CN115725069A - Bio-based transparent polyamide and preparation method thereof - Google Patents
Bio-based transparent polyamide and preparation method thereof Download PDFInfo
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- CN115725069A CN115725069A CN202111002306.7A CN202111002306A CN115725069A CN 115725069 A CN115725069 A CN 115725069A CN 202111002306 A CN202111002306 A CN 202111002306A CN 115725069 A CN115725069 A CN 115725069A
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Abstract
The invention discloses a bio-based transparent polyamide and a preparation method thereof. The bio-based transparent polyamide provided by the invention has high light transmittance and transparency, excellent mechanical properties, economy and practicability. The preparation method of the bio-based transparent polyamide is simple, the process parameters are easy to control, and the quantitative production is convenient to carry out.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a bio-based transparent polyamide with high light transmittance and excellent mechanical properties and a preparation method thereof.
Background
The polyamide has excellent mechanical properties and molding properties, and is widely applied to processing of original parts such as automobile parts, parts of electrical and electronic equipment, spectacle frames, spectacle lenses or other lenses, cups/bottles for drinking water treatment and the like. However, since the molecular chain arrangement of ordinary polyamide is regular and the transparency is poor, it is difficult to exert the function in a special field.
In the actual use process, the traditional transparent plastics cannot completely meet the requirements of specific use scenes, for example, the main transparent plastics PC (polycarbonate) and PMMA (polymethyl methacrylate) in the market have the problems of small molecule residues, poor chemical corrosion resistance, poor wear resistance and the like. The polyamide macromolecules contain amide groups with strong polarity, terminal amino groups and terminal carboxyl groups at the tail ends, the groups have strong interaction, hydrogen bonds are easily formed, and therefore the polyamide macromolecules are easy to highly crystallize, and the size of spherulites formed by the polyamide is often larger than the wavelength (400-700 nm) of visible light, so that the polyamide macromolecules are opaque. In order to produce polyamides with higher transparency, amorphous polyamides can be produced by reducing the crystallinity; reducing the crystal size to within the visible wavelength range; the optimized blending and copolymerization methods are realized by making the refractive indexes of crystalline regions and amorphous regions similar, but the methods may cause the loss of other properties, for example, the inhibition of crystallization can cause the hardness of polyamide to be reduced, the heat distortion temperature to be reduced and even the use value to be lost, and part of the commonly used cyclic lipoamine with side groups on the commercial transparent polyamide is expensive.
Disclosure of Invention
The invention provides a bio-based transparent polyamide prepared by taking pentanediamine prepared by a biological method as a main monomer and a preparation method thereof.
The invention provides a bio-based transparent polyamide, which contains structural units shown in the following general formulas (I) to (III), wherein the structural units are connected through amide bonds;
the general formula (I) is
The general formula (II) is
The general formula (III) is
The bio-based transparent polyamide contains at least 30mol% of formula (III);
preferably, the molar ratio of the general formula (I) to the general formula (II) is 1.
In one embodiment, in the bio-based transparent polyamide, the ratio of the sum of the moles of the general formula (I) and the moles of the general formula (II) to the moles of the general formula (III) is 0.95 to 1.1:1; and/or the presence of a gas in the gas,
the mass content of the general formulas (I) - (III) in the bio-based transparent polyamide is more than 95wt%, preferably more than 97 wt%; and/or the presence of a gas in the gas,
the mol percent of the general formula (I) is 40-50 mol percent, and the mol percent of the general formula (II) is 1-10 mol percent; the mol percentage of the general formula (III) is 30-50 mol%, and the sum of the mol percentages of the general formulas (I) - (III) is less than or equal to 100mol%.
In one embodiment, the mole percent of formula (I) is 40 mole percent and the mole percent of formula (II) is 10 mole percent; the molar percentage of the general formula (III) is 50mol%.
