CN114656598A - Nylon toughening agent and preparation method thereof - Google Patents
Nylon toughening agent and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
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- 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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses a nylon toughening agent and a preparation method thereof. The preparation method of the nylon toughening agent comprises the following steps: glutaric acid is completely dissolved in dimethyl sulfoxide, then methyl cyclohexanediamine is added to successfully prepare a cross-linked mixture, 4-dimethylaminopyridine is further added to be connected in the cross-linked mixture through a grafting reaction to synthesize a synergist, and then the synergist is mixed with an olefin-based polymer, a plasticizer, a curing agent, a first grafting monomer, a second grafting monomer and an initiator and then is melted and extruded to prepare the nylon toughening agent. Compared with the prior art, the nylon toughening agent prepared by the invention can promote the gelation of nylon, greatly improve the strength and toughness of the nylon, and can also construct a flame-retardant layer to improve the flame-retardant effect of the nylon.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a dragon toughening agent and a preparation method thereof.
Background
Nylon, also called Polyamide (PA), is used as a synthetic thermoplastic engineering plastic and has good wear resistance, fatigue resistance, corrosion resistance, oil resistance, high strength and modulus. However, their inherent brittleness and low toughness are still to be overcome in many fields of application in competition with other polymers having an excellent combination of properties. In order to meet the needs of industrial and social development, the preparation of super-tough nylon has received extensive attention. From a technical standpoint, the most feasible method of increasing toughness is to melt blend nylon with an elastomer or other tough polymer. Most two-component or multi-component blending systems are mutually incompatible, and because the interface adhesion is weak, the performance is reduced due to simple melt blending.
Therefore, good compatibility between the components in the polymer blend system is a prerequisite for satisfactory performance. Reactive compatibilization is an effective method of making incompatible polymers compatible by chemical reaction at the interface. Effective interfacial compatibilization is believed to be responsible for significantly increasing the notched impact strength of the blend. In this way, toughening of nylon has been achieved. The toughening effect of this approach is yet to be further explored.
Patent No. CN102391431A discloses a nylon toughening agent, which is prepared from the following raw materials in percentage by weight: 80 to 90 percent of olefin polymer, 5.5 to 15.5 percent of polyethylene wax, 0.5 to 2.5 percent of first grafting monomer, 0.5 to 2.5 percent of second grafting monomer, 0.2 to 1.0 percent of chain initiator and 1.0 to 5.0 percent of grafting synergist, the nylon toughening agent has better fluidity, the dispersing ability of the nylon toughening agent in a nylon system is improved, and simultaneously, because two grafting monomers are used, the reaction activity of the nylon toughening agent and a nylon material is improved, thereby improving the impact strength of nylon and improving the flow processing performance of the material. The invention also discloses a preparation method of the nylon toughening agent, which has the advantages of simplicity, strong operability, good controllability, good reproducibility, easiness in industrial production and better economic benefit. However, the nylon toughening agent has limited toughening effect on nylon, has single reaction functional substance and does not contain a curing agent and a reinforcing agent, thereby influencing subsequent processing.
CN103421148A provides a cold-resistant nylon toughening agent and a preparation method thereof. The cold-resistant nylon toughening agent is prepared from the following components in parts by weight: 80-95 parts of ethylene-alpha-octene copolymer, 5-20 parts of EPDM (ethylene-propylene-diene monomer), 0.5-5 parts of first grafting monomer, 0.5-5 parts of second grafting monomer, 2-5 parts of compatibilizer, 0.01-0.5 part of initiator, 0.1-1 part of anti-sticking agent, 0.1-2 parts of diluent and 0.1-2 parts of liquid auxiliary agent. The invention takes the compound of POE and EPDM with good low-temperature flexibility as the base material, has convenient processing, difficult agglomeration of the cut particles and excellent low-temperature toughness, and ensures that the nylon product has better cold resistance. However, the toughening agent prepared by the invention has the defects of poor high temperature resistance and low toughening effect.
