CN115260584B - Environment-friendly stabilizer for new energy charging cable - Google Patents

Environment-friendly stabilizer for new energy charging cable Download PDF

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CN115260584B
CN115260584B CN202210971738.7A CN202210971738A CN115260584B CN 115260584 B CN115260584 B CN 115260584B CN 202210971738 A CN202210971738 A CN 202210971738A CN 115260584 B CN115260584 B CN 115260584B
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parts
stabilizer
weight
new energy
environment
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CN115260584A (en
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王万龙
黄青利
陈志峰
孙健洋
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Guangdong Shangnuo New Material Technology Co ltd
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Abstract

The invention discloses an environment-friendly stabilizer for a new energy charging cable, which is prepared from the following raw materials in parts by weight: 15-35 parts of main stabilizer A, 15-35 parts of main stabilizer B, 5-10 parts of auxiliary stabilizer, 10-20 parts of hydrotalcite, 2-8 parts of antioxidant, 1-5 parts of modifier, 1-5 parts of surfactant, 1-5 parts of toughening agent and 1-5 parts of light stabilizer. Compared with the prior art, the environment-friendly stabilizer for the new energy charging cable has the advantages that the product has excellent high temperature resistance and excellent electrical insulation property; moreover, the high-temperature-resistant polyvinyl chloride material prepared by the stabilizer can be commonly used for a cable insulating layer and a sheath layer, and the prepared cable has the advantages of good wear resistance, high flexibility, tear resistance and ageing resistance.

Description

Environment-friendly stabilizer for new energy charging cable
Technical Field
The invention belongs to the technical field of heat stabilizers, and particularly relates to an environment-friendly stabilizer for a new energy charging cable.
Background
The plastic industry has been improved and developed for many years, and has been in communication with the lives of people. In recent years, with the improvement of the living standard of people, the number of passenger cars is rapidly increasing, and the fields of home appliances and wires and cables for automobiles are rapidly developing. At the same time, the country goes out of the way in time and updates the corresponding material use standard. For example, the electric appliance wire has GB/T8815-2008 soft polyvinyl chloride plastics for wires and cables, and the passenger car charging wire has CQC 1103-1105-2015 Cable technical Specification for electric automobile conduction charging System.
New national standard GB/T33594-2017 for electric automobile charging Cable was issued in 2017, month 5, and formally implemented in 2017, month 12 and day 1. The cable for charging the electric automobile is incorporated into a standard system, so that a unified standard can be used as a reference for manufacturing enterprises, and the cable can also be used for quality safety driving and protecting navigation.
The electric automobile charging cable is used as a basic component of an electric automobile charging facility, and the performance of the electric automobile charging cable has an important influence on the whole charging process. Charging cables are needed to connect the automobile and a power supply for charging the electric automobile, and the cables are a key part of a charging system and directly influence the charging safety of the electric automobile.
Charging cable materials currently sold in the market are generally divided into: low temperature resistant-40 ℃ to high temperature 125 ℃ and low temperature resistant-40 ℃ to high temperature resistant 105 ℃. According to market research, the material with the temperature resistance of 125 ℃ is almost TPE elastomer, the feeding channel is mostly introduced overseas, the feeding period is longer, and the price is high. The material with the temperature resistant of 105 ℃ is mainly PVC, and can not meet the performance requirements of insulation and the like at one time according to the new national standard requirements of the charging cable.
According to the standard requirement of a charging cable, the high-temperature resistant elastomer TPE material with the temperature of 125 ℃ lasts for 3000 hours in a 125 ℃ test environment, lasts for 240 hours in a 150 ℃ test environment, has the thermal overload test temperature of 175 ℃, requires no obvious fading of the material, has excellent tear resistance (more than 6N/mm according to a rubber cable test method), and has extremely high requirement. If TPE articles are subjected to external or environmental factors, mainly light, oxygen, heat, moisture, mechanical stress, high energy radiation, electricity, industrial gases (e.g., carbon dioxide, hydrogen sulfide), etc., for a long period of time, aging may occur, such that the TPE material quickly loses its performance.
In order to prolong the service life of the material, the selected base material can realize the crosslinking reaction of macromolecules through a chemical crosslinking technology or an irradiation crosslinking technology, so that the linear polymer is changed into a polymer with a three-dimensional network structure. The prepared cable material has higher heat resistance, excellent flame retardance, insulating property and mechanical and physical properties by combining the crosslinking technology and the flame retardant technology. It is known that the equipment investment cost of irradiation crosslinking technology is high and the environmental pollution is large. The chemical crosslinking technology has complex process and certain uncertainty of product quality. The cost input of the TPE elastomer charging cable is also increased through the flame-retardant technology.
In addition, most of the TPE flame retardant materials on the market have poor stress cracking resistance and notch growth resistance due to the inclusion of the phenyl ether component, and the requirement on the material of the electric wire is critical, and the poor tear resistance can cause short circuit of the electric wire, which has serious consequences. The problem of oil resistance is also serious, and because the current charging stations are mostly built with gas stations, cables are required to resist various oils, and the risks of failure after oil pollution can be faced. Meanwhile, TPE cables are not wear resistant and are prone to scratching, and are also well known.
