CN113583235A - Transparent polyamide resin and preparation method and application thereof - Google Patents
Transparent polyamide resin and preparation method and application thereof Download PDFInfo
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- CN113583235A CN113583235A CN202110871087.XA CN202110871087A CN113583235A CN 113583235 A CN113583235 A CN 113583235A CN 202110871087 A CN202110871087 A CN 202110871087A CN 113583235 A CN113583235 A CN 113583235A
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- 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
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
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Abstract
The invention provides a transparent polyamide resin and a preparation method and application thereof, wherein the preparation raw material of the transparent polyamide resin comprises the combination of hexamethylene diamine, adipic acid, N- (4-aminocyclohexyl) -1, 4-cyclohexane diamine and an ultraviolet absorbent; the obtained polyamide can be completely in an amorphous state and has a transparent characteristic by adding N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine as a structural breaking monomer into the preparation raw material; and simultaneously, the ultraviolet absorbent is added into the preparation raw materials, so that the obtained transparent polyamide resin also has excellent ultraviolet resistance, and is suitable for being used as a material of a lens.
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to a transparent polyamide resin and a preparation method and application thereof.
Background
The polyamide 66 is a high molecular polymer which has a certain function and is prepared by gradually increasing the molecular weight to a certain value through a polycondensation reaction of adipic acid and hexamethylene diamine; polyamide 66 has applications in both engineering plastics and spinning.
It is known that ultraviolet rays are extremely harmful to the skin, and if the eyes are irradiated with ultraviolet rays for a long time, vision problems such as pterygium, keratitis, cataract, maculopathy and the like are caused. On one hand, for myopes, particularly for high-myopia patients, the appropriate sunglasses are difficult to be matched, and meanwhile, the existing spectacle lenses are basically made of PMMA (polymethyl methacrylate) and PC (polycarbonate) materials, so that the density is high, and the high-myopia lenses are thick, so that the spectacles are heavy and the comfort is poor; on the other hand, the ultraviolet protection in daily life is not in place, and the damage to eyes cannot be ignored even under long-term and chronic ultraviolet irradiation.
At present, the research on the transparent polyamide 66 resin is a major concern. CN107513163A discloses a preparation method of a high-transparency high-toughness nylon resin, which comprises the following steps: (1) reacting an olefin salt, an organic acid with amino and an organic base under the protection of nitrogen, and separating the organic base to obtain a mixture solution; (2) and (2) carrying out polycondensation reaction on the mixture solution obtained in the step (1), adipic acid hexamethylene diamine salt, a catalyst and a blocking agent to obtain nylon 66 resin. The nylon 66 resin prepared by the method has excellent toughness and excellent transparency. In addition, the nylon 66 resin obtained by the invention can also overcome the problem of fiber floating on the surface, and the prepared glass fiber modified nylon 66 resin has smoother appearance. CN106916297A discloses a method for preparing transparent polyamide and transparent polyamide, wherein acid-base neutralization reaction is performed in polar aprotic solvent, the solubility of the product polyamide salt in the polar aprotic solvent is poor, and the product polyamide salt can be separated out from the reaction mixture after reaction, which is beneficial to separating the transparent polyamide salt from the reaction mixture, and the purity of the transparent polyamide salt is high. Meanwhile, solid transparent polyamide salt is adopted for carrying out polymerization reaction, the polymerization reaction is divided into three stages of pressurization reaction, normal pressure reaction and reduced pressure reaction, wherein the reduced pressure reaction stage can enable condensation polymerization reaction byproducts to be smoothly removed from a reaction system, reaction balance forward movement is facilitated, and transparent polyamide with higher molecular weight can be obtained.
However, the polyamide 66 resin obtained in the above patent is required to have improved transparency and resistance to ultraviolet radiation.
