High-temperature-resistant nylon resin and preparation method thereof
阅读说明：本技术 一种耐高温尼龙树脂及其制备方法 (High-temperature-resistant nylon resin and preparation method thereof ) 是由 徐惠祥 王文志 于 2019-03-15 设计创作，主要内容包括：本发明公开了一种耐高温尼龙树脂及其制备方法,以及该耐高温尼龙树脂用作阻隔薄膜的用途,该耐高温尼龙树脂由二元酸、二元胺和内酰胺制备,其中,二元酸选自具有R<Sub>1</Sub>结构的二元酸、脂肪族二元酸和芳香族二元酸中的一种或多种,R<Sub>1</Sub>选自式(1)-(4)所示结构中的一种或几种,二元胺选自脂肪族二元胺和/或芳香族二元胺中的一种或几种。本发明的耐高温尼龙树脂具有优异的力学性能,玻璃化转变温度较高、阻隔性能好、透光率高、尺寸稳定性好,且本发明所提供的耐高温尼龙树脂的制备方法简单、成本低廉、易于实现,有利于工业化大规模生产。(The invention discloses a high-temperature-resistant nylon resin, a preparation method thereof and application of the high-temperature-resistant nylon resin as a barrier film 1 One or more of structural dibasic acids, aliphatic dibasic acids and aromatic dibasic acids, R 1 Is selected from one or more structures shown in formulas (1) to (4), and the diamine is selected from one or more of aliphatic diamine and/or aromatic diamine. The high-temperature-resistant nylon resin provided by the invention has excellent mechanical properties, higher glass transition temperature, good barrier property, high light transmittance and good dimensional stability, and the preparation method of the high-temperature-resistant nylon resin provided by the invention is simple, low in cost, easy to realize and beneficial to industrial large-scale production.)
1. A high temperature resistant nylon resin is characterized in that the high temperature resistant nylon resin is prepared from dibasic acid, diamine and lactam,
wherein the dibasic acid is selected from the group consisting of R1One or more of structural dibasic acid, aliphatic dibasic acid and aromatic dibasic acid,
R1one or more selected from the structures shown in the following formulas (1) to (4):
the diamine is selected from one or more of aliphatic diamine and/or aromatic diamine.
2. The high temperature resistant nylon resin according to claim 1,
the aliphatic dibasic acid is selected from one or more of adipic acid, sebacic acid, dodecanedioic acid and tridecanedioic acid; and/or
The aromatic dibasic acid is selected from one or more of terephthalic acid, isophthalic acid and phthalic acid.
3. The nylon resin of claim 1 or 2, wherein the aliphatic diamine is selected from one or more of hexamethylenediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, and tridecanediamine; and/or
The aromatic diamine is selected from one or more of p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, p-xylylenediamine, m-xylylenediamine and o-xylylenediamine; and/or
The lactam is selected from one or more of caprolactam, caprylolactam, caprilactam, undecanolactam and laurolactam.
4. The high temperature resistant nylon resin of any one of claims 1 to 3, having R1A is prepared from dibasic acid with structure and aliphatic diamine, B is prepared from aromatic diamine and aliphatic diamine, and the high-temp nylon resin is prepared from A, B and lactam through fusion polycondensation.
5. The nylon resin of claim 4, having R1The molar ratio of the dibasic acid with the structure to the aliphatic diamine is 1: (1.0 to 1.06); and/or
The aromatic diamine and aliphatic dibasic acid are salified in water, and the ratio of the aromatic diamine to the aliphatic dibasic acid is (1.0-1.06): 1.
6. A method for preparing a high temperature resistant nylon resin according to any one of claims 1 to 5, comprising the steps of:
step 1, having R1Reacting dibasic acid with aliphatic diamine to obtain A;
step 2, reacting aromatic diamine with aliphatic dibasic acid to obtain B;
and 3, reacting A, B with lactam to obtain the high-temperature-resistant nylon resin.
7. The method of claim 6, wherein in step 3, a catalyst and an initiator are further added to the reaction,
the catalyst is selected from one or more of phosphoric acid, hypophosphorous acid, phosphite, hydrogen phosphate, hypophosphite and hypophosphite; and/or
The initiator is water.