Disclosure of Invention
The nylon toughening agent in the prior art has the defects of complex preparation process and poor toughening effect. In order to solve the defects, glutaric acid, methylcyclohexanediamine and 4-dimethylaminopyridine are subjected to a series of chemical reactions to synthesize a synergist, and then the synergist is mixed with an olefin-based polymer, a plasticizer, a curing agent, a grafting monomer and an initiator and then is subjected to melt extrusion to prepare the nylon toughening agent.
In order to achieve the purpose, the invention provides a nylon toughening agent which comprises the following components in percentage by weight: 50-60% of an olefin-based polymer, 25-40% of a synergist, 5-10% of a plasticizer, 0.2-1% of a curing agent, 1-5% of a first grafting monomer, 0.5-3% of a second grafting monomer and 0.1-0.5% of an initiator.
Preferably, the olefin-based polymer is at least one of 4-vinyl-4 '-propyl-1, 1' -bicyclohexane, triphenylbromoethylene, 3-methyl-2-butene-1-thiol, 8- (3-methyl-2-butenyloxy) psoralen, and p-acetoxystyrene.
Preferably, the plasticizer is triethylene glycol.
Preferably, the curing agent is 4,4' -diaminodicyclohexylmethane.
Preferably, the first grafting monomer is at least one of maleic anhydride, acrylic acid and phthalic anhydride.
Preferably, the second grafting monomer is at least one of allyl methacrylate and vinyl trimethoxy silane.
Preferably, the initiator is at least one of azodiisobutyramidine, tert-butyl peroxy-2-ethylhexanoate and dibenzoyl peroxide.
Preferably, the preparation steps of the synergist are as follows:
s1, adding glutaric acid into dimethyl sulfoxide, and stirring at 140-160 ℃ for 20-40 min to prepare a solution; then adding N, N-dicyclohexylcarbodiimide into the solution, and reacting for 10-30 min to prepare a pretreatment solution;
s2, dissolving methylcyclohexanediamine and 4-dimethylaminopyridine in dimethyl sulfoxide to obtain a reaction solution, dripping the reaction solution into the pretreatment solution prepared in the step S1, and stirring for reaction for 10-20 hours; and then carrying out oil bath evaporation concentration on the obtained solid material, wherein the oil bath evaporation temperature is 180-220 ℃, washing with water, and drying to obtain the synergist.
Further preferably, the preparation steps of the synergist are as follows, and the parts are all parts by weight:
s1, adding 10-20 parts of glutaric acid into 80-120 parts of dimethyl sulfoxide, and stirring at 140-160 ℃, at a stirring speed of 200-400 r/min for 20-40 min to prepare a solution; then adding 5-10 parts of N, N-dicyclohexylcarbodiimide into the solution, and reacting for 10-30 min to prepare a pretreatment solution;
s2, dissolving 5-15 parts of methylcyclohexanediamine and 1-4 parts of 4-dimethylaminopyridine in 80-120 parts of dimethyl sulfoxide to obtain a reaction solution, dripping the reaction solution into the pretreatment solution prepared in the step S1 at a speed of 1-10 mL/min, and stirring for 10-20 hours at a stirring speed of 50-200 r/min; and then carrying out oil bath evaporation concentration on the obtained solid material, wherein the oil bath evaporation temperature is 180-220 ℃, washing the solid material for 2-3 times by using water, and drying the solid material for 0.5-2 hours at the temperature of 80-120 ℃ to obtain the synergist.
Preferably, the preparation method of the nylon toughening agent comprises the following steps of:
step 1, mixing an olefin-based copolymer, a synergist, a plasticizer, a curing agent, a first grafting monomer, a second grafting monomer and an initiator for 30-40 min at a mixing speed of 500-800 r/min; drying for 1-3 h at 70-90 ℃, 1-3 h at 110-130 ℃ and 1-3 h at 140-160 ℃ in a vacuum drying oven to prepare a cured material;
step 2, extruding 90-110 parts of the solidified material prepared in the step 1, wherein the parameters of an extruder are as follows: the temperatures of four parts of the extruder from the hopper to the die are 210-220 ℃, 230-240 ℃, 235-245 ℃ and 230-240 ℃, the rotating speed of the main screw is 50-300 r/min, and the rotating speed of the feeding screw is 30-100 r/min; and (4) sequentially carrying out traction, cooling, drying and grain cutting on the extruded material to prepare the nylon toughening agent.
