CN112920596A - Preparation method of high-transparency nylon material - Google Patents
Preparation method of high-transparency nylon material Download PDFInfo
- Publication number
- CN112920596A CN112920596A CN202110112376.1A CN202110112376A CN112920596A CN 112920596 A CN112920596 A CN 112920596A CN 202110112376 A CN202110112376 A CN 202110112376A CN 112920596 A CN112920596 A CN 112920596A
- Authority
- CN
- China
- Prior art keywords
- nylon
- reaction
- salt
- transparency
- nylon material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention relates to the field of high polymer materials, and discloses a preparation method of a high-transparency nylon material aiming at the problems that the existing transparent nylon preparation process is difficult to control and the light transmittance of a product is poor, which comprises the following steps: placing an amino compound and a carboxyl compound into a polymerization kettle according to a molar ratio, adding deionized water, heating under the protection of nitrogen, continuously stirring for reaction to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain a nylon salt; adding the nylon salt A, PA6I, the catalyst and deionized water into a reaction kettle in proportion, heating and stirring for reaction, injecting nitrogen after the reaction is finished to discharge water generated by the reaction, then pressurizing to discharge a transparent nylon melt, carrying out die head casting belt molding on the melt, and cooling and dicing to obtain the high-transparency nylon material. The high-transparency nylon material with the light transmittance of 95 percent is prepared by fully destroying the regularity of a molecular chain, the strength of the material is improved, and the service life of the product is prolonged.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of a high-transparency nylon material.
Background
Polyamides, also known as nylon (PA), are high molecular weight polymers having polar amide groups (-NHCO-) in the repeat unit. Compared with other polymer materials, nylon has the advantages of higher mechanical property, good heat resistance, excellent wear resistance and solvent resistance and the like, so that the nylon is widely applied to the fields of machinery industry, automobile industry, electronic equipment and the like, and is a polymer material with the maximum production, the maximum product types and the widest application range in five engineering plastics. However, for ordinary nylon, due to the regular molecular chain arrangement and intermolecular forces generated by polarity and hydrogen bonds, the degree of crystallinity is high and the crystal size is much larger than the visible wavelength, so that the nylon product is opaque, thereby limiting the application of the nylon product in some special fields. Therefore, high transparency nylon is an important research direction in the field of nylon articles.
Currently, the reported methods for preparing transparent nylon can be divided into physical methods and chemical methods. Among them, the physical methods include a quenching method and a microcrystallization method, and the chemical method mainly obtains stable light transmittance through branching or copolycondensation. The quenching method among the physical methods is to quench the polymer from the melt state to below the glass transition temperature as quickly as possible to freeze the randomly arranged polymer melt in an amorphous state. Quenching methods are generally used for preparing thin-walled products, and the optical properties obtained are unstable, when the temperature is raised above the glass transition temperature again, molecular chains are rearranged regularly, nylon products can be crystallized again, and the transparency is lost. The microcrystallization method is characterized in that a crystallization nucleating agent is added during nylon polymerization or molding, so that the size of microcrystals is reduced to be below a visible wavelength, and transparent nylon is obtained. However, the crystallization rate of nylon is high, the crystallization is difficult to control, and the product prepared by the micro crystallization method has poor optical performance and low light transmittance which is only about 60 percent.
The copolymerization method is to select a plurality of monomers to carry out polymerization simultaneously, and utilizes a plurality of aliphatic diamine and dibasic acid with different lengths, so that the obtained nylon product has low crystallinity, is in an amorphous state and has certain transmittance. The copolymerization method can reduce the capital investment of production, but the aliphatic diamine and the dibasic acid have limited capability of destroying the regularity of molecular chains, and the preparation process is difficult to control.
The patent No. CN201410716153.6 entitled "a preparation method of transparent nylon 610 and toothbrush filament thereof", the invention discloses a preparation method of transparent nylon 610, and toothbrush filament prepared from the transparent nylon 610. The preparation method comprises the steps of taking mixed dibasic acid consisting of sebacic acid and dibasic acid containing a benzene ring structure and mixed diamine consisting of hexamethylenediamine and alicyclic diamine as main raw materials, neutralizing to obtain amide salt, preparing amide salt aqueous dispersion, adding a catalyst and an antioxidant, raising the temperature and the pressure, carrying out polymerization reaction to obtain transparent nylon 610, and finally spinning the transparent nylon 610 according to a conventional method to obtain the transparent nylon 610 toothbrush filament.
