CN110669335A - PA66 composite material with excellent fluidity and low-temperature toughness for cable ties and preparation method thereof - Google Patents
PA66 composite material with excellent fluidity and low-temperature toughness for cable ties and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of cable ties, in particular to a PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie and a preparation method thereof. The PA66 composite material with excellent fluidity and low-temperature toughness for the cable tie comprises the following raw materials in parts by weight: PA 66850-950 parts, TPV-g-MAH 40-150 parts, thermal stabilizer 2-8 parts, and demolding nucleating agent 4-10 parts. The PA66 composite material for the cable tie takes PA66 as a main raw material, TPV-g-MAH, a heat stabilizer and a demolding nucleating agent are added, and on the premise of ensuring that the PA66 composite material has excellent fluidity and good molding efficiency, the PA66 composite material also has excellent normal temperature toughness and low temperature toughness, and meanwhile has good rigidity, heat aging resistance and moldability.
Description
Technical Field
The invention relates to the technical field of cable ties, in particular to a PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie and a preparation method thereof.
Background
The automobile is provided with a plurality of automobile wire harnesses in a carriage, wherein the automobile wire harnesses are equivalent to a neural network of the automobile and are used for transmitting various instruction information and telecommunication signals, so that the whole automobile is in a better control and running state. However, in the existing automobile wire harness, the arrangement is scattered in the automobile, the scattered wire harnesses are connected together and are difficult to assemble, but the stability is not high after the assembly, and the fault is easy to occur.
PA66 (polyhexamethylene adipamide) is widely used due to good mechanical property and processability, and the impact strength, the heat aging resistance and other properties of the modified polyamide are further improved after toughening and aging resistance, so that the polyamide is widely applied to the field of non-standard cable ties such as automobile cable ties. When the automobile cable tie is used, the tail end of the cable tie can be firmly buckled by pulling the tail end of the cable tie through the end with the hole. The traditional non-standard binding belt has high requirements on low-temperature toughness, forming efficiency and processability of materials; the low-temperature toughness ensures that the binding belt can keep the toughness in low-temperature weather and does not lose efficacy; the forming efficiency ensures the production efficiency, reduces the processing cost and improves the enterprise competitiveness; because the structures of the non-standard binding tapes are diversified, some special-shaped structures are complicated, the requirement on the flowability of the material is high, and the good flowability can ensure that the material is easy to mold and process. The traditional PA66 toughening modification is to improve the normal temperature toughness and the low temperature toughness of PA66 by adding a toughening agent, selecting high molecular weight PA66 or adding PA6 (polyamide-6), but the addition of the toughening agent or the selection of the high molecular weight PA66 can reduce the fluidity of PA66 and influence the processability of a belt prepared from PA66, and the addition of the toughening agent or the PA6 can reduce the rigidity of the PA66 and reduce the pulling resistance of the belt. In addition, in the prior art, the rigidity of the PA66 is improved by adopting glass fibers, but the glass fibers have a large influence on the melt flow property, bring certain adverse effects on the forming processing, and also cause the impact toughness of the PA66 to be reduced, so that the material becomes brittle and is easy to crack.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the PA66 composite material for the cable tie with excellent fluidity and low-temperature toughness, which is prepared by taking PA66 as a main raw material, adding TPV-g-MAH, a heat stabilizer and a demolding nucleating agent, and has excellent normal-temperature toughness and low-temperature toughness, good rigidity, heat aging resistance and moldability on the premise of ensuring that the PA66 composite material has excellent fluidity and good molding efficiency.
The invention also aims to provide a preparation method of the PA66 composite material for the ribbon, which has the advantages of excellent fluidity and low-temperature toughness, simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production.
