the temperature is kept at 0 ℃ under the nitrogen atmosphere, the reaction solution A is dropwise added for 30 minutes, and the reaction is carried out for 3 hours; and (3) continuing the reaction for 24 hours at room temperature, adding sodium hydroxide for neutralization, washing and drying to obtain the anti-aging agent.
Step 2: (1) Dispersing 10g of an anti-aging agent in 50g of dichloromethane, maintaining the temperature at 0 ℃, adding 0.5g of dimethyl aluminum chloride, adding 0.6g of 11-mercaptoundecanoic acid, stirring for 30 minutes, reacting for 24 hours at room temperature, washing and drying to obtain a modified anti-aging agent; (2) 10g of modified anti-aging agent is dispersed in 490g of deionized water to obtain solution A; 3g of aluminum nitrate and 5g of magnesium nitrate were dissolved in 492g of deionized water to obtain a metal solution; dispersing sodium hydroxide in deionized water to obtain a solution B with the weight percent of 10; dropwise adding the solution B into the solution A, adjusting the pH=9.8, and dropwise adding a metal solution, wherein the volume ratio of the solution A to the metal solution is 1:1, maintaining the pH unchanged in the process, aging for 4 hours, washing and drying to obtain the composite reinforcing agent.
Step 3: dispersing 8 parts of a composite reinforcing agent and 16 parts of polypropylene in 60 parts of dimethylbenzene according to parts by weight, carrying out reflux reaction for 4 hours at 140 ℃, adding 60 parts of n-hexane, cooling, washing and drying to obtain a raw material A;
step 4: drying and uniformly mixing the raw materials A, 55 parts of polypropylene, 15 parts of high-density polyethylene, 12 parts of ethylene propylene diene monomer and 1 part of polyethylene wax, granulating by a double-screw extruder, wherein the temperature of a first zone 185 ℃, a second zone 190 ℃, a third zone 200 ℃, a fourth zone 205 ℃ and a mould is 210 ℃, and the rotating speed of a screw is 10rpm; extrusion molding by a screw extruder, a machine barrel: 180 ℃ in the first region, 185 ℃ in the second region, 190 ℃ in the third region and 195 ℃ in the fourth region, and die: 185 ℃ in the first area, 190 ℃ in the second area, 195 ℃ in the third area, 210 ℃ in the die temperature, 15rpm in the screw speed, 5MPa in the pressure and 4m/min in the traction speed; annealing at 120 ℃ for 1 hour to obtain the impact-resistant type Kela tube.
Example 3:
step 1: sequentially dispersing 10g of fumaryl chloride and 8g of triethylamine in 40g of dichloromethane to obtain a reaction liquid A; 15g of 4-amino-2, 6-tetramethylpiperidine and 8g of 3, 5-di-tert-butyl-4-hydroxybenzylamine are dispersed in 60g of dichloromethane in sequence, the temperature is kept at 0 ℃ under the nitrogen atmosphere, the reaction solution A is dropwise added for 30 minutes, and the reaction is carried out for 3 hours; and (3) continuing the reaction for 24 hours at room temperature, adding sodium hydroxide for neutralization, washing and drying to obtain the anti-aging agent.
Step 2: (1) Dispersing 10g of an anti-aging agent in 50g of dichloromethane, maintaining the temperature at 0 ℃, adding 0.5g of dimethyl aluminum chloride, adding 0.5g of 11-mercaptoundecanoic acid, stirring for 30 minutes, reacting for 24 hours at room temperature, washing and drying to obtain a modified anti-aging agent; (2) 10g of modified anti-aging agent is dispersed in 490g of deionized water to obtain solution A; 3g of aluminum nitrate and 5g of magnesium nitrate were dissolved in 492g of deionized water to obtain a metal solution; dispersing sodium hydroxide in deionized water to obtain a solution B with the weight percent of 10; dropwise adding the solution B into the solution A, adjusting the pH=9.5, and dropwise adding a metal solution, wherein the volume ratio of the solution A to the metal solution is 1:1, maintaining the pH unchanged in the process, aging for 4 hours, washing and drying to obtain the composite reinforcing agent.