The method has the disadvantages of complicated preparation steps and low nylon light transmittance.
Disclosure of Invention
The invention aims to overcome the problems that the existing transparent nylon preparation process is difficult to control and the light transmittance of products is poor, and provides a preparation method of a high-transparency nylon material, which is characterized in that the molecular chain regularity is fully destroyed, the preparation process is easy to control, no additional process is added, the cost is low, the pollution is less, the high-transparency nylon material with the light transmittance of 95 percent is prepared by the method, the material strength is improved, and the service life of the products is prolonged.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-transparency nylon material comprises the following preparation steps:
(1) preparing nylon salt: placing amino compounds containing cycloalkyl and carboxyl compounds into a polymerization kettle according to a molar ratio, adding deionized water, heating under the protection of nitrogen, continuously stirring for reaction to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain a nylon salt;
(2) preparing a transparent nylon material: adding the nylon salt A, PA6I, the catalyst and deionized water into a reaction kettle in proportion, heating and stirring for reaction, injecting nitrogen after the reaction is finished to discharge water generated by the reaction, then pressurizing to discharge a transparent nylon melt, carrying out die head casting belt molding on the melt, and cooling and dicing to obtain the high-transparency nylon material.
The reaction equation is as follows:
wherein, formula (1) is a reaction equation of the nylon salt A, and formula (2) is a reaction equation of the transparent nylon synthesis. R in the formula (1)2The molecular chain containing cycloalkyl leads to poor structural symmetry and low regularity of the nylon molecular chain copolymerized with PA6I salt, and reduces the number of hydrogen bonds among the molecular chains, thereby obtaining the transparent nylon material.
According to the invention, the amino compound and the carboxyl compound are synthesized by adopting a branching method to prepare the high-transparency nylon material, the light transmittance is up to 95%, the tensile strength of the material is improved by 16%, the bending strength is improved by 46%, and the impact strength is improved by 77%. And the service life of the product is prolonged, and the sustainable development of the nylon industry is promoted.
Preferably, in the step (1), the amine-based compound includes at least one of 3, 3' -dimethyl-4, 4-diaminodicyclohexylmethane, 2-bis (4-aminophenyl) propane, 2,4-/2,4, 4-trimethylhexamethylenediamine, p-phenylenediamine, and m-xylylenediamine. More preferably, 2, 2-bis (4-aminophenyl) propane is used.
The amino compound has a naphthenic base in the structure, so that hydrogen bonds among the molecular chains of the prepared and synthesized nylon are difficult to form, the molecular chains cannot be orderly arranged, and the prepared nylon is transparent.
Preferably, in the step (1), the carboxyl compound includes at least one of 1, 1-cyclobutane dicarboxylic acid, 3, 4-furandicarboxylic acid, 2, 5-furandicarboxylic acid, terephthalic acid, and isophthalic acid. More preferably, isophthalic acid. The carboxyl compound containing the naphthenic base is selected instead of aliphatic dibasic acid such as sebacic acid, dodecanedioic acid and the like, and the phenomenon of strength reduction caused by reduction of nylon crystallinity can be avoided due to the rigid structure of the naphthenic base dibasic acid.
Preferably, in the step (1), the molar ratio of the amine compound to the carboxyl compound is 1.00 to 1.03: 1.
preferably, in the step (1), the concentration of the salt solution is 40-60 wt%.
Preferably, in the step (1), the heating temperature is 60-100 ℃, and the stirring reaction time is 3-5 h.
Preferably, in the step (2), the addition components and the mass ratio thereof are as follows: nylon salt A5-30 wt%, PA6I nylon salt 45-70 wt%, catalyst 0.1-1 wt% and deionized water 15-25 wt%.
The nylon salt A and the PA6I nylon salt are used as raw materials of the transparent nylon, and when the content of the PA6I nylon salt is increased, the strength of the material is increased, but the toughness is reduced. Adding catalyst to make the polycondensation reaction of transparent nylon proceed forward to obtain transparent nylon with higher molecular weight. If the catalyst content is too high, the reaction is violent and the molecular weight is uncontrollable. The deionized water is used as a solvent in the reaction process and is heated to form water vapor, so that the pressure in the reaction kettle is increased, the reaction is accelerated, and the yield is improved.
Preferably, in the step (2), the pressure in the reaction kettle is 1-25 bar.
Preferably, in the step (2), the heating temperature is 220-320 ℃, and the stirring reaction time is 2-4 h.