The purpose of the invention is realized by the following technical scheme: a PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie comprises the following raw materials in parts by weight:
the PA66 composite material for the cable tie disclosed by the invention is prepared by taking PA66 as a main raw material and adding TPV-g-MAH, a heat stabilizer and a demolding nucleating agent, and has excellent normal-temperature toughness and low-temperature toughness, and good rigidity, heat aging resistance and moldability on the premise of ensuring that the PA66 composite material has excellent flowability and good molding efficiency. The TPV-g-MAH replaces the traditional toughening agent, the compatibility of the TPV-g-MAH in PA66 is greatly improved under the action of the MAH functional group, the TPV-g-MAH plays a normal-temperature and low-temperature toughening role in the PA66 composite material as a whole, the rigidity reduction of PA66 is avoided, the MAH functional group and the demolding nucleating agent are in synergistic action, and the fluidity, the moldability and the molding efficiency of the PA66 composite material are improved. The PA66 composite material is used for preparing the cable tie, in particular to an automobile cable tie, which not only improves the processing efficiency of producing the automobile cable tie and reduces the processing cost, but also improves the low-temperature toughness, the heat aging resistance and the drawing resistance of the automobile cable tie.
Preferably, the intrinsic viscosity of the PA66 resin is 2.4-3.2 dL/g.
The intrinsic viscosity of the PA66 resin is controlled to be 2.4-3.2dL/g, so that the PA66 resin is ensured to have better rigidity and toughness and better fluidity, and is conveniently mixed and modified with TPV-g-MAH, a heat stabilizer and a demolding nucleating agent on the basis, more excellent fluidity, molding efficiency, normal-temperature toughness and low-temperature toughness are obtained, the processing fluidity and toughness of the composite material are greatly improved, the processing is more facilitated, the processing cost is reduced, the processing efficiency is improved, and the reduction of the rigidity caused by the reduction of the molecular weight due to the internal friction of PA66 in the processing process is avoided; if the intrinsic viscosity of the PA66 resin is higher than 3.2dL/g, the molecular weight of the PA66 resin is increased, the fluidity of the composite material is greatly reduced, the processing difficulty is increased, the energy consumption is increased, and the fluidity of the composite material is difficult to greatly improve even if TPV-g-MAH is added. More preferably, the intrinsic viscosity of the PA66 resin is 2.5-2.8 dL/g.
Preferably, the TPV-g-MAH has a grafting ratio of 1.0 to 1.2%.
The invention adopts TPV-g-MAH with the grafting ratio of 1.0-1.2% to improve the utilization ratio of the TPV-g-MAH with lower molecular weight and avoid the poor processing rheological property caused by the increase of the molecular weight when the TPV-g-MAH is added. If the grafting rate of TPV-g-MAH is too high, although the MAH functional groups are increased, the compatibility of TPV-g-MAH in PA66 is improved, and the TPV-g-MAH is synergistic with a demolding nucleating agent to improve the moldability and molding efficiency of the PA66 composite material, the molecular weight is increased due to the increased MAH functional groups, so that the processing rheological property of the PA66 composite material is poor, the grafting rate of TPV-g-MAH is high, the raw material cost is higher, the TPV-g-MAH is not beneficial to enterprise development, and the market demand is not met. If the grafting ratio of TPV-g-MAH is too low, the compatibility in the PA66 composite material is poor, the fluidity of the PA66 composite material is reduced, and the normal-temperature and low-temperature toughening effect of the PA66 composite material cannot be fully exerted.
Preferably, the preparation method of the TPV-g-MAH comprises the following steps:
(R1) adding 10-30 parts by weight of ethylene propylene diene monomer and 0.1-2 parts by weight of vulcanizing agent into 50-80 parts by weight of polyolefin for dynamic vulcanization to prepare TPV;
(R2) adding 1-5 parts of maleic anhydride and 0.05-0.3 part of initiator into the TPV prepared in the step (R1), uniformly mixing, carrying out melt blending by a double-screw extruder, carrying out grafting reaction, and carrying out extrusion granulation to obtain the TPV-g-MAH.