In one embodiment, the starting material of the bio-based transparent polyamide comprises pentanediamine, bis (4-amino-3-methylcyclohexyl) methane (MACM) or bis (4-aminocyclohexyl) methane (PACM), isophthalic acid and/or derivatives thereof; and/or the presence of a gas in the gas,
the sum of the mole numbers of the pentamethylene diamine, the bis (4-amino-3-methylcyclohexyl) methane (MACM) or the bis (4-aminocyclohexyl) methane (PACM) and the mole number of the isophthalic acid and/or the derivative thereof is 0.95 to 1.1:1; and/or the presence of a gas in the atmosphere,
preferably, the feedstock comprises:
40-50 parts of pentamethylene diamine;
1-10 parts of bis (4-amino-3-methylcyclohexyl) methane (MACM) or bis (4-aminocyclohexyl) methane (PACM);
30-50 parts of isophthalic acid and/or derivatives thereof;
wherein all parts are calculated as mole parts;
preferably, the isophthalic acid derivative is selected from one or more of isophthalic chloride, dimethyl isophthalate and diethyl isophthalate.
In one embodiment, the bio-based transparent polyamide further comprises structural units of the general formula (IV),
the general formula (IV) is
The ratio of the sum of the number of moles of the general formulae (I) and (II) to the sum of the number of moles of the general formulae (III) and (IV) is 0.95 to 1.1:1.
in one embodiment, the mass content of the general formulae (I) to (IV) in the bio-based transparent polyamide is 95wt% or more, preferably 97wt% or more; and/or the presence of a gas in the atmosphere,
the mol percent of the general formula (I) is 40-50 mol percent, and the mol percent of the general formula (II) is 1-10 mol percent; the mol percent of the general formula (III) is 30-50 mol percent, the mol percent of the general formula (IV) is 5-30 mol percent, and the sum of the mol percent of the general formulas (I) - (IV) is less than or equal to 100mol percent.
In one embodiment, the starting material for the bio-based transparent polyamide comprises pentanediamine, bis (4-amino-3-methylcyclohexyl) methane (MACM) or bis (4-aminocyclohexyl) methane (PACM), isophthalic acid and/or derivatives thereof, terephthalic acid and/or derivatives thereof; and/or the presence of a gas in the gas,
the ratio of the sum of the mole numbers of the pentamethylene diamine, the bis (4-amino-3-methylcyclohexyl) methane (MACM) or the bis (4-aminocyclohexyl) methane (PACM) to the mole numbers of the isophthalic acid and/or the derivative thereof and the terephthalic acid and/or the derivative thereof is 0.95-1.1: 1; and/or the presence of a gas in the gas,
preferably, the raw materials comprise:
40-50 parts of pentamethylene diamine;
1-10 parts of bis (4-amino-3-methylcyclohexyl) methane (MACM) or bis (4-aminocyclohexyl) methane (PACM);
30-50 parts of isophthalic acid and/or derivatives thereof;
5-30 parts of terephthalic acid and/or derivatives thereof;
wherein all parts are calculated as mole parts;
preferably, the isophthalic acid derivative is selected from one or more of isophthalic chloride, dimethyl isophthalate and diethyl isophthalate; the terephthalic acid derivative is one or more selected from terephthalic acid chloride, dimethyl terephthalate and diethyl terephthalate.
In one embodiment, the bio-based transparent polyamide has at least one of the following properties,
the number average molecular weight of the bio-based transparent polyamide is 10000-50000; and/or the presence of a gas in the gas,
the relative viscosity of the bio-based transparent polyamide is 1.60-3.0, preferably 1.7-2.5; and/or the presence of a gas in the atmosphere,
the glass transition temperature of the bio-based transparent polyamide is more than 135 ℃; and/or the presence of a gas in the atmosphere,
the tensile strength of the bio-based transparent polyamide is more than 90 MPa; and/or the presence of a gas in the gas,
the bending strength of the bio-based transparent polyamide is more than 140 MPa; and/or the presence of a gas in the gas,
the IZOD notch impact strength of the bio-based transparent polyamide is more than 9KJ/m 2; and/or the presence of a gas in the gas,
the haze of the bio-based transparent polyamide is 6.0% or less, preferably 4.5% or less; and/or the presence of a gas in the gas,
the light transmittance of the bio-based transparent polyamide is 85% or more, and more preferably 90% or more.