Preferably, in the step (2), the catalyst is at least one of dibutyl phosphate, sodium hypophosphite, trimethyl phosphate, triphenyl phosphite, and the like. Further preferably, dibutyl phosphate. Compared with other commercial catalysts, the phosphoric acid catalyst has good catalytic effect and high thermal decomposition temperature.
Therefore, the invention has the following beneficial effects:
the invention has the following beneficial effects:
(1) the high-transparency nylon material prepared by the method has obvious effect, the light transmittance can reach 95 percent, the mechanical property is improved, and the service life of the product is prolonged;
(2) the preparation cost is reduced, the nylon synthesized by the branching method has diversified structures, and different monomers can be selected to prepare the high-transparency nylon according to the requirements of different application fields on the light transmittance of products;
(3) the amino compound and the carboxyl compound containing the naphthenic base are synthesized by adopting a branching method, the molecular chain regularity is fully destroyed, and the light transmittance of the nylon is further improved while the stability of the final high-transparency nylon material system is ensured.
Detailed Description
The invention is further described with reference to specific embodiments.
General examples
A preparation method of a high-transparency nylon material comprises the following preparation steps:
(1) preparing nylon salt: mixing an amino compound (at least one of 3, 3' -dimethyl-4, 4-diaminodicyclohexylmethane, 2-bis (4-aminophenyl) propane, 2,4-/2,4, 4-trimethylhexamethylenediamine, p-phenylenediamine and m-xylylenediamine) and a carboxyl compound (at least one of 1, 1-cyclobutanedicarboxylic acid, 3, 4-furandicarboxylic acid, 2, 5-furandicarboxylic acid, terephthalic acid and isophthalic acid) in a molar ratio of 1.00 to 1.03:1, placing the mixture into a polymerization kettle, adding deionized water, heating the mixture at the temperature of 60-100 ℃ under the protection of nitrogen, continuously stirring the mixture for reacting for 3-5 hours to obtain a salt solution with the concentration of 40-60 wt%, and cooling, crystallizing, filtering and drying the salt solution to obtain nylon salt; (2) preparing a transparent nylon material: adding 5-30 wt% of the nylon salt A, 45-70 wt% of PA6I nylon salt, 0.1-1 wt% of a catalyst (at least one of dibutyl phosphate, sodium hypophosphite, trimethyl phosphate, triphenyl phosphite and the like) and 15-25 wt% of deionized water into a reaction kettle with the pressure of 1-25 bar according to a proportion, heating and stirring at 220-320 ℃ for reaction for 2-4 h, injecting nitrogen after the reaction is finished to discharge water generated by the reaction, then pressurizing to discharge a transparent nylon melt, casting the melt through a die head, molding, cooling and cutting into granules to obtain the high-transparency nylon material.
Example 1
(1) Preparation of Nylon salt
Adding deionized water into a polymerization kettle according to the mol ratio of 3, 3' -dimethyl-4, 4-diaminodicyclohexylmethane to isophthalic acid of 1.01:1 and the mass ratio of 50 wt% of salt solution, stirring and reacting for 4 hours at 70 ℃ to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain the nylon salt A.
(2) Preparation of high-transparency nylon material
30wt% of nylon salt A, 55 wt% of PA6I nylon salt, 0.3 wt% of catalyst dibutyl phosphate and 15 wt% of deionized water are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the moisture generated by the reaction, then the transparent nylon melt is discharged by pressurization, the melt is cast and formed by a die head, and the high-transparency nylon is obtained by cooling and granulating.
Example 2
(1) Preparation of Nylon salt
Adding 3, 3' -dimethyl-4, 4-diaminodicyclohexyl methane and 1, 1-cyclobutane dicarboxylic acid into a polymerization kettle according to the mol ratio of 1.02:1, controlling the mass ratio of 50 wt% of salt solution, stirring and reacting for 4 hours at 70 ℃ to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain the nylon salt A.
(2) Preparation of high-transparency nylon material
20 wt% of nylon salt A, 60wt% of PA6I nylon salt, 0.2 wt% of catalyst trimethyl phosphate and 20 wt% of deionized water are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the moisture generated by the reaction, then the transparent nylon melt is discharged by pressurization, the melt is cast and formed by a die head, and the high-transparency nylon is obtained by cooling and granulating.