The grafting rate of the TPV-g-MAH prepared by the preparation method can reach 1.0-1.2%, and the preparation method has the advantages of simple operation, convenient control and high production efficiency. In the step (R1), the ethylene propylene diene monomer and the polyolefin are dynamically vulcanized under the action of a vulcanizing agent, and then the maleic anhydride is grafted while extruding in the step (R2), so that the high-performance ethylene propylene diene monomer rubber has good compatibility, high fluidity, excellent ageing resistance, low-temperature toughness and good weather resistance and heat resistance. Further, in the step (R1), the apparatus used for dynamic vulcanization is a twin-screw extruder or an internal mixer. The length-diameter ratio of the screw of the double-screw extruder in the step (R2) is 20-35: 1; the screw rotating speed of the double-screw extruder is 200-; the temperature of each section of the double-screw extruder is as follows: the first zone 158-; the double-screw extruder is adopted, the dosage of the maleic anhydride is controlled to be 1-5 parts by weight, and the dosage of the initiator is controlled to be 0.05-0.3 part by weight, so that the TPV and the maleic anhydride are fully reacted, and the grafting rate of the TPV-g-MAH reaches 1.0-1.2%.
Preferably, the polyolefin is polypropylene or a polyolefin elastomer; the melt flow rate of the polypropylene under the conditions that the temperature is 230 ℃ and the pressure load is 2.16kg is 16-18g/10min, and the shrinkage rate of the polypropylene under the temperature condition of 23 ℃ is 1.4-1.8%; the melt flow rate of the polyolefin elastomer under the conditions of 190 ℃ of temperature and 2.16kg of pressure load is 28-32g/10min, and the Mooney viscosity of the polyolefin elastomer under the conditions of ML (1+4) and 121 ℃ is 1.8-2.2 MU.
By adopting the technical scheme, the surface energy of the polyolefin and the ethylene propylene diene monomer rubber are matched, the polyolefin and the ethylene propylene diene monomer rubber have better compatibility, the polypropylene or the polyolefin elastomer with the physical property is selected, the length of the polyolefin molecular chain entangled by the ethylene propylene diene monomer rubber is lower, and the TPV after dynamic vulcanization has excellent ageing resistance, low-temperature toughness, weather resistance and good fluidity. More preferably, the polypropylene includes, but is not limited to, K9017, H1501, or J-160H; the polyolefin elastomer includes, but is not limited to, ENGAGE8400, ENGAGE 8401, or ENGAGE 8402.
Preferably, the vulcanizing agent is at least one of 2, 5-bis (t-butylperoxy) -2, 5-dimethyl-3-hexyne, 2, 5-bis (t-butylperoxy) -2, 5-dimethylhexane, dicumyl peroxide, t-butylperoxyisopropyl carbonate, t-butylcumyl peroxide, 1, 4-di-t-butylperoxyisopropyl benzene, tetramethylthiuram disulfide and tetraethylthiuram disulfide; the initiator is at least one of dicumyl peroxide, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
By adopting the technical scheme, the vulcanizing agent promotes the ethylene propylene diene monomer and the polyolefin to be vulcanized to form a three-dimensional net structure, so that the mechanical and physical properties of the TPV are obviously improved. More preferably, the vulcanizing agent is dicumyl peroxide and tetramethylthiuram disulfide according to the weight ratio of 3-4: 1, so that side reactions in the dynamic vulcanization process of the ethylene propylene diene monomer and the polyolefin are reduced. The invention has good initiating effect by strictly controlling the type, compounding and proportion of the initiator, promotes the polymerization of the maleic anhydride in the step (R2), improves the polymerization rate and improves the production efficiency. More preferably, the initiator is prepared by mixing benzoyl peroxide, dicumyl peroxide and azobisisobutyronitrile in a weight ratio of 1:0.5-1.5: 1.5-2.5.
Preferably, in the step (R1), the vulcanization time of the dynamic vulcanization is 10-20min, and the vulcanization temperature of the dynamic vulcanization is 160-220 ℃.
The vulcanization temperature is controlled at 160-220 ℃, the vulcanization time can be shortened to 10-20min by combining the specific vulcanizing agent and the polyolefin, and the TPV prepared by dynamic vulcanization has excellent aging resistance, low-temperature toughness, weather resistance and good fluidity. If the vulcanization time is too long, the vulcanization cost is increased, the hardness of TPV is easily increased, the toughness is deteriorated, and the normal-temperature toughness and the low-temperature toughness of the PA66 composite material are not enhanced.