High brittleness is a recognized disadvantage of common nylon materials. According to the invention, glutaric acid is completely dissolved in dimethyl sulfoxide, methylcyclohexanediamine is successfully grafted to prepare a three-dimensional crosslinking network, and partial amino functional groups are generated, the amino functional groups are effective connecting agents grafted by 4-dimethylaminopyridine, the prepared synergist is used for treating nylon, and in the nylon curing process, the synergist is introduced into a molecular chain, so that the regularity of the molecular chain can be broken, the diffusion and arrangement of molecular fragments are inhibited, the synergist has flexible amido bonds and large gaps generated by a hyperbranched macromolecular structure, and the gelation of nylon is promoted, so that the number of dendritic nylon is increased, the strength and toughness are improved, and the toughness of the nylon is greatly improved.
Wherein the thermal degradation process of the synergist is divided into two stages. Before 300 ℃, the synergist is mainly involved in the dehydration of the carboxylic acid, which promotes the production of the anhydride. The second degradation stage mainly occurs at 300-400 ℃, which is the result of intramolecular cross-linking reactions. Compared with the high-temperature sublimed methylcyclohexanediamine, the chemical bond between glutaric acid and methylcyclohexanediamine inhibits the subliming behavior of methylcyclohexanediamine, and makes amino groups condensed to form a cross-linked structure. The further methylcyclohexanediamine and glutaric acid have obvious synergistic effect. The three-dimensional cross-linked network formed by combining the two forms a flame-retardant system. The methyl cyclohexanediamine decomposes at 300 ℃ to release moisture and nitrogen-containing gas, and substances generated in the methyl cyclohexanediamine can effectively catalyze glutaric acid to dehydrate and deaminate to form a condensation phase. In addition, the generated water vapor and the nitrogen-containing gas further enable the condensed phase foam to expand to form a high expansion structure, and due to the synergistic effect, the dehydration and deamination of the nylon material are faster, so that heat is absorbed in advance, and the flame retardant property is improved. Due to the adoption of the technical scheme, compared with the prior art, the nylon toughening agent has the advantages that: 1) glutaric acid is completely dissolved in dimethyl sulfoxide, methylcyclohexanediamine is successfully grafted to prepare a three-dimensional cross-linked network macromolecule, 4-dimethylaminopyridine is further connected to the cross-linked macromolecule, and the prepared synergist is used for treating nylon, so that gelation of nylon can be promoted, and the strength and toughness of the nylon are greatly improved. 2) The prepared synergist can be decomposed into water and nitrogen-containing gas for heat absorption and flame retardance in the flame retardant process, and a flame retardant layer can be constructed to improve the flame retardant effect. 3) The synthesis process is simple, the effect is obvious, and the feasibility of large-scale preparation is realized.
Detailed Description
Sources of the main raw materials in the examples:
3-methyl-2-butene-1-thiol: wuhananabai pharmaceutical chemicals ltd, molecular weight: 102.2, CAS number: 5287-45-6.
Glutaric acid: hubei Handa Fei Biotech, Inc., boiling point 302 ℃, CAS number: 110-94-1.
Methylcyclohexanediamine: kandis chemical (Hubei) Co., Ltd., molecular weight: 128.2153, CAS number: 13897-55-7.
4-dimethylaminopyridine: shandong Xuchen chemical science and technology Co., Ltd, CAS number: 1122-58-3.
Allyl methacrylate: kandis chemical (Hubei) Co., Ltd., molecular weight: 126.153, CAS number: 96-05-9.
Triethylene glycol: the chemical company Limited liability of Saian Weber Liyang, CAS number: 112-27-6.
4,4' -diaminodicyclohexylmethane: jaboticaying chemical technology ltd, molecular weight: 210.36, CAS number: 1761-71-3.
3,4, 5-trihydroxybenzoic acid: wuhan fuxin remote technologies ltd, molecular weight: 170.12, CAS number: 149-91-7.