In one embodiment, the bio-based transparent polyamide further comprises additives including end-capping agents, UV stabilizers, heat stabilizers, free radical scavengers and/or processing aids, impurity inhibitors, lubricants, mold release aids, plasticizers, functional additives for affecting optical properties, particularly refractive index, impact modifiers, nanofillers and/or additives, gloss enhancers, dyes or mixtures thereof; and/or the presence of a gas in the gas,
the mass content of the additive in the bio-based transparent polyamide is 0-10 wt%, or 0-5 wt%.
In one embodiment, the raw material of the bio-based transparent polyamide further comprises additives including end-capping agents, UV stabilizers, heat stabilizers, radical scavengers and/or processing aids, impurity inhibitors, lubricants, mold release aids, plasticizers, functional additives for influencing optical properties, in particular refractive index, impact modifiers, nanofillers and/or additives, gloss enhancers, dyes or mixtures thereof.
In one embodiment, the blocking agent preferably includes one or more of a monobasic acid, a dibasic acid, a monoamine or a diamine, and further preferably includes one or more of acetic acid, benzoic acid, stearic acid, lauric acid, succinic acid, adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid or octadecanedioic acid, and one or more of decylamine, dodecylamine, hexamethylenediamine, decamethylenediamine, etc.
In one embodiment, the heat stabilizer preferably comprises one or more of phosphoric acid, phosphorous acid, trimethyl phosphite, triphenyl phosphite, trimethyl phosphate, triphenyl phosphate, sodium hypophosphite, zinc hypophosphite, calcium hypophosphite, and potassium hypophosphite.
In one embodiment, the crystallization promoter preferably includes a long carbon chain carboxylic acid metal salt, the number of carbon atoms of the long carbon chain carboxylic acid is preferably 10 to 30, and the metal preferably includes one or more of calcium, magnesium and zinc, and may be, for example, one or more of a long carbon chain carboxylic acid calcium salt, a long carbon chain carboxylic acid magnesium salt or a long carbon chain carboxylic acid zinc salt, and further may be one or more of calcium laurate, sodium myristate, calcium heptadecanoate, calcium stearate, sodium lauryl sulfate and sodium myristyl sulfate.
In one embodiment, the inorganic filler preferably includes one or more of glass fiber, glass bead, carbon fiber, carbon black, and graphite.
In one embodiment, the mineral preferably includes one or more additives of titanium dioxide, calcium carbonate and barium sulfate.
In another aspect of the present invention, there is provided a method for preparing the bio-based transparent polyamide, the method comprising the steps of: mixing the raw materials with water to prepare a polyamide salt solution; controlling the system pressure to be 1.2-2.2 Mpa, such as 1.75Mpa and 2.0Mpa, raising the temperature of the polyamide salt solution to 210-300 ℃, further to be 220-290 ℃, stirring and reacting for 2-4 hours, then reducing the system pressure to atmospheric pressure within 0.2-1.5 hours, vacuumizing, continuing to react for 0.2-2 hours under the conditions that the vacuum degree is (-0.07) to (-0.09) Mpa and the temperature is 240-280 ℃, melting and discharging, and cooling to obtain the bio-based transparent polyamide;
the raw material at least contains pentanediamine, bis (4-amino-3-methylcyclohexyl) methane (MACM) or bis (4-aminocyclohexyl) methane (PACM), isophthalic acid and/or derivatives thereof; alternatively, the first and second liquid crystal display panels may be,
the feedstock also contains terephthalic acid and/or derivatives thereof.