In view of the above, there is a need for development of an environmentally friendly stabilizer which has good heat resistance, excellent electrical insulation properties, high toughness and aging resistance in the modification of polyvinyl chloride for new energy charging cables.
Disclosure of Invention
The invention aims at: aiming at the defects of the prior art, the environment-friendly stabilizer for the new energy charging cable has the advantages of good heat resistance, excellent electrical insulation property, high flexibility, tear resistance and aging resistance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the environment-friendly stabilizer for the new energy charging cable is prepared from the following raw materials in parts by weight:
the main stabilizer A is cerium stearate;
the main stabilizer B is 2-amino lanthanum terephthalate;
the auxiliary stabilizer is polysiloxane capped by epoxy groups;
the hydrotalcite is a mixture formed by zinc-aluminum-lanthanum hydrotalcite and calcium-aluminum-lanthanum hydrotalcite according to a weight ratio of 1:1;
the modifier is methyl methacrylate-styrene-organosilicon polymer, the modifier has a core-shell structure, the core of the modifier is crosslinked styrene and organosilicon, the shell is grafted polymethyl methacrylate, and the organosilicon methylphenyl silicone oil;
the toughening agent is a mixture formed by acetyl tributyl citrate and polyoxypropylene glycerol ether according to a weight ratio of 2:1.
Preferably, the adhesive also comprises 5-10 parts by weight of silane end-capped polyether, wherein the silane end-capped polyether is silane end-capped polyether with trimethoxysilane and molecular weight of 30000-50000. The main chain of the silane end-capped polyether resin is polyether, the end group is hydrolyzable silane, the silane end-capped polyether resin is not foamed during solidification, and meanwhile, the silane end-capped polyether resin has good elasticity, has excellent resilience, can absorb and compensate dynamic load, uniformly transfer stress and prevent premature fatigue of materials, and in the presence of moisture, siloxane groups are hydrolyzed to obtain unstable silanol, the unstable silanol generates a stable polyether silicon-oxygen-silicon crosslinked network structure through intermolecular dehydration condensation or dehydration condensation with hydroxyl groups on the surface of a substrate, and the bond energy of Si-O bonds is higher than that of C-C bonds, so that the heat resistance and weather resistance of PVC materials can be further improved after the silane end-capped polyether is added.
Preferably, the composition further comprises 1-5 parts by weight of 1, 3-dimethyl-6-amino uracil. The 1, 3-dimethyl-6-amino uracil can absorb HCl generated in the PVC production process, can replace unstable chlorine atoms, prevents zinc burning, and greatly enhances the long-term stability of PVC products.
Preferably, the paint also comprises 1 to 5 parts by weight of zinc glycerate and 1 to 5 parts by weight of pentaerythritol. The compound of the magnesium stearate and the cerium stearate serving as the main stabilizer A can play a synergistic role, so that the thermal stability is further improved.
Preferably, the composition further comprises 1-4 parts by weight of stearoyl benzoyl methane and 2-8 parts by weight of pentaerythritol. The compound of the compound and the main stabilizer B2-amino lanthanum terephthalate can play a synergistic role, and further improve the thermal stability.
Preferably, the adhesive also comprises 1-5 parts by weight of acrylic ester processing aid, wherein the acrylic ester processing aid is a mixture formed by methyl methacrylate and methyl acrylate according to a weight ratio of 1:1. The mixed acrylic ester processing aid is added, so that the plasticizing processing performance is excellent, yellowing is avoided, and the light transmittance is high; meanwhile, the water ripple phenomenon on the surface of the rolled PVC product can be improved, and the surface smoothness and flatness are improved; and overcomes the defects of poor processability and poor plasticization of PVC products.
Preferably, the surfactant is polyethylene glycol with an average molecular weight of 800-1200, and the average molecular weight is preferably 1100-1200. Because the charging cable has extremely high heat-resistant requirements, the dosage of auxiliary agents such as heat stabilizer and the like is higher, the viscosity of a formula system is obviously improved, and the processing is difficult, the barriers on the processing link are generally solved by compensating the lubricant, such as excessive lubricant compensation or improper quality of used products, and the risk of precipitation is extremely high in the later stage. Precipitation of the auxiliary agent is highly likely to cause a decrease in volume resistivity and a deterioration in electrical insulation ability. The polyethylene glycol adopted by the invention fully utilizes the function of the surfactant, on one hand, plays the role of coating and lubricating materials, and simultaneously has a certain plasticizing function, thereby being beneficial to the sustainability of production and processing.
Preferably, the antioxidant is a mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tri (2, 4-di-tert-butylphenyl) phosphite in a weight ratio of 1:1. The mixed antioxidant solves the problem that the hindered phenol antioxidants of a single class are used, and the balance of the initial coloring and the later aging strength is not found, so that the product has thermal stability, light stability and precipitation resistance.
Preferably, the light stabilizer is a mixture of 2- (2 ',4' -dihydroxyphenyl) -5, 6-dihydroxybenzotriazole and 1, 6-dihydroxybenzotriazole in a weight ratio of 1-2:1. The light stabilizer can inhibit or weaken photodegradation and improve the ageing resistance of the product.
