CN113999392B - Dimer amine modified copolyamide and preparation method thereof - Google Patents
Dimer amine modified copolyamide and preparation method thereof Download PDFInfo
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- CN113999392B CN113999392B CN202111539389.3A CN202111539389A CN113999392B CN 113999392 B CN113999392 B CN 113999392B CN 202111539389 A CN202111539389 A CN 202111539389A CN 113999392 B CN113999392 B CN 113999392B
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- 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
- C08G69/40—Polyamides containing oxygen in the form of ether groups
Abstract
The invention belongs to the technical field of polyamide, and particularly relates to a diamine modified copolyamide and a preparation method thereof, wherein the diamine modified copolyamide comprises the following raw materials: organic acids and organic amines; the molar ratio of the organic acid to the organic amine is 1:0.95 to 2.65; the organic amine comprises the following raw materials in percentage by mass: 1% -80% of dimer amine, and the rest raw materials of the organic amine are selected from any one or more than one of diamine, polybasic aliphatic amine, alicyclic amine, polyether amine, aromatic diamine, lactam or alcohol amine compound. The dimer amine modified copolyamide can simultaneously enhance low temperature resistance, thermal oxidation resistance, hydrolysis resistance, salt fog resistance, chemical corrosion resistance and ultraviolet radiation resistance, and has excellent comprehensive performance.
Description
Technical Field
The invention belongs to the technical field of polyamide, and particularly relates to a diamine modified copolyamide and a preparation method thereof.
Background
Polyamide is commonly called Nylon (Nylon), and the English name Polyamide (PA) is a thermoplastic resin general term containing repeated amide groups- (NHCO) on a molecular main chain, and comprises aliphatic PA, aliphatic-aromatic PA and aromatic PA. The aliphatic PA has a large variety, high yield and wide application, and the naming of the aliphatic PA depends on the specific carbon number of the synthetic monomer.
Copolyamide synthesized by reacting organic carboxylic acid with aliphatic amine and aromatic amine is usually very hard and brittle at normal temperature; in order to make the synthesized polyamide have low temperature resistance, polyether amine is usually added for copolymerization synthesis, but polyether amine contains ether bond structure, has the defects of high water absorption rate, easy thermal oxidation and ultraviolet irradiation resistance, and is difficult to obtain satisfactory comprehensive performance.
Disclosure of Invention
The invention aims to provide a diamine modified copolyamide and a preparation method thereof, and aims to solve the technical problems that in the prior art, in order to ensure that the synthesized polyamide has low temperature resistance, polyether amine is commonly added for copolymerization synthesis, but the polyether amine contains an ether bond structure, has the defects of high water absorption rate, easiness in thermal oxidation and ultraviolet irradiation resistance, and is difficult to obtain satisfactory comprehensive performance.
In order to achieve the above object, the embodiment of the invention provides a diamine modified copolyamide, which comprises the following raw materials: organic acids and organic amines; the molar ratio of the organic acid to the organic amine is 1:0.95 to 2.65; the organic amine comprises the following raw materials in percentage by mass: 1% -80% of dimer amine, and the rest raw materials of the organic amine are selected from any one or more than one of diamine, polybasic aliphatic amine, alicyclic amine, polyether amine, aromatic diamine, lactam or alcohol amine compound.
Optionally, the structural general formula of the polyamine is H 2 NCH 2 —R1—CH 2 NH 2 Wherein the R1 group has a structure as shown in formula (1):
wherein the R2 group in formula (1) is C 4-6 Alkyl or C of (2) 5-7 Alkenyl of (c); the R3 radical being C 4-6 Alkyl or C of (2) 6-8 Alkenyl of (c); r4 is C 6-8 Alkyl or C of (2) 9-11 Alkenyl of (c); r5 is C 6-8 Alkyl or C of (2) 8-10 Alkenyl groups of (c).
Optionally, the polyamine is one of the compounds represented by P1 to P8:
optionally, the organic amine comprises the following raw materials in percentage by mass: 1 to 80 percent of diamine, 0 to 99 percent of polybasic fatty amine, 0 to 33 percent of alicyclic amine, 0 to 50 percent of polyether amine, 0 to 25 percent of aromatic diamine, 0 to 60 percent of lactam and 0 to 55 percent of alcohol amine compound.