Therefore, the development of a transparent polyamide resin having high light transmittance and resistance to ultraviolet radiation is a technical problem to be solved urgently in the field.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a transparent polyamide resin and a preparation method and application thereof, wherein the preparation raw material of the transparent polyamide resin comprises the combination of hexamethylene diamine, adipic acid, N- (4-aminocyclohexyl) -1, 4-cyclohexane diamine and an ultraviolet absorbent; n- (4-aminocyclohexyl) -1, 4-cyclohexanediamine is added to raw materials for preparation to serve as a structural destruction monomer, so that the polyamide crystal structure can be destroyed to be in a completely amorphous state, the transparent polyamide resin is endowed with the transparent characteristic, and the prepared transparent polyamide resin has high light transmittance and ultraviolet resistance by matching with an ultraviolet-resistant absorbent, and is suitable for being used as a material of spectacle lenses.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a transparent polyamide resin, which is prepared from the following raw materials: a combination of hexamethylenediamine, adipic acid, N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine, an ultraviolet absorber and an end group regulator.
The transparent polyamide resin provided by the invention is added with N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine as a structural destructive monomer in the raw materials for preparation, and due to the inherent structure of the molecule, the single chain of the transparent polyamide resin is difficult to rotate, the flexibility is poorer, the crystallization is more difficult, and the transparent polyamide resin can be further used as the structural destructive monomer of the polyamide resin, and a small amount of the transparent polyamide resin is added in the raw materials for preparation to obtain a transparent polymer; compared with aliphatic diamine, the N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine has one N in the molecular chain, so that the mechanical strength of the diamine is higher; therefore, the invention destroys the polyamide crystal structure by adding N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine into the raw materials, so that the polyamide is in a completely amorphous state, and the polyamide is endowed with transparent characteristics and mechanical strength; meanwhile, the anti-ultraviolet absorbent is added in the preparation raw materials, so that the prepared transparent polyamide resin has high light transmittance and anti-ultraviolet performance, is suitable for being used as a material of a spectacle lens, can replace the existing spectacle lens, has the function of protecting eyes from being damaged by ultraviolet rays for a long time, and has important research value.
The N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine is preferably used in an amount of 1 to 8%, for example, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, or the like, preferably 3 to 5%, based on 100% of polyhexamethylene adipamide obtained by reacting the hexamethylenediamine with adipic acid.
In a preferred embodiment of the present invention, when the amount of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine used is 1 to 8% based on 100% of polyhexamethylene adipamide obtained by reacting the hexamethylenediamine with adipic acid, a polyamide resin having an optimum performance can be obtained, while when the amount of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine added is too large, the polymerization process is affected, the viscosity of the obtained product is low, and granulation is difficult; on the other hand, if the amount of addition is too small, the light transmittance of the product is deteriorated.
Preferably, the molar ratio of the adipic acid to the N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine reacted therewith is 1 (1-1.05), such as 1:1.005, 1:1.01, 1:1.015, 1:1.02, 1:1.025, 1:1.03, 1:1.035, 1:1.04, 1:1.045, and the like.
Preferably, the molar ratio of the adipic acid to the hexamethylenediamine reacted therewith is 1 (1-1.05), such as 1:1.005, 1:1.01, 1:1.015, 1:1.02, 1:1.025, 1:1.03, 1:1.035, 1:1.04, or 1:1.045, etc.
The raw materials for preparing the transparent polyamide resin comprise hexamethylene diamine, adipic acid and N- (4-aminocyclohexyl) -1, 4-cyclohexane diamine, wherein the added adipic acid can react with the hexamethylene diamine, and the mass ratio of the adipic acid to the hexamethylene diamine is 1 (1-1.05); the added adipic acid may be reacted with N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine, and the molar ratio of the adipic acid to the N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine is 1 (1-1.05).
The amount of the ultraviolet absorber is preferably 0.1 to 20%, for example, 0.2%, 0.5%, 1.0%, 5.0%, 10.0%, 15.0%, or 20.0%, and more preferably 1 to 10%, based on 100% of polyhexamethylene adipamide obtained by reacting the hexamethylenediamine with adipic acid.
Preferably, the ultraviolet absorber is an ultraviolet absorber containing a dihydroxy group and a benzene ring structure.
The ultraviolet absorbent in the raw materials for preparing the transparent polyamide provided by the invention needs to have a benzene ring structure; the UV absorbers Synsorb-BP6 or BP8 may be chosen as examples.
Preferably, the raw materials for preparing the transparent polyamide resin further comprise any one or a combination of at least two of an antioxidant, a terminal group regulator or other auxiliary agents.
