CN111303407B - Transparent polyamide and process for producing the same - Google Patents
Transparent polyamide and process for producing the same Download PDFInfo
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- CN111303407B CN111303407B CN201811509991.0A CN201811509991A CN111303407B CN 111303407 B CN111303407 B CN 111303407B CN 201811509991 A CN201811509991 A CN 201811509991A CN 111303407 B CN111303407 B CN 111303407B
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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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/32—Phosphorus-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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Abstract
The invention discloses transparent polyamide, which comprises the following monomer raw materials: long chain dibasic acid or mixed long chain dibasic acid: 100 parts of pentamethylene diamine: 20-70 parts of alicyclic-containing diamine: 80-30 parts of a solvent; the molecular formula of the long-chain dibasic acid is as follows: HOOC-R1-COOH; r1 includes: (CH2) n, n being 7, 9, 11, 13 or 15; alicyclic ring-containing diamines include: 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane (MACM), 4' -diaminodicyclohexylmethane (PACM), and 2, 2-bis (4-aminocyclohexane) propane (PACP). The transparent polyamide of the invention has proper hydrogen bond density and lower crystallization degree, thereby achieving better toughness and better transparency.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to transparent polyamide containing long-chain dibasic acid with odd carbon number and a preparation method thereof.
Background
The polyamide has excellent mechanical properties and forming properties, and is widely applied to processing of parts of automobile parts and electrical and electronic equipment. 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 of the traditional transparent plastic, the requirements of specific use scenes cannot be completely met, for example, the main transparent plastics PC (polycarbonate) and PMMA (polymethyl methacrylate) in the market have the problems of small molecule residue, poor chemical corrosion resistance, poor wear resistance and the like.
In the prior art, the synthesis of transparent polyamide mainly uses dibasic acid with even number carbon as main material, such as transparent polyamide with TR55 and TR90 of EMS company, the used dibasic acid is C12 dibasic acid, polyamide with G350 and G830 of Arkema company uses C14 and C10 dibasic acid respectively, polyamide with T40 of Bayer company and polyamide with KR4601 of BASF uses C6 dibasic acid; the amine monomer used is essentially an even-numbered hexamethylenediamine or p-phenylenediamine, in addition to the cyclic aliphatic amine containing pendant groups. According to the structure of polyamide, even-numbered dibasic acid and diamine can ensure the formation of more hydrogen bonds, namely, the formation of larger intermolecular hydrogen bond density, but the toughness, touch and size of the material cannot meet the requirements in certain specific application fields.
Disclosure of Invention
In order to overcome the defects of the transparent polyamide in the prior art, the invention provides a novel transparent polyamide, and the transparent polyamide has proper hydrogen bond density and lower crystallization degree, so that better toughness and better transparency are achieved.
One of the objects of the present invention is to provide a transparent polyamide, wherein the monomer raw materials for preparing the transparent polyamide comprise:
long chain dibasic acid or mixed long chain dibasic acid: 100 parts of (a) a water-soluble polymer,
pentanediamine: 20 to 70 parts of (A) a water-soluble polymer,
alicyclic group-containing diamine: 80-30 parts of a solvent; the parts are mole parts;
wherein the molecular formula of the long-chain dibasic acid is as follows: HOOC-R1-COOH; r1 includes: (CH2) n, n being 7, 9, 11, 13 or 15;
the alicyclic group-containing diamine includes: 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane (MACM), 4' -diaminodicyclohexylmethane (PACM), and 2, 2-bis (4-aminocyclohexane) propane (PACP).
In a preferred technical scheme of the invention, the mole parts of the pentanediamine, the diamine containing alicyclic ring and the long-chain dibasic acid or the mixed long-chain dibasic acid are preferably (30-60): (70-40): 100.
in a preferred embodiment of the present invention, the ratio of the sum of the moles of the pentamethylene diamine and the alicyclic diamine to the moles of the long-chain dibasic acid or the mixed long-chain dibasic acid is: (1-1.05): 1.