Preferably, the preparation method of the epoxy-terminated polysiloxane comprises the following steps: adding bisphenol A epoxy resin into a container, adding toluene as a solvent, heating to raise the temperature, adding zinc octoate as a catalyst when the temperature reaches more than 110 ℃, then adding hydroxy-terminated polymethylphenylsiloxane, preserving the heat for 2-4 hours, continuously steaming out water and toluene in the reaction process, and drying the obtained solid product in an oven to obtain the epoxy-terminated polysiloxane.
Preferably, the new energyThe environment-friendly stabilizer for the source charging cable also comprises 1-5 parts by weight of naloxone. Naloxone is known as 17-allyl-4, 5 a-epoxy-3, 14-dihydroxymorphinan-6-one and has the molecular formula C 19 H 21 NO 4 The naloxone is introduced into the formula, the naloxone has a great improvement effect on the performance of the stabilizer, and the complex space structure of the naloxone is like a protection net, so that the surface of the stabilizer can be prevented from being oxidized, the stabilizer has good stability, and the service life of the stabilizer is greatly prolonged. In addition, the PVC sheet can keep a stable state in a static state, has good flowing property at low temperature, can adjust the viscosity of the stabilizer, and can prevent the PVC sheet from aging and cracking at low temperature.
Compared with the prior art, the invention has at least the following beneficial effects:
1) The heat stability of the added main stabilizer A cerium stearate is better than that of calcium zinc stabilizers such as calcium stearate/zinc stearate, and the like, because the (cerium Ce in the cerium stearate δ+ ) Belonging to the group of stearic acid and a plurality of unstable chlorine atoms (Cl) on the molecular chain of PVC δ- ) The PVC molecular chain has strong coordination capability to form a complex bond, so that the PVC molecular chain tends to be stable. Meanwhile, cerium has two valence of +3 and +4, and is easy to convert, so that free radicals can be captured to stop the HCl removal reaction. In addition, cerium atoms can adsorb a plurality of HCl molecules, so that the concentration of HCl is greatly reduced, the degradation of PVC molecular chains is effectively slowed down, and the thermal stability of PVC is improved. Compared with the calcium zinc stabilizer, the cerium stearate stabilizer has small maximum torque and balanced torque, which is beneficial to reducing electricity consumption in the production and processing process; and the cerium stearate stabilizer can prolong the plasticizing time, which is beneficial to the more complete plasticizing of the PVC.
2) The main stabilizer B2-amino terephthalic acid lanthanum added in the invention can absorb HCl released in the PVC degradation process, and LaCl is generated by reaction 3 The catalysis of HCl on PVC degradation is reduced, so that the thermal stability of the PVC sheet is improved.
3) The added auxiliary stabilizer is polysiloxane capped by epoxy groups; the polysiloxane is generally formed by condensing polyfunctional organic silanol or organic siloxane and has a three-dimensional crosslinked network structure, wherein an Si-O main chain is coated with R groups connected with Si, so that the Si-O main chain is not easy to attack by impurities, and is not easy to break, so that the polysiloxane has more excellent thermal stability than other resins, the Si-O main chain can bear the corrosion of temperature more than a C-C main chain, the good space network structure of the polysiloxane can effectively improve other performances, such as anti-drop and the like, on the basis of better temperature resistance, and the polysiloxane has the characteristics of high temperature resistance (more than 200 ℃), high humidity resistance, yellowing resistance and the like. The epoxy group is taken as a functional group to enter a terminal end part of polysiloxane, so that the reactivity and adhesive force of the polysiloxane can be improved, and the modified polysiloxane keeps good flexibility at low temperature and has the advantages of small curing shrinkage rate and the like. The light transmittance of the glass fiber can reach more than 97%, and the glass fiber can completely meet the requirement of high transparency.
4) The modifier added in the invention is different from common modifier such as MBS impact modifier, and the modifier replaces butadiene with low weather resistance by organic silicon, thus having excellent weather resistance. Meanwhile, the modifier S has a core-shell structure, wherein the core of the modifier S is crosslinked styrene and organosilicon, and the shell is grafted polymethyl methacrylate. The core-shell structure enables the product to be dispersed into the resin base material as single particles, and improves the impact performance. The excellent elasticity of the organosilicon material can also lead a part of plasticizer to be reduced in the modification process of the polyvinyl chloride to obtain good softness, and the electrical insulation property is obviously improved. The organic silicon methyl phenyl silicone oil adopted by the invention is water-insoluble, while the hydrophilic silicone oil can be regarded as a weak semiconductor due to moisture absorption, and has obvious insulation performance.
5) The mixed toughening agent added in the invention can play a role in obviously toughening and tearing resistance of products.
6) The zinc-aluminum-lanthanum hydrotalcite and calcium-aluminum-lanthanum hydrotalcite added by the invention can improve the thermal stability and compatibility of PVC. The HCl is gradually removed to form a conjugated polyene structure after the PVC main chain is heated, and the color of the product is deepened; in the calcium/zinc hydrotalcite composite heat stable system, lanthanum of the water-skid layer in the heating early stage stabilizes part of active chlorine on a PVC chain through coordination, and meanwhile, the increase of the interlayer spacing of the hydrotalcite can absorb more part of removed HCl, so that the formation of conjugated polyene is slowed down, and the initial whiteness of a sample is maintained.