Preferably, the antioxidant is used in an amount of 0.05 to 0.15%, for example, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, or 0.14%, based on 100% of polyhexamethylene adipamide obtained by reacting the hexamethylenediamine with adipic acid.
Preferably, the antioxidant comprises sodium hypophosphite and/or phosphorous acid.
Preferably, the end group regulator comprises dibasic acid with 4-10 (5, 6, 7, 8 or 9) carbon atoms.
Preferably, the dibasic acid comprises any one of glutaric acid, adipic acid or sebacic acid or a combination of at least two thereof.
In a second aspect, the present invention provides a method for preparing the transparent polyamide resin according to the first aspect, the method comprising the steps of:
(1) dissolving hexamethylene diamine and adipic acid in a solvent, and reacting to obtain a polyamide salt solution; reacting N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine with adipic acid to obtain a reaction salt;
(2) concentrating the polyamide salt obtained in the step (1), mixing the polyamide salt with the reaction salt obtained in the step (1), an optional end group regulator and an optional antioxidant, and reacting to obtain a prepolymer;
(3) heating the prepolymer obtained in the step (2) to obtain low-molecular polyamide;
(4) and (3) reacting the low-molecular-weight polyamide obtained in the step (3) with an ultraviolet absorbent, and granulating to obtain the transparent polyamide resin.
Preferably, the solvent of step (1) is desalted water.
Preferably, the temperature of the reaction in step (1) is 40-60 ℃, such as 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃ or 58 ℃.
Preferably, the reaction time in step (1) is 45-60 min, such as 47min, 49min, 51min, 53min, 55min, 57min or 59 min.
Preferably, the concentration in step (2) is carried out at a temperature of 140 to 160 ℃, for example, 142 ℃, 144 ℃, 146 ℃, 148 ℃, 150 ℃, 152 ℃, 154 ℃, 156 ℃ or 158 ℃.
Preferably, the pressure for concentration in step (2) is 0.1-0.3 MPa, such as 0.12MPa, 0.14MPa, 0.16MPa, 0.18MPa, 0.2MPa, 0.22MPa, 0.24MPa, 0.26MPa or 0.28 MPa.
Preferably, the temperature of the reaction in the step (2) is 180-220 ℃, such as 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃ or 215 ℃.
Preferably, the pressure of the reaction in the step (2) is 1.5 to 2Mpa, such as 1.55Mpa, 1.6Mpa, 1.65Mpa, 1.7Mpa, 1.75Mpa, 1.8Mpa, 1.85Mpa, 1.9Mpa or 1.95 Mpa.
Preferably, the reaction time in step (2) is 100-150 min, such as 105min, 110min, 115min, 120min, 1250min, 130min, 135min, 140min or 145 min.
Preferably, the heating temperature in step (3) is 250-300 ℃, such as 255 ℃, 260 ℃, 265 ℃, 270 ℃, 275 ℃, 280 ℃, 285 ℃, 290 ℃ or 295 ℃, and the like.
Preferably, the heating time in the step (3) is 50-100 min, such as 55min, 60min, 65min, 70min, 75min, 80min, 85min, 90min or 95 min.
Preferably, the pressure of the reaction in step (4) is-0.02-0.01 MPa, such as-0.05 MPa, -0.01MPa, 0.0005MPa, 0.006MPa, 0.0065MPa, 0.007MPa, 0.0075MPa, 0.008MPa, 0.0085MPa, 0.009MPa or 0.0095 MPa.
Preferably, the reaction time in step (4) is 30-60 min, such as 33min, 36min, 39min, 43min, 46min, 49min, 53min, 56min or 59 min.
Preferably, the granulation in step (4) is underwater granulation.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) dissolving hexamethylene diamine and adipic acid in a solvent, and reacting for 45-60 min at 40-60 ℃ to obtain a polyamide salt solution; reacting N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine with adipic acid to obtain a reaction salt;
(2) concentrating the polyamide salt obtained in the step (1) at 140-160 ℃ and 0.1-0.3 Mpa, mixing the concentrated polyamide salt with the reaction salt obtained in the step (1), optionally an antioxidant and optionally an end group regulator, and reacting for 100-150 min at 180-220 ℃ and 1.5-2 Mpa to obtain a prepolymer;
(3) heating the prepolymer obtained in the step (2) at 250-300 ℃ for 50-100 min to obtain low-molecular polyamide;
(4) and (3) reacting the low molecular weight polyamide obtained in the step (3) with an ultraviolet absorbent under-0.02-0.01 Mpa for 30-60 min, cooling and granulating to obtain the transparent polyamide resin.