the inventor finds out through a great deal of research that: the preparation of the transparent polyamide can be carried out from the following points of view. First, since polyamide molecules contain many polar amide groups and hydrogen bonds are easily formed to improve the crystallization ability, it is necessary to reduce the crystallinity during the polymerization process to obtain an amorphous transparent polyamide. Secondly, the polyamide generates a spherulite structure in the crystallization process, and when the spherulite structure grows to a diameter exceeding the wavelength of visible light, the visible light cannot penetrate through the crystal, so that the polyamide is opaque, and therefore measures are needed to reduce the size of a crystal area of the polyamide to be lower than the wavelength range of the visible light. In the scheme, due to the irregular distribution of amino and carbonyl in the plane structure of the pentanediamine and the long-chain dibasic acid with odd carbon number, the crystal regularity is further reduced, and a better transparent effect is obtained.
A second object of the present invention is a process for the preparation of a transparent polyamide, said process comprising the steps of:
(1) the following raw material monomers were mixed to prepare a polyamide salt solution:
long chain dibasic acid or mixed long chain dibasic acid: 100 parts of (a) a water-soluble polymer,
pentanediamine: 20 to 70 parts of (A) a water-soluble polymer,
alicyclic group-containing diamine: 80-30 parts of a solvent;
wherein the molecular formula of the long-chain dibasic acid is as follows: HOOC-R1-COOH; r1 includes: (CH2) n, n being 7, 9, 11, 13 or 15;
the alicyclic group-containing diamine includes: one or more of 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane (MACM), 4' -diaminodicyclohexylmethane (PACM), and 2, 2-bis (4-aminocyclohexane) propane (PACP);
the parts are mole parts;
(2) heating the polyamide salt solution to raise the pressure in the reaction system to 0.3-2.2MPa, exhausting, maintaining the pressure for 2-5 h, wherein the temperature of the reaction system is 232-265 ℃ when the pressure maintaining is finished, reducing the pressure in the reaction system to 0-0.2MPa (gauge pressure) and the temperature of the reaction system is 230-270 ℃ after the pressure reducing is finished; vacuumizing to ensure that the vacuum degree is between-0.02 and-0.1 MPa, and the vacuumizing time is 20 to 60min to obtain a melt;
(3) drawing a strand and cutting into granules to obtain the polyamide resin.
In a preferred embodiment of the present invention, in the step (1), the ratio of the sum of the number of moles of the pentamethylenediamine and the alicyclic group-containing diamine to the number of moles of the long-chain dibasic acid or the mixed long-chain dibasic acid is: (1-1.05): 1.
in a preferred embodiment of the present invention, in the step (1), the preparation of the polyamide salt solution is performed under inert gas conditions; the inert gas comprises: nitrogen, argon or helium.
In a preferred embodiment of the present invention, in the step (1), the concentration of the polyamide salt solution is 40 to 75% by mass.
In a preferred embodiment of the invention, in step (1), the pH of the solution of polyamide salt at a concentration of 10% by weight is from 7.0 to 8.2.
According to a preferable technical scheme of the invention, in the step (2), the reaction system is heated, and the pressure in the reaction system is increased to 0.3-2.2MPa within 1-2 hours.
In a preferable technical scheme of the invention, in the step (2), the pressure is reduced, and the pressure in the reaction system is reduced to 0-0.2MPa (gauge pressure) within 40min-2 h.
In a preferred technical scheme of the invention, before the vacuumizing in the step (2), a crystallization promoter is added. The crystallization accelerator is one or more of calcium salt, magnesium salt and zinc salt of long carbon chain carboxylic acid of C10-30. The addition amount of the crystallization promoter is 0.001-0.3 part, and the parts are mole parts.
The crystallization promoter is added in the form of a suspension; the concentration of the suspension may be 2-10%, for example: 3%, 4%, 5%, 6%, 7%, 8%, 9%, the percentages being mass percentages.
In a preferred embodiment of the present invention, a thermal stabilizer is added before the heating in step (2). The heat stabilizer includes: 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. The addition amount of the heat stabilizer is 0.001-0.3 part, and the parts are mole parts.
In a preferred technical scheme of the invention, the relative viscosity of the transparent polyamide is 1.0-3.5.