7) Compared with the prior art, the environment-friendly stabilizer for the new energy charging cable has the advantages that the product has excellent high temperature resistance and excellent electrical insulation property; moreover, the high-temperature-resistant polyvinyl chloride material prepared by the stabilizer can be commonly used for a cable insulating layer and a sheath layer, and the prepared cable has the advantages of good wear resistance, high flexibility, tear resistance and ageing resistance.
Detailed Description
In order to make the technical solution and advantages of the present invention more apparent, the technical solution of the present invention will be clearly and completely described in conjunction with specific embodiments, and it is apparent that the described embodiments are 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.
The environment-friendly stabilizer for the new energy charging cable is prepared from the following raw materials in parts by weight:
the main stabilizer A is cerium stearate;
the main stabilizer B is 2-amino lanthanum terephthalate;
the auxiliary stabilizer is polysiloxane capped by epoxy groups;
the hydrotalcite is a mixture formed by zinc-aluminum-lanthanum hydrotalcite and calcium-aluminum-lanthanum hydrotalcite according to a weight ratio of 1:1;
the modifier is methyl methacrylate-styrene-organosilicon polymer, the modifier has a core-shell structure, the core of the modifier is crosslinked styrene and organosilicon, the shell is grafted polymethyl methacrylate, and the organosilicon methylphenyl silicone oil;
the toughening agent is a mixture formed by acetyl tributyl citrate and polyoxypropylene glycerol ether according to a weight ratio of 2:1.
The preparation method of the epoxy group end-capped polysiloxane comprises the following steps: adding bisphenol A epoxy resin into a container, adding toluene as a solvent, heating to raise the temperature, adding zinc octoate as a catalyst when the temperature reaches more than 110 ℃, then adding hydroxy-terminated polymethylphenylsiloxane, preserving the heat for 2-4 hours, continuously steaming out water and toluene in the reaction process, and drying the obtained solid product in an oven to obtain the epoxy-terminated polysiloxane.
The preparation method of the 2-lanthanum amino terephthalate comprises the following steps: weighing a proper amount of 2-amino terephthalic acid, placing the 2-amino terephthalic acid into a container, dissolving the 2-amino terephthalic acid in dilute ammonia water, and regulating the pH value of the solution to be 6-7 to prepare the 2-amino terephthalic acid ammonia water solution. Placing the container in a constant-temperature water bath kettle at 60 ℃, stirring, taking 2-amino terephthalic acid ammonia according to the molar ratio of n (lanthanum chloride) to n (2-amino terephthalic acid ammonia) =2:3, dropwise adding lanthanum chloride solution by a peristaltic pump, adjusting the pH value of the solution to 6-7 by dilute ammonia water after the dropwise addition, and stirring at the constant temperature of the water bath at 60 ℃ for 4-5 hours. And standing the container, cooling to room temperature, carrying out suction filtration by using a vacuum pump, washing with deionized water for 3-5 times, and drying the obtained complex at 75 ℃ to obtain the 2-lanthanum amino terephthalate.
The heat stability of the added main stabilizer A cerium stearate is better than that of calcium zinc stabilizers such as calcium stearate/zinc stearate, and the like, because the (cerium Ce in the cerium stearate δ+ ) Belonging to the group of stearic acid and a plurality of unstable chlorine atoms (Cl) on the molecular chain of PVC δ- ) The PVC molecular chain has strong coordination capability to form a complex bond, so that the PVC molecular chain tends to be stable. Meanwhile, cerium has two valence of +3 and +4, and is easy to convert, so that free radicals can be captured to stop the HCl removal reaction. In addition, cerium atoms can adsorb a plurality of HCl molecules, so that the concentration of HCl is greatly reduced, the degradation of PVC molecular chains is effectively slowed down, and the thermal stability of PVC is improved. And compared with the calcium zinc stabilizer, the maximum torsion of the cerium stearate stabilizerThe moment and the balance torque are small, which is beneficial to reducing the electricity consumption in the production and processing process; and the cerium stearate stabilizer can prolong the plasticizing time, which is beneficial to the more complete plasticizing of the PVC.
The main stabilizer B2-amino terephthalic acid lanthanum added in the invention can absorb HCl released in the PVC degradation process, and LaCl is generated by reaction 3 The catalysis of HCl on PVC degradation is reduced, so that the thermal stability of the PVC sheet is improved.