In a third aspect, the present invention provides an ultraviolet resistance spectacle lens, which is produced from a raw material comprising the transparent polyamide resin according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the transparent polyamide resin provided by the invention is prepared by adding N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine as a structural failure monomer into a preparation raw material; the crystal structure of the polyamide is destroyed in the polymerization process of the polyamide resin, so that the polyamide can be in a completely amorphous state and is endowed with the transparent characteristic; meanwhile, an ultraviolet absorbent is added into the preparation raw materials, so that the prepared transparent polyamide resin has high light transmittance and ultraviolet resistance; specifically, the light transmittance of the polyamide resin provided by the invention is 72-96%, the yellowing index change value before and after irradiation is 4-9, and the change value of the tensile strength before and after irradiation is 9-20 MPa; suitable for use as a material for ophthalmic lenses.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A transparent polyamide resin is prepared from the following raw materials: a combination of hexamethylenediamine, adipic acid, N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine, an ultraviolet absorber, an end group regulator and phosphorous acid; based on 100 percent of polyhexamethylene adipamide obtained by the reaction of the hexamethylene diamine and adipic acid, the use amounts of the components are respectively 5 percent of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine, 9.4 per mill of ultraviolet absorbent (PB-6(274)), the molar ratio of the ultraviolet absorbent to the end group regulator is 1:1.04 and 0.1 per mill of phosphorous acid;
the preparation method comprises the following steps:
(1) dissolving hexamethylene diamine and adipic acid with the molar ratio of 1.01:1 in desalted water, and reacting for 50min at 25 ℃ to obtain a polyamide salt solution with the mass percentage concentration of 53%; reacting N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine with a molar ratio of 1:1 with adipic acid to obtain a reaction salt;
(2) concentrating the polyamide salt solution obtained in the step (1) at 149 ℃ and 0.2Mpa to obtain polyamide salt solution with the mass percentage concentration of 75%, mixing the polyamide salt solution with the reaction salt obtained in the step (1), phosphorous acid and a terminal regulator (adipic acid), and reacting for 20min in a reaction kettle with the temperature of 200 ℃ and the pressure of 1.7Mpa to obtain a prepolymer;
(3) opening an exhaust valve of the reaction kettle, keeping the system pressure constant, and heating the prepolymer obtained in the step (2) at 275 ℃ for 75min to obtain low-molecular polyamide;
(4) and (3) reacting the low molecular weight polyamide obtained in the step (3) with an ultraviolet absorbent under the pressure of 0.01Mpa in a reaction kettle for 50min, cooling and granulating to obtain the transparent polyamide resin.
Example 2
A transparent polyamide resin is prepared from the following raw materials: a combination of hexamethylenediamine, adipic acid, N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine, an ultraviolet absorber, an end group regulator and phosphorous acid; based on 100 percent of polyhexamethylene adipamide obtained by the reaction of the hexamethylene diamine and adipic acid, the use amounts of the components are respectively 3 percent of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine, 3.76 per mill of ultraviolet absorbent (PB-6(274)), the molar ratio of the ultraviolet absorbent to the end group regulator is 1:1 and 0.1 per mill of sodium phosphite;
the preparation method comprises the following steps:
(1) dissolving hexamethylene diamine and adipic acid with the molar ratio of 1.02:1 in a solvent, and reacting for 45min at 25 ℃ to obtain a polyamide salt solution with the mass percentage concentration of 53%; reacting N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine with adipic acid in a molar ratio of 1.02:1 to obtain a reaction salt;
(2) concentrating the polyamide salt solution obtained in the step (1) at 149 ℃ and 0.2Mpa to obtain a polyamide salt solution with the mass percentage concentration of 75%, mixing the polyamide salt solution with the reaction salt obtained in the step (1), sodium phosphite and a terminal regulator (adipic acid), and reacting for 20min in a reaction kettle with the temperature of 200 ℃ and the pressure of 1.7Mpa to obtain a prepolymer;
(3) opening an exhaust valve of the reaction kettle, keeping the system pressure constant, and heating the prepolymer obtained in the step (2) at 275 ℃ for 75min to obtain low-molecular polyamide;
(4) and (3) reacting the low molecular weight polyamide obtained in the step (3) with an ultraviolet absorbent under the pressure of-0.02 Mpa in a reaction kettle for 50min, cooling and granulating to obtain the transparent polyamide resin.
