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CN-121991427-A - Anti-aging waterproof coiled material and preparation process thereof

CN121991427ACN 121991427 ACN121991427 ACN 121991427ACN-121991427-A

Abstract

The invention discloses an anti-aging waterproof coiled material and a preparation process thereof, and relates to the technical field of waterproof coiled materials prepared from high molecular compounds. The waterproof coiled material takes linear low density polyethylene as a matrix and is matched with components such as an antioxidant, a light stabilizer, an ultraviolet absorber, a synergistic agent, a rare earth cerium complex, carbon black and the like. The preparation process comprises the steps of mixing ingredients, premixing and melting, extrusion molding, on-line rheological monitoring, dynamic temperature adjustment, cooling and shaping and the like. The waterproof coiled material prepared by the method has excellent ultraviolet aging resistance and thermal oxidation aging resistance, high product quality stability, balanced comprehensive performance, long service life and good application prospect and economic value.

Inventors

  • CHEN CHANGYOU

Assignees

  • 辽宁长友防水科技发展有限公司

Dates

Publication Date
20260508
Application Date
20260303

Claims (10)

  1. 1. An anti-aging waterproof coiled material is characterized by comprising the following components in parts by weight: Linear low density polyethylene LLDPE, LLDPE is copolymer of ethylene and hexene, has short branched structure, and has molecular formula of- (CH 2 -CH 2 ) n -, wherein n is 1000-10000,100 parts; Antioxidant 1010, namely pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] with a molecular formula of C 73 H 108 O 12 and 0.2-0.6 part; light stabilizer 770, namely bis (2, 6-tetramethyl-4-piperidinyl) sebacate with molecular formula of C 28 H 52 N 2 O 4 , 0.3-0.8 part; Ultraviolet absorber UV-326, chemical name is 2- (2-hydroxy-3-tertiary butyl-5-methylphenyl) -5-chlorobenzotriazole, molecular formula is C 19 H 21 ClN 3 O, 0.2-0.5 part; A synergistic agent 168, the chemical name of which is tris (2, 4-di-tert-butylphenyl) phosphite, and the molecular formula of which is C 42 H 63 O 3 P, 0.04-0.12 part; The rare earth cerium complex has a chemical formula of Ce (C 18 H 35 O 2 ) 3 , wherein C 18 H 35 O 2 is stearate, and 0.05-0.15 part; 1-3 parts of carbon black.
  2. 2. The anti-aging waterproof roll as claimed in claim 1, wherein the preparation method of the linear low density polyethylene comprises the following steps: (1) Adding hexene as comonomer with concentration of 3-8wt% into a reaction kettle at 75-85deg.C and pressure of 0.5-1.5MPa, adding Ziegler-Natta catalyst system composed of triethylaluminum and titanium trichloride, and catalyst concentration of 0.01-0.05wt%; (2) Introducing ethylene gas, keeping the pressure stable, and carrying out polymerization reaction for 3-5 hours under the stirring condition; (3) Terminating the reaction by adding a small amount of ethanol, cooling to 40-50 ℃, and discharging; (4) And granulating the polymer through an extrusion granulating process, and controlling the melt flow rate to be 1.5-3.0 g/10min to obtain the linear low-density polyethylene resin with the density of 0.915-0.925g/cm 3 .
  3. 3. The anti-aging waterproof roll as claimed in claim 1, wherein the preparation method of the ultraviolet absorber UV-326 comprises the following steps: (1) Condensing 2-chloro-5-aminobenzotriazole and 2-tertiary butyl-5-methylphenol for 5-6 hours at 130-140 ℃ by taking phosphorus pentoxide as a dehydrating agent; (2) Washing the reaction product with 10% sodium hydroxide solution and then with water to neutrality; (3) The product is filtered and dried, and recrystallized by ethanol to obtain pale yellow powdery ultraviolet absorber UV-326 with purity more than or equal to 98 percent.
  4. 4. The anti-aging waterproof coiled material according to claim 1, wherein the preparation method of the rare earth cerium complex comprises the following steps: (1) Reacting stearic acid with sodium hydroxide for 1-2 hours at the temperature of 80-90 ℃ according to the molar ratio of 1:1 to obtain sodium stearate aqueous solution; (2) Cerium chloride (CeCl 3 ·7H 2 O) is dissolved in deionized water to prepare a solution with the concentration of 0.1-0.2 mol/L; (3) Slowly dripping the sodium stearate solution into the cerium chloride solution at the temperature of 60-70 ℃ at the dripping speed of 2-5 mL/min, stirring while dripping, and continuing stirring for 30-60 minutes after dripping is completed; (4) Filtering, washing and vacuum drying to obtain pale yellow powdery rare earth cerium complex, wherein the drying temperature is 60-80 ℃ and the drying time is 8-12 hours.
  5. 5. The anti-aging waterproof coiled material according to claim 1, wherein the carbon black is N330 type carbon black, the iodine adsorption value is 80-90 g/kg, and the DBP oil absorption value is 100-110 mL/100g.
  6. 6. The process for preparing the anti-aging waterproof coiled material as claimed in claims 1 to 5, which comprises the following steps: s1, proportioning and mixing, weighing the components according to a formula, and uniformly mixing an antioxidant 1010, a light stabilizer 770, an ultraviolet absorber UV-326, a synergistic agent 168 and a rare earth cerium complex in advance, then mixing with carbon black, and finally mixing with linear low-density polyethylene resin for 10-20 minutes; S2, premixing and melting, namely putting the mixture obtained in the step S1 into a high-speed mixer for premixing and melting, and controlling the material temperature and the mixing time; S3, extrusion molding, namely adding the premix obtained in the step S2 into a single screw extruder, setting the initial temperature of each heating area, plasticizing, mixing and conveying the materials through screw rotation, and extrusion molding through a die head; s4, online rheological monitoring and dynamic temperature adjustment, wherein melt viscosity is monitored in real time through an online rotary rheometer arranged at the tail end of a screw in the extrusion process, and the temperature of each heating area is dynamically adjusted according to viscosity deviation; S5, cooling and shaping, wherein the extruded coiled material is subjected to cooling and shaping through a multi-section cooling system; And S6, traction and winding, wherein the coiled material after cooling and shaping is drawn at a constant speed through a traction device, and the finished waterproof coiled material is obtained through winding.