Azobisisobutylamidine: jining Sanshi Biotech, Inc., molecular formula: c8H20N6Cl2The CAS number: 2997-92-4.
N, N-dicyclohexylcarbodiimide: new Guangzhou Yangda materialCompany Limited, molecular formula: c13H22N2Molecular weight: 206.327, CAS number: 538-75-0.
Example 1
The preparation method of the nylon toughening agent comprises the following steps of:
step 1, mixing 55 parts of 3-methyl-2-butene-1-thiol, 35 parts of synergist, 8 parts of triethylene glycol, 0.7 part of 4,4' -diaminodicyclohexylmethane, 3 parts of maleic anhydride, 1.5 parts of allyl methacrylate and 0.3 part of azodiisobutyramidine in a high-speed mixer at the mixing speed of 600r/min for 35 min; baking at 80 deg.C for 2h, 120 deg.C for 2h, and 150 deg.C for 2h in a vacuum oven to obtain a cured material;
and 2, putting 100 parts of the cured material prepared in the step 1 into an extruder for extrusion, wherein the parameters of the extruder are as follows: the temperatures of four parts of the extruder from the hopper to the die are 215 ℃, 235 ℃, 240 ℃ and 235 ℃, the rotating speed of the main screw is 200r/min, and the rotating speed of the feeding screw is 50 r/min; and (3) sequentially carrying out traction, cooling, drying and grain cutting on the material extruded by the extruder to prepare the nylon toughening agent.
The preparation steps of the synergist in the step 1 are as follows, and the parts are all parts by weight:
s1, adding 14 parts of glutaric acid into 100 parts of dimethyl sulfoxide, stirring at 150 ℃ at a rotation speed of 300r/min for 30min to prepare a solution; then adding 7 parts of N, N-dicyclohexylcarbodiimide into the solution, and reacting for 20min to prepare a pretreatment solution;
s2, dissolving 10 parts of methylcyclohexanediamine and 2 parts of 4-dimethylaminopyridine in 100 parts of dimethyl sulfoxide to obtain a reaction solution, and dripping the reaction solution into 120 parts of the pretreatment solution prepared in the step S1 at a speed of 5 mL/min; stirring for reaction for 15h at a stirring speed of 100r/min, carrying out oil bath evaporation and concentration to obtain a solid material, carrying out oil bath evaporation at a temperature of 200 ℃, washing with water for 3 times, and drying at 100 ℃ for 1h to obtain the synergist.
Example 2
A preparation method of a nylon toughening agent, which is basically the same as that of the example 1, and only differs from the following steps: the preparation method of the synergist in the step 1 is inconsistent.
The preparation method of the synergist in the step 1 comprises the following steps of:
s1, stirring 100 parts of dimethyl sulfoxide at the stirring temperature of 150 ℃ and the stirring speed of 300r/min for 30min to prepare a solution; then adding 7 parts of N, N-dicyclohexylcarbodiimide into the solution, and reacting for 20min to prepare a pretreatment solution;
s2, dissolving 10 parts of methylcyclohexanediamine and 2 parts of 4-dimethylaminopyridine in 100 parts of dimethyl sulfoxide to obtain a reaction solution, and dripping the reaction solution into 120 parts of the pretreatment solution prepared in the step S1 at a speed of 5 mL/min; stirring for reaction for 15h at a stirring speed of 100r/min, carrying out oil bath evaporation and concentration to obtain a solid material, carrying out oil bath evaporation at a temperature of 200 ℃, washing with water for 3 times, and drying at 100 ℃ for 1h to obtain the synergist.
Example 3
A preparation method of a nylon toughening agent, which is basically the same as that of the example 1, and only differs from the following steps: the preparation method of the synergist in the step 1 is inconsistent.