The invention takes pentanediamine, long-chain dibasic acid with odd carbon number or the mixture thereof and diamine containing alicyclic ring as monomer raw materials, and utilizes the characteristic that functional groups such as carbonyl, amino and the like with odd carbon chain in the formed polymer are distributed more unevenly than those with even carbon chain to prepare the transparent polyamide. The polyamide prepared by the invention has unchanged or even enhanced mechanical property while ensuring high transparency, and can further improve the anti-falling performance and visibility of the material in some special application fields such as lenses, spectacle frames, wind shields, dial cover plates, helmet plastic baffles and the like. The preparation method of the polyamide is simple, the process parameters are easy to control, large instruments are not needed for assistance, 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 clearer, 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.
1. Method for detecting relative viscosity eta r
Concentrated sulfuric acid method with Ubbelohde viscometer: the dried polyamide sample was weighed accurately at 0.5. + -. 0.0002g, dissolved by adding 50mL of concentrated sulfuric acid (98%), and the concentrated sulfuric acid flow time t0 and the polyamide solution flow time t were measured and recorded in a thermostatic water bath at 25 ℃.
Relative viscosity calculation formula:
relative viscosity eta r t/t0
Wherein: t: the time of solution flow; t 0: the solvent was run through time.
2. Mechanical property testing method
2.1 bending test reference standard ISO-178, test conditions: 2 mm/min;
2.2 tensile test reference standard ISO-572-2, test conditions: 50 mm/min;
2.3 the impact test is a notched izod impact reference test standard ISO-180/1a, test conditions: 23 ℃;
3. the light transmittance and haze test is carried out according to the national standard: GB-T2410-2008.
Example 1
(1) Under the condition of nitrogen, 1, 5-pentanediamine (DN5), MACM, undecanedioic acid (DC11) and water are mixed uniformly, wherein the molar ratio of DN 5: MACM: DC11 ═ 20: 80: 100, preparing a 60% salt solution of polyamide, wherein the salt weighs 20 kg; adding 1, 5-pentanediamine to adjust the pH value of the salt solution to 7.80 when the salt solution is diluted to 10 wt.%, and adding a stabilizer potassium hypophosphite with the addition of 0.015 mol part;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.6Mpa, taking 1 hour and 20 minutes, exhausting, maintaining the pressure, keeping the pressure for 4 hours, reducing the temperature of the reaction system to 240 ℃ when the pressure is maintained, reducing the pressure in the reaction system to 0.01Mpa (gauge pressure) when the pressure is reduced for 50min, and keeping the temperature of the reaction system to 263 ℃ after the pressure is reduced;
(3) preparing 5% suspension of crystallization accelerator zinc dodecyl sulfate (the addition amount is 0.01 mol fraction), adding into a reaction kettle through a feed inlet, vacuumizing and maintaining at-0.08 Mpa for 30min, wherein the temperature after vacuumizing is 271 ℃, and obtaining polyamide transparent polyamide melt;
(4) and melting, discharging, drawing strips and cutting into granules to obtain the polyamide transparent polyamide resin.
Example 2
(1) Under the condition of nitrogen, 1, 5-pentanediamine (DN5), MACM, undecanedioic acid (DC11) and water are mixed uniformly, wherein the molar ratio of DN 5: MACM: DC11 ═ 40: 60: 100, preparing a 60% salt solution of polyamide, wherein the salt weighs 20 kg; adding 1, 5-pentanediamine to adjust the pH value of the salt solution to 7.80 when the salt solution is diluted to 10 wt.%, and adding a stabilizer potassium hypophosphite with the addition of 0.015 mol part;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.6Mpa, taking 1 hour and 20 minutes, exhausting, maintaining the pressure, keeping the pressure for 4 hours, reducing the temperature of the reaction system to 240 ℃ when the pressure is maintained, reducing the pressure in the reaction system to 0.01Mpa (gauge pressure) when the pressure is reduced for 50min, and keeping the temperature of the reaction system to 263 ℃ after the pressure is reduced;
(3) preparing 5% suspension of crystallization accelerator zinc dodecyl sulfate (the addition amount is 0.01 mol fraction), adding into a reaction kettle through a feed inlet, vacuumizing and maintaining at-0.08 Mpa for 30min, wherein the temperature after vacuumizing is 271 ℃, and obtaining polyamide transparent polyamide melt;
(4) and melting, discharging, drawing strips and cutting into granules to obtain the polyamide transparent polyamide resin.