In one embodiment, the polyamide salt solution is adjusted to a pH of 7.5 to 9.5, for example 8.3, 8.4, using pentanediamine, at a concentration of 10%.
In one embodiment, the method is performed under a nitrogen or inert gas atmosphere, including argon or helium.
In one embodiment, the concentration of the solution of polyamide salts is between 40 and 85%, said percentage being in mass% with respect to the solution of polyamide salts, for example 50%,60%.
In one embodiment, the polyamide salt solution may be concentrated by heating to increase the concentration.
In one embodiment, the aforementioned additives are added to the polyamide salt solution in amounts of 100 to 2000ppm each (based on the total mass of the starting materials).
In one embodiment, the aforementioned antioxidant is added to the polyamide salt solution in an amount of 200 to 1500ppm (based on the total mass of the raw materials), for example 300ppm, 700ppm, respectively.
In one embodiment, the end-capping agent is added to the polyamide salt solution in an amount of 100 to 1500ppm (based on the total mass of the starting materials), for example 200ppm.
In another aspect of the present invention, there is provided a molded article comprising the bio-based transparent polyamide as described above as a raw material.
Compared with the prior art, the implementation of the invention has at least the following advantages: the bio-based transparent polyamide synthesized by the invention not only has good transparent light transmission, but also has excellent mechanical properties, and the application range of the transparent polyamide is expanded. The preparation method of the bio-based transparent polyamide is simple, the source of the polymerized monomer is stable, the raw material price is low, the process parameters are easy to control, and the quantitative production is convenient to carry out.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The inventor selects the pentanediamine which is derived from a biological group and contains a single carbon number, and introduces a benzene ring structure in a molecular chain, controls the content ratio of monomers, and unexpectedly discovers that the obtained polyamide has high transparency, and has excellent mechanical properties such as tensile strength, bending strength and the like and excellent impact toughness, so that the polyamide can meet the requirements of different transparent products.
The polyamide and the preparation thereof according to one embodiment of the present invention will be further described with reference to the following specific examples.
The relevant tests involved are as follows:
1) Bending test: the test is according to the standard ISO 178-2010, and the test conditions are as follows: 2mm/min, spline size 10mm × 4mm × 80mm.
2) And (3) tensile test: the test is referred to the standard ISO 572-2-2012, and the test conditions are as follows: 50mm/min.
3) And (3) impact test: for notched Izod impact, reference is made to the test standard ISO 180/1A, test condition 23 ℃.
4) Light transmittance and haze: the test refers to a color plate with the national standard GB/T2410-2008 and the thickness of 2 mm.
5) Relative viscosity: concentrated sulfuric acid method by Ubbelohde viscometer: accurately weighing 0.25 +/-0.0002 g of dried polyamide resin slices, and adding 50mL of concentrated sulfuric acid (96 wt%) for dissolution; the time t0 of concentrated sulfuric acid flow and the time t of polyamide sample solution flow were measured and recorded in a thermostated water bath at 25 ℃. Viscosity number calculation formula: relative viscosity = t/t0; t-solution flow time; t 0-time of solvent flow.
6) Glass transition temperature (Tg): the temperature corresponding to the transition from the glass state to the high elastic state is detected by a differential scanning calorimetry method.
The following examples and comparative examples used starting materials, reagents, and reagents that were commercially available. Pentanediamine was purchased from Kaiser (Jinxiang) biomaterials Co.
Example 1
1. Under the nitrogen atmosphere, uniformly mixing pentanediamine, MACM, isophthalic acid, terephthalic acid and water, heating and concentrating to obtain a polyamide salt solution with the concentration of 65%, wherein the molar ratio of the pentanediamine is as follows: MACM: isophthalic acid: terephthalic acid =85:15:60:40, the pH of the polyamide salt solution was adjusted to 8.0 when diluted to 10wt% using pentamethylenediamine, and 300ppm of sodium hypophosphite as an antioxidant was added.