The preparation method of the synergist in the step 1 comprises the following steps of:
s1, adding 14 parts of glutaric acid into 100 parts of dimethyl sulfoxide, stirring at 150 ℃ at a rotation speed of 300r/min for 30min to prepare a solution; then adding 7 parts of N, N-dicyclohexylcarbodiimide into the solution, and reacting for 20min to prepare a pretreatment solution;
s2, dissolving 2 parts of 4-dimethylaminopyridine in 100 parts of dimethyl sulfoxide to obtain a reaction solution, and dripping the reaction solution into 120 parts of the pretreatment solution prepared in the step S1 at a speed of 5 mL/min; stirring for reaction for 15h at a stirring speed of 100r/min, carrying out oil bath evaporation and concentration to obtain a solid material, carrying out oil bath evaporation at a temperature of 200 ℃, washing with water for 3 times, and drying at 100 ℃ for 1h to obtain the synergist.
Example 4
A preparation method of a nylon toughening agent, which is basically the same as that of the example 1, and only differs from the following steps: the preparation method of the synergist in the step 1 is inconsistent.
The preparation method of the synergist in the step 1 comprises the following steps of:
s1, adding 14 parts of glutaric acid into 100 parts of dimethyl sulfoxide, stirring at 150 ℃ at a rotation speed of 300r/min for 30min to prepare a solution; then adding 7 parts of N, N-dicyclohexylcarbodiimide into the solution, and reacting for 20min to prepare a pretreatment solution;
s2, dissolving 10 parts of methylcyclohexanediamine in 100 parts of dimethyl sulfoxide to obtain a reaction solution, and dripping the reaction solution into 120 parts of the pretreatment solution prepared in the step S1 at a speed of 5 mL/min; stirring for reaction for 15h at a stirring speed of 100r/min, carrying out oil bath evaporation and concentration to obtain a solid material, carrying out oil bath evaporation at a temperature of 200 ℃, washing with water for 3 times, and drying at 100 ℃ for 1h to obtain the synergist.
Comparative example 1
A preparation method of a nylon toughening agent, which is basically the same as that of the example 1, and only differs from the following steps: no synergist is added in the step 1.
Test example 1
The nylon toughening agent synthesized in the examples and the comparative examples adopts a standard preparation method, wherein the weight percentage of the raw material PA6 is 92 wt%, the weight percentage of the nylon toughening agent is 7.4 wt%, the weight percentage of the main antioxidant (1010) is 0.2 wt%, the weight percentage of the auxiliary antioxidant (168) is 0.2 wt%, and the weight percentage of the lubricant (PETS) is 0.2 wt%. The method comprises the steps of drying a raw material PA6 for 4 hours at 120 ℃, mixing the raw material PA6, mixing the raw material PA6, a toughening agent, a main antioxidant (1010), an auxiliary antioxidant (168) and a lubricant (PETS) in a high-speed mixer, uniformly mixing the mixture, putting the mixture in a double-screw extruder with set process parameters, extruding the mixture into strips, passing through circulating cooling water in a water tank, and granulating the strips by a granulator to obtain PA6 particles toughened by the toughening agent. The technological parameters of the double-screw extruder in the processing process are as follows: 350r/min, feeding frequency of a double-screw extruder: 28Hz, granulator speed: 340r/min, and the temperatures of the extruder from the hopper to the die are 225 ℃, 230 ℃, 235 ℃, 240 ℃, 235 ℃ and 240 ℃ respectively.
Drying the prepared PA6 sample particles in an oven at 150 ℃ for about 5 hours, putting the dried sample particles into an injection molding machine for preparing a standard sample, vacuumizing by using an aluminum foil packaging bag after the preparation is finished, placing the sample in a sample chamber at the temperature of 25 ℃ and the humidity of 50% for 24 hours, and testing the mechanical properties of the sample. The processing parameters of the injection molding machine are shown in table 1.
TABLE 1 injection molding machine parameters
Flow Performance test
The test was carried out according to GB/T3682-2000 "determination of melt mass flow rate and melt volume flow rate of thermoplastics", at a test temperature of 275 ℃, under a load of 2.16kg, and for the melt index of the material, the grams of melt flowing out of the melt through a standard capillary within 10min, in g/10 min. The melt index is an important index for judging the processability of a resin material. The larger the melt index value is, the better the flow property of the sample is, the flow property can directly reflect the viscosity of the material, the low viscosity has good flow property, and the melt index is large. The melt index of the thermoplastic plastic is moderate during the production and processing, and the too large or too small has influence on the processing performance. The average was taken after 5 measurements of each sample.