Step 3: dispersing 10 parts of a composite reinforcing agent and 20 parts of polypropylene in 60 parts of dimethylbenzene according to parts by weight, carrying out reflux reaction for 4 hours at 140 ℃, adding 60 parts of n-hexane, cooling, washing and drying to obtain a raw material A;
step 4: drying and uniformly mixing the raw materials A, 49 parts of polypropylene, 20 parts of high-density polyethylene, 10 parts of ethylene propylene diene monomer and 1 part of polyethylene wax, granulating by a double-screw extruder, wherein the temperature of the die is 210 ℃ at 185 ℃ in the first region, 190 ℃ in the second region, 200 ℃ in the third region and 205 ℃ in the fourth region, and the rotating speed of the screw is 10rpm; extrusion molding by a screw extruder, a machine barrel: 180 ℃ in the first region, 185 ℃ in the second region, 190 ℃ in the third region and 195 ℃ in the fourth region, and die: 185 ℃ in the first area, 190 ℃ in the second area, 195 ℃ in the third area, 210 ℃ in the die temperature, 15rpm in the screw speed, 5MPa in the pressure and 4m/min in the traction speed; annealing at 120 ℃ for 1 hour to obtain the impact-resistant type Kela tube.
Comparative example 1: the grafting amounts of 4-amino-2, 6-tetramethylpiperidine and 3, 5-di-t-butyl-4-hydroxybenzylamine were changed, and the other matters were the same as in example 1.
The specific changes are as follows: sequentially dispersing 10g of fumaryl chloride and 8g of triethylamine in 40g of dichloromethane to obtain a reaction liquid A; 10g of 4-amino-2, 6-tetramethylpiperidine and 13g of 3, 5-di-tert-butyl-4-hydroxybenzylamine are dispersed in 60g of dichloromethane in sequence, the temperature is kept at 0 ℃ under the nitrogen atmosphere, the reaction solution A is dropwise added for 30 minutes, and the reaction is carried out for 3 hours; and (3) continuing the reaction for 24 hours at room temperature, adding sodium hydroxide for neutralization, washing and drying to obtain the anti-aging agent.
Comparative example 2: 4-amino-2, 6-tetramethylpiperidine, 3, 5-di-t-butyl-4-hydroxybenzylamine, mg/Al-LDH were added separately, and the remainder was the same as in example 1;
step 1: dispersing 4 parts of Mg/Al-LDH and 18 parts of polypropylene in 60 parts of dimethylbenzene, carrying out reflux reaction for 4 hours at 140 ℃, adding 60 parts of n-hexane, cooling, washing and drying to obtain a raw material A;
step 2: drying and uniformly mixing raw materials A, 52 parts of polypropylene, 16 parts of high-density polyethylene, 11 parts of ethylene propylene diene monomer, 1 part of polyethylene wax, 3 parts of 4-amino-2, 6-tetramethylpiperidine and 2 parts of 3, 5-di-tert-butyl-4-hydroxybenzylamine, granulating by a double screw extruder, wherein the temperature of a first zone 185 ℃, a second zone 190 ℃, a third zone 200 ℃, a fourth zone 205 ℃ and a mould temperature 210 ℃ and the screw speed of 10rpm; extrusion molding by a screw extruder, a machine barrel: 180 ℃ in the first region, 185 ℃ in the second region, 190 ℃ in the third region and 195 ℃ in the fourth region, and die: 185 ℃ in the first area, 190 ℃ in the second area, 195 ℃ in the third area, 210 ℃ in the die temperature, 15rpm in the screw speed, 5MPa in the pressure and 4m/min in the traction speed; annealing at 120 ℃ for 1 hour to obtain the impact-resistant type Kela tube.