Example 3
(1) Preparation of Nylon salt
Adding deionized water into a polymerization kettle according to the mol ratio of 2, 2-bis (4-aminophenyl) propane to terephthalic acid of 1.03:1 and the mass ratio of the salt solution with the concentration of 50 wt%, stirring and reacting for 4 hours at 70 ℃ to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain the nylon salt A.
(2) Preparation of high-transparency nylon material
20 wt% of nylon salt A, 60wt% of PA6I nylon salt, 0.1 wt% of dibutyl phosphate as a catalyst and 20 wt% of deionized water are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the moisture generated by the reaction, then the transparent nylon melt is discharged by pressurization, the melt is cast and formed by a die head, and the high-transparency nylon is obtained by cooling and granulating.
Example 4
(1) Preparation of Nylon salt
Adding 2,2,4-/2,4, 4-trimethylhexamethylenediamine and 3, 4-furandicarboxylic acid into a polymerization kettle according to the molar ratio of 1.03:1 and controlling the mass ratio of 50 wt% of salt solution, stirring and reacting for 4 hours at 70 ℃ to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain the nylon salt A.
(2) Preparation of high-transparency nylon material
20 wt% of nylon salt A, 60wt% of PA6I nylon salt, 0.1 wt% of dibutyl phosphate as a catalyst and 20 wt% of deionized water are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the moisture generated by the reaction, then the transparent nylon melt is discharged by pressurization, the melt is cast and formed by a die head, and the high-transparency nylon is obtained by cooling and granulating.
Example 5
(1) Preparation of Nylon salt
Adding 2,2,4-/2,4, 4-trimethylhexamethylenediamine and 1, 1-cyclobutane dicarboxylic acid into a polymerization kettle according to the molar ratio of 1.03:1 and controlling the mass ratio of 50 wt% of salt solution, stirring and reacting for 4 hours at 70 ℃ to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain the nylon salt A.
(2) Preparation of high-transparency nylon material
10 wt% of nylon salt A, 65 wt% of PA6I nylon salt, 0.1 wt% of catalyst triphenyl phosphite and 25wt% of deionized water are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the moisture generated by the reaction, then the transparent nylon melt is discharged by pressurization, the melt is cast and formed by a die head, and the high-transparency nylon is obtained by cooling and granulating.
Example 6
(1) Preparation of Nylon salt
Adding deionized water into a polymerization kettle according to the mol ratio of 2, 2-bis (4-aminophenyl) propane to isophthalic acid of 1.02:1 and the mass ratio of the salt solution with the concentration of 50 wt%, stirring and reacting for 4 hours at 70 ℃ to obtain a salt solution, cooling, crystallizing, filtering and drying to obtain the nylon salt A.
(2) Preparation of high-transparency nylon material
10 wt% of nylon salt A, 65 wt% of PA6I nylon salt, 0.1 wt% of catalyst triphenyl phosphite and 25wt% of deionized water are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the moisture generated by the reaction, then the transparent nylon melt is discharged by pressurization, the melt is cast and formed by a die head, and the high-transparency nylon is obtained by cooling and granulating.
Example 7
(1) Preparation of Nylon salt
Adding deionized water into a polymerization kettle according to the mol ratio of 2, 2-bis (4-aminophenyl) propane to isophthalic acid of 1.03:1 and the mass ratio of the salt solution with the concentration of 50 wt%, stirring and reacting for 4 hours at 70 ℃ to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain the nylon salt A.
(2) Preparation of high-transparency nylon material
30wt% of nylon salt A, 50 wt% of PA6I nylon salt, 0.1 wt% of dibutyl phosphate as a catalyst and 20 wt% of deionized water are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the moisture generated by the reaction, then the transparent nylon melt is discharged by pressurization, the melt is cast and formed by a die head, and the high-transparency nylon is obtained by cooling and granulating.
Example 8
(1) Preparation of Nylon salt
Adding deionized water into a polymerization kettle according to the mol ratio of 2, 2-bis (4-aminophenyl) propane to isophthalic acid of 1.03:1 and the mass ratio of the salt solution with the concentration of 50 wt%, stirring and reacting for 4 hours at 70 ℃ to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain the nylon salt A.
(2) Preparation of high-transparency nylon material
20 wt% of nylon salt A, 60wt% of PA6I nylon salt, 0.1 wt% of dibutyl phosphate as a catalyst and 20 wt% of deionized water are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the moisture generated by the reaction, then the transparent nylon melt is discharged by pressurization, the melt is cast and formed by a die head, and the high-transparency nylon is obtained by cooling and granulating.