Example 3
(1) Under the condition of nitrogen, 1, 5-pentanediamine (DN5), MACM, undecanedioic acid (DC11) and water are mixed uniformly, wherein the molar ratio of DN 5: MACM: DC11 ═ 50: 50: 100, preparing a 60% salt solution of polyamide, wherein the salt weighs 20 kg; then adding 1, 5-pentanediamine to adjust the pH value of the salt solution to 7.85 when the salt solution is diluted to 10 wt.%, and adding 0.015 mol part of potassium hypophosphite as a stabilizer;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.6Mpa, taking 1 hour and 20 minutes, exhausting, maintaining the pressure, keeping the pressure for 4 hours, reducing the temperature of the reaction system to 240 ℃ when the pressure is maintained, reducing the pressure in the reaction system to 0.01Mpa (gauge pressure) when the pressure is reduced for 50min, and keeping the temperature of the reaction system to 263 ℃ after the pressure is reduced;
(3) preparing 5% suspension of crystallization accelerator zinc dodecyl sulfate (the addition amount is 0.01 mol fraction), adding into a reaction kettle through a feed inlet, vacuumizing and maintaining at-0.08 Mpa for 30min, wherein the temperature after vacuumizing is 271 ℃, and obtaining polyamide transparent polyamide melt;
(4) and melting, discharging, drawing strips and cutting into granules to obtain the polyamide transparent polyamide resin.
Example 3A
(1) Under the condition of nitrogen, 1, 5-pentanediamine (DN5), MACM, undecanedioic acid (DC11) and water are mixed uniformly, wherein the molar ratio of DN 5: MACM: DC11 ═ 50: 50: 100, preparing a 60% salt solution of polyamide, wherein the salt weighs 20 kg; then adding 1, 5-pentanediamine to adjust the pH value of the salt solution to 7.85 when the salt solution is diluted to 10 wt.%, and adding 0.015 mol part of potassium hypophosphite as a stabilizer;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.6Mpa, taking 1 hour and 20 minutes, exhausting, maintaining the pressure, keeping the pressure for 4 hours, reducing the temperature of the reaction system to 240 ℃ when the pressure is maintained, reducing the pressure in the reaction system to 0.01Mpa (gauge pressure) when the pressure is reduced for 50min, and keeping the temperature of the reaction system to 263 ℃ after the pressure is reduced;
(3) vacuumizing at-0.08 Mpa for 30min at 271 deg.C to obtain transparent polyamide melt;
(4) and melting, discharging, drawing strips and cutting into granules to obtain the polyamide transparent polyamide resin.
Example 3B
(1) Under the condition of nitrogen, 1, 5-pentanediamine (DN5), MACM, undecanedioic acid (DC11) and water are mixed uniformly, wherein the molar ratio of DN 5: MACM: DC11 ═ 50: 50: 100, preparing a 60% salt solution of polyamide, wherein the salt weighs 20 kg; then adding 1, 5-pentanediamine to adjust the pH value of the salt solution, so that the pH value is 7.85 when the salt solution is diluted to 10 wt.%;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.6Mpa, taking 1 hour and 20 minutes, exhausting, maintaining the pressure, keeping the pressure for 4 hours, reducing the temperature of the reaction system to 240 ℃ when the pressure is maintained, reducing the pressure in the reaction system to 0.01Mpa (gauge pressure) when the pressure is reduced for 50min, and keeping the temperature of the reaction system to 263 ℃ after the pressure is reduced;
(3) preparing 5% suspension of crystallization accelerator zinc dodecyl sulfate (the addition amount is 0.01 mol fraction), adding into a reaction kettle through a feed inlet, vacuumizing and maintaining at-0.08 Mpa for 30min, wherein the temperature after vacuumizing is 271 ℃, and obtaining polyamide transparent polyamide melt;
(4) and melting, discharging, drawing strips and cutting into granules to obtain the polyamide transparent polyamide resin.