Preferably, the heat stabilizer is a copper salt bromine-free heat stabilizer.
By adopting the technical scheme, the long-term thermal aging performance, the chemical corrosion resistance and the weather resistance can be provided, the copper salt of the copper salt non-bromine heat stabilizer and the amide group of PA66 are chelated to form a stable complex in the processing process, so that the amide group is protected from being attacked by a thermal oxygen group and other active groups in a long-term ultraviolet and thermal oxygen working environment, the molecular chain is prevented from being broken and degraded, the thermal stability of the PA66 composite material is finally improved by combining the self weather resistance of TPV-g-MAH, the problem of color pollution and yellowing of the current steel salt stabilizer is solved, the material can be freely matched in color, the requirement of customers on multiple color samples is met, and the long-term stability is provided under the condition of the temperature as high as 150 ℃ to resist the reduction of the mechanical performance. In addition, bromine is avoided, and the thermal decomposition resistance of the thermal stabilizer is greatly improved. Further, the copper salt bromine-free heat stabilizer includes but is not limited to PS201 or H3350.
Preferably, the demolding nucleating agent is montan wax containing sodium ions.
Adopt above-mentioned technical scheme, can increase substantially PA66 combined material's crystallization temperature for it has faster crystallization rate, can accelerate the crystallization and shorten the time of moulding plastics in the course of working, thereby shortens the shaping cycle, has improved PA66 combined material's shaping efficiency and drawing of patterns formability in the course of working greatly, has improved the machining efficiency of ribbon, more is favorable to the enterprise to enlarge the ribbon output, improves enterprise competitiveness. The demolding nucleating agent is carbon chain with length C22-C28The long-chain linear saturated carboxylic acid sodium salt nucleating agent comprises but is not limited to montan wax sodium salt. The sodium ion-containing montan wax can remarkably improve the crystallization speed and the formability of the PA66 composite material.
The other purpose of the invention is realized by the following technical scheme: the preparation method of the PA66 composite material for the cable tie with excellent fluidity and low-temperature toughness comprises the following steps:
(S1) weighing the raw materials in parts by weight for later use;
(S2), uniformly mixing the PA66, the TPV-g-MAH, the heat stabilizer and the demolding nucleating agent, and extruding and granulating by a double-screw extruder to obtain the PA66 composite material.
The preparation method of the PA66 composite material for the ribbon has the advantages of simple operation, convenient control, high production efficiency and low production cost, and can be used for large-scale production. Wherein, the processing temperatures of the twin-screw extruder in the step (S2) in the zones from the feeding section are respectively: the temperature of the first zone is 200-220 ℃, the temperature of the second zone is 260-280 ℃, the temperature of the third zone is 260-280 ℃, the temperature of the fourth zone is 260-280 ℃, the temperature of the fifth zone is 260-280 ℃, the temperature of the sixth zone is 260-280 ℃, the temperature of the head is 260-280 ℃ and the rotation speed of the screw is 200-300 r/min.
The invention has the beneficial effects that: the PA66 composite material for the cable tie with excellent fluidity and low-temperature toughness, disclosed by the invention, is prepared by taking PA66 as a main raw material and adding TPV-g-MAH, a heat stabilizer and a demolding nucleating agent, and has excellent normal-temperature toughness and low-temperature toughness, good rigidity, heat aging resistance and moldability on the premise of ensuring the excellent fluidity and good molding efficiency of the PA66 composite material.
The preparation method disclosed by the invention is simple to operate, convenient to control, high in production efficiency and low in production cost, and can be used for large-scale production.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie comprises the following raw materials in parts by weight:
the intrinsic viscosity of the PA66 resin was 2.5 dL/g.
The grafting ratio of the TPV-g-MAH is 1.1 percent.