Comparative example 1 (different from example 1 in that nylon 66 synthesized in comparative example 1 is opaque nylon)
(1) Preparation of Nylon 66 salt
Adding 1, 6-hexamethylene diamine and adipic acid into a polymerization kettle according to the mol ratio of 1.03:1 and controlling the concentration of a salt solution to be 50 wt%, adding deionized water into the polymerization kettle, stirring and reacting for 4 hours at 70 ℃ to obtain the salt solution, and cooling, crystallizing, filtering and drying to obtain the nylon 66 salt.
(2) Preparation of Nylon 66
99.9 weight percent of nylon salt and 0.1 weight percent of dibutyl phosphate serving as a catalyst are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the moisture generated by the reaction, then the nylon 66 melt is discharged under pressure, and the melt is cast and formed by a die head and is cooled and cut into particles to obtain the nylon 66.
Comparative example 2 (different from example 1 in that comparative example 2 nylon 6I is a homopolymer having a more regular molecular chain than example 1, thereby allowing the light transmittance of nylon to be relatively low)
(1) Preparation of Nylon 6I salt
Adding 1, 6-hexamethylene diamine and isophthalic acid into a polymerization kettle according to the mol ratio of 1.03:1 and controlling the concentration of a salt solution to be 50 wt%, adding deionized water into the polymerization kettle, stirring and reacting for 4 hours at 70 ℃ to obtain the salt solution, and cooling, crystallizing, filtering and drying to obtain the nylon 6I salt.
(2) Preparation of Nylon 6I
99.9 weight percent of nylon salt and 0.1 weight percent of dibutyl phosphate serving as a catalyst are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. And after the reaction, injecting nitrogen to discharge water generated by the reaction, then pressurizing to discharge a nylon 6I melt, carrying out die head casting belt molding on the melt, and cooling and pelletizing to obtain the nylon 6I.
Comparative example 3 (different from example 1 in that the preparation procedure is different from that of comparative example 3 in that the melting method is adopted, and example 1 is the solution polymerization method)
(1) Preparation of Nylon salt A
Adding deionized water into a polymerization kettle according to the mol ratio of 3, 3' -dimethyl-4, 4-diaminodicyclohexylmethane to isophthalic acid of 1.01:1 and the mass ratio of 50 wt% of salt solution, stirring and reacting for 4 hours at 70 ℃ to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain the nylon salt A.
(2) Preparation of high-transparency nylon material
Placing 35 wt% of nylon salt A, 65 wt% of PA6I nylon salt and 0.3 wt% of dibutyl phosphate as a catalyst in a reaction kettle with the pressure of 15bar and the temperature of 290 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the small molecular compounds generated in the reaction process, then the transparent nylon melt is discharged by pressurization, the melt is cast and formed by a die head, and the transparent nylon is obtained by cooling and granulating.
Comparative example 4 (different from example 1 in the ratio of the amino compound to the carboxyl compound in the course of synthesizing Nylon A)
(1) Preparation of Nylon salt A
Adding deionized water into a polymerization kettle according to the mol ratio of 3, 3' -dimethyl-4, 4-diaminodicyclohexylmethane to isophthalic acid of 0.8:1 and the mass ratio of the salt solution with the concentration of 50 wt%, stirring and reacting for 4 hours at 70 ℃ to obtain a salt solution, cooling, crystallizing, filtering and drying to obtain the nylon salt A.
(2) Preparation of high-transparency nylon material
30wt% of nylon salt A, 55 wt% of PA6I nylon salt, 0.3 wt% of catalyst dibutyl phosphate and 15 wt% of deionized water are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the moisture generated by the reaction, then the transparent nylon melt is discharged by pressurization, the melt is cast and formed by a die head, and the high-transparency nylon is obtained by cooling and granulating.
Comparative example 5 (different from example 1 in that the nylon salt 6T synthesized in comparative example 5 has a symmetrical molecular structure) (1) preparation of nylon salt 6T
Adding p-xylylenediamine and adipic acid into a polymerization kettle according to the molar ratio of 1.01:1 and the mass ratio of 50 wt% of salt solution, stirring and reacting for 4 hours at 70 ℃ to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain the nylon salt 6T.
(2) Preparation of high-transparency nylon material
30wt% of nylon salt 6T, 55 wt% of PA6I nylon salt, 0.3 wt% of catalyst dibutyl phosphate and 15 wt% of deionized water are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the moisture generated by the reaction, then the transparent nylon melt is discharged under pressure, the melt is cast and formed by a die head, and the high-transparency nylon PA6I/6T is obtained after cooling and cutting.