Example 3
A transparent polyamide resin is prepared from the following raw materials: a combination of hexamethylenediamine, adipic acid, N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine, an ultraviolet absorber, an end group regulator and phosphorous acid; based on 100 percent of polyhexamethylene adipamide obtained by the reaction of the hexamethylene diamine and adipic acid, the use amounts of the components are respectively 8 percent of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine, 1.88 per mill of ultraviolet absorbent (PB-6(274)), 1:0.95 mole ratio of end group regulator to ultraviolet absorbent and 0.15 per mill of sodium phosphite;
the preparation method comprises the following steps:
(1) dissolving hexamethylene diamine and adipic acid with the molar ratio of 1.05:1 in a solvent, and reacting for 45min at 25 ℃ to obtain a polyamide salt solution with the mass percentage concentration of 53%; reacting N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine with a molar ratio of 1:1 with adipic acid to obtain a reaction salt;
(2) concentrating the polyamide salt solution obtained in the step (1) at 149 ℃ and 0.2Mpa to obtain a polyamide salt solution with the mass percentage concentration of 75%, mixing the polyamide salt solution with the reaction salt obtained in the step (1), sodium phosphite and a terminal regulator (adipic acid), and reacting for 20min in a reaction kettle with the temperature of 200 ℃ and the pressure of 1.7Mpa to obtain a prepolymer;
(3) opening an exhaust valve of the reaction kettle, keeping the system pressure constant, and heating the prepolymer obtained in the step (2) at 275 ℃ for 75min to obtain low-molecular polyamide;
(4) and (3) reacting the low molecular weight polyamide obtained in the step (3) with an ultraviolet absorbent under the pressure of-0.02 Mpa in a reaction kettle for 50min, cooling and granulating to obtain the transparent polyamide resin.
Example 4
A transparent polyamide resin is prepared from the following raw materials: a combination of hexamethylenediamine, adipic acid, N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine, an ultraviolet absorber, and an end-group regulator; based on 100 percent of polyhexamethylene adipamide obtained by the reaction of the hexamethylene diamine and adipic acid, the use amounts of the components are respectively 1 percent of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine, 7 per mill of an ultraviolet absorbent (PB-8(244)), and the molar ratio of a terminal regulator to the ultraviolet absorbent is 1: 1;
the preparation method comprises the following steps:
(1) dissolving hexamethylene diamine and adipic acid with the molar ratio of 1.02:1 in a solvent, and reacting for 45min at 25 ℃ to obtain a polyamide salt solution with the mass percentage concentration of 53%; reacting N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine with adipic acid in a molar ratio of 1.05:1 to obtain a reaction salt;
(2) concentrating the polyamide salt solution obtained in the step (1) at 149 ℃ and 0.2Mpa to obtain a polyamide salt solution with the mass percentage concentration of 75%, mixing the polyamide salt solution with the reaction salt obtained in the step (1) and an end group regulator (adipic acid), and reacting for 20min in a reaction kettle with the temperature of 200 ℃ and the pressure of 1.7Mpa to obtain a prepolymer;
(3) opening an exhaust valve of the reaction kettle, keeping the system pressure constant, and heating the prepolymer obtained in the step (2) at 275 ℃ for 75min to obtain low-molecular polyamide;
(4) and (3) reacting the low molecular weight polyamide obtained in the step (3) with an ultraviolet absorbent under the pressure of-0.02 Mpa in a reaction kettle for 50min, cooling and granulating to obtain the transparent polyamide resin.