8. The method according to claim 7 or 8, wherein in the step 3, the weight ratio of A, B to lactam is (5-30): (60-80): (5-20), preferably (10-30): (65-80): (10-20).
9. Method according to one of claims 6 to 8, characterized in that step 3 comprises:
step 1), adding A, B and lactam into a reaction kettle, adding a catalyst and an initiator, replacing air in the reaction kettle with inert gas for 3-10 times, heating to 180-220 ℃, and keeping the pressure in the kettle at 1.5-2.5 MPa;
and 2) continuously heating to 260-350 ℃, keeping the pressure in the kettle at 1.5-2.0 MPa, maintaining the pressure for 0.5-4 h, discharging the gas to the normal pressure, discharging the water in the system, gradually vacuumizing to reduce the pressure of the system to-0.03-0.07 MPa, and discharging to obtain the high-temperature resistant nylon resin for the barrier film.
10. Use of a high temperature resistant nylon resin according to any one of claims 1 to 5 or made by the process of any one of claims 6 to 9, preferably for the preparation of a barrier film.
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a high-temperature-resistant nylon resin and a preparation method thereof.
Background
Polyamide (PA), commonly known as nylon, is obtained by polycondensation of dibasic acid and diamine or amino acid, and is a general name for resins containing recurring amide groups on the molecular chain. The nylon has outstanding advantages in the aspects of mechanical property, chemical property, thermal property and the like.
With the progress of society, the demand of barrier materials is getting larger, and barrier polymer materials have more and more important status in the packaging field due to the advantages of light weight, easy forming and processing, difficult breakage, corrosion resistance and the like. At present, the plastic packaging material produced in China can not meet the requirement of international market competition in terms of high barrier property, and the requirement of domestic high barrier property packaging for food and medicine is higher and higher, so that the vigorous development of the high barrier property packaging material can obtain obvious social benefit and economic benefit.
The nylon has strong polar amide groups on the main chain, so that hydrogen bonds can be formed, the acting force among molecules is increased, and the nylon has good gas barrier property, good chemical stability and solvent resistance. Nylon is widely used as a barrier material in automobile plastic fuel tanks and barrier packaging materials. However, nylon has poor moisture resistance, and the dimensional stability and barrier properties of polyamide products are affected by changes in ambient humidity.
However, the currently reported barrier nylon has the problems of poor dimensional stability, high haze of the film, poor transparency and the like.
Therefore, in view of the above problems, there is a need to develop a high temperature resistant nylon resin with simple preparation process, good dimensional stability of film products, high light transmittance and excellent barrier property.
Disclosure of Invention
In order to overcome the problems, the inventors of the present invention have conducted intensive studies to develop a high temperature resistant nylon resin, which is a triblock copolymer, and the main chain of the macromolecule contains bulky side groups, imide rings and benzene rings with high density, so that the nylon resin has high glass transition temperature, high light transmittance, good dimensional stability and good barrier property, and the main chain of the macromolecule also contains a lactam ring-opening copolymer, so as to adjust the melting point of the nylon resin and reduce the cost.
The invention aims to provide a high-temperature resistant nylon resin which is prepared from dibasic acid, diamine and lactam,
wherein the dibasic acid is selected from the group consisting of R1One or more of a structural diacid, an aliphatic diacid, and an aromatic diacid.
R1One or more selected from the structures shown in the following formulas (1) to (4):
the diamine is selected from one or more of aliphatic diamine and/or aromatic diamine.
Another object of the present invention is a method for preparing the high temperature resistant nylon resin according to the first aspect of the present invention, which comprises the steps of:
step 2, reacting aromatic diamine with aliphatic dibasic acid to obtain B;
and 3, reacting A, B with lactam to obtain the high-temperature-resistant nylon resin.
A third aspect of the invention provides the use of a high temperature resistant nylon resin as described in the first aspect of the invention and as prepared by the process of the second aspect of the invention, for a barrier film.