Comparative example 6 (different from example 1 in that aliphatic dibasic acid was used as the carboxyl compound as the starting material for nylon salt A) (1) preparation of nylon salt A
Adding deionized water into a polymerization kettle according to the mol ratio of 3, 3' -dimethyl-4, 4-diaminodicyclohexylmethane to sebacic acid of 1.01:1 and the mass ratio of 50 wt% of salt solution, stirring and reacting for 4 hours at 70 ℃ to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain the nylon salt A.
(2) Preparation of high-transparency nylon material
30wt% of nylon salt A, 55 wt% of PA6I nylon salt, 0.3 wt% of catalyst dibutyl phosphate and 15 wt% of deionized water are placed in a reaction kettle with the pressure of 15bar and the temperature of 270 ℃ for continuous reaction for 3 hours. After the reaction, nitrogen is injected to discharge the moisture generated by the reaction, then the transparent nylon melt is discharged by pressurization, the melt is cast and formed by a die head, and the high-transparency nylon is obtained by cooling and granulating.
TABLE 1 Properties of nylons for examples and comparative examples
And (4) conclusion: as can be seen from Table 1, the light transmittance of the highly transparent nylons prepared in examples 1 to 8 is increased compared to nylon 66 of comparative example 1 and nylon 6I of comparative example 2. Because a side substituent group is introduced into a structural unit of the nylon by a branching method, the symmetry and the regularity of a macromolecular chain are reduced, and the number of hydrogen bonds in unit volume is reduced, so that a product presents an amorphous state and has certain light transmittance. The light transmittance of the embodiment 8 is improved by 90% compared with that of the comparative example 1 and is improved by 27% compared with that of the comparative example 2, the mechanical properties are improved, and the comprehensive performance is optimal.
Comparative example 1 is a synthesis process of nylon 66, and nylon 66 has high crystallinity and low light transmittance due to the symmetrical molecular structure and the large number of hydrogen bonds between molecular chains.
Comparative example 2 the molecular chain structure of nylon 6I was asymmetric due to the meta arrangement of the two carboxyl groups on the isophthalic acid molecule. However, compared with example 1, the number of hydrogen bonds between the nylon 6I molecular chains is large, the molecular crystallinity is high, and the light transmittance of the material is low.
In comparative example 3, the reaction temperature is above the melting point of the reaction monomer and the polymerization product, and the monomer acid is easy to decarboxylate and the diamine is easy to volatilize, so that the monomer proportion is unbalanced, the experimental yield and the relative molecular mass of the polymer are reduced, and the mechanical property of the material is reduced.
In comparative example 4, the addition amount of the amino compound is small, and the synthesized nylon salt is easy to crack and volatilize the amino compound under high temperature, so that the content of the amino compound in the reaction process is too small, the molecular weight of the synthesized nylon is too low, and the mechanical property of the material is further reduced.
The PA6T synthesized in the comparative example 5 has a symmetrical molecular structure, is easy to regularly arrange nylon molecular chains and tends to crystallize, so that the light transmittance of the nylon 6I/6T is reduced. And a rigid structure benzene ring is introduced into the molecular structure, so that the toughness of the material is reduced.
The comparative example 6 selects aliphatic dibasic acid as the raw material of the nylon salt A, and the mechanical property of the material is reduced because the number of hydrogen bonds between the molecular chains of the material is small and the crystallinity is reduced due to copolymerization of the amino compound of the naphthenic base.
As can be seen from the data of examples 1-8 and comparative examples 1-6, the above requirements can be satisfied in all aspects only by the scheme within the scope of the claims of the present invention, an optimized scheme can be obtained, a nylon material with high transparency can be obtained, and the material utilization and recovery rate can be maximized by each process parameter. The change of the mixture ratio, the replacement/addition/subtraction of raw materials or the change of the feeding sequence can bring corresponding negative effects.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a high-transparency nylon material is characterized by comprising the following preparation steps:
(1) preparing nylon salt: placing amino compounds containing cycloalkyl and carboxyl compounds into a polymerization kettle according to a molar ratio, adding deionized water, heating under the protection of nitrogen, continuously stirring for reaction to obtain a salt solution, and cooling, crystallizing, filtering and drying to obtain a nylon salt;
(2) preparing a transparent nylon material: adding the nylon salt A, PA6I, the catalyst and deionized water into a reaction kettle in proportion, heating and stirring for reaction, injecting nitrogen after the reaction is finished to discharge water generated by the reaction, then pressurizing to discharge a transparent nylon melt, carrying out die head casting belt molding on the melt, and cooling and dicing to obtain the high-transparency nylon material.