Example 5
A transparent polyamide resin which is different from example 4 in that the amount of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine used in the starting materials for the preparation was 3% and the amount of an ultraviolet absorber (PB-8(244)) was 0.2% o, and the other components, amounts and preparation methods were the same as in example 1.
Example 6
A transparent polyamide resin which differs from example 4 in that the amount of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine used in the starting materials for its preparation was 3% and the amount of the ultraviolet absorber (PB-8(244)) was 12% o, and the other components, amounts and preparation were the same as in example 1.
Example 7
A transparent polyamide resin which differs from example 1 only in that the amount of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine used in the starting materials for its preparation was 1%, and the other components, amounts and preparation methods were the same as in example 1.
Example 8
A transparent polyamide resin which differs from example 1 only in that the amount of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine used in the starting materials for its preparation was 8%, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 1
A transparent polyamide resin which differs from example 1 only in that N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine was not added to the starting materials for the preparation, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 2
A transparent polyamide resin which differs from example 1 only in that no ultraviolet absorber is added to the raw materials for preparation, and the other components, amounts and preparation methods are the same as those of example 1.
Comparative example 3
A transparent polyamide resin which differs from example 1 only in that the same weight of bis- (4-aminocyclohexyl) methane was used in place of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine in the starting materials for the preparation, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 4
A transparent polyamide resin which differs from example 1 only in that the same weight of bis (4-amino-3-methylcyclohexyl) methane was used in place of N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine in the starting materials for the preparation, and the other components, amounts and preparation methods were the same as in example 1.
And (3) performance testing:
(1) yellow index before and after ultraviolet irradiation: testing according to the testing method provided by HG-T3862;
(2) tensile strength before and after ultraviolet irradiation: testing according to a testing method provided by GB/T1040.1-2006;
(3) light transmittance: and testing by using a luminometer.
The transparent polyamide resins obtained in examples 1 to 8 and comparative examples 1 to 4 were tested according to the above test methods, and the test results are shown in Table 1:
TABLE 1
As can be seen from the data in table 1:
the polyamide resins provided in examples 1 to 8 have a light transmittance of 72 to 96%, a yellowing index change value of 4 to 9 before and after irradiation, and a change value of tensile strength of 9 to 20MPa before and after irradiation;
comparing the data of example 1 and comparative example 1, it can be seen that the polyamide resin obtained without adding N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine to the starting materials for preparation has a low light transmittance and a significant decrease in tensile strength after being irradiated with ultraviolet rays; comparing example 1 with comparative example 2, it can be found that the polyamide resin obtained without adding an ultraviolet absorber to the raw materials for preparation has a low light transmittance, a high yellowing index after being irradiated with ultraviolet rays, and a low tensile strength; comparing example 1 with comparative examples 3 to 4, it was found that the light transmittance of the polyamide resin obtained by replacing N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine in the raw material for production with bis- (4-aminocyclohexyl) methane or bis (4-amino-3-methylcyclohexyl) methane was somewhat lowered and the tensile strength after ultraviolet irradiation was significantly lowered.
Further comparing example 4 with examples 5 to 6, it can be seen that the light transmittance and the retention rate of tensile strength are low because the N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine added in example 4 is low; further, by comparing example 1 with examples 7 to 8, it was found that the tensile strength retention of the polyamide resin was reduced by adding too much or too little N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine.
The applicant states that the present invention is illustrated by the above examples to a transparent polyamide resin and a method for preparing and using the same, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by means of the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A transparent polyamide resin is characterized in that the transparent polyamide resin is prepared from the following raw materials: a combination of hexamethylenediamine, adipic acid, N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine and an ultraviolet absorber.
2. The transparent polyamide resin according to claim 1, wherein the amount of the N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine is 1 to 8%, preferably 3 to 5%, based on 100% of polyhexamethylene adipamide obtained by reacting the hexamethylenediamine with adipic acid;
preferably, the molar ratio of the N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine to the adipic acid reacted with the N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine is (1-1.05): 1;
preferably, the amount of the ultraviolet absorbent is 0.1 to 20 per thousand, and more preferably 1 to 10 per thousand, based on 100% of polyhexamethylene adipamide obtained by reacting the hexamethylene diamine with adipic acid;
preferably, the ultraviolet absorbent is an ultraviolet absorbent containing a dihydroxy group and a benzene ring structure;
preferably, the molar ratio of the adipic acid to the hexamethylene diamine reacted with the adipic acid is 1 (1-1.05).