Example 3C
(1) Under the condition of nitrogen, 1, 5-pentanediamine (DN5), MACM, undecanedioic acid (DC11) and water are mixed uniformly, wherein the molar ratio of DN 5: MACM: DC11 ═ 50: 50: 100, preparing a 60% salt solution of polyamide, wherein the salt weighs 20 kg; then adding 1, 5-pentanediamine to adjust the pH value of the salt solution, so that the pH value is 7.85 when the salt solution is diluted to 10 wt.%;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.6Mpa, taking 1 hour and 20 minutes, exhausting, maintaining the pressure, keeping the pressure for 4 hours, reducing the temperature of the reaction system to 240 ℃ when the pressure is maintained, reducing the pressure in the reaction system to 0.01Mpa (gauge pressure) when the pressure is reduced for 50min, and keeping the temperature of the reaction system to 263 ℃ after the pressure is reduced;
(3) vacuumizing at-0.08 Mpa for 30min at 271 deg.C to obtain transparent polyamide melt;
(4) and melting, discharging, drawing strips and cutting into granules to obtain the polyamide transparent polyamide resin.
Example 4
(1) Under the condition of nitrogen, 1, 5-pentanediamine (DN5), MACM, tridecyl dibasic acid (DC13) and water are uniformly mixed, wherein the molar ratio of DN 5: MACM: DC13 ═ 40: 60: 100, preparing a 60% salt solution of polyamide, wherein the salt weighs 20 kg; adding 1, 5-pentanediamine to adjust the pH value of the salt solution to 7.90 when the salt solution is diluted to 10 wt.%, and adding a stabilizer sodium hypophosphite with the addition of 0.015 mol part;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.7Mpa, taking 1 hour and 30 minutes, exhausting, maintaining the pressure, keeping the pressure for 4 hours, reducing the temperature of the reaction system to 240 ℃ when the pressure is maintained, reducing the pressure in the reaction system to 0.01Mpa (gauge pressure) when the pressure is reduced for 60 minutes, and controlling the temperature of the reaction system to 265 ℃ after the pressure is reduced;
(3) preparing a crystallization promoter magnesium dodecyl sulfate (the addition amount is 0.015 mol part) into 5 percent of suspension, adding the suspension into a reaction kettle through a charging hole, vacuumizing and maintaining the pressure at-0.08 MPa for 35min, and obtaining the transparent polyamide melt at the temperature of 270 ℃ after vacuum;
(4) and melting, discharging, drawing strips and cutting into granules to obtain the polyamide transparent polyamide resin.
Comparative example 1
(1) Under the condition of nitrogen, MACM, undecanedioic acid (DC11) and water are mixed uniformly, wherein the molar ratio of MACM: DC11 ═ 100: 100, preparing a 60% salt solution of polyamide, wherein the salt weighs 20 kg; adding MACM to adjust the pH value of the salt solution to be 7.92 when the salt solution is diluted to 10 wt.%, and adding 0.015 mol part of stabilizer potassium hypophosphite;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.7Mpa, taking 1 hour and 30 minutes, exhausting, maintaining the pressure, keeping the pressure for 4 hours, keeping the temperature of the reaction system at 245 ℃ when the pressure is finished, reducing the pressure in the reaction system to 0.01Mpa (gauge pressure) when the pressure is reduced for 65min, and keeping the temperature of the reaction system at 265 ℃ after the pressure is reduced;
(3) preparing a crystallization accelerator zinc octadecyl alkyl (the addition amount is 0.01 mol part) into 5 percent suspension, adding the suspension into a reaction kettle through a charging hole, vacuumizing and maintaining the pressure at-0.08 MPa for 35min, wherein the temperature after vacuumizing is 272 ℃, and obtaining a polyamide transparent polyamide melt;
(4) and melting, discharging, drawing strips and cutting into granules to obtain the polyamide transparent polyamide resin.