The invention has the following beneficial effects:
(1) the macromolecular chain of the high-temperature-resistant nylon resin is a triblock copolymer, wherein one block unit is prepared from dibasic acid containing a benzene ring, an imide ring and a large-volume side group and aliphatic diamine, so that the finally prepared high-temperature-resistant nylon resin has high glass transition temperature (such as the glass transition temperature is higher than 170 ℃, preferably higher than 179 ℃ and even reaches 188.5 ℃), good dimensional stability (such as the water absorption is less than or equal to 1.2%) and high light transmittance (such as the light transmittance is more than or equal to 89% and even reaches 90.6%);
(2) the other block unit of the macromolecular chain of the high-temperature-resistant nylon resin is prepared from aromatic diamine and aliphatic dibasic acid, so that the macromolecular chain of the nylon resin has higher contentBenzene rings with density and rigid molecular chains endow the nylon resin with excellent barrier property (such as oxygen permeability of 7.5 ml/m)2day below, even as low as 6.5ml/m2day) and heat resistance;
(3) the macromolecular chain of the high-temperature-resistant nylon resin contains a block unit formed by a lactam ring-opening polymer, and the block unit has the effects of adjusting the melting point of the nylon resin on one hand, can reduce the cost on the other hand, and is favorable for large-scale industrial production of the nylon resin;
(4) the invention prepares the high-temperature resistant nylon resin by a plurality of different monomers, endows the nylon resin with multiple functions, can obtain the nylon resin with different functions by adjusting the content of three block units, and has simple synthetic route and easy realization.
Drawings
FIG. 1 shows an IR spectrum of a high temperature resistant nylon resin obtained in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to preferred embodiments. The features and advantages of the present invention will become more apparent from the description.
According to the present invention, in one aspect, there is provided a high temperature resistant nylon resin prepared from a dibasic acid, a diamine and a lactam.
According to the invention, the dibasic acids are chosen from those having R1One or more of a structural diacid, an aliphatic diacid, and an aromatic diacid.
According to the invention, having R1The dibasic acid of structure may be represented as HOOC-R1-COOH，R1One or more selected from the structures shown in the following formulas (1) to (4):
when R is1When the structure is represented by the formulas (1) to (4), R is1The dibasic acids are 2-phenyl-4, 6-diphenyl sym-triazine-N-carboxyl phenyl phthalimide and 2-imidazole respectivelyAzolyl-4, 6-bisphenyl symmetric triazine-N-carboxyphenyl phthalimide, 2-diphenylamino-4, 6-bisphenyl symmetric triazine-N-carboxyphenyl phthalimide and 2- (9-carbazolyl) -4, 6-bisphenyl symmetric triazine-N-carboxyphenyl phthalimide.
According to the invention, when R1When the structure is represented by the formula (1), R is1The structural diacid is preferably made by a process comprising the steps of: 0.1mol of 4-phenyl-2, 6-bis [3, 4-dicarboxyphenyl group]Dissolving triazine dianhydride in 250ml of glacial acetic acid, adding 0.105mol of p-aminobenzoic acid, refluxing for reaction for 3h, cooling with ice, filtering, vacuum drying, and recrystallizing with toluene to obtain R shown in formula (1)1Structural diacid monomers, analogous, when R1When the structure is represented by the formula (2), (3) or (4), R is present1The structural dibasic acids can be prepared in the same manner as described above.
In the present invention, R1The structure contains a large number of benzene rings, imide rings and bulky side groups, and then the structure has R1The copolymerization component prepared from the structural dibasic acid and diamine and the macromolecular main chain of the high-temperature resistant nylon resin prepared from the copolymerization component are provided with R1The structure of (A) is that benzene rings endow molecular chains with rigidity, the mechanical property and the heat resistance of the nylon resin are improved, imide rings have strong polarity and can form hydrogen bonds, so that the intermolecular force is increased, and the gas barrier property of the material is good (or the oxygen permeability is low, for example, the oxygen permeability is 7.5ml/m2day below), good heat resistance, higher char forming rate of imide ring, anti-dripping property of material, excellent mechanical property, good dimensional stability and high light transmittance (such as light transmittance more than or equal to 89%) due to existence of large-volume side group.