The added auxiliary stabilizer is polysiloxane capped by epoxy groups; the polysiloxane is generally formed by condensing polyfunctional organic silanol or organic siloxane and has a three-dimensional crosslinked network structure, wherein an Si-O main chain is coated with R groups connected with Si, so that the Si-O main chain is not easy to attack by impurities, and is not easy to break, so that the polysiloxane has more excellent thermal stability than other resins, the Si-O main chain can bear the corrosion of temperature more than a C-C main chain, the good space network structure of the polysiloxane can effectively improve other performances, such as anti-drop and the like, on the basis of better temperature resistance, and the polysiloxane has the characteristics of high temperature resistance (more than 200 ℃), high humidity resistance, yellowing resistance and the like. The epoxy group is taken as a functional group to enter a terminal end part of polysiloxane, so that the reactivity and adhesive force of the polysiloxane can be improved, and the modified polysiloxane keeps good flexibility at low temperature and has the advantages of small curing shrinkage rate and the like. The light transmittance of the glass fiber can reach more than 97%, and the glass fiber can completely meet the requirement of high transparency.
The modifier added in the invention is different from common modifier such as MBS impact modifier, and the modifier replaces butadiene with low weather resistance by organic silicon, thus having excellent weather resistance. Meanwhile, the modifier S has a core-shell structure, wherein the core of the modifier S is crosslinked styrene and organosilicon, and the shell is grafted polymethyl methacrylate. The core-shell structure enables the product to be dispersed into the resin base material as single particles, and improves the impact performance. The excellent elasticity of the organosilicon material can also lead a part of plasticizer to be reduced in the modification process of the polyvinyl chloride to obtain good softness, and the electrical insulation property is obviously improved. The organic silicon methyl phenyl silicone oil adopted by the invention is water-insoluble, while the hydrophilic silicone oil can be regarded as a weak semiconductor due to moisture absorption, and has obvious insulation performance.
The mixed toughening agent added in the invention can play a role in obviously toughening and tearing resistance of products.
The zinc-aluminum-lanthanum hydrotalcite and calcium-aluminum-lanthanum hydrotalcite added by the invention can improve the thermal stability and compatibility of PVC. The HCl is gradually removed to form a conjugated polyene structure after the PVC main chain is heated, and the color of the product is deepened; in the calcium/zinc hydrotalcite composite heat stable system, lanthanum of the water-skid layer in the heating early stage stabilizes part of active chlorine on a PVC chain through coordination, and meanwhile, the increase of the interlayer spacing of the hydrotalcite can absorb more part of removed HCl, so that the formation of conjugated polyene is slowed down, and the initial whiteness of a sample is maintained.
Compared with the prior art, the environment-friendly stabilizer for the new energy charging cable has the advantages that the product has excellent high temperature resistance and excellent electrical insulation property; moreover, the high-temperature-resistant polyvinyl chloride material prepared by the stabilizer can be commonly used for a cable insulating layer and a sheath layer, and the prepared cable has the advantages of good wear resistance, high flexibility, tear resistance and ageing resistance.
Preferably, the adhesive also comprises 5-10 parts by weight of silane end-capped polyether, wherein the silane end-capped polyether is silane end-capped polyether with trimethoxysilane and molecular weight of 30000-50000. The main chain of the silane end-capped polyether resin is polyether, the end group is hydrolyzable silane, the silane end-capped polyether resin is not foamed during solidification, and meanwhile, the silane end-capped polyether resin has good elasticity, has excellent resilience, can absorb and compensate dynamic load, uniformly transfer stress and prevent premature fatigue of materials, and in the presence of moisture, siloxane groups are hydrolyzed to obtain unstable silanol, the unstable silanol generates a stable polyether silicon-oxygen-silicon crosslinked network structure through intermolecular dehydration condensation or dehydration condensation with hydroxyl groups on the surface of a substrate, and the bond energy of Si-O bonds is higher than that of C-C bonds, so that the heat resistance and weather resistance of PVC materials can be further improved after the silane end-capped polyether is added.
Preferably, the composition further comprises 1-5 parts by weight of 1, 3-dimethyl-6-amino uracil. The 1, 3-dimethyl-6-amino uracil can absorb HCl generated in the PVC production process, can replace unstable chlorine atoms, prevents zinc burning, and greatly enhances the long-term stability of PVC products.
Preferably, the paint also comprises 1 to 5 parts by weight of zinc glycerate and 1 to 5 parts by weight of pentaerythritol. The compound of the magnesium stearate and the cerium stearate serving as the main stabilizer A can play a synergistic role, so that the thermal stability is further improved.
Preferably, the composition further comprises 1-4 parts by weight of stearoyl benzoyl methane and 2-8 parts by weight of pentaerythritol. The compound of the compound and the main stabilizer B2-amino lanthanum terephthalate can play a synergistic role, and further improve the thermal stability.
Preferably, the adhesive also comprises 1-5 parts by weight of acrylic ester processing aid, wherein the acrylic ester processing aid is a mixture formed by methyl methacrylate and methyl acrylate according to a weight ratio of 1:1. The mixed acrylic ester processing aid is added, so that the plasticizing processing performance is excellent, yellowing is avoided, and the light transmittance is high; meanwhile, the water ripple phenomenon on the surface of the rolled PVC product can be improved, and the surface smoothness and flatness are improved; and overcomes the defects of poor processability and poor plasticization of PVC products.