The preparation method of the TPV-g-MAH comprises the following steps:
(R1), adding 20 parts by weight of ethylene propylene diene monomer and 1 part by weight of vulcanizing agent into 65 parts by weight of polyolefin for dynamic vulcanization to prepare TPV;
(R2) adding 2.5 parts of maleic anhydride and 0.1 part of initiator into the TPV prepared in the step (R1), uniformly mixing, carrying out melt blending by a double-screw extruder, carrying out grafting reaction, and carrying out extrusion granulation to obtain the TPV-g-MAH.
The length-diameter ratio of the screw of the double-screw extruder in the step (R2) is 27: 1; the screw rotating speed of the double-screw extruder is 300 r/min; the temperature of each section of the double-screw extruder is as follows: 160 ℃ in the first zone, 165 ℃ in the second zone, 170 ℃ in the third zone, 174 ℃ in the fourth zone, 180 ℃ in the fifth zone, 180 ℃ in the sixth zone, 174 ℃ in the seventh zone, 170 ℃ in the eighth zone, 165 ℃ in the ninth zone, 178 ℃ in the die head, and the residence time in each zone being 3 s.
The polyolefin is polypropylene; the polypropylene is K9017.
The vulcanizing agent is dicumyl peroxide and tetramethyl thiuram disulfide according to the weight ratio of 3.5: 1, mixing; the initiator is prepared by mixing benzoyl peroxide, dicumyl peroxide and azobisisobutyronitrile according to the weight ratio of 1:1: 2.
In the step (R1), the vulcanization time for dynamic vulcanization is 15min, and the vulcanization temperature for dynamic vulcanization is 180 ℃.
The heat stabilizer is a copper salt bromine-free heat stabilizer. The copper salt bromine-free heat stabilizer is PS 201.
The demolding nucleating agent is montan wax containing sodium ions. The montan wax containing sodium ions is montan wax sodium salt, and the model is NaV 101.
A preparation method of PA66 composite material for a cable tie with excellent fluidity and low-temperature toughness as described above comprises the following steps:
(S1) weighing the raw materials in parts by weight for later use;
(S2), uniformly mixing the PA66, the TPV-g-MAH, the heat stabilizer and the demolding nucleating agent, and extruding and granulating by a double-screw extruder to obtain the PA66 composite material.
The processing temperatures of the twin-screw extruder in the step (S2) in the respective zones from the feeding section are: the first zone temperature is 210 ℃, the second zone temperature is 265 ℃, the third zone temperature is 263 ℃, the fourth zone temperature is 268 ℃, the fifth zone temperature is 270 ℃, the sixth zone temperature is 275 ℃, the head temperature is 270 ℃ and the screw rotation speed is 250 r/min.
Example 2
A PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie comprises the following raw materials in parts by weight:
the intrinsic viscosity of the PA66 resin was 2.4 dL/g.
The grafting rate of the TPV-g-MAH is 1.0 percent.
The preparation method of the TPV-g-MAH comprises the following steps:
(R1), adding 10 parts by weight of ethylene propylene diene monomer and 0.1 part by weight of vulcanizing agent into 50 parts by weight of polyolefin for dynamic vulcanization to prepare TPV;
(R2) adding 1 part of maleic anhydride and 0.05 part of initiator into the TPV prepared in the step (R1), uniformly mixing, carrying out melt blending by a double-screw extruder, carrying out grafting reaction, and carrying out extrusion granulation to obtain the TPV-g-MAH.
The length-diameter ratio of the screws of the twin-screw extruder in the step (R2) is 20: 1; the screw rotating speed of the double-screw extruder is 200 r/min; the temperature of each section of the double-screw extruder is as follows: first zone 158 deg.C, second zone 162 deg.C, third zone 168 deg.C, fourth zone 172 deg.C, fifth zone 177 deg.C, sixth zone 176 deg.C, seventh zone 172 deg.C, eighth zone 168 deg.C, ninth zone 162 deg.C, die temperature 175 deg.C, residence time per zone 2 s.
The polyolefin is polypropylene; the polypropylene is H1501.
The vulcanizing agent is dicumyl peroxide and tetramethyl thiuram disulfide according to the weight ratio of 3: 1, mixing; the initiator is prepared by mixing benzoyl peroxide, dicumyl peroxide and azobisisobutyronitrile according to the weight ratio of 1:0.5: 1.5.