In the test results, the melt indexes of the examples and the comparative examples are both 6.0-10.0 g/10min, which shows that the prepared nylon toughening agent has little influence on the fluidity of nylon in the processing process, and the double-sided consideration of the mechanical property and the processability of the material is considered.
Test example 2
Tensile Property test
Test of tensile strength and elongation at break: according to the test of GB/T1040-2006 "determination of tensile properties of plastics", a static tensile force is applied in the longitudinal direction of the specimen until the specimen is broken, and the maximum tensile stress is applied in units of megapascals (MPa). Elongation at break refers to the percentage of distance from elongation in the gauge length that is tested until break during the tensile test, and the results are expressed in%. The test parameters are that the distance between the clamps is 100mm, the test speed is 50mm/min, 5 standard samples are tested, and the average value of the results is taken. The test results are shown in Table 2.
Table 2 tensile properties test results
As can be seen from table 2, the tensile strength and elongation at break of example 1 are the highest, and the possible reason is that glutaric acid is completely dissolved in dimethyl sulfoxide, and can generate a grafting reaction with methylcyclohexanediamine to prepare a three-dimensional cross-linked network and generate a part of amino functional groups, and the amino functional groups are effective linking agents grafted by 4-dimethylaminopyridine.
Test example 3
Determination of impact Strength
The impact strength is tested according to GB/T1843-2008 & ltPlastic cantilever beam impact test method & gt, and is used for evaluating the impact resistance of the material and judging the brittleness and toughness of the material. Impact strength is the ratio of the energy absorbed by a sample when subjected to an external impact to the original cross-sectional area of the sample. The unit is kilojoule per square meter (kJ/m)2). Type I standard splines with notches were used. The test results are shown in Table 3.
Table 3: results of impact Strength test
It can be seen from table 3 that the notch impact strength of example 1 is the most excellent, probably because the methyl cyclohexanediamine is successfully grafted to prepare a three-dimensional crosslinked network by completely dissolving glutaric acid in dimethyl sulfoxide, the generated amino functional group reacts with 4-dimethylaminopyridine to graft and connect with macromolecules, and the prepared synergist is used for treating nylon, so that the gelation of nylon can be promoted, and the strength and toughness of nylon are greatly improved. The high brittleness is a recognized disadvantage of common nylon materials, the synergist is introduced into a molecular chain, the regularity of the original nylon molecular chain is broken, a three-dimensional cross-linked network formed by the synergist has flexible amido bonds and large gaps generated by a hyperbranched macromolecular structure, and the gelation of nylon is promoted, so that the number of dendritic nylon is increased, the internal parts of nylon molecules are re-connected and filled, and the toughness of the nylon is greatly improved.
Test example 4
Oxygen index test
Part 1 of the combustion behaviour was determined according to GB/T2406.1-2008 "oxygen index for plastics: the standard test of guide rule is measured by an oxygen index meter. The size of OI represents the relative burning difficulty of the material and is calculated according to the formula:
OI＝O2/(O2+N2)×100％
in the formula: o is2-oxygen flow rate;
N2nitrogen flow.
Each specimen was tested five times and the test results were averaged. The test results are shown in Table 4.
Table 4: oxygen index test results
From table 4 it can be seen that the flame retardant performance of example 1 is the best, probably due to the addition of the complete synergist therein. The thermal degradation process is divided into two stages, the synergist mainly involves dehydration of the carboxylic acid before 300 ℃, which promotes the production of the anhydride. The second degradation stage occurs primarily at 300 ℃ and 400 ℃ as a result of the intramolecular cross-linking reaction. Compared with the high-temperature sublimed methylcyclohexanediamine, the chemical bond between glutaric acid and methylcyclohexanediamine inhibits the subliming behavior of methylcyclohexanediamine, and makes amino groups condensed to form a cross-linked structure. The further methylcyclohexanediamine and glutaric acid have obvious synergistic effect. The three-dimensional cross-linked network formed by combining the two forms a flame-retardant system. The methyl cyclohexanediamine decomposes at 300 ℃ to release moisture and nitrogen-containing gas, and substances generated in the methyl cyclohexanediamine can effectively catalyze glutaric acid to dehydrate and deaminate to form a condensation phase. In addition, the generated water vapor and the nitrogen-containing gas further enable the condensed phase foam to expand to form a high expansion structure, and due to the synergistic effect, the dehydration and deamination of the nylon material are faster, so that heat is absorbed in advance, and the flame retardant property is improved.