Preferably, the surfactant is polyethylene glycol with an average molecular weight of 800-1200, and the average molecular weight is preferably 1100-1200. Because the charging cable has extremely high heat-resistant requirements, the dosage of auxiliary agents such as heat stabilizer and the like is higher, the viscosity of a formula system is obviously improved, and the processing is difficult, the barriers on the processing link are generally solved by compensating the lubricant, such as excessive lubricant compensation or improper quality of used products, and the risk of precipitation is extremely high in the later stage. Precipitation of the auxiliary agent is highly likely to cause a decrease in volume resistivity and a deterioration in electrical insulation ability. The polyethylene glycol adopted by the invention fully utilizes the function of the surfactant, on one hand, plays the role of coating and lubricating materials, and simultaneously has a certain plasticizing function, thereby being beneficial to the sustainability of production and processing.
Preferably, the antioxidant is a mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tri (2, 4-di-tert-butylphenyl) phosphite in a weight ratio of 1:1. The mixed antioxidant solves the problem that the hindered phenol antioxidants of a single class are used, and the balance of the initial coloring and the later aging strength is not found, so that the product has thermal stability, light stability and precipitation resistance.
Preferably, the light stabilizer is a mixture of 2- (2 ',4' -dihydroxyphenyl) -5, 6-dihydroxybenzotriazole and 1, 6-dihydroxybenzotriazole in a weight ratio of 1-2:1. The light stabilizer can inhibit or weaken photodegradation and improve the ageing resistance of the product.
Preferably, the environment-friendly stabilizer for the new energy charging cable further comprises 1-5 parts by weight of naloxone. Naloxone is known as 17-allyl-4, 5 a-epoxy-3, 14-dihydroxymorphinan-6-one and has the molecular formula C 19 H 21 NO 4 The naloxone is introduced into the formula, the naloxone has a great improvement effect on the performance of the stabilizer, and the complex space structure of the naloxone is like a protection net, so that the surface of the stabilizer can be prevented from being oxidized, the stabilizer has good stability, and the service life of the stabilizer is greatly prolonged. In addition, the PVC sheet can keep a stable state in a static state, has good flowing property at low temperature, can adjust the viscosity of the stabilizer, and can prevent the PVC sheet from aging and cracking at low temperature.
In addition, the invention also provides a preparation method of the environment-friendly stabilizer for the new energy charging cable, which comprises the following steps:
1) Weighing the raw materials according to parts by weight;
2) Putting all the raw materials weighed in the step 1) into a high-speed mixer to mix for 10-30 minutes at 60-80 ℃ at the rotating speed of 1000-2000 rpm, and uniformly mixing;
3) And (3) cooling the mixed material obtained in the step (2) to 35 ℃ to obtain the environment-friendly stabilizer for the new energy charging cable.
In order to further understand the present invention, the environmental protection stabilizer for new energy charging cable and the preparation method thereof provided by the present invention are described in detail with reference to the following examples, but the scope of protection of the present invention is not limited by the following examples.
Example 1
The embodiment provides an environment-friendly stabilizer for a new energy charging cable, which is prepared from the following raw materials in parts by weight: 15 parts of main stabilizer A, 15 parts of main stabilizer B, 5 parts of auxiliary stabilizer, 10 parts of hydrotalcite, 2 parts of antioxidant, 1 part of modifier, 1 part of surfactant, 1 part of toughening agent and 1 part of light stabilizer.
Wherein the main stabilizer A is cerium stearate;
the main stabilizer B is 2-amino lanthanum terephthalate;
the auxiliary stabilizer is polysiloxane capped by epoxy groups;
the hydrotalcite is a mixture formed by zinc-aluminum-lanthanum hydrotalcite and calcium-aluminum-lanthanum hydrotalcite according to a weight ratio of 1:1;
the modifier is methyl methacrylate-styrene-organosilicon polymer, the modifier has a core-shell structure, the core of the modifier is crosslinked styrene and organosilicon, the shell is grafted polymethyl methacrylate, and the organosilicon methylphenyl silicone oil;
the toughening agent is a mixture formed by acetyl tributyl citrate and polyoxypropylene glycerol ether according to a weight ratio of 2:1.
The surfactant is polyethylene glycol with an average molecular weight of 1100.
The antioxidant is a mixture of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tri (2, 4-di-tert-butylphenyl) phosphite according to a weight ratio of 1:1.
The light stabilizer is a mixture of 2- (2 ',4' -dihydroxyphenyl) -5, 6-dihydroxybenzotriazol and 1, 6-dihydroxybenzotriazol according to a weight ratio of 2:1.
The preparation method of the environment-friendly stabilizer for the new energy charging cable comprises the following steps:
1) Weighing the raw materials according to parts by weight;
2) Placing all the raw materials weighed in the step 1) into a high-speed mixer to mix for 20 minutes at 75 ℃, wherein the rotating speed is 1500 rpm, and uniformly mixing;
3) And (3) cooling the mixed material obtained in the step (2) to 35 ℃ to obtain the environment-friendly stabilizer for the new energy charging cable.
Example 2
Unlike example 1, this example provides an environment-friendly stabilizer for new energy charging cables, which is prepared from the following raw materials in parts by weight: 35 parts of main stabilizer A, 35 parts of main stabilizer B, 10 parts of auxiliary stabilizer, 20 parts of hydrotalcite, 8 parts of antioxidant, 5 parts of modifier, 5 parts of surfactant, 5 parts of toughening agent and 5 parts of light stabilizer.