The inventors have found that1In the dibasic acid with the structure, carboxyl is directly connected to a benzene ring, and the compound has higher reaction activity and can be obtained when melt polycondensation is carried out
According to the invention, the aliphatic dibasic acid is selected from one or more of adipic acid, sebacic acid, dodecanedioic acid and tridecanedioic acid, preferably adipic acid or suberic acid, such as adipic acid.
According to the invention, the aromatic dibasic acid is selected from one or more of terephthalic acid, isophthalic acid and phthalic acid.
According to the invention, the aliphatic diamine is selected from one or more of hexamethylene diamine, nonane diamine, decamethylene diamine, undecane diamine, dodecane diamine and tridecane diamine, preferably hexamethylene diamine or decamethylene diamine, and more preferably hexamethylene diamine.
According to the present invention, the aromatic diamine is selected from one or more of p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, p-xylylenediamine, m-xylylenediamine, and o-xylylenediamine, preferably one or more of p-xylylenediamine, m-xylylenediamine, and o-xylylenediamine, and more preferably m-xylylenediamine. Compared with p-xylylenediamine and o-xylylenediamine, the high temperature resistant nylon resin obtained by introducing m-xylylenediamine has higher transparency.
According to the invention, the lactam is selected from one or more of butyrolactam, valerolactam, caprolactam, enantholactam, caprylolactam, decalactam, undecanolactam, and dodecanolactam, preferably from one or more of valerolactam, caprolactam, caprylolactam, decalactam, and dodecanolactam, for example caprolactam.
According to the present invention, the high temperature resistant nylon resin is composed of a resin having R1Dibasic acid with a structure, aliphatic dibasic acid, aliphatic diamine, aromatic diamine and lactam.
According to a preferred embodiment of the invention, R is1A is prepared from dibasic acid with structure and aliphatic diamine, B is prepared from aromatic diamine and aliphatic diamine, and the high-temp nylon resin is prepared from A, B and lactam through fusion polycondensation.
According to the present invention, the high temperature resistant nylon resin is a triblock copolymer comprising A, B and polylactam, A, B and the polylactam respectively form three block units, and the three block units impart multifunctionalization to the high temperature resistant nylon.
According to a preferred embodiment of the invention, a is obtained having a structural moiety represented by the following formula (I):
wherein a is 6-13, preferably one or more selected from 6, 9, 10, 11, 12 and 13, more preferably 6 or 10, and more preferably 6.
In the invention, the structure A contains a large number of benzene rings, bulky side groups and imide rings, so that the nylon resin prepared from the A has higher glass transition temperature and can increase the transparency and dimensional stability of the nylon resin.
According to a preferred embodiment of the present invention, m-xylylenediamine and an aliphatic dibasic acid are salified in water to give B, preferably B having a structural moiety represented by the formula (II):
wherein b is 4-13, preferably selected from 4, 8, 12 or 13, preferably 4 or 8, and more preferably 4.
In the invention, the B contains benzene rings, and a certain amount of benzene rings endow the high-temperature-resistant nylon resin with excellent heat resistance, mechanical property and barrier property.
A, B reacts with lactam to obtain high-temp nylon resin, during which the lactam is ring-opened and polymerized to obtain lactam polymer, which is then melt polycondensed with A and B to obtain high-temp nylon resin.
According to the invention, the products obtained by ring-opening polymerization of lactams have a structural part as shown in formula (III):
wherein c is 5-13, preferably selected from 5, 7, 11, 12 or 13, more preferably 5, 7 or 11, and more preferably 5.
According to the invention, lactam is obtained through ring-opening polymerization, and in the high-temperature-resistant nylon resin containing a lactam polymer block unit, due to the introduction of lactam, the melting point of the nylon resin can be adjusted, and meanwhile, the cost can be reduced, thereby being beneficial to the industrial production of the high-temperature-resistant nylon resin.
The inventor finds that the addition amounts of A, B and lactam have important influence on the performance of the high-temperature-resistant nylon, and the high-temperature-resistant nylon resin with excellent barrier property, mechanical property, higher glass transition temperature, high light transmittance and good dimensional stability can be obtained by adjusting the addition amount ratio of the A, B and the lactam.