2. Controlling the system pressure to be 1.7Mpa, raising the temperature of the polyamide salt solution to 245 ℃, stirring and reacting for 2 hours, reducing the system pressure to atmospheric pressure within 1 hour, vacuumizing, continuously reacting for 0.5 hour under the conditions of vacuum degree of-0.07 Mpa and temperature of 240 ℃, melting and discharging, cooling to obtain the bio-based transparent polyamide, wherein the performance test is shown in Table 1.
Example 2
The polyamide was prepared in the same manner as in example 1, except that the monomer raw materials in step 1 were pentamethylenediamine: MACM: isophthalic acid: terephthalic acid =85:15:80:20, obtaining the bio-based transparent polyamide resin, and testing the performance as shown in the table 1.
Example 3
The preparation method of the bio-based transparent polyamide is the same as that of example 1, except that the monomer raw materials of step 1 are: pentanediamine, MACM and isophthalic acid, wherein the molar ratio of the pentanediamine is as follows: MACM: isophthalic acid =85:15:100, obtaining the bio-based transparent polyamide resin, and the performance test is shown in the table 1.
Example 4
1. Under the nitrogen atmosphere, uniformly mixing pentanediamine, PACM, isophthalic acid, terephthalic acid and water, heating and concentrating to obtain a polyamide salt solution with the concentration of 70%, wherein the molar ratio of the pentanediamine is as follows: and (4) PACM: isophthalic acid: terephthalic acid =85:15:80:20, the pH of the polyamide salt solution was adjusted to 8.3 when diluted to 10% by weight using pentamethylenediamine, and 300ppm of sodium hypophosphite as an antioxidant was added.
2. Controlling the system pressure to be 1.7Mpa, raising the temperature of the polyamide salt solution to 250 ℃, stirring and reacting for 2 hours, reducing the system pressure to atmospheric pressure within 1 hour, vacuumizing, continuously reacting for 0.5 hour under the conditions of vacuum degree of-0.07 Mpa and temperature of 245 ℃, melting and discharging, cooling to obtain the bio-based transparent polyamide, wherein the performance test is shown in Table 1.
Example 5
1. Under the nitrogen atmosphere, uniformly mixing pentanediamine, MACM, isophthalic acid, terephthalic acid and water, heating and concentrating to obtain a polyamide salt solution with the concentration of 70%, wherein the molar ratio of the pentanediamine is as follows: and MACM: isophthalic acid: terephthalic acid =90:10:60:40, the pH of the polyamide salt solution was adjusted to 8.4 by diluting it to 10% by weight with pentamethylenediamine, and 300ppm of sodium hypophosphite as an antioxidant was added.
2. Controlling the system pressure to be 1.8Mpa, raising the temperature of the polyamide salt solution to 260 ℃, stirring and reacting for 2 hours, reducing the system pressure to atmospheric pressure within 1.5 hours, vacuumizing, continuously reacting for 0.5 hour under the conditions of vacuum degree of-0.07 Mpa and temperature of 245 ℃, melting and discharging, cooling to obtain the bio-based transparent polyamide, and the performance test is shown in Table 1.
Example 6
The polyamide was prepared in the same manner as in example 5, except that the monomer raw materials in step 1 were pentamethylenediamine: and MACM: isophthalic acid: terephthalic acid =90:10:80:20, obtaining the bio-based transparent polyamide resin, and testing the performance of the bio-based transparent polyamide resin as shown in the table 1.
Example 7
The polyamide was prepared in the same manner as in example 5, except that the monomer raw materials of step 1 were: pentanediamine, MACM and isophthalic acid, wherein the molar ratio of the pentanediamine is as follows: MACM: isophthalic acid =90:10:100, obtaining the bio-based transparent polyamide resin, and the performance test is shown in the table 1.