Wherein the main stabilizer A is cerium stearate;
the main stabilizer B is 2-amino lanthanum terephthalate;
the auxiliary stabilizer is polysiloxane capped by epoxy groups;
the hydrotalcite is a mixture formed by zinc-aluminum-lanthanum hydrotalcite and calcium-aluminum-lanthanum hydrotalcite according to a weight ratio of 1:1;
the modifier is methyl methacrylate-styrene-organosilicon polymer, the modifier has a core-shell structure, the core of the modifier is crosslinked styrene and organosilicon, the shell is grafted polymethyl methacrylate, and the organosilicon methylphenyl silicone oil;
the toughening agent is a mixture formed by acetyl tributyl citrate and polyoxypropylene glycerol ether according to a weight ratio of 2:1.
The surfactant is polyethylene glycol with an average molecular weight of 1200.
The antioxidant is a mixture of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tri (2, 4-di-tert-butylphenyl) phosphite according to a weight ratio of 1:1.
The light stabilizer is a mixture of 2- (2 ',4' -dihydroxyphenyl) -5, 6-dihydroxybenzotriazol and 1, 6-dihydroxybenzotriazol according to a weight ratio of 1:1.
Other details are not repeated here in the same way as in embodiment 1.
Example 3
Unlike example 1, this example provides an environment-friendly stabilizer for new energy charging cables, which is prepared from the following raw materials in parts by weight: 25 parts of main stabilizer A, 25 parts of main stabilizer B, 8 parts of auxiliary stabilizer, 15 parts of hydrotalcite, 5 parts of antioxidant, 3 parts of modifier, 3 parts of surfactant, 3 parts of toughening agent and 2 parts of light stabilizer.
Other details are not repeated here in the same way as in embodiment 1.
Example 4
Unlike example 1, this example provides an environment-friendly stabilizer for a new energy charging cable, which further comprises 8 parts by weight of silane-terminated polyether, wherein the silane-terminated polyether is silane-terminated polyether with trimethoxysilane as a terminal group and has a molecular weight of 30000-50000.
Other details are not repeated here in the same way as in embodiment 1.
Example 5
Unlike example 1, this example provides an environment-friendly stabilizer for a new energy charging cable, which further comprises 3 parts by weight of 1, 3-dimethyl-6-aminouracil.
Other details are not repeated here in the same way as in embodiment 1.
Example 6
Unlike example 1, this example provides an environment-friendly stabilizer for a new energy charging cable, which further comprises zinc glycerolate 2 parts by weight and pentaerythritol 4 parts by weight.
Other details are not repeated here in the same way as in embodiment 1.
Example 7
Unlike example 1, this example provides an environment-friendly stabilizer for a new energy charging cable, which further comprises 2 parts by weight of stearoyl benzoyl methane and 6 parts by weight of pentaerythritol.
Other details are not repeated here in the same way as in embodiment 1.
Example 8
Unlike example 1, this example provides an environment-friendly stabilizer for a new energy charging cable, which further includes 2 parts by weight of an acrylic ester processing aid, wherein the acrylic ester processing aid is a mixture of methyl methacrylate and methyl acrylate in a weight ratio of 1:1.
Other details are not repeated here in the same way as in embodiment 1.
Example 9
Unlike example 1, this example provides an environment-friendly stabilizer for a new energy charging cable, which further comprises 3 parts by weight of naloxone.
Other details are not repeated here in the same way as in embodiment 1.
Example 10
Unlike example 1, this example provides an environment-friendly stabilizer for a new energy charging cable, which further comprises 8 parts by weight of silane-terminated polyether and 3 parts by weight of 1, 3-dimethyl-6-aminouracil.
Other details are not repeated here in the same way as in embodiment 1.
Example 11
Unlike example 1, this example provides an environment-friendly stabilizer for a new energy charging cable, which further comprises 8 parts by weight of silane-terminated polyether and 3 parts by weight of naloxone.
Other details are not repeated here in the same way as in embodiment 1.
Example 12
Unlike example 1, this example provides an environment-friendly stabilizer for a new energy charging cable, which further comprises 8 parts by weight of silane-terminated polyether, 2 parts by weight of zinc glycerolate and 4 parts by weight of pentaerythritol.
Other details are not repeated here in the same way as in embodiment 1.
Example 13
Unlike example 1, this example provides an environmentally friendly stabilizer for a new energy charging cable, further comprising 8 parts by weight of silane-terminated polyether, 2 parts by weight of stearoyl benzoyl methane and 6 parts by weight of pentaerythritol.
Other details are not repeated here in the same way as in embodiment 1.
Example 14
Unlike example 1, this example provides an environment-friendly stabilizer for a new energy charging cable, which further comprises 2 parts by weight of zinc glycerate, 2 parts by weight of stearoyl benzoyl methane and 10 parts by weight of pentaerythritol.
Other details are not repeated here in the same way as in embodiment 1.