Comparative example 2
(1) Uniformly mixing dodecanedioic acid (DC12), MACM and water under the condition of nitrogen, wherein the molar ratio of MACM: DC12 ═ 100: 100, preparing a 60% salt solution of polyamide, wherein the salt weighs 20 kg; adding MACM to adjust the pH value of the salt solution to be 7.95 when the salt solution is diluted to 10 wt.%, and adding a stabilizer sodium hypophosphite with the addition of 0.015 mol part;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.7Mpa, taking 1 hour and 25 minutes, exhausting, maintaining the pressure, keeping the pressure for 4 hours, reducing the pressure in the reaction system to 0.01Mpa (gauge pressure) at the temperature of 245 ℃ after the pressure maintaining is finished, taking 65 minutes for pressure reduction, and keeping the temperature of the reaction system at 267 ℃ after the pressure reduction is finished;
(3) preparing 5% suspension of crystallization accelerator calcium octadecyl alkyl (the addition amount is 0.01 mol part) into a reaction kettle through a charging hole, vacuumizing and maintaining the pressure at-0.08 Mpa for 34min, wherein the temperature after vacuum is 272 ℃, and obtaining a polyamide transparent polyamide melt;
(4) and melting, discharging, drawing strips and cutting into granules to obtain the polyamide transparent polyamide resin.
Comparative example 3
(1) Under the condition of nitrogen, 1, 5-pentanediamine (DN5), MACM, dodecanedioic acid (DC12) and water are uniformly mixed, wherein the molar ratio of DN 5: MACM: DC12 ═ 40: 60: 100, preparing a 60% salt solution of polyamide, wherein the salt weighs 20 kg; adding 1, 5-pentanediamine to adjust the pH value of the salt solution to 7.80 when the salt solution is diluted to 10 wt.%, and adding a stabilizer potassium hypophosphite with the addition of 0.015 mol part;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.6Mpa, taking 1 hour and 20 minutes, exhausting, maintaining the pressure, keeping the pressure for 4 hours, reducing the temperature of the reaction system to 240 ℃ when the pressure is maintained, reducing the pressure in the reaction system to 0.01Mpa (gauge pressure) when the pressure is reduced for 50min, and keeping the temperature of the reaction system to 263 ℃ after the pressure is reduced;
(3) preparing 5% suspension of crystallization accelerator zinc dodecyl sulfate (the addition amount is 0.01 mol fraction), adding the suspension into a reaction kettle through a charging hole, vacuumizing and maintaining the pressure at-0.08 MPa for 30min, wherein the temperature after vacuumizing is 271 ℃, and obtaining a polyamide transparent polyamide melt;
(4) and melting, discharging, drawing strips and cutting into granules to obtain the polyamide transparent polyamide resin.
Comparative example 4
(1) Under the condition of nitrogen, 1, 5-pentanediamine (DN5), MACM, tetradecanedioic acid (DC14) and water are uniformly mixed, wherein the molar ratio of DN 5: MACM: DC14 ═ 40: 60: 100, preparing a 60% salt solution of polyamide, wherein the salt weighs 20 kg; adding 1, 5-pentanediamine to adjust the pH value of the salt solution to 7.90 when the salt solution is diluted to 10 wt.%, and adding a stabilizer sodium hypophosphite with the addition of 0.015 mol part;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.7Mpa, taking 1 hour and 30 minutes, exhausting, maintaining the pressure, keeping the pressure for 4 hours, reducing the temperature of the reaction system to 240 ℃ when the pressure is maintained, reducing the pressure in the reaction system to 0.01Mpa (gauge pressure) when the pressure is reduced for 60 minutes, and controlling the temperature of the reaction system to 265 ℃ after the pressure is reduced;
(3) preparing a crystallization promoter magnesium dodecyl sulfate (the addition amount is 0.015 mol part) into 5 percent of suspension, adding the suspension into a reaction kettle through a charging hole, vacuumizing and maintaining the pressure at-0.08 MPa for 30min, and obtaining the transparent polyamide melt at the temperature of 270 ℃ after vacuum;
(4) and melting, discharging, drawing strips and cutting into granules to obtain the polyamide transparent polyamide resin.
Carrying out relative viscosity test, light transmittance test and haze test on the prepared transparent polyamide, and testing the tensile, bending and impact properties of the resin by using an electronic universal Tester (TA); the results are shown in Table 1.