Example 8
The polyamide was prepared in the same manner as in example 5, except that the monomer raw materials of step 1 were: the parts by mole of the pentanediamine, PACM, isophthalic acid and terephthalic acid are as follows: PACM: isophthalic acid: terephthalic acid =90:10:80:20, obtaining the bio-based transparent polyamide resin, and testing the performance as shown in the table 1.
Example 10
1. Under the atmosphere of nitrogen, uniformly mixing pentamethylene diamine, MACM, isophthalic acid, terephthalic acid and water, heating and concentrating to obtain a polyamide salt solution with the concentration of 75%, wherein the molar ratio of pentamethylene diamine: MACM: isophthalic acid: terephthalic acid =95:5:80: the pH of the polyamide salt solution was adjusted to 8.4 when diluted to 10% by weight using pentanediamine, and 700ppm of sodium hypophosphite as an antioxidant and 200ppm of dodecanedioic acid as an end-capping agent were added 20.
2. Controlling the system pressure to be 1.8Mpa, raising the temperature of the polyamide salt solution to be 255 ℃, stirring and reacting for 4 hours, reducing the system pressure to be atmospheric pressure within 1 hour, vacuumizing, continuously reacting for 0.5 hour under the conditions of vacuum degree of-0.08 Mpa and temperature of 260 ℃, melting and discharging, cooling to obtain the bio-based transparent polyamide, wherein the performance test is shown in Table 1.
Example 11
The polyamide was prepared in the same manner as in example 10, except that the monomer raw materials of step 1 were: pentanediamine, MACM and isophthalic acid, wherein the molar ratio of the pentanediamine is as follows: MACM: isophthalic acid =95:5:100, obtaining the bio-based transparent polyamide resin, and the performance test is shown in the table 1.
Example 12
The polyamide was prepared by the same method as in example 10, except that the monomer raw materials of step 1 were: pentanediamine, PACM, isophthalic acid and terephthalic acid, wherein the molar part ratio of the pentanediamine is as follows: PACM: isophthalic acid: terephthalic acid =95:5:80:20, obtaining the bio-based transparent polyamide resin, and testing the performance of the bio-based transparent polyamide resin as shown in the table 1.
Comparative example 1
The polyamide was prepared in the same manner as in example 1 except that the monomer raw materials of step 1 were in the molar ratio of pentamethylenediamine: and MACM: isophthalic acid: terephthalic acid =85:15:40:60, a polyamide resin was obtained, and the property test was as shown in Table 1.
Comparative example 2
The polyamide was prepared in the same manner as in example 5, except that the monomer raw materials in step 1 were pentamethylenediamine: and MACM: isophthalic acid: terephthalic acid =90:10:35:65, a polyamide resin was obtained, and the property test was as shown in Table 1.
Comparative example 3
The polyamide was prepared in the same manner as in example 4 except that the monomer raw materials of step 1 were in the molar ratio of pentamethylenediamine: PACM: isophthalic acid: terephthalic acid =85:15:30:70, a polyamide resin was obtained, and the property test was as shown in Table 1.
TABLE 1
In conclusion, through comparison, the bio-based transparent polyamide disclosed by the invention has very excellent comprehensive performance and very wide application prospect in the field of general polyamide.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A bio-based transparent polyamide, characterized in that it comprises structural units of the following general formulae (I) to (III), said structural units being linked by amide bonds;
the general formula (I) is
The general formula (II) is
The general formula (III) is
The bio-based transparent polyamide contains at least 30mol% of formula (III);
preferably, the molar ratio of the general formula (I) to the general formula (II) is 1.
2. The bio-based transparent polyamide according to claim 1, wherein the ratio of the sum of the moles of the general formulae (I) and (II) to the moles of the general formula (III) in the bio-based transparent polyamide is 0.95 to 1.1:1; and/or the presence of a gas in the gas,
the mass content of the general formulas (I) to (III) in the bio-based transparent polyamide is more than 95wt%, preferably more than 97 wt%; and/or the presence of a gas in the gas,
the mol percent of the general formula (I) is 40-50 mol percent, and the mol percent of the general formula (II) is 1-10 mol percent; the mol percentage of the general formula (III) is 30-50 mol%, and the sum of the mol percentages of the general formulas (I) - (III) is less than or equal to 100mol%.