Comparative example 3: 11-mercaptoundecanoic acid modification was not used, the remainder being the same as in example 1;
the specific modification is as follows: 10g of anti-aging agent is dispersed in 490g of deionized water to obtain solution A; 3g of aluminum nitrate and 5g of magnesium nitrate were dissolved in 492g of deionized water to obtain a metal solution; dispersing sodium hydroxide in deionized water to obtain a solution B with the weight percent of 10; dropwise adding the solution B into the solution A, adjusting the pH=9.5, and dropwise adding a metal solution, wherein the volume ratio of the solution A to the metal solution is 1:1, maintaining the pH unchanged in the process, aging for 4 hours, washing and drying to obtain the composite reinforcing agent.
Comparative example 4: the composite reinforcing agent was previously mixed with polypropylene using a screw extruder, and the rest was the same as in example 1;
the specific modification is as follows: 9 parts of composite reinforcing agent and 18 parts of polypropylene are mixed and placed in a double-screw extruder for granulation, and the average temperature is 190 ℃, so as to obtain a raw material A.
Comparative example 5: the amount of ethylene propylene diene monomer introduced was increased by 11 parts, and the remainder was the same as in example 1;
the specific modification is as follows: step 4: drying and uniformly mixing the raw materials A, 52 parts of polypropylene, 16 parts of high-density polyethylene, 18 parts of ethylene propylene diene monomer and 1 part of polyethylene wax, granulating by a double-screw extruder, wherein the temperature of a first zone 185 ℃, a second zone 190 ℃, a third zone 200 ℃, a fourth zone 205 ℃ and a mould is 210 ℃, and the rotating speed of a screw is 10rpm; extrusion molding by a screw extruder, a machine barrel: 180 ℃ in the first region, 185 ℃ in the second region, 190 ℃ in the third region and 195 ℃ in the fourth region, and die: 185 ℃ in the first area, 190 ℃ in the second area, 195 ℃ in the third area, 210 ℃ in the die temperature, 15rpm in the screw speed, 5MPa in the pressure and 4m/min in the traction speed; annealing at 120 ℃ for 1 hour to obtain the impact-resistant type Kela tube.
Experiment: the impact-resistant type clara tubes prepared in examples and comparative examples; impact performance is tested according to GB/T1843-2008, at 23 ℃, the pendulum is 4J, the lifting angle is 160 ℃, and the impact strength is tested; and placing in an aging test chamber with relative humidity of 20%, temperature of 80deg.C and illumination intensity of 0.6W/m 2 The impact strength was again measured after aging at a wavelength of 340nm for 500 hours.
The data in the above table indicate that: the anti-aging agent prepared in the scheme obviously enhances the anti-aging performance of the Clar pipe; and the composite reinforcing agent obtained by coprecipitation of the anti-aging agent and the layered double hydroxide and ethylene propylene diene monomer cooperatively improve the shock resistance of the Kela pipe. The data of comparative examples 1 to 5 show that: the different grafting ratio of 4-amino-2, 6-tetramethylpiperidine and 3, 5-di-tert-butyl-4-hydroxybenzylamine affects the anti-aging performance, and the performance of comparative example 1 is reduced due to the ratio change. In comparative example 2, there was a significant decrease in performance due to separate addition. In comparative example 3, since 11-mercaptoundecanoic acid modification was not used, the composite properties of the aging inhibitor and the layered double hydroxide were lowered, resulting in lowered properties; in comparative example 4, since the solvent was not pre-compounded, but the screw extruder was pre-mixed, the interfacial force was lowered and the performance was lowered. In comparative example 5, the performance was lowered due to the excessive amount of ethylene propylene diene monomer introduced.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A processing technology of an impact-resistant type clarinet is characterized in that: the method comprises the following steps:
step 1: reacting 4-amino-2, 6-tetramethylpiperidine, 3, 5-di-tert-butyl-4-hydroxybenzylamine with fumaryl chloride to prepare an anti-aging agent; wherein the mass ratio of the fumaroyl chloride to the 4-amino-2, 6-tetramethylpiperidine to the 3, 5-di-tert-butyl-4-hydroxybenzylamine is 1: (1.2-1.5): (0.8-1);
step 2: sequentially using 11-mercaptoundecanoic acid as an anti-aging agent, and modifying the anti-aging agent by using layered double hydroxide to obtain a composite reinforcing agent;
step 3: the mass ratio is 1:2, sequentially dispersing the composite reinforcing agent and the polypropylene in the dimethylbenzene, carrying out reflux reaction for 3-4 hours at 137-142 ℃, adding n-hexane, cooling, washing and drying to obtain a raw material A;
step 4: drying and uniformly mixing the raw material A, the rest of polypropylene, high-density polyethylene, ethylene propylene diene monomer and a lubricant, granulating by a screw extruder, extruding by the screw extruder for molding, and annealing to obtain an impact-resistant type Kela tube;
the raw materials of the impact-resistant type clara pipe comprise the following components: 65-75 parts of polypropylene, 15-20 parts of high-density polyethylene, 10-12 parts of ethylene propylene diene monomer rubber, 8-10 parts of composite reinforcing agent and 1-2 parts of lubricant.