In the step (R1), the vulcanization time for dynamic vulcanization is 10min, and the vulcanization temperature for dynamic vulcanization is 160 ℃.
The heat stabilizer is a copper salt bromine-free heat stabilizer. The copper salt bromine-free heat stabilizer is H3350.
The demolding nucleating agent is montan wax containing sodium ions. The montan wax containing sodium ions is montan wax sodium salt, and the model is NaV 101.
A preparation method of PA66 composite material for a cable tie with excellent fluidity and low-temperature toughness as described above comprises the following steps:
(S1) weighing the raw materials in parts by weight for later use;
(S2), uniformly mixing the PA66, the TPV-g-MAH, the heat stabilizer and the demolding nucleating agent, and extruding and granulating by a double-screw extruder to obtain the PA66 composite material.
The processing temperatures of the twin-screw extruder in the step (S2) in the respective zones from the feeding section are: the first zone temperature is 200 ℃, the second zone temperature is 280 ℃, the third zone temperature is 260 ℃, the fourth zone temperature is 280 ℃, the fifth zone temperature is 260 ℃, the sixth zone temperature is 280 ℃, the head temperature is 260 ℃ and the screw rotation speed is 200 r/min.
Example 3
A PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie comprises the following raw materials in parts by weight:
the intrinsic viscosity of the PA66 resin was 3.2 dL/g.
The grafting ratio of the TPV-g-MAH is 1.2 percent.
The preparation method of the TPV-g-MAH comprises the following steps:
(R1), adding 30 parts by weight of ethylene propylene diene monomer and 2 parts by weight of vulcanizing agent into 80 parts by weight of polyolefin for dynamic vulcanization to prepare TPV;
(R2) adding 5 parts of maleic anhydride and 0.3 part of initiator into the TPV prepared in the step (R1), uniformly mixing, carrying out melt blending by a double-screw extruder, carrying out grafting reaction, and carrying out extrusion granulation to obtain the TPV-g-MAH.
The length-diameter ratio of the screws of the twin-screw extruder in the step (R2) is 35: 1; the screw rotating speed of the double-screw extruder is 200-; the temperature of each section of the double-screw extruder is as follows: one zone 163 ℃, two zone 167 ℃, three zone 173 ℃, four zone 176 ℃, five zone 183 ℃, six zone 182 ℃, seven zone 175 ℃, eight zone 173 ℃, nine zone 167 ℃, die temperature 182 ℃, 4s residence time per zone.
The polyolefin is a polyolefin elastomer; the polyolefin elastomer is ENGAGE 8401.
The vulcanizing agent is dicumyl peroxide and tetramethyl thiuram disulfide according to a weight ratio of 4: 1, mixing; the initiator is prepared by mixing benzoyl peroxide, dicumyl peroxide and azobisisobutyronitrile according to the weight ratio of 1:1.5: 2.5.
In the step (R1), the vulcanization time of the dynamic vulcanization is 20min, and the vulcanization temperature of the dynamic vulcanization is 220 ℃.
The heat stabilizer is a copper salt bromine-free heat stabilizer. The copper salt bromine-free heat stabilizer is PS 201.
The demolding nucleating agent is montan wax containing sodium ions. The montan wax containing sodium ions is montan wax sodium salt, and the model is NaV 101.
A preparation method of PA66 composite material for a cable tie with excellent fluidity and low-temperature toughness as described above comprises the following steps:
(S1) weighing the raw materials in parts by weight for later use;
(S2), uniformly mixing the PA66, the TPV-g-MAH, the heat stabilizer and the demolding nucleating agent, and extruding and granulating by a double-screw extruder to obtain the PA66 composite material.
The processing temperatures of the twin-screw extruder in the step (S2) in the respective zones from the feeding section are: the first zone temperature is 220 ℃, the second zone temperature is 260 ℃, the third zone temperature is 280 ℃, the fourth zone temperature is 260 ℃, the fifth zone temperature is 280 ℃, the sixth zone temperature is 260 ℃, the head temperature is 280 ℃ and the screw rotation speed is 300 r/min.