  7. 7. The preparation process according to claim 6, wherein in S1, the specific method of mixing ingredients is as follows: S11, weighing an antioxidant 1010, a light stabilizer 770, an ultraviolet absorber UV-326 and a synergistic agent 168 according to a proportion, and then adding the mixture into a V-shaped mixer for mixing for 5-8 minutes at a rotating speed of 20-30rpm to obtain an anti-aging agent premix, wherein all components in the premix are uniformly dispersed without obvious agglomeration; S12, after the rare earth cerium complex is weighed independently, the rare earth cerium complex and carbon black are dispersed and mixed in a high-speed dispersing machine at the rotating speed of 800-1200rpm for 3-5 minutes to obtain modified carbon black, and the rare earth cerium complex is loaded on the surface of the modified carbon black, so that the modified carbon black has enhanced ultraviolet resistance; And S13, adding the anti-aging agent premix of S11 and the modified carbon black of S12 into the linear low-density polyethylene resin at the same time, and mixing for 15-20 minutes in a low-speed mixer at a rotating speed of 15-25rpm to obtain a uniformly dispersed mixture.
  8. 8. The preparation process according to claim 6, wherein in S2, the specific method of premixing and melting is as follows: S21, putting the mixture obtained in the step S1 into a high-speed mixer, setting the initial rotating speed to 300-500rpm, and gradually increasing the temperature of the material; s22, when the temperature of the materials reaches 70-85 ℃, the rotating speed is reduced to 200-300rpm, and the materials are continuously mixed; And S23, stopping mixing when the temperature of the materials reaches 90-100 ℃ and the mixing time reaches 5-15 minutes, and rapidly discharging and cooling to room temperature to obtain the premix particles.
  9. 9. The preparation process according to claim 6, wherein in S3, the specific method of extrusion molding is as follows: S31, adopting a single screw extruder with a screw diameter of 90-150 mm and an aspect ratio of 25:1-30:1, wherein the screw is divided into a feeding area, a compression area and a metering area, and the compression ratio is 2.5:1-3.5:1; s32, setting the initial temperature of each heating area, wherein the temperature of a feeding area is 130-145 ℃, the temperature of the front section of a compression area is 145-160 ℃, the temperature of the rear section of the compression area is 160-175 ℃, the temperature of a metering area is 170-185 ℃, and the temperature of a die head is 165-180 ℃, so that a reasonable temperature gradient is formed, and the gradual melting and uniform mixing of materials are ensured; s33, setting the rotating speed of the screw to 40-80rpm, and mixing the materials under the action of shearing force; s34, starting an extruder, starting feeding after the temperature of each zone is stable, and entering the step S4 after the extruder runs for 30 minutes to ensure the stability of the extrusion process; in the step S4, the specific method for on-line rheological monitoring and dynamic temperature adjustment is as follows: S41, installing an online rotary rheometer at the joint of the tail end of the screw rod and the die head, wherein the measuring shearing rate range is 10-1000S -1 , the temperature measuring precision is +/-0.5 ℃, and the viscosity measuring precision is +/-2%; S42, setting a target viscosity range to be 5000-8000 Pa.s, wherein the range is suitable flow viscosity of the linear low-density polyethylene at extrusion temperature, so that good fluidity of the material is ensured, and molding instability caused by excessive flow is avoided; S43, collecting actual viscosity every 30 seconds, and calculating viscosity deviation, namely, the percentage of the difference value between the actual viscosity and the target viscosity to the target viscosity; s44, when the viscosity deviation is greater than 5%, the temperature of each heating area is adjusted according to the deviation, the adjustment amplitude of a feeding area is +/-2 ℃, the adjustment amplitude of a compression area is +/-5 ℃, the adjustment amplitude of a metering area is +/-3 ℃, and the adjustment amplitude of a die head area is +/-4 ℃; And S45, sending the calculated temperature adjustment quantity to a PLC controller, and regulating the heating power of a corresponding heating zone by the controller to realize temperature regulation.
  10. 10. The preparation process according to claim 6, wherein in S5, the specific method of cooling and shaping is as follows: S51, adopting a three-section water cooling system, wherein the first section is a pre-cooling area, the second section is a rapid cooling area, the third section is a stable area, and the total cooling length is 4-6 meters; S52, setting the temperature of cooling water of each section, wherein the water temperature of the first section of pre-cooling area is 50-60 ℃, the water temperature of the second section of rapid cooling area is 25-35 ℃, and the water temperature of the third section of stabilizing area is 15-25 ℃; and S53, controlling the stay time of the coiled material in a cooling system to be 60-90 seconds, and reducing the surface temperature of the coiled material to be below 40 ℃.