TABLE 1
As can be seen from Table 1:
1. as can be seen from comparative examples 1 and 2, when transparent polyamide products synthesized by two dibasic acids DC11 and DC12 are independently compared under the synergistic effect of no pentanediamine, under the condition of similar viscosity, a sample synthesized by DC11 has higher light transmittance and lower haze, the transparency is excellent, the tensile strength and the bending strength are similar, and the notch impact strength DC11 is superior to that of DC 12. In conclusion, the polyamide obtained by polymerizing the monomer of the odd-carbon DC11 has better performance, because the polyamide obtained by polymerizing the monomer of the odd-carbon long-chain dibasic acid has poorer intermolecular regularity of an amide group, thereby reducing the crystallinity and the size of crystal grains to achieve better transparent effect.
2. From a comparison of example 2 and comparative example 3, and example 4 and comparative example 4, it can be seen that: in the presence of pentanediamine and MACM with the same content, polyamide obtained by polymerizing long-chain dibasic acid with odd carbon as a monomer has higher light transmittance, lower haze and excellent transparency; meanwhile, the impact resistance of polyamide obtained by polymerizing the long-chain dibasic acid with odd carbon number as a monomer is superior to that of polyamide obtained by polymerizing the long-chain dibasic acid with even carbon number as a monomer, and other mechanical properties are similar.
3. By comparing example 1, example 2, example 3: it can be known that the polyamide has higher light transmittance and lower haze by controlling the proportion of the pentanediamine, the MACM and the long-chain dibasic acid with odd number carbon, and the light transmittance is as follows, in DN 5: MACM: molar ratio of DC11 (30-60): (70-40):100, the light transmittance and haze effects are outstanding; this is due to the fact that pentanediamine, MACM and long chain dibasic acids with odd numbers of carbons, as comonomers, further reduce the regularity of the polymer chain, thereby increasing transparency. A comparison of example 1, example 2, example 3 and comparative example 1 at the same time shows that: the tensile strength and the bending strength of the polyamide are enhanced by adding DN5, and the inventor believes that: this is because the polymer per unit mass has more amide groups after the addition of pentamethylenediamine, thereby increasing the mechanical properties.
4. From a comparison of example 3 and example 3A, it can be seen that: after the crystallization promoter is added, the light transmittance is improved, the haze is reduced, and simultaneously, the impact strength is improved, which shows that a trace amount of crystal regions exist in the polymer, the size of crystals is reduced by adding the crystallization promoter, so that the improvement of the transparency is promoted, and the toughness of the polymer is enhanced due to the reduction of the crystal size, so that the impact strength is improved.
From a comparison of example 3 and example 3B, it can be seen that: after the heat stabilizer is added, the light transmittance is increased, the haze is reduced, and the mechanical strength is improved. The thermal oxidative degradation of the polymer chain is reduced and the attenuation of the molecular weight of the polymer chain is reduced due to the addition of the stabilizer, so that the mechanical property of the polymer is improved, and meanwhile, the oxidative discoloration in the reaction process is reduced due to the existence of the heat stabilizer, so that the transparent property of the polymer is improved.
Compared with the examples 3A, 3B and 3C, the combination property of the two additives is the best in all aspects when the two additives are added simultaneously, and the two additives have no repulsive effect and have a more favorable additive effect on the performance of the polymer.
In summary, the transparent polyamide synthesized by the present invention has a novel structural composition and superior performance to the transparent polyamide synthesized by the conventional monomer, and the result is obvious.
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 the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A transparent polyamide is prepared from monomer raw materials comprising:
long chain dibasic acid or mixed long chain dibasic acid: 100 parts of (a) a water-soluble polymer,
pentanediamine: 20 to 70 parts of (A) a water-soluble polymer,
alicyclic group-containing diamine: 80-30 parts of a solvent; the parts are mole parts;
wherein the molecular formula of the long-chain dibasic acid is as follows: HOOC-R1-COOH; r1 is: (CH)2) n, n ═ 7, 9, 11, 13, or 15;
the alicyclic group-containing diamine is selected from: 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane (MACM), 4' -diaminodicyclohexylmethane (PACM), and 2, 2-bis (4-aminocyclohexane) propane (PACP).
2. The transparent polyamide according to claim 1, wherein: the mole parts of the pentanediamine, the diamine containing alicyclic ring and the long-chain binary acid or the mixed long-chain binary acid are preferably (30-60): 70-40): 100.