2. The method as claimed in claim 1, wherein in the step (1), the amine-based compound includes at least one of 3, 3' -dimethyl-4, 4-diaminodicyclohexylmethane, 2-bis (4-aminophenyl) propane, 2,4-/2,4, 4-trimethylhexamethylenediamine, p-phenylenediamine and m-xylylenediamine.
3. The method as claimed in claim 1, wherein in the step (1), the carboxyl compound comprises at least one of 1, 1-cyclobutane dicarboxylic acid, 3, 4-furandicarboxylic acid, 2, 5-furandicarboxylic acid, terephthalic acid and isophthalic acid.
4. The method for synthesizing the high-transparency nylon material according to claim 1, wherein in the step (1), the molar ratio of the amino compound to the carboxyl compound is 1.00-1.03: 1.
5. the method for synthesizing the high-transparency nylon material according to claim 1, wherein in the step (1), the concentration of the salt solution is 40-60 wt%.
6. The method for synthesizing the high-transparency nylon material according to claim 1 is characterized in that in the step (1), the heating temperature is 60-100 ℃, and the stirring reaction time is 3-5 hours.
7. The synthesis method of the preparation method of the high-transparency nylon material according to claim 1, wherein in the step (2), the addition components and the mass ratio thereof are as follows: 5-30 wt% of nylon salt A, 45-70 wt% of PA6I nylon salt, 0.1-1 wt% of catalyst and 15-25 wt% of deionized water.
8. The method for synthesizing the high-transparency nylon material according to claim 2, wherein in the step (2), the pressure in the reaction kettle is 1-25 bar.
9. The method for synthesizing the high-transparency nylon material according to claim 2 is characterized in that in the step (2), the heating temperature is 220-320 ℃, and the stirring reaction time is 2-4 h.
10. The method as claimed in claim 1 or 7, wherein in the step (2), the catalyst is at least one of dibutyl phosphate, sodium hypophosphite, trimethyl phosphate, triphenyl phosphite, etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110112376.1A CN112920596A (en) | 2021-01-27 | 2021-01-27 | Preparation method of high-transparency nylon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110112376.1A CN112920596A (en) | 2021-01-27 | 2021-01-27 | Preparation method of high-transparency nylon material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112920596A true CN112920596A (en) | 2021-06-08 |
Family
ID=76167104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110112376.1A Pending CN112920596A (en) | 2021-01-27 | 2021-01-27 | Preparation method of high-transparency nylon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112920596A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461934A (en) * | 2021-06-18 | 2021-10-01 | 山东东辰瑞森新材料科技有限公司 | High-melting-point transparent nylon material and preparation method thereof |
| CN113698594A (en) * | 2021-09-08 | 2021-11-26 | 湖南工业大学 | Polyamide resin and preparation method thereof |
| CN115975181B (en) * | 2023-01-09 | 2024-02-13 | 华润化学材料科技股份有限公司 | Ternary polymerization transparent nylon and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974342A (en) * | 2014-12-02 | 2015-10-14 | 淮安市欣佳尼龙有限公司 | Preparation method of transparent nylon 610, and toothbrush bristles |
| CN105330851A (en) * | 2015-12-07 | 2016-02-17 | 中北大学 | Long carbon chain transparent nylon and synthesizing method thereof |
| CN105949456A (en) * | 2016-05-09 | 2016-09-21 | 山东东辰工程塑料有限公司 | Transparent nylon and preparation method thereof |
| CN107286340A (en) * | 2017-07-27 | 2017-10-24 | 株洲时代新材料科技股份有限公司 | A kind of copolymerization transparent nylon and preparation method thereof |
| CN108774317A (en) * | 2018-06-21 | 2018-11-09 | 株洲时代新材料科技股份有限公司 | A kind of super toughness nylon resin and preparation method thereof |
| CN109970970A (en) * | 2019-04-18 | 2019-07-05 | 东华大学 | A kind of high-strength and high ductility transparent nylon material and its preparation and application |
| CN110092906A (en) * | 2019-05-30 | 2019-08-06 | 辰东意普万新材料(广东)有限公司 | Copolymerization transparent nylon and preparation method thereof |
-
2021