According to the invention, the mass ratio of A, B to lactam is (5-30): (60-80): (5-20), preferably (10-30): (65-80): (10-20), more preferably (10-25): (65-75): (10-15).
According to the present invention, it is presumed that the high temperature resistant nylon resin obtained by melt polycondensation of A, B and lactam has a structural portion represented by the following formula (IV):
in the formula (IV), the compound is shown in the specification,
The mass fraction of each block unit in the product is determined by the previous charge ratio.
Another aspect of the present invention provides a method for preparing a high temperature resistant nylon resin, preferably a method for preparing a high temperature resistant nylon resin according to the first aspect of the present invention, the method comprising the steps of:
According to the invention, in
According to the invention, in
According to the invention, in
The inventors have found that1The reaction system for the salt formation of the dibasic acid and the aliphatic diamine needs to be in an alkaline environment, the pH value of the reaction system is preferably 7.5-8.5, the diamine can be lost in the polymerization temperature rise process, the use amount of the diamine can be properly increased to ensure that the molar weight of the dibasic acid and the diamine are subjected to polymerization reaction in a 1:1 molar ratio, the molar weight of the diamine is slightly higher than that of the dibasic acid, the reaction system is in an alkaline environment, the dibasic acid and the diamine are polymerized in a 1:1 molar ratio, and the A with higher molecular weight is obtained.
According to the invention, in
In the present invention, A is represented by R1The copolymer obtained by the reaction of dibasic acid with aliphatic diamine has a molecular main chain containing R1Structure R1The high-temperature resistant nylon resin contains benzene rings, bulky side groups and imide rings, can endow the high-temperature resistant nylon resin obtained by using A as a copolymerization component with higher glass transition temperature, and can improve the light transmittance and the dimensional stability of the nylon resin.
And 2, reacting aromatic diamine with aliphatic dibasic acid to obtain B.
According to the invention, in step 2, B has a structural moiety as shown in formula (II).
According to a preferred embodiment of the present invention, m-xylylenediamine is reacted with an aliphatic dibasic acid in water to form a salt in step 2, thereby preparing B.
The inventor finds that the salt formation of the aliphatic dibasic acid and the aromatic diamine requires that a reaction system is in an alkaline environment, the pH of the reaction system is preferably 7.5-8.5, the aromatic diamine is lost in the polymerization temperature rise process, the use amount of the aromatic diamine can be properly increased to ensure that the aliphatic dibasic acid and the aromatic diamine are subjected to polymerization reaction at a molar ratio of 1:1, the molar amount of the aromatic diamine is slightly higher than that of the aliphatic dibasic acid, the reaction system is in an alkaline environment, the aliphatic dibasic acid and the aromatic diamine are ensured to be polymerized into the salt at a ratio of 1:1, and the copolymerization component B with a higher molecular weight is obtained.
According to the invention, in step 2, the molar ratio of the aliphatic dibasic acid to the aromatic diamine is 1: (1.0 to 1.06), preferably 1: (1.0 to 1.04), for example, 1: 1.02.
In the invention, the B contains a large number of benzene rings, and when the high-temperature-resistant nylon resin is prepared, the macromolecular main chain of the obtained nylon resin has higher benzene ring density and endows the molecular chain with certain rigidity, so that the high-temperature-resistant nylon resin has low oxygen permeability, excellent mechanical property and good heat resistance (such as higher glass transition temperature).
And 3, reacting A, B with lactam to obtain the high-temperature-resistant nylon resin.
According to the invention, in the step 3, A, B and lactam are subjected to melt polycondensation reaction in a reaction kettle to obtain the high-temperature-resistant nylon resin.
According to the invention, in step 3, a catalyst and an initiator are added in the reaction to catalyze and initiate the reaction.
According to the invention, in step 3, the catalyst is selected from one or more of phosphoric acid, hypophosphorous acid, phosphites, hydrogen phosphates, hypophosphites and hypophosphites.