Description

Anti-aging waterproof coiled material and preparation process thereof Technical Field The invention belongs to the technical field of waterproof coiled materials prepared from high molecular compounds, and particularly relates to an anti-aging waterproof coiled material and a preparation process thereof. Background The waterproof coiled material is an indispensable functional material in building engineering, is mainly used for waterproof and seepage prevention of roofing, basements, tunnels, bridges and other parts of a building, and has an important effect on protecting a building structure from water erosion and prolonging the service life of the building. With the development of construction technology and the improvement of engineering quality requirements, the performance requirements of waterproof materials are higher and higher, so that the waterproof materials are required to have good waterproof performance and long-term durability, and can maintain stable waterproof functions for a long time under various complex environmental conditions. The high polymer waterproof coiled material has been widely used in waterproof engineering due to its excellent mechanical properties, good flexibility, convenient construction, etc., wherein the waterproof coiled material using polyethylene as the base material occupies an important market share due to its moderate price and excellent performance. Polyethylene-based waterproof rolls, while having many advantages, face severe aging problems during actual use. The waterproof coiled material is exposed in the outdoor environment for a long time, is subjected to the comprehensive effects of various environmental factors such as ultraviolet irradiation, high-temperature insolation, oxygen erosion, temperature rapid change and the like, and the polymer molecular chain undergoes photo-oxidative degradation reaction, so that the mechanical property of the material is gradually reduced, and finally the waterproof function is lost. Ultraviolet light is one of the main factors causing the aging of the polymer, and the energy of the ultraviolet light is enough to break chemical bonds in the molecular chains of the polymer, trigger free radical chain reaction and accelerate the degradation process of the polymer. The reaction rate of oxygen and polymer molecular chains is accelerated under the high temperature condition, and thermal oxidative aging becomes another important degradation path. The aging degradation processes lead to the reduction of the tensile strength, the reduction of the elongation at break and the brittleness and easy cracking of the material, and cracks, chalking and even complete failure can occur when the materials are serious, so that the waterproof effect cannot be continuously exerted, the building leakage can be caused, and a series of engineering quality problems can be caused. The maintenance and replacement of the waterproof layer not only needs to put in a large amount of manpower and material resources, but also can influence the normal use of the building, and bring economic loss and inconvenient use to the owners. Therefore, the anti-aging performance of the waterproof coiled material is improved, the service life of the waterproof coiled material is prolonged, and the waterproof coiled material has important engineering practical significance and economic value. In order to improve the aging resistance of the polyethylene-based waterproof roll, a method of adding an aging inhibitor to a polyethylene matrix is generally used in the prior art. Commonly used anti-aging agents include antioxidants, light stabilizers, ultraviolet absorbers, and the like, which retard the aging degradation process of the polymer through different mechanisms. However, the main problem in the prior art is that the kinds of the anti-aging agents are single or unreasonable in combination, resulting in limited anti-aging effect. Many products use only a single type of anti-aging agent, such as an antioxidant or an ultraviolet absorber, and such a single protection system can only provide protection against a certain degradation mechanism, and cannot achieve comprehensive protection against a complex multi-factor synergistic aging process. The aging degradation of the polymer is a complex process involving multiple reaction paths and multiple reaction stages, and comprises multiple links such as direct damage of ultraviolet light, generation of photoinduced free radicals, chain transfer of free radicals, decomposition of hydroperoxide, accumulation of oxidation products and the like, wherein a single anti-aging agent can only play a role in one link, and the protection force on other links is insufficient, so that the overall anti-aging effect is not ideal. Even with the combination of various anti-aging agents, if the ingredients lack synergistic effect, only simple superposition is achieved, the effect is very limited, and the expected anti-aging aim cannot be achie