TW201437260A - Process for the production of polyamides - Google Patents

Abstract

The invention relates to process for the production of a PA-MXDT/ZT polyamide comprising the following steps: (i) providing a solid MXDT/ZT salt, wherein MXD is meta-xylylenediamine, T is terephthalic acid, Z is a linear aliphatic diamine having from 2 to 12 carbon atoms and wherein the amount of Z is from 0 to 40 mole % with respect to the total of the amount of MXD and Z units in the polymer, (ii) solid state polymerizing the MXDT/ZT salt to obtain the polyamide, wherein the solid state polymerization is carried out at least partly under a diamine atmosphere. The invention further relates to a PA-MXDT/ZT polyamide, wherein the polymer has a glass transition temperature fulfilling the following relation: Tg > 226-475*Y, wherein Y is the weight ratio g/g of all CH2 groups in the polymer with respect to the total weight of the polyamide.

Description

Polyamide manufacturing method Field of invention

The present invention relates to a process for producing a PA-MXDT/ZT polyamine, wherein MXD is m-phenylenediamine, T is p-nonylphenol, and Z is a linear fat having from 2 to 12 carbon atoms. Group diamine. The invention further relates to a PA-MXDT/ZT polyamine.

Background of the invention

A method for producing an identical polyamine is known from US 2009/0012229 A1. US 2009/0012229 A1 describes a process in which an aqueous solution containing p-nonylphenol, isodecylphenol, hexamethylenediamine and an aromatic diamine is heated to a temperature in an autoclave under high pressure. Between 280 and 330 ° C, the prepolymer is then separated from the vapor and the prepolymer is passed into a polycondensation reaction zone and subjected to polycondensation. While one of the objectives of US 2009/0012229 A1 is to provide a semi-crystalline semi-aromatic copolyamine molding composition having a high glass transition temperature, a glass transition temperature (Tg) between 125 and 138 ° C is obtained. ) Still quite low. A higher Tg improves the barrier to gases. Another advantage of a higher Tg is that a small difference between the melting point and the glass transition temperature promotes the manufacture of the transparent material.

Summary of invention

It is an object of the present invention to provide a process for the manufacture of polyamido which provides a polyamine having a higher Tg value.

According to the invention, this object is achieved by the nature of claim 1.

Thus, according to the present invention, the process can be made into a polyamine having a glass transition temperature much higher than the glass transition temperature obtained by the known method for producing polyamine.

The first step of the method of the present invention is to provide a solid MXDT/ZT salt, wherein MXD is m-phenylenediamine, T is p-citric acid, and Z is a linear aliphatic diamine having from 2 to 12 carbon atoms. And wherein the amount of Z is from 0 to 40 mol% in terms of the total number of MXD and Z units in the polymer. The molar ratios of the MXDT units and the ZT units are in the range of 60/40 to 100/0. A solid MXDT/ZT salt can be made by any method known in the art, such as a process in which the MXDT/ZT salt is prepared from an aqueous solution of diamines MXD and Z.

In the context of "from x to y", where x and y are numerical values, such as "from 2 to 12 carbon atoms" and "from 0 to 40 mole %" are used herein to mean including the values x and y. Therefore, "from x to y" should be interpreted as "from x up to and including y".

The solid MXDT/ZT salt is preferably provided by a method wherein the MXDT/ZT salt is prepared by dispensing liquid diamines MXD and Z to a stirred powder of citric acid. One of the advantages of this method can be omitted from the solvent or The powder separates the step of forming the salt, so the cost of solvent treatment and recycling can be omitted, and energy costs can be saved. The salt obtained in step (i) is already a powder and therefore does not need to be crushed and ground as is the case with the salt made from the solution. This method can be carried out under very mild conditions. It is not necessary to operate under high pressure, or in an atmosphere of a heat-treating system, or in a spin-controlled diamine atmosphere. The process can be carried out using a nitrogen purge which accelerates the removal of water from the neutralization reaction, thereby reducing the risk of agglomeration of the reaction mixture.

The second step comprises a method of subjecting the MXDT/ZT salt to a direct solid state polymerization (also referred to herein as DSSP) to obtain the polyamine, wherein the solid state polymerization is carried out at least partially under a diamine atmosphere.