2. The process for manufacturing an impact-resistant claret, as recited in claim 1, characterized in that: the preparation method of the anti-aging agent comprises the following steps: sequentially dispersing fumaryl chloride and triethylamine in dichloromethane to obtain a reaction solution A; dispersing 4-amino-2, 6-tetramethyl piperidine and 3, 5-di-tert-butyl-4-hydroxybenzylamine in methylene dichloride in sequence, keeping the temperature at 0-5 ℃ in nitrogen atmosphere, dropwise adding a reaction solution A for 30-40 minutes, and reacting for 2-3 hours; and (3) continuing to react for 20-24 hours at room temperature, adding sodium hydroxide for neutralization, washing and drying to obtain the anti-aging agent.
3. The process for manufacturing an impact-resistant claret, as recited in claim 1, characterized in that: in the step 2, the preparation method of the composite reinforcing agent comprises the following steps: (1) Dispersing the anti-aging agent in methylene dichloride, keeping the temperature at 0-5 ℃, adding dimethyl aluminum chloride, adding 11-mercaptoundecanoic acid, stirring for 30-40 minutes, reacting for 20-24 hours at room temperature, washing and drying to obtain the modified anti-aging agent; (2) Dispersing the modified anti-aging agent in deionized water to obtain a solution A; dissolving aluminum nitrate and magnesium nitrate in deionized water to obtain a metal solution; dispersing sodium hydroxide in deionized water to obtain a solution B; and (3) dropwise adding the solution B into the solution A, adjusting the pH value to be 9.5-10, dropwise adding a metal solution, keeping the pH value unchanged in the process, aging for 4-5 hours, washing and drying to obtain the composite reinforcing agent.
4. A process for manufacturing an impact-resistant claret, as in claim 3, characterized by: the mass ratio of the anti-aging agent to the 11-mercaptoundecanoic acid is 1: (0.5 to 0.6); the concentration of the solution A is 2wt%, the concentration of the metal solution is 1.6wt%, and the volume ratio of the solution A to the metal solution is 1:1, the concentration of the solution B is 8-10wt%.
5. The process for manufacturing an impact-resistant claret, as recited in claim 1, characterized in that: in the step 4, the granulating temperature is 185-210 ℃; the extrusion temperature is 180-210 ℃, the extrusion pressure is 5-10 MPa, the traction speed is 3-5 m/min, and the screw rotating speed is 10-20 rpm; the annealing temperature is 110-120 ℃, and the annealing time is 1-1.5 hours.
6. An impact-resistant clara tube produced by the process of any one of claims 1-5.
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| US5096974A (en) * | 1987-08-12 | 1992-03-17 | Atochem North America, Inc. | Process for preparing multipurpose polymer bound stabilizers and polymer bound stabilizer produced thereby |
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