- 2021-01-27 CN CN202110112376.1A patent/CN112920596A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974342A (en) * | 2014-12-02 | 2015-10-14 | 淮安市欣佳尼龙有限公司 | Preparation method of transparent nylon 610, and toothbrush bristles |
| CN105330851A (en) * | 2015-12-07 | 2016-02-17 | 中北大学 | Long carbon chain transparent nylon and synthesizing method thereof |
| CN105949456A (en) * | 2016-05-09 | 2016-09-21 | 山东东辰工程塑料有限公司 | Transparent nylon and preparation method thereof |
| CN107286340A (en) * | 2017-07-27 | 2017-10-24 | 株洲时代新材料科技股份有限公司 | A kind of copolymerization transparent nylon and preparation method thereof |
| CN108774317A (en) * | 2018-06-21 | 2018-11-09 | 株洲时代新材料科技股份有限公司 | A kind of super toughness nylon resin and preparation method thereof |
| CN109970970A (en) * | 2019-04-18 | 2019-07-05 | 东华大学 | A kind of high-strength and high ductility transparent nylon material and its preparation and application |
| CN110092906A (en) * | 2019-05-30 | 2019-08-06 | 辰东意普万新材料(广东)有限公司 | Copolymerization transparent nylon and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈林飞等: "半芳香共聚透明尼龙5T/5I的合成及其性能的研究", 《塑料工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461934A (en) * | 2021-06-18 | 2021-10-01 | 山东东辰瑞森新材料科技有限公司 | High-melting-point transparent nylon material and preparation method thereof |
| CN113698594A (en) * | 2021-09-08 | 2021-11-26 | 湖南工业大学 | Polyamide resin and preparation method thereof |
| CN113698594B (en) * | 2021-09-08 | 2023-08-04 | 湖南工业大学 | Polyamide resin and preparation method thereof |
| CN115975181B (en) * | 2023-01-09 | 2024-02-13 | 华润化学材料科技股份有限公司 | Ternary polymerization transparent nylon and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112920596A (en) | Preparation method of high-transparency nylon material | |
| JP3380654B2 (en) | Process for producing precondensates of partially crystalline or amorphous, thermoplastically processable, partially aromatic polyamides or copolyamides | |
| KR100346823B1 (en) | Process for preparing precondensates of partially aromatic or amorphous, thermoplastically processable, partially aromatic polyamides or copolyamides | |
| KR102234828B1 (en) | Process for the continuous preparation of an aliphatic or partially aromatic polyamide | |
| CN102356113B (en) | Method for making polyamide | |
| JP2741795B2 (en) | Polyamide having improved color and processability and method for producing the same | |
| KR101351763B1 (en) | Modified polyamide, method for preparing same, and article obtained from said polyamide | |
| JPS5946974B2 (en) | transparent polymer copolyamide | |
| CN110156985B (en) | High-fluidity random copolymerization semi-aromatic nylon and preparation method thereof | |
| US10676569B2 (en) | Method for continuously producing polyamide oligomers and producing semicrystalline or amorphous polyamides that can be thermoplastically processed | |
| JP5481776B2 (en) | Method for producing polyamide | |
| EP2726537A1 (en) | Branched polyamide with different blocks | |
| WO2014198770A1 (en) | Method for producing aliphatic or partially aromatic polyamides, said method comprising a solid-phase polymerization process | |
| JPS59161428A (en) | Crystalline copolyamide from terephthalic acid, isophthalic acid and c6 diamine | |
| EP1007582B2 (en) | Process for preparing polyamides | |
| CN116874771B (en) | Continuous production method of high-temperature nylon powder with narrow molecular weight distribution | |
| EP3008107B1 (en) | Method for the continuous manufacture of an aliphatic or partially aromatic polyamide oligomer | |
| CN105339415A (en) | Process for producing a semi-aromatic semi-crystalline polyamide | |
| JPH0680775A (en) | Preparation of m-aramid for fiber formation | |
| JP2013525555A (en) | Process for producing polyamide | |
| KR101563250B1 (en) | Xylylenediamine composition, and method for producing polyamide resin | |
| US9534083B2 (en) | Production of polyamides by polycondensation | |
| CN115286785B (en) | High-temperature-resistant nylon based on m-xylylenediamine and preparation method thereof | |
| CN113651957A (en) | Black-spot-free polyamide composition and polymerization process thereof | |
| JPH0343417A (en) | Production of polyamide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210608 |