3. The bio-based transparent polyamide according to claim 1, wherein the raw material of the bio-based transparent polyamide comprises pentanediamine, bis (4-amino-3-methylcyclohexyl) methane (MACM) or bis (4-aminocyclohexyl) methane (PACM), isophthalic acid and/or derivatives thereof; and/or the presence of a gas in the gas,
the sum of the mole numbers of the pentamethylene diamine, the bis (4-amino-3-methyl cyclohexyl) methane (MACM) or the bis (4-amino cyclohexyl) methane (PACM) and the mole number ratio of the isophthalic acid and/or the derivative thereof is 0.95-1.1: 1; and/or the presence of a gas in the atmosphere,
preferably, the feedstock comprises:
40-50 parts of pentamethylene diamine;
1-10 parts of bis (4-amino-3-methylcyclohexyl) methane (MACM) or bis (4-aminocyclohexyl) methane (PACM);
30-50 parts of isophthalic acid and/or derivatives thereof;
wherein all parts are calculated as mole parts;
preferably, the isophthalic acid derivative is selected from one or more of isophthalic chloride, dimethyl isophthalate and diethyl isophthalate.
4. The bio-based transparent polyamide according to claim 1, characterized in that the bio-based transparent polyamide further comprises structural units of the general formula (IV),
the general formula (IV) is
The ratio of the sum of the moles of the general formulae (I) and (II) to the sum of the moles of the general formulae (III) and (IV) is 0.95 to 1.1:1.
5. bio-based transparent polyamide according to claim 4, wherein the mass content of the compounds of the general formulae (I) to (IV) in the bio-based transparent polyamide is more than 95 wt.%, preferably more than 97 wt.%; and/or the presence of a gas in the gas,
the mol percent of the general formula (I) is 40-50 mol percent, and the mol percent of the general formula (II) is 1-10 mol percent; the mol percent of the general formula (III) is 30-50 mol percent, the mol percent of the general formula (IV) is 5-30 mol percent, and the sum of the mol percent of the general formulas (I) - (IV) is less than or equal to 100mol percent.
6. The bio-based transparent polyamide according to claim 4, wherein the raw material of the bio-based transparent polyamide comprises pentanediamine, bis (4-amino-3-methylcyclohexyl) methane (MACM) or bis (4-aminocyclohexyl) methane (PACM), isophthalic acid and/or derivatives thereof, terephthalic acid and/or derivatives thereof; and/or the presence of a gas in the gas,
the ratio of the sum of the mole numbers of the pentamethylene diamine, the bis (4-amino-3-methylcyclohexyl) methane (MACM) or the bis (4-aminocyclohexyl) methane (PACM) to the mole numbers of the isophthalic acid and/or the derivative thereof and the terephthalic acid and/or the derivative thereof is 0.95-1.1: 1; and/or the presence of a gas in the gas,
preferably, the feedstock comprises:
40-50 parts of pentamethylene diamine;
1-10 parts of bis (4-amino-3-methylcyclohexyl) methane (MACM) or bis (4-aminocyclohexyl) methane (PACM);
30-50 parts of isophthalic acid and/or derivatives thereof;
5-30 parts of terephthalic acid and/or derivatives thereof;
wherein all parts are calculated as mole parts;
preferably, the isophthalic acid derivative is selected from one or more of isophthalic chloride, dimethyl isophthalate and diethyl isophthalate; the terephthalic acid derivative is one or more selected from terephthalic acid chloride, dimethyl terephthalate and diethyl terephthalate.