Optionally, the diamine is selected from any one or more than one of 1, 2-ethylenediamine, 1, 5-pentanediamine, 1, 6-hexanediamine or 1, 10-decanediamine; the polybasic aliphatic amine is selected from any one or more than one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; the alicyclic amine is selected from any one or more than one of N-aminoethylpiperazine, isophoronediamine or 4, 4-diamine dicyclohexylmethane; the polyether amine is obtained by ammoniating polyethylene glycol, polypropylene glycol or ethylene glycol/propylene glycol copolymer; the aromatic diamine is selected from any one or more than one of p-phenylenediamine, m-phenylenediamine or 4,4' -diaminodiphenyl methane; the lactam is selected from any one or more than one of caprolactam, octalactam or dodecalactam; the alcohol amine is selected from any one or more of hydroxyethyl ethylenediamine, ethanolamine or diethanolamine.
Optionally, the molecular weight of the polyetheramine is 200-5000.
Optionally, the organic acid comprises the following raw materials in percentage by mass: 0 to 95 percent of aliphatic dicarboxylic acid, 0 to 33 percent of aromatic dicarboxylic acid, 0 to 18 percent of aliphatic tricarboxylic acid and 0 to 20 percent of aliphatic unit acid.
Optionally, the aliphatic dicarboxylic acid is selected from any one or more than one of 1, 4-succinic acid (anhydride), 1, 6-adipic acid, 1, 8-suberic acid, 1, 10-sebacic acid, 1, 12-dodecanedioic acid, 1, 14-tetradecanedioic acid, octadecanedioic acid or dimer acid; the aromatic dicarboxylic acid is selected from terephthalic acid and/or isophthalic acid; the aliphatic tricarboxylic acid is a trimer acid fatty acid; the aliphatic acid is selected from any one or more of acetic acid, lauric acid, stearic acid and oleic acid.
Optionally, the aliphatic tricarboxylic acid is an octadecadienoic acid trimer; the dimer acid is octadecadienoic acid dimer.
In order to achieve the above object, the preparation method of the diamine modified copolyamide provided by the embodiment of the invention comprises the following steps:
(1) Starting the reaction kettle for stirring, and adding organic amine into the reaction kettle;
(2) Adding organic acid into the system finished in the step (1), and keeping the self-reaction heating temperature of the system not rising any more;
(3) Starting the reaction kettle to heat, and enabling the system to complete the reaction at 140-260 ℃;
(4) At the reaction temperature of>After 180 ℃, the pressure of the reaction kettle is controlled to be 1 multiplied by 10 2 ～1.013×10 5 And Pa, carrying out polycondensation until the required viscosity is reached, and discharging to obtain the diamine modified copolyamide.
The one or more technical schemes in the diamine modified copolyamide and the preparation method thereof provided by the embodiment of the invention have at least one of the following technical effects:
1. the dimer amine modified copolyamide can simultaneously enhance low temperature resistance, thermal oxidation resistance, hydrolysis resistance, salt fog resistance, chemical corrosion resistance and ultraviolet radiation resistance, and has excellent comprehensive performance.
2. The preparation method can slow down self-reaction heating and heating of the system during feeding, so that the system reaction is more uniform and stable, and the prepared copolyamide has the characteristics of uniform molecular weight, stable material performance, good melt fluidity and the like, and greatly improves the performance and the use stability of the copolyamide material.
Detailed Description
The present invention will be further described with reference to examples, but the embodiments of the present invention are not limited thereto.
In an embodiment of the present invention, there is provided a diamine-modified copolyamide comprising the following raw materials: organic acids and organic amines; the molar ratio of the organic acid to the organic amine is 1:0.95 to 2.65; the organic amine comprises the following raw materials in percentage by mass: 1% -80% of dimer amine, and the rest raw materials of the organic amine are selected from any one or more than one of diamine, polybasic aliphatic amine, alicyclic amine, polyether amine, aromatic diamine, lactam or alcohol amine compound.