Claims (9)
1. The nylon toughening agent is characterized by comprising the following components in percentage by weight:
50-60% of an olefin-based polymer, 25-40% of a synergist, 5-10% of a plasticizer, 0.2-1% of a curing agent, 1-5% of a first grafting monomer, 0.5-3% of a second grafting monomer and 0.1-0.5% of an initiator.
2. The nylon toughening agent of claim 1, wherein: the olefin-based polymer is at least one of 4-vinyl-4 '-propyl-1, 1' -bicyclohexane, triphenyl bromoethylene, 3-methyl-2-butylene-1-mercaptan, 8- (3-methyl-2-butylene oxide) psoralen and p-acetoxy styrene.
3. The nylon toughening agent of claim 1, wherein: the plasticizer is triethylene glycol.
4. The nylon toughening agent of claim 1, wherein: the curing agent is 4,4' -diaminodicyclohexyl methane.
5. The nylon toughening agent of claim 1, wherein: the first grafting monomer is at least one of maleic anhydride, acrylic acid and phthalic anhydride.
6. The nylon toughening agent of claim 1, wherein: the second grafting monomer is at least one of allyl methacrylate and vinyl trimethoxy silane.
7. The nylon toughening agent according to claim 1, wherein: the initiator is at least one of azodiisobutyramidine, tert-butyl peroxy-2-ethyl hexanoate and dibenzoyl peroxide.
8. The nylon toughening agent according to claim 1, wherein the synergist is prepared by the following steps:
s1, adding glutaric acid into dimethyl sulfoxide, and stirring at 140-160 ℃ for 20-40 min to prepare a solution; then adding N, N-dicyclohexylcarbodiimide into the solution, and reacting for 10-30 min to prepare a pretreatment solution;
s2, dissolving methylcyclohexanediamine and 4-dimethylaminopyridine in dimethyl sulfoxide to obtain a reaction solution, dripping the reaction solution into the pretreatment solution prepared in the step S1, and stirring for reaction for 10-20 hours; and then carrying out oil bath evaporation concentration on the obtained solid material, wherein the oil bath evaporation temperature is 180-220 ℃, washing with water, and drying to obtain the synergist.
9. The preparation method of the nylon toughening agent according to any one of claims 1 to 8, wherein the parts are all by weight:
step 1, mixing an olefin-based copolymer, a synergist, a plasticizer, a curing agent, a first grafting monomer, a second grafting monomer and an initiator for 30-40 min at a mixing speed of 500-800 r/min; drying for 1-3 h at 70-90 ℃, 1-3 h at 110-130 ℃ and 1-3 h at 140-160 ℃ in a vacuum drying oven to prepare a cured material;
and 2, extruding 90-110 parts of the cured material prepared in the step 1, wherein the parameters of an extruder are as follows: the temperatures of four parts of the extruder from the hopper to the die are 210-220 ℃, 230-240 ℃, 235-245 ℃ and 230-240 ℃, the rotating speed of the main screw is 50-300 r/min, and the rotating speed of the feeding screw is 30-100 r/min; and (3) sequentially carrying out traction, cooling, drying and grain cutting on the extruded material to prepare the nylon toughening agent.
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| CN202210467339.7A Pending CN114656598A (en) | 2022-04-29 | 2022-04-29 | Nylon toughening agent and preparation method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN114656598A (en) |
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2022
- 2022-04-29 CN CN202210467339.7A patent/CN114656598A/en active Pending
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