A diamine atmosphere can be obtained by adding a small amount of a diamine at the beginning or during the second step. Too high amounts of diamine should be avoided as it will result in a polymer having too low molecular weight due to high amine end group content. According to the present invention, the diamine atmosphere is provided to obtain a polymer having a concentration of an amine end group [NH ₂ ] and a concentration of a carboxylic acid end group [COOH], wherein the concentration [COOH]-[NH ₂ ] The difference was at most 150 meq/kg, and the concentrations of the end groups were measured by 1H-NMR as described below. A diamine atmosphere can also be provided by applying a separation column for separating water and diamine, allowing the diamines to return to the reaction vessel during the polymerization to a liquid form. Another way of providing a diamine atmosphere during at least a portion of the second step is to avoid, for example, the formation of the second step in the second step by a low nitrogen stream or by a vacuum applied at a low pressure. Escape of the amine. For small scale experiments, the reaction was carried out in a 0.05 ml reactor (which is typically made of aluminum), and the diamine atmosphere was obtained by evaporating a small amount of diamine from the salt and maintaining it. In the reactor (which is located in an inert atmosphere), the reactor is surrounded by a gas stream passing through the reactor by limiting the pore size in the reactor lid (typically from 0.02 to 0.1 mm and preferably About 0.05 mm) and the vaporized gas was removed. Preferably, such a reactor is a TGA or DSC crucible which is heated in a TGA, DSC or combined TGA/DSC apparatus.

The direct solid state polymerization in this second step can be divided into two sub-steps. In the first sub-step, the solid MXDT/ZT salt can be heated to a first condensation temperature (Tc1), thereby condensing the solid salt to produce a solid polyamido prepolymer wherein the Tc1 system is lower than The melting temperature of the salt (Tm-salt). If all of the salts are converted to a prepolymer, the first substep of the condensation reaction is considered complete, or nearly complete. In terms of complete conversion, it was found that the salt did not have residual melting. The DSC method and conditions as described above can be applied by DSC to verify that one of the melting peaks of the salt is not present.

In order to increase the molecular weight of the prepolymer, a second substep may be performed after the first substep, the second substep comprising a second condensation reaction temperature below the melting temperature of the polyamid prepolymer ( The solid polyamido prepolymer is condensed under Tc2) to produce a polyamido copolymer having a higher degree of polymerization.

These condensation reaction substeps can be carried out in any manner suitable for conventional DSSP processes, such as in a fixed bed reactor or a stirred bed reactor. The use of a stirred bed reactor, such as a rotating vessel or a mechanically agitated reactor wherein the solid MXDT/ZT salt and solid copolymer are stirred to produce and maintain a flowable powder, helps to achieve the following results: The polymer particulate material obtained by this method contributes to the formation of a non-sticky powder material. In the case of the second sub-step of the condensation reaction, a fixed bed can be a more economical alternative.

During the sub-steps of the condensation reaction, it is preferred to rinse with an inert gas to remove any water originally present in the MXDT/ZT salt and, more importantly, to remove water produced by the condensation reaction. Alternatively, a portion of the water vapor pressure is reduced by applying a vacuum, or a combination of inert gas flushing and a reduced pressure.

This method can be carried out, for example, as follows. Preparing the solid MXDT/ZT salt in a reactor or charging it into the reactor and heating to a predetermined temperature in the range of 100-200 ° C, preferably at about 130 ° C, to allow for the salt Any water removed by evaporation and carried away by the flushing gas while maintaining the temperature of the reactor wall and internal device at or above the same temperature to avoid significant condensation reactions on the surfaces, It is preferred to treat the solid MXDT/ZT salt in stages at the predetermined temperature as long as it is necessary to remove the water in the salt. It can be checked, for example, by a water collector. Once the water removal is complete, or nearly complete, the solid MXDT/ZT salt is heated to a predetermined point equal to Tc1. The first condensation reaction substep can be traced by the rate of formation of the condensate, which begins slowly and then increases with increasing temperature. The prepolymer is typically discharged until the condensate collection rate drops significantly. DSC can also be used to check the degree of completion of the conversion of the salt by the absence of residual melting enthalpy which indicates the melting peak of the salt. In the sub-step of the second condensation reaction, the solid prepolymer formed can be maintained at the same temperature, that is, Tc2 is equal to Tc1, or can be equal to Tc2 and higher than Tc1, but lower than Melting of the polyamine produced in the first substep Heating at a predetermined point of temperature. The polyamine is maintained at this temperature until the desired degree of polymerization is obtained. Once the polymerization is complete, the polymer is cooled and discharged from the reactor.

Instead of using the separate substeps, the method can also be carried out by using a temperature gradient that gradually increases to Tc1 and from Tc1 to Tc2. This heating step can be carried out by using a temperature rise. The heating and cooling steps can be accomplished by heating the inert gas for rinsing, or by heating the reactor walls or their internal devices, or any combination thereof.

The heating and cooling steps can be accomplished by heating the inert gas for rinsing, or by heating the reactor walls or their internal devices, or any combination thereof.