According to the invention, the phosphite is selected from one or more of potassium phosphite, sodium phosphite, magnesium phosphite, calcium phosphite, aluminum phosphite, zinc phosphite.
According to the invention, the hydrogen phosphate is selected from one or more of magnesium hydrogen phosphate, potassium hydrogen phosphate and sodium hydrogen phosphate.
According to the invention, the hypophosphite is selected from one or more of sodium hypophosphite, calcium hypophosphite and magnesium hypophosphite.
According to the invention, the hypophosphite is selected from one or more of sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite and zinc hypophosphite.
According to a preferred embodiment of the invention, the catalyst is one or more of phosphoric acid, phosphorous acid and sodium hypophosphite, such as sodium hypophosphite.
According to the invention, in step 3, the amount of catalyst added is 0.1 to 2%, preferably 0.1 to 1%, more preferably 0.1 to 0.5%, for example 0.5% of the total weight of A, B and lactam addition.
According to the invention, the initiator is water, preferably deionized or distilled water.
According to the invention, in step 3, the amount of the initiator added is 1 to 10%, preferably 1.5 to 8%, more preferably 2 to 5%, for example 5% of the total weight of A, B and lactam.
According to the invention, in the step 3, the weight ratio of A, B to lactam is (5-30): (60-80): (5-20), preferably (10-30): (65-80): (10-20), more preferably (10-25): (65-75): (10-15).
According to the invention, step 3 comprises: step 1), adding A, B and lactam into a reaction kettle, adding a catalyst and an initiator, replacing air in the reaction kettle with inert gas for 3-10 times, heating to 180-220 ℃, and keeping the pressure in the kettle at 1.5-2.5 MPa;
according to the invention, in step 1), prepolymerization is carried out, water in the reaction kettle is preliminarily removed, and the salt solution is further concentrated, wherein the salt solution is preferably a nylon salt solution formed by A and B.
And 2) continuously heating to 260-350 ℃, keeping the pressure in the kettle at 1.5-2.0 MPa, maintaining the pressure for 0.5-4 h, discharging the gas to the normal pressure, discharging the water in the system, gradually vacuumizing to reduce the pressure of the system to-0.03-0.07 MPa, and discharging to obtain the high-temperature resistant nylon resin.
In the step 2), A, B reacts with the lactam ring-opening polymerization product, and the pressure reduction polycondensation is carried out, so that the polymerization reaction is carried out forward, namely in the direction of synthesizing the nylon resin, the molecular weight of the nylon resin is improved, and finally the ternary block copolymer, namely the high-temperature resistant nylon resin is obtained.
A further aspect of the invention provides the use of a high temperature resistant nylon resin according to the first aspect of the invention and/or according to the second aspect of the invention for a barrier film.
According to the invention, A, B and lactam are subjected to melt polycondensation to prepare the high-temperature-resistant nylon resin, the macromolecular chain of the high-temperature-resistant nylon resin comprises a A, B triblock structure and a lactam polymer triblock structure, the three block units enable the high-temperature-resistant nylon to be multifunctional, and the structure and the performance of the high-temperature-resistant nylon resin can be adjusted by adjusting the structure and the content of the three block units.
According to the invention, the ternary polymerization high temperature resistant nylon has excellent mechanical properties and barrier properties, high light transmission, low water absorption and higher glass transition temperature, such as excellent mechanical properties: the tensile strength of the obtained high-temperature resistant nylon resin is more than 100MPa, preferably more than 110MPa, more preferably more than 117MPa, and even reaches 123.9 MPa; the bending strength is higher than 150MPa, preferably higher than 160MPa, more preferably higher than 167MPa, and even reaches 176.3 MPa; the notch impact strength is more than 4.9MPa, even reaches 6.1 MPa; higher glass transition temperature: the glass transition temperature is higher than 170 ℃, even higher than 179 ℃, even reaches 188.5 ℃; excellent barrier properties: the oxygen permeability is 7.5ml/m2day below, even as low as 6.5ml/m2day; high light transmittance: the light transmittance is more than or equal to 89 percent and even reaches 90.6 percent; low water absorption: the water absorption is less than or equal to 0.5 percent.
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