In an embodiment of the present invention, the structure of the diamineThe general formula is H 2 NCH 2 —R1—CH 2 NH 2 Wherein the R1 group has a structure as shown in formula (1):
wherein the R2 group in formula (1) is C 4-6 Alkyl or C of (2) 5-7 Alkenyl of (c); the R3 radical being C 4-6 Alkyl or C of (2) 6-8 Alkenyl of (c); r4 is C 6-8 Alkyl or C of (2) 9-11 Alkenyl of (c); r5 is C 6-8 Alkyl or C of (2) 8-10 Alkenyl groups of (c).
In an embodiment of the present invention, the polyamine is one of the compounds represented by P1 to P8:
in the embodiment of the invention, the organic amine comprises the following raw materials in percentage by mass: 1 to 80 percent of diamine, 0 to 99 percent of polybasic fatty amine, 0 to 33 percent of alicyclic amine, 0 to 50 percent of polyether amine, 0 to 25 percent of aromatic diamine, 0 to 60 percent of lactam and 0 to 55 percent of alcohol amine compound.
In the embodiment of the invention, the diamine is selected from any one or more than one of 1, 2-ethylenediamine, 1, 5-pentanediamine, 1, 6-hexanediamine or 1, 10-decanediamine; the polybasic aliphatic amine is selected from any one or more than one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; the alicyclic amine is selected from any one or more than one of N-aminoethylpiperazine, isophoronediamine or 4, 4-diamine dicyclohexylmethane; the polyether amine is obtained by ammoniating polyethylene glycol, polypropylene glycol or ethylene glycol/propylene glycol copolymer; the aromatic diamine is selected from any one or more than one of p-phenylenediamine, m-phenylenediamine or 4,4' -diaminodiphenyl methane; the lactam is selected from any one or more than one of caprolactam, octalactam or dodecalactam; the alcohol amine is selected from any one or more of hydroxyethyl ethylenediamine, ethanolamine or diethanolamine.
In the embodiment of the invention, the molecular weight of the polyether amine is 200-5000.
In the embodiment of the invention, the organic acid comprises the following raw materials in percentage by mass: 0 to 95 percent of aliphatic dicarboxylic acid, 0 to 33 percent of aromatic dicarboxylic acid, 0 to 18 percent of aliphatic tricarboxylic acid and 0 to 20 percent of aliphatic unit acid.
In the embodiment of the invention, the aliphatic dicarboxylic acid is selected from any one or more than one of 1, 4-succinic acid (anhydride), 1, 6-adipic acid, 1, 8-suberic acid, 1, 10-sebacic acid, 1, 12-dodecanedioic acid, 1, 14-tetradecanedioic acid, octadecanedioic acid or dimer acid; the aromatic dicarboxylic acid is selected from terephthalic acid and/or isophthalic acid; the aliphatic tricarboxylic acid is a trimer acid fatty acid; the aliphatic acid is selected from any one or more of acetic acid, lauric acid, stearic acid and oleic acid.
In the embodiment of the invention, the aliphatic tricarboxylic acid is octadecadienoic acid trimer; the dimer acid is octadecadienoic acid dimer.
The embodiment of the invention also provides a preparation method of the diamine modified copolyamide, which comprises the following steps:
(1) Starting the reaction kettle for stirring, and adding organic amine into the reaction kettle;
(2) Adding organic acid into the system finished in the step (1), and keeping the self-reaction heating temperature of the system not rising any more;
(3) Starting the reaction kettle to heat, and enabling the system to complete the reaction at 140-260 ℃;
(4) At the reaction temperature of>After 180 ℃, the pressure of the reaction kettle is controlled to be 1 multiplied by 10 2 ～1.013×10 5 And Pa, carrying out polycondensation until the required viscosity is reached, and discharging to obtain the diamine modified copolyamide.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention. The raw materials used in the examples of the present invention were all obtained commercially.
The test method of the invention is as follows:
water absorption rate: test reference standard ASTM D570. Soaking in distilled water at 23 ℃ for 96 hours, taking out and wiping the surface, and weighing the mass change before and after the surface is dried, so that the moisture resistance of the material is reflected, and the smaller the water absorption rate is, the better the moisture resistance is.