This step (i), in which the solid MXDT/ZT salt is provided, is a process in which the MXDT/ZT salt is prepared by dispensing liquid diamines MXD and Z to a stirred powder containing p-citric acid. Within the process, as is the condition of the agitated powder, the salt preparation (and the second step (ii)) in a stirred powder is typically in the absence of a liquid reaction medium, any solvent or dispersant. get on. It is an inherent condition of the temperature of the ingredient above the melting temperature of the diamine. Step (i) is also carried out in the absence of a low temperature coolant. It does not exclude the following: Liquid components may be added or formed during the course of the process.

During the preparation of the salt, a small amount of water may also be present in the starting materials or to be formed during the compounding step. A small amount of water does not pose a problem as long as a loose and flowable powder can be maintained. The water can be removed later during the heating in the first DSSP step.

As provided in step (i) and used in step (ii) of the solid The MXDT/ZT salt can comprise, for example, about 5% by weight water and still maintain the formation of a flowable solid powder material. The MXDT/ZT salt preferably comprises up to 2.5% by weight water, more preferably up to 1% by weight or even more preferably up to 0.5% by weight water, wherein the weight % (by weight) is relative to the total weight of the salt comprising the water . Within this DSSP process, water must be removed anyway because water will form within the polycondensation reaction.

In the salt preparation step, the diamines are dispensed at a compounding temperature above the melting temperature of the diamine mixture and below the melting temperature at which the salt and any intermediates thereof are formed.

For the preparation of the salt, the temperature of the ingredient is preferably at least 40 ° C, more preferably at least 60 ° C below the melting temperature (Tm - salt) of the salt. By using a compounding temperature that is further below the Tm-salt, the occurrence of premature reaction of the diamine and citric acid can be reduced.

The temperature of the ingredients is also preferably between 35 and 200 °C.

By using a lower ingredient temperature, the problem that the released gaseous water is condensed at the cold spot and the powder peels off at such cold spots can be reduced.

The diamine is dispensed to the stirred powder to form a powdered reaction mixture while retaining the form of agitated powder. Therefore, in the stirred powder, the diamine is preferably not added and mixed with the dicarboxylic acid because it is not in the form of a stirring powder, and also causes agglomeration and non-wetting of the wetted portion. Partial incomplete neutralization reaction. It can be severely complicated and even inhibits the proper mixing of the reaction components. It is preferred to limit the rate of the ingredients to prevent local accumulation of liquid diamine, thereby preventing excessive wetting, local overheating and premature reaction with water release (which can cause excessive adhesion and cause the bed to Mobile complexity).

Preferably, the diamine is partitioned at an average compounding rate of: 0.05 mole % diamine per minute (mppm) (which is equivalent to 33.3 hours of total ingredient time) and 5 mole % (20 minutes) of diamine per minute. Between (mppm), preferably between 0.1 mppm (16.7 hours) and 4 mppm (25 minutes), such as between 0.2 mppm (8.35 hours) and 2 mppm (50 minutes), or between 0.25 mppm (6.7 hours) Between 1 mppm (100 minutes), wherein the mole % of the diamine is relative to the molar amount of the dicarboxylic acid. The time between brackets indicates the corresponding ingredient time.

Long dosing times and low dosing rates can be used separately and have no significant effect on the salt preparation itself, and can allow more time for the diamines to react with the p-quinone acid without causing the acid or solid The MXDT/ZT salt produces softening or melting, but it gives the process a low solubility.

If necessary, short dosing times and higher dosing rates can be used separately. However, more energy is required to perform the mechanical stirring of the p-acid and the reaction mixture well to effectively disperse the diamine in the reaction. The mixture is subjected to heat removal from the neutralization reaction between the diamines and the hydrazine acid to prevent severe adhesion and agglomeration of the reaction mixture. The preferred rate of compounding can depend on the mode of movement of the agitated powder, the flow properties of the powder, the method of dispersion of the liquid diamine, the reaction components, the reaction rate, and the reaction conditions employed during dry mixing. The fastest ingredient rate in each case can be determined by routine experimentation with different dosing rates.

The MXDT/ZT salt is not necessarily the first molar salt. For example, if With less than one equivalent of the diamine, the MXDT/ZT salt may still contain a small amount of unreacted tereic acid. For example, if more than one equivalent of a diamine is used, the salt may also contain a small amount of unreacted diamine. The MXDT/ZT salt has been found to contain small amounts of excess diamine and still exhibits characteristics of dry solids.