Example 4
A PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie comprises the following raw materials in parts by weight:
the intrinsic viscosity of the PA66 resin was 2.8 dL/g.
The grafting ratio of the TPV-g-MAH is 1.1 percent.
The preparation method of the TPV-g-MAH comprises the following steps:
(R1), adding 17 parts by weight of ethylene propylene diene monomer and 1.5 parts by weight of vulcanizing agent into 72 parts by weight of polyolefin for dynamic vulcanization to prepare TPV;
(R2) adding 3 parts of maleic anhydride and 0.15 part of initiator into the TPV prepared in the step (R1), uniformly mixing, carrying out melt blending by a double-screw extruder, carrying out grafting reaction, and carrying out extrusion granulation to obtain the TPV-g-MAH.
The length-diameter ratio of the screws of the twin-screw extruder in the step (R2) is 30: 1; the screw rotating speed of the double-screw extruder is 250 r/min; the temperature of each section of the double-screw extruder is as follows: first zone 161 ℃, second zone 164 ℃, third zone 171 ℃, fourth zone 175 ℃, fifth zone 179 ℃, sixth zone 180 ℃, seventh zone 174 ℃, eighth zone 172 ℃, ninth zone 164 ℃, die temperature 179 ℃, residence time 2s per zone.
The polyolefin is a polyolefin elastomer; the polyolefin elastomer is ENGAGE 8400.
The vulcanizing agent is 2, 5-bis (tert-butylperoxy) -2, 5-dimethyl-3-hexyne; the initiator is dicumyl peroxide.
In the step (R1), the vulcanization time for dynamic vulcanization is 18min, and the vulcanization temperature for dynamic vulcanization is 180 ℃.
The heat stabilizer is a copper salt bromine-free heat stabilizer. The copper salt bromine-free heat stabilizer is PS 201.
The demolding nucleating agent is montan wax containing sodium ions. The montan wax containing sodium ions is montan wax sodium salt, and the model is NaV 101.
A preparation method of PA66 composite material for a cable tie with excellent fluidity and low-temperature toughness as described above comprises the following steps:
(S1) weighing the raw materials in parts by weight for later use;
(S2), uniformly mixing the PA66, the TPV-g-MAH, the heat stabilizer and the demolding nucleating agent, and extruding and granulating by a double-screw extruder to obtain the PA66 composite material.
The processing temperatures of the twin-screw extruder in the step (S2) in the respective zones from the feeding section are: the first zone temperature is 215 ℃, the second zone temperature is 270 ℃, the third zone temperature is 265 ℃, the fourth zone temperature is 278 ℃, the fifth zone temperature is 268 ℃, the sixth zone temperature is 272 ℃, the head temperature is 280 ℃ and the screw rotation speed is 280 r/min.
Example 5
This example differs from example 1 in that: the polyolefin is a polyolefin elastomer; the polyolefin elastomer is ENGAGE 8400.
Comparative example 1
This comparative example differs from example 1 in that: the TPV-g-MAH is replaced by a toughening agent MD 715.
Comparative example 2
This comparative example differs from example 1 in that: the TPV-g-MAH is replaced by a toughening agent EXXELOR VA 1801.
Comparative example 3
This comparative example differs from example 1 in that: the TPV-g-MAH is replaced by a toughening agent, namely, Acoma 4700.
Example 6 Performance testing
The PA66 composites prepared in examples 1-5 and comparative examples 1-3 were tested for melt index, tensile strength, flexural modulus and notched impact strength, and the results are shown in Table 1 below:
TABLE 1
As can be seen from table 1 above, although the notched impact strength is comparable in example 1 to comparative example 1, the melt index, tensile strength and flexural modulus are higher in example 1 than in comparative example 1; example 1 compared to comparative example 2, although comparative example 2 has a higher melt index, example 1 has higher notched impact strength, tensile strength and flexural modulus than comparative example 2; example 5 compared to comparative example 3, while comparative example 3 has a higher flexural modulus, example 5 has higher notched impact strength, tensile strength and melt index than comparative example 3. The results in table 1 show that the PA66 composite material for a cable tie, according to the present invention, has excellent fluidity and low-temperature toughness, and also has good rigidity, while ensuring excellent fluidity and good molding efficiency of the PA66 composite material.