Fire retardant rating: test reference standard UL94. The flammability UL94 rating is the most widely used flammability standard for plastic materials, and is used to evaluate the ability of a material to extinguish after ignition, with the plastic flame retardant rating being progressively increased from HB, V-2, V-1 to V-0.
Oxidation Induction Time (OIT): the test is referred to standard GB/T19466.6. The method is used for measuring the time of starting the autocatalytic oxidation reaction of the sample under the high-temperature (220 ℃ adopted in the patent) oxygen condition, and is an index for evaluating the thermal oxidative degradation resistance of the material in production, storage and use. The longer the oxidation induction time, the better the thermal oxidation resistance of the plastic.
Flexibility low temperature: the test is referred to standard ASTM D3111. The flexibility of the hot melt adhesive is determined through a mandrel bending test, an environmental temperature test is adjusted, and the brittle failure starting temperature of the spline is determined, wherein the lower the temperature is, the better the low temperature resistance is.
Ultraviolet aging rate of change: test reference standards ISO4892, ISO 4582. The change of the characteristics of the high polymer material such as the mechanical property, the average molecular weight and the like before and after ultraviolet irradiation is tested, and the change rate of the mechanical property is selected to represent the ultraviolet aging change rate.
Tensile strength and elongation at break: the test is referred to standard ISO 527. And in the environment of 25 ℃, an I-type dumbbell sample is adopted, the gauge length is 25mm, the test loading speed is 50mm/min, and the mechanical property is characterized.
Shore hardness: the test is referred to standard ISO 868. Is a physical measure of the degree of deformation under pressure or puncture resistance of a material. In a 25 ℃ environment, a type a durometer was used.
Viscosity: test reference standard ASTM D1084. The viscosity of the liquid at a certain temperature characterizes the fluidity of the liquid. The patent uses a rotational viscometer to test the viscosity of a liquid at 40 ℃.
Density: the test is referred to standard GB/T1884. Liquid petroleum product density laboratory determination (densitometry).
Amine number: test reference ASTM D974. The curing agent is dissolved in isopropanol, and acid-base titration is carried out by using 0.1-0.5mol/L hydrochloric acid solution (the indicator is bromocreosote blue, and the titration color changes from blue-green to yellow).
The examples of the present invention were tested from both hot melt copolyamide (PA) and polyamide based Curing Agent (CA). The test results of the hot melt copolyamide (PA) are shown in Table 1 and the test results of the polyamide-based Curing Agent (CA) are shown in Table 2.
TABLE 1
TABLE 2
From the test data in tables 1 and 2, it is known that the modified hot melt copolyamide (PA) and the polyamide-based Curing Agent (CA) can simultaneously enhance low temperature resistance, thermal oxidation resistance, hydrolysis resistance, salt spray resistance, chemical corrosion resistance, ultraviolet radiation resistance, and have excellent comprehensive properties.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
1. A dimer amine modified copolyamide comprising the following materials: organic acids and organic amines; the molar ratio of the organic acid to the organic amine is 1: 0.95-2.65;
the organic acid comprises the following raw materials in percentage by mass: 0% -95% of aliphatic dicarboxylic acid, 0% -33% of aromatic dicarboxylic acid, 0% -18% of aliphatic tricarboxylic acid and 0% -20% of aliphatic monoacid;
the organic amine comprises the following raw materials in percentage by mass: 1% -80% of a polyamine, 0% -99% of a diamine, 0% -99% of a polybasic fatty amine, 0% -33% of an alicyclic amine, 0% -50% of a polyether amine, 0% -25% of an aromatic diamine, 0% -60% of a lactam and 0% -55% of an alcohol amine compound;
the structural general formula of the diamine is H 2 NCH 2 —R1—CH 2 NH 2 Wherein the R1 group has a structure as shown in formula (1):
（1）
wherein the R2 group in formula (1) is C 4-6 Alkyl or C of (2) 5-7 Alkenyl of (c); the R3 radical being C 4-6 Alkyl or C of (2) 6-8 Alkenyl of (c); r4 is C 6-8 Alkyl or C of (2) 9-11 Alkenyl of (c); r5 is C 6-8 Alkyl or C of (2) 8-10 Alkenyl of (c);
the R4 and R5 groups are each independently bonded to-CH 2 NH 2 Connecting;
the preparation method of the dimer amine modified copolyamide comprises the following steps:
(1) Starting the reaction kettle for stirring, and adding organic amine into the reaction kettle;
(2) Adding organic acid into the system finished in the step (1), and keeping the self-reaction heating temperature of the system not rising any more;
(3) Starting the reaction kettle to heat, and enabling the system to complete the reaction at 140-260 ℃;
(4) At the reaction temperature of>After 180 ℃, the pressure of the reaction kettle is controlled to be 1 multiplied by 10 2 ~1.013×10 5 And Pa, carrying out polycondensation until the required viscosity is reached, and discharging to obtain the diamine modified copolyamide.