7. The bio-based transparent polyamide according to any one of claims 1 to 6, wherein the bio-based transparent polyamide has at least one of the following properties,
the number average molecular weight of the bio-based transparent polyamide is 10000-50000; and/or the presence of a gas in the gas,
the relative viscosity of the bio-based transparent polyamide is 1.60-3.0, preferably 1.7-2.5; and/or the presence of a gas in the atmosphere,
the glass transition temperature of the bio-based transparent polyamide is more than 135 ℃; and/or the presence of a gas in the atmosphere,
the tensile strength of the bio-based transparent polyamide is more than 90 MPa; and/or the presence of a gas in the gas,
the bending strength of the bio-based transparent polyamide is more than 140 MPa; and/or the presence of a gas in the gas,
the IZOD notch impact strength of the bio-based transparent polyamide is 9KJ/m 2 The above; and/or the presence of a gas in the gas,
the haze of the bio-based transparent polyamide is 6.0% or less, preferably 4.5% or less; and/or the presence of a gas in the atmosphere,
the light transmittance of the bio-based transparent polyamide is 85% or more, and more preferably 90% or more.
8. The bio-based transparent polyamide according to any one of claims 1 to 6, characterized in that the bio-based transparent polyamide further comprises additives comprising end-capping agents, UV stabilizers, heat stabilizers, radical scavengers and/or processing aids, impurity inhibitors, lubricants, mold release aids, plasticizers, functional additives for influencing optical properties, in particular refractive index, impact modifiers, nanofillers and/or additives, gloss enhancers, dyes or mixtures thereof; and/or the presence of a gas in the gas,
the mass content of the additive in the bio-based transparent polyamide is 0-10 wt%.
9. A process for the preparation of a bio-based transparent polyamide according to any one of claims 1 to 6, characterized in that it comprises the following steps: mixing the raw materials with water to prepare a polyamide salt solution; controlling the system pressure to be 1.2-2.2 Mpa, raising the temperature of the polyamide salt solution to 210-300 ℃, stirring and reacting for 2-4 hours, reducing the system pressure to atmospheric pressure within 0.2-1.5 hours, vacuumizing, continuing to react for 0.2-2 hours under the conditions that the vacuum degree is (-0.07) to (-0.09) Mpa and the temperature is 240-280 ℃, melting and discharging, and cooling to obtain the bio-based transparent polyamide;
the raw material at least contains pentanediamine, bis (4-amino-3-methylcyclohexyl) methane (MACM) or bis (4-aminocyclohexyl) methane (PACM), isophthalic acid and/or derivatives thereof; alternatively, the first and second liquid crystal display panels may be,
the feedstock also contains terephthalic acid and/or derivatives thereof.
10. The method for producing bio-based transparent polyamide as claimed in claim 9, wherein the pH of the polyamide salt solution is adjusted using pentanediamine so that the pH value of the polyamide salt solution is 7.5 to 9.5 at a concentration of 10%;
and/or the concentration of the polyamide salt solution is 40-85%.
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| CN108203507A (en) * | 2016-12-16 | 2018-06-26 | Ems 专利股份公司 | Transparent polyamide molding compositions with high break-draw strain |
| CN113015759A (en) * | 2018-10-03 | 2021-06-22 | 阿科玛法国公司 | Improved process for producing transparent polyamides |
| CN113214472A (en) * | 2020-01-21 | 2021-08-06 | 上海凯赛生物技术股份有限公司 | Low-water-absorption high-toughness polyamide copolymer 513TI and preparation method thereof |
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|---|---|---|---|---|
| US4345066A (en) * | 1979-09-12 | 1982-08-17 | Chemische Werke Huls Ag | Transparent copolyamides and their application to transparent, impact resistant molded articles |
| CN108203507A (en) * | 2016-12-16 | 2018-06-26 | Ems 专利股份公司 | Transparent polyamide molding compositions with high break-draw strain |
| CN113015759A (en) * | 2018-10-03 | 2021-06-22 | 阿科玛法国公司 | Improved process for producing transparent polyamides |
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