It has further been found that in the case of an excess of diamine, the molar balance is partially corrected by evaporation of the diamine during the sub-step of the first condensation reaction, however, in the case of excess of citric acid, the second condensation can be The molar balance is corrected during the sub-step of the reaction by adding a diamine during the course of the step. Accordingly, the solid MXDT/ZT salt used in the processes according to the present invention preferably has a diamine/p-quinone molybdenum in the range of from 1.10 to 0.90, preferably from 1.05 to 0.95, and more preferably from 1.02 to 0.98. Ear ratio.

This salt preparation step (i) can be carried out in different ways and using different types of reactors. Preferably, the diamines are contacted with the para-acid by spraying or dripping the diamine onto the pair of citric acid powders. Preferably, in a batch operation, the diamine is sprayed or dripped onto the stirred citric acid powder, and the diamine is added, and then the diamine is sprayed on the formed salt and the citric acid. The diamine is contacted with the powder to expose the diamine to the paraic acid. Suitable reactors wherein the diamines and the pair of phthalic acid can be contacted and mixed are, for example, tumbler mixer plowshare mixers. Conical mixer, planetary screw mixer and fluidized bed reactor. These mixers are all low shear mixers. Further information on these and other low shear mixer devices can be found in the following book: "Handbook of Industrial Mixing-Science and Practice" edited by: Paul, Edward L.; Atiemo-Obeng, Victor A.; Kresta , Suzanne M. (Publisher: John Wiley &Sons;2004;; ISBN: 978-0-471-26919-9; Electronic ISBN: 978-1-60119-414-5), especially in Chapter 15, Part 15.4 and 15.11. In terms of the neutralization heat generated upon reacting the diamines with the para-xamic acid to form the MXDT/ZT salt, a heat exchanger can be used.

The fact that the salt preparation step in the process according to the invention can be carried out without still applying high shear and still achieves a high degree of conversion is surprising. In fact, a stirring powder having a low shear agitation effect can be produced, so that the wear of the tannic acid can be avoided. In fact, the wear can be very low, or even completely absent, so that the degree distribution is almost unaffected, which differs from the fact that the size of the p-citric acid powder particles can even increase during the reaction with the diamine. . In the case where the pair of acid powders are not worn, the advantage of this low shear agitation is that the amount of fine powder produced during the process is small, and the scale, dust, and weight which occur once stored can be reduced. Drooping, and the problem of reduced flowability due to blockage of fine powder.

In a preferred embodiment of the method according to the invention, the pair of citric acid powders used herein comprise a small amount of particles having a small particle size. It is also preferred to have a narrow distribution of citric acid powder. The advantage of the MXDT/ZT salt thus produced is also small particles, a relatively narrow particle size distribution, and optionally even better flow properties. It is preferred to use a combination of a low amount of small particles and/or a narrow particle size distribution of citric acid and low ground agitation.

Preferably, the salt preparation step in the process according to the invention is carried out in an inert gas atmosphere. For the inert gas atmosphere, suitable gases which are conventionally known in the art for the polymerization of polyamido can be used. This inert gas is typically oxygen free or substantially oxygen free and free of other oxidation reactive gases such as O ₃ , HNO ₃ , HClO ₄ and the like. It is preferred to use nitrogen as the inert gas. The salt preparation and the polymerization steps are preferably carried out under the following conditions: atmospheric pressure, or micro-overpressure, for example in the range from 1 to 5 bar, for example about 1.5 bar, or 2 or 3 bar. The advantage of using overpressure is that it reduces the loss of diamine during salt preparation, which is rare, if any.

The PA-MADT/ZT polymer having an increased glass transition temperature (Tg) is a novel polymer within the state of the art. The Tg of the polyamines prepared according to the process of the present invention depends on the number of CH ₂ groups present in the MXD and Z.

Figure 1 is a graph showing the relationship between the Tg value and the CH ₂ content (g/g), wherein the example of the present invention is a diamond symbol ◆, the example of the comparative experiment is a square symbol ■, and a solid line represents the formula Tg = 226-475 *Y, where Y is the CH ₂ content expressed in grams per gram.

Detailed description of the preferred embodiment

Accordingly, the present invention is directed to a PA-MXDT/ZT polydecylamine wherein MXD is m-phenylenediamine. T is a tereic acid, Z is a linear aliphatic diamine having from 2 to 12 carbon atoms, and Z is from 0 to 40 mol% with respect to the total number of MXD and Z units in the copolymer. The polymer has a glass transition temperature which is in accordance with the following relationship: Tg > 226 - 475 * Y, wherein the weight of all CH ₂ groups within the polyamine relative to the total weight of the polyamine Ratio (g/g). For the purposes of the present invention, Y is at most 0.15 and at least 0.105. Wherein the Tg is determined after the first heating/cooling cycle in accordance with ISO 11357-1/2, wherein the polyamine is heated to a temperature of 20 ° C/min to 350 ° C and passed through 20 ° C / The rate of minutes was immediately cooled to 0 °C. This second heating step was carried out by heating to 350 ° C using a scan rate of 20 ° C / min.