The PA66 composites prepared in examples 1-5 and comparative examples 1-3 were heat aged at 150 ℃ for 1000 hours and then tested for tensile strength, flexural modulus and notched impact strength, the results of which are shown in Table 2 below:
TABLE 2
As can be seen from the comparison between table 1 and table 2, the thermal stabilizer used in the present invention provides long-term stability at a temperature as high as 150 ℃ to resist the decrease of mechanical properties, and after thermal aging at 150 ℃ for 1000h, the mechanical property retention rate is greater than 75%, and the thermal aging resistance is good; in addition, the tensile strength of the PA66 composite material after heat aging treatment is improved, and the tensile strength is improved because the crystallinity of the PA66 composite material is improved, molecular chains in crystals are arranged closely and orderly, and intermolecular force is enhanced.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. A PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie is characterized in that: the feed comprises the following raw materials in parts by weight:
2. the PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie as claimed in claim 1, wherein: the intrinsic viscosity of the PA66 resin is 2.4-3.2 dL/g.
3. The PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie as claimed in claim 1, wherein: the grafting rate of the TPV-g-MAH is 1.0-1.2%.
4. The PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie as claimed in claim 1, wherein: the preparation method of the TPV-g-MAH comprises the following steps:
(R1) adding 10-30 parts by weight of ethylene propylene diene monomer and 0.1-2 parts by weight of vulcanizing agent into 50-80 parts by weight of polyolefin for dynamic vulcanization to prepare TPV;
(R2) adding 1-5 parts of maleic anhydride and 0.05-0.3 part of initiator into the TPV prepared in the step (R1), uniformly mixing, carrying out melt blending by a double-screw extruder, carrying out grafting reaction, and carrying out extrusion granulation to obtain the TPV-g-MAH.
5. The PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie, as claimed in claim 4, wherein: the polyolefin is polypropylene or polyolefin elastomer; the melt flow rate of the polypropylene under the conditions that the temperature is 230 ℃ and the pressure load is 2.16kg is 16-18g/10min, and the shrinkage rate of the polypropylene under the temperature condition of 23 ℃ is 1.4-1.8%; the melt flow rate of the polyolefin elastomer under the conditions of 190 ℃ of temperature and 2.16kg of pressure load is 28-32g/10min, and the Mooney viscosity of the polyolefin elastomer under the conditions of ML (1+4) and 121 ℃ is 1.8-2.2 MU.
6. The PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie, as claimed in claim 4, wherein: the vulcanizing agent is at least one of 2, 5-bis (tert-butylperoxy) -2, 5-dimethyl-3-hexyne, 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane, dicumyl peroxide, tert-butylperoxyisopropyl carbonate, tert-butylcumyl peroxide, 1, 4-di-tert-butylperoxyisopropyl benzene, tetramethylthiuram disulfide and tetraethylthiuram disulfide; the initiator is at least one of dicumyl peroxide, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
7. The PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie, as claimed in claim 4, wherein: in the step (R1), the vulcanization time of the dynamic vulcanization is 10-20min, and the vulcanization temperature of the dynamic vulcanization is 160-220 ℃.
8. The PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie as claimed in claim 1, wherein: the heat stabilizer is a copper salt bromine-free heat stabilizer.
9. The PA66 composite material with excellent fluidity and low-temperature toughness for a cable tie as claimed in claim 1, wherein: the demolding nucleating agent is montan wax containing sodium ions.
10. A method for preparing PA66 composite material for a cable tie having excellent fluidity and low temperature toughness according to any one of claims 1 to 9, wherein: the method comprises the following steps:
(S1) weighing the raw materials in parts by weight for later use;
(S2), uniformly mixing the PA66, the TPV-g-MAH, the heat stabilizer and the demolding nucleating agent, and extruding and granulating by a double-screw extruder to obtain the PA66 composite material.
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