Example 15
Unlike example 1, this example provides an environment-friendly stabilizer for a new energy charging cable, which further comprises, by weight, 1, 3-dimethyl-6-aminouracil, 2 parts of zinc glycerate, 2 parts of stearoyl benzoyl methane, and 10 parts of pentaerythritol.
Other details are not repeated here in the same way as in embodiment 1.
The stabilizers of examples 1 to 15 were each subjected to a performance test, and the test results are shown in Table 1.
TABLE 1 thermal stability and UV resistance test results
From the test results in table 1, it can be seen that:
1) The heat stability test duration of the product at 200 ℃ is more than 55min, which shows that the product has good heat resistance; in the ultraviolet absorbance (wavelength range 230-360 nm) is less than or equal to 0.3 test, the embodiment of the invention is less than 0.2, which shows that the ultraviolet aging resistance is better.
2) Comparative examples 1, 4, and 10 to 13 show that the silane-terminated polyether has better thermal stability and ultraviolet aging resistance than the silane-terminated polyether without addition, and the silane-terminated polyether has better thermal stability and ultraviolet aging resistance when compounded with 1, 3-dimethyl-6-aminouracil, zinc glycerolate and pentaerythritol, stearylbenzoylmethane and pentaerythritol, or naloxone.
3) Comparative examples 1, 5, 10, 15 show that the addition of 1, 3-dimethyl-6-aminouracil results in a product having better heat stability and anti-UV aging than the product without the addition of 1, 3-dimethyl-6-aminouracil, and further has better heat stability when compounded with a silane-terminated polyether, or zinc glycerate, stearoyl-benzoyl-methane, and pentaerythritol.
4) Comparative examples 1, 9, 11 show that the thermal stability of the product is significantly better than the properties without addition due to the three-dimensional network structure of naloxone, which effectively improves the heat resistance of the stabilizer, and better when naloxone is compounded with the silane-terminated polyether.
5) Comparative examples 1,6, 12, 14-15 demonstrate that zinc glycerate and pentaerythritol are both more thermally stable than the products without addition, and that zinc glycerate and pentaerythritol are more thermally stable when compounded with silane-terminated polyethers, stearoyl-benzoyl-methane, or 1, 3-dimethyl-6-aminouracil.
6) Comparative examples 1, 7, 13, 14-15 demonstrate that the addition of stearylbenzoyl methane and pentaerythritol provides better heat stability than the products without the addition, and that stearylbenzoyl methane and pentaerythritol provide better heat stability when compounded with silane terminated polyethers, zinc glycerate, or 1, 3-dimethyl-6-aminouracil.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the invention pertains from the foregoing disclosure and teachings. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.

Claims (3)

1. The environment-friendly stabilizer for the new energy charging cable is characterized by comprising the following raw materials in parts by weight:
the main stabilizer A is cerium stearate;
the main stabilizer B is 2-amino lanthanum terephthalate;
the auxiliary stabilizer is polysiloxane capped by epoxy groups;
the hydrotalcite is a mixture formed by zinc-aluminum-lanthanum hydrotalcite and calcium-aluminum-lanthanum hydrotalcite according to a weight ratio of 1:1;
the modifier is methyl methacrylate-styrene-organosilicon polymer, the modifier has a core-shell structure, the core of the modifier is crosslinked styrene and organosilicon, the shell is grafted polymethyl methacrylate, and the organosilicon is methyl phenyl silicone oil;
the toughening agent is a mixture formed by acetyl tributyl citrate and polyoxypropylene glycerol ether according to the weight ratio of 2:1;
the adhesive also comprises 5-10 parts by weight of silane end-capped polyether, wherein the silane end-capped polyether is silane end-capped polyether with trimethoxy silane and the molecular weight of 30000-50000;
also comprises 1 to 4 parts by weight of stearoyl benzoyl methane and 2 to 8 parts by weight of pentaerythritol;
the surfactant is polyethylene glycol with the average molecular weight of 800-1200;
the antioxidant is a mixture formed by pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tri (2, 4-di-tert-butylphenyl) phosphite according to a weight ratio of 1:1;
the light stabilizer is a mixture formed by 2- (2 ',4' -dihydroxyphenyl) -5, 6-dihydroxybenzotriazol and 1, 6-dihydroxybenzotriazol according to the weight ratio of 1-2:1;
the preparation method of the epoxy-terminated polysiloxane comprises the following steps: adding bisphenol A epoxy resin into a container, adding toluene as a solvent, heating to raise the temperature, adding zinc octoate as a catalyst when the temperature reaches more than 110 ℃, then adding hydroxy-terminated polymethylphenylsiloxane, preserving the heat for 2-4 hours, continuously steaming out water and toluene in the reaction process, and drying the obtained solid product in an oven to obtain the epoxy-terminated polysiloxane.
2. The environment-friendly stabilizer for new energy charging cables according to claim 1, wherein: also comprises 1 to 5 parts by weight of 1, 3-dimethyl-6-amino uracil.
3. The environment-friendly stabilizer for new energy charging cables according to claim 1, wherein: the acrylic ester processing agent is a mixture of methyl methacrylate and methyl acrylate in a weight ratio of 1:1.
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