3. The transparent polyamide resin as claimed in claim 1 or 2, wherein the raw material for preparing the transparent polyamide resin further comprises any one or a combination of at least two of an antioxidant, a terminal group regulator or other auxiliary agents;
preferably, the amount of the antioxidant is 0.05-0.15 per thousand calculated by 100% of polyhexamethylene adipamide obtained by the reaction of the hexamethylene diamine and adipic acid;
preferably, the antioxidant comprises sodium hypophosphite and/or phosphorous acid;
preferably, the molar ratio of the ultraviolet absorbent to the end group regulator is 1 (0.95-1.05);
preferably, the end group regulator comprises dibasic acid with 4-10 carbon atoms;
preferably, the dibasic acid comprises any one of glutaric acid, adipic acid or sebacic acid or a combination of at least two thereof.
4. A method for producing a transparent polyamide resin according to any one of claims 1 to 3, characterized in that the production method comprises the steps of:
(1) dissolving hexamethylene diamine and adipic acid in a solvent, and reacting to obtain a polyamide salt solution; reacting N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine with adipic acid to obtain a reaction salt;
(2) concentrating the solution of the polyamide salt obtained in the step (1), mixing the concentrated solution of the polyamide salt with the reaction salt obtained in the step (1), an optional terminal regulator and an optional antioxidant, and reacting to obtain a prepolymer;
(3) heating the prepolymer obtained in the step (2) to obtain low-molecular polyamide;
(4) and (3) reacting the low-molecular-weight polyamide obtained in the step (3) with an ultraviolet absorber, and granulating to obtain the transparent polyamide resin.
5. The method according to claim 4, wherein the solvent of step (1) is desalted water;
preferably, the temperature of the reaction in the step (1) is 40-60 ℃;
preferably, the reaction time in the step (1) is 45-60 min.
6. The method according to claim 4 or 5, wherein the concentration in step (2) is carried out at a temperature of 140 to 160 ℃;
preferably, the pressure for concentration in the step (2) is 0.1-0.3 Mpa;
preferably, the temperature of the reaction in the step (2) is 180-220 ℃;
preferably, the pressure of the reaction in the step (2) is 1.5-2 Mpa;
preferably, the reaction time in the step (2) is 100-150 min.
7. The method according to any one of claims 4 to 6, wherein the heating temperature in the step (3) is 250 to 300 ℃;
preferably, the heating time in the step (3) is 50-100 min.
8. The method according to any one of claims 4 to 7, wherein the pressure of the reaction in the step (4) is-0.02 to 0.01 MPa;
preferably, the reaction time in the step (4) is 30-60 min;
preferably, the granulation in step (4) is underwater granulation.
9. The method according to any one of claims 4 to 8, wherein the method comprises the steps of:
(1) dissolving hexamethylene diamine and adipic acid in a solvent, and reacting for 45-60 min at 40-60 ℃ to obtain a polyamide salt solution; reacting N- (4-aminocyclohexyl) -1, 4-cyclohexanediamine with adipic acid to obtain a reaction salt;
(2) concentrating the polyamide salt obtained in the step (1) at 140-160 ℃ and 0.1-0.3 Mpa, mixing the concentrated polyamide salt with the reaction salt obtained in the step (1), optionally an end group regulator and optionally an antioxidant, and reacting for 100-150 min at 180-220 ℃ and 1.5-2 Mpa to obtain a prepolymer;
(3) heating the prepolymer obtained in the step (2) at 250-300 ℃ for 50-100 min to obtain low-molecular polyamide;
(4) and (3) reacting the low molecular weight polyamide obtained in the step (3) with an ultraviolet absorbent under-0.02-0.01 Mpa for 30-60 min, cooling, and carrying out underwater granulation to obtain the transparent polyamide resin.
10. An ultraviolet-resistant spectacle lens, characterized in that a raw material for producing the ultraviolet-resistant spectacle lens comprises the transparent polyamide resin according to any one of claims 1 to 3.
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