2. The dimer amine-modified copolyamide according to claim 1, wherein the diamine is one of the compounds represented by P1-P8:
P1
P2
P3
P4
P5
P6
P7
P8。
3. the dimer amine-modified copolyamide according to claim 1, wherein the diamine is selected from any one or a combination of more than one of 1, 2-ethylenediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, or 1, 10-decanediamine; the polybasic aliphatic amine is selected from any one or more than one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; the alicyclic amine is selected from any one or more than one of N-aminoethylpiperazine, isophoronediamine or 4, 4-diaminodicyclohexylmethane; the polyether amine is obtained by ammoniating polyethylene glycol, polypropylene glycol or ethylene glycol/propylene glycol copolymer; the aromatic diamine is selected from any one or more than one of p-phenylenediamine, m-phenylenediamine or 4,4' -diaminodiphenyl methane; the lactam is selected from any one or more than one of caprolactam, octalactam or dodecalactam; the alcohol amine is selected from any one or more of hydroxyethyl ethylenediamine, ethanolamine or diethanolamine.
4. The dimer amine-modified copolyamide according to claim 3, wherein the polyetheramine has a molecular weight of 200 to 5000.
5. The dimer amine-modified copolyamide according to claim 1, characterized in that the aliphatic dicarboxylic acid is selected from any one or a combination of more than one of 1, 4-succinic acid, 1, 6-adipic acid, 1, 8-suberic acid, 1, 10-sebacic acid, 1, 12-dodecanedioic acid, 1, 14-tetradecanedioic acid, octadecanedioic acid or dimer acid; the aromatic dicarboxylic acid is selected from terephthalic acid and/or isophthalic acid; the aliphatic tricarboxylic acid is a trimer acid fatty acid; the aliphatic acid is selected from any one or more of acetic acid, lauric acid, stearic acid and oleic acid.
6. The dimer amine modified copolyamide according to claim 5, characterized in that the aliphatic tricarboxylic acid is an octadecadienoic acid trimer; the dimer acid is octadecadienoic acid dimer.
7. The process for the preparation of a dimer amine modified copolyamide according to any of claims 1 to 6, characterized in that it comprises the steps of:
(1) Starting the reaction kettle for stirring, and adding organic amine into the reaction kettle;
(2) Adding organic acid into the system finished in the step (1), and keeping the self-reaction heating temperature of the system not rising any more;
(3) Starting the reaction kettle to heat, and enabling the system to complete the reaction at 140-260 ℃;
(4) At the reaction temperature of>After 180 ℃, the pressure of the reaction kettle is controlled to be 1 multiplied by 10 2 ~1.013×10 5 And Pa, carrying out polycondensation until the required viscosity is reached, and discharging to obtain the diamine modified copolyamide.
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| JPH0912712A (en) * | 1995-06-27 | 1997-01-14 | Lion Corp | Polyamide resin originated from dimer diamine and optical material made of synthetic resin containing the polyamide |
| US7160979B2 (en) * | 2003-11-24 | 2007-01-09 | Henkel Corporation | Polyamides |
| CN107709462A (en) * | 2015-08-26 | 2018-02-16 | 日本化药株式会社 | Polyamide and its resin combination containing dimer |
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