3. The transparent polyamide according to claim 1, wherein: the ratio of the sum of the mole numbers of the pentanediamine and the diamine containing the alicyclic ring to the mole number of the long-chain dibasic acid or the mixed long-chain dibasic acid is as follows: (1-1.05):1.
4. A process for the preparation of a transparent polyamide, said process comprising the steps of:
(1) the following raw material monomers were mixed to prepare a polyamide salt solution:
long chain dibasic acid or mixed long chain dibasic acid: 100 parts of (a) a water-soluble polymer,
pentanediamine: 20 to 70 parts of (A) a water-soluble polymer,
alicyclic group-containing diamine: 80-30 parts of a solvent; the parts are mole parts;
wherein the molecular formula of the long-chain dibasic acid is as follows: HOOC-R1-COOH; r1 is: (CH)2) n, n ═ 7, 9, 11, 13, or 15;
the alicyclic group-containing diamine is selected from: one or more of 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane (MACM), 4' -diaminodicyclohexylmethane (PACM), and 2, 2-bis (4-aminocyclohexane) propane (PACP);
(2) heating the polyamide salt solution to raise the pressure in the reaction system to 0.3-2.2Mpa, exhausting, maintaining the pressure for 2-5 h, wherein the temperature of the reaction system is 232-265 ℃ when the pressure maintaining is finished, and then reducing the pressure to reduce the pressure in the reaction system to 0-0.2Mpa, wherein the pressure is gauge pressure, and the temperature of the reaction system is 230-270 ℃ after the pressure reduction is finished; vacuumizing to ensure that the vacuum degree is between-0.02 and-0.1 MPa, and the vacuumizing time is 20 to 60min to obtain a melt;
(3) drawing a strand and cutting into granules to obtain the polyamide resin.
5. The method of claim 4, wherein: in the step (1), the ratio of the sum of the mole numbers of the pentamethylene diamine and the alicyclic diamine to the mole number of the long-chain dibasic acid or the mixed long-chain dibasic acid is as follows: (1-1.05):1.
6. The method of claim 4, wherein: in the step (2), heating is carried out, and the pressure in the reaction system is increased to 0.3-2.2MPa within 1-2 h;
and/or, in the step (2), reducing the pressure, and reducing the pressure in the reaction system to 0-0.2MPa within 40min-2h, wherein the pressure is gauge pressure.
7. The method of claim 4, wherein: and (3) adding a crystallization promoter before vacuumizing in the step (2).
8. The method of claim 7, wherein: the crystallization accelerator is one or more of C10-30 long carbon chain carboxylic acid calcium salt, magnesium salt and zinc salt; the addition amount of the crystallization promoter is 0.001-0.3 part, and the parts are mole parts.
9. The method of claim 4, wherein: adding a heat stabilizer before the heating in the step (2).
10. The method of claim 9, wherein: the heat stabilizer includes: 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; the addition amount of the heat stabilizer is 0.001-0.3 part, and the parts are mole parts.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103147152A (en) * | 2013-02-26 | 2013-06-12 | 上海凯赛生物技术研发中心有限公司 | Nylon fiber |
| WO2015076233A1 (en) * | 2013-11-19 | 2015-05-28 | 東レ株式会社 | Polyamide resin, polyamide resin pellets, and method for producing polyamide resin |
| CN104672444A (en) * | 2015-03-26 | 2015-06-03 | 金发科技股份有限公司 | Polyamide resin and polyamide composition formed by same |
| CN105949456A (en) * | 2016-05-09 | 2016-09-21 | 山东东辰工程塑料有限公司 | Transparent nylon and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103147152A (en) * | 2013-02-26 | 2013-06-12 | 上海凯赛生物技术研发中心有限公司 | Nylon fiber |
| WO2015076233A1 (en) * | 2013-11-19 | 2015-05-28 | 東レ株式会社 | Polyamide resin, polyamide resin pellets, and method for producing polyamide resin |
| CN104672444A (en) * | 2015-03-26 | 2015-06-03 | 金发科技股份有限公司 | Polyamide resin and polyamide composition formed by same |
| CN105949456A (en) * | 2016-05-09 | 2016-09-21 | 山东东辰工程塑料有限公司 | Transparent nylon and preparation method thereof |
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