Figure 1 shows a graph in which Tg represents a comparison of the CH ₂ content expressed in grams per gram according to an example of the present invention (diamond symbol ◆) and an example of a comparative experiment (square symbol ■), and a solid line represents the The formula Tg = 226-475 * Y, where Y is the CH ₂ content expressed in grams per gram.

Another advantage of the process of the present invention is that it has fewer side reactions and degradation phenomena than the polymers produced by the process described in U.S. Patent Application Serial No. 2009/0012229 A1. The polyamine of the present invention has a viscosity value of at least 20 ml/g, preferably at least 35 ml/g, more preferably at least 50 ml/g, or even at least 65 ml/g. The viscosity values herein are determined at 96 ° C in 96% sulfuric acid (0.005 g/ml) according to the method of ISO 307 (fourth edition).

In the polyamine of the present invention, Z is a linear aliphatic diamine having from 2 to 12 carbon atoms. Z is preferably 1,4-diaminobutane, 1,5-aminopentane, 1,6-diaminohexane, or a combination thereof. Therefore, Z may be a linear aliphatic diamine or a composition of more than one linear aliphatic diamine. If Z is a combination of more than one diamine, the copolymer is the present invention. The target) may be referred to as MXDT/Z ¹ T/Z ² T or MXDT/Z ¹ T/Z ² T/Z ³ T. The mixture of such diamines is preferably selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane and hexamethylenediamine.

These PA-MXDT/ZT polyamines with a high Tg are novel polyamines in the latest technology, and the surprising fact is the DSSP method. It can be used to make these transparent copolymers. Even more surprising is the fact that the copolymers having a Z number from 5 to 40 mole % have a melting of at least 25 Joules/gram, preferably at least 40 Joules/gram, and most preferably at least 50 Joules/gram. The first DSC heating cycle of the crucible has a melting point. During the polymerization, higher melting enthalpy reduces the risk of reactor fouling or powder cohesion.

In a second heating by DSC, the copolymers represent a low melting enthalpy, typically less than 25 joules per gram, or even less than 20 joules per gram. The advantage of lower melting enthalpy in this second heating step is that the materials are more transparent in injection molding or extrusion applications.

Accordingly, the present invention is also directed to a novel class of polyamidamide copolymers having a melting point in a first DSC heating cycle having a melting enthalpy of at least 25 Joules per gram.

In a particular embodiment of the invention, the polyamine is a PA-MXDT homopolymer, i.e., the new PA-MXDT homopolymer has a Tg of at least 176 °C. The glass transition temperature (Tg) is determined by performing DSC at a scan rate of 20 ° C/min during the second heating cycle after heating to 350 ° C and directly cooling, and by the method according to ISO 11357-1/2. And measured. The advantage is that the polymer retains its mechanical and energy barrier properties, such as stiffness that can withstand higher temperatures.

In another particular embodiment of the invention, the polyamine is a PA-MXDT/ZT copolymer having a Tg of at least 156 ° C, which conforms to the following relationship: Tg > 195-240-Y, wherein Y is The weight ratio of all CH ₂ (g/g), and wherein the Tg is determined as listed above.

The invention further relates to a polyamine containing the invention Molding the composition. The molding composition can include a filler (e.g., a fibrous reinforcement), an impact modifier (e.g., an elastomer), and other additives or processing adjuvants.

Preferred fibrous reinforcing materials are carbon fibers, potassium titanate whiskers, aromatic aramid fibers, and more particularly glass fibers. If glass fibers are used, these may be added with a coupling agent and their size helps to improve compatibility with the thermoplastic polyamide. Suitable particulate fillers are amorphous cerium oxide, magnesium carbonate (white peony), kaolin (especially calcined kaolin), powdered quartz, mica, talc, feldspar and especially calcium silicate, such as wollastonite. .

Preferred elastomers are the known ethylene propylene (EPM) and ethylene, propylene, diene (EPDM) rubbers. EPM and EPDM rubbers are preferably grafted with a reactive carboxylic acid or a derivative thereof. Examples of such are acrylic acid, methacrylic acid and the like, such as glycidyl (meth)acrylate, and maleic acid ester.

Examples of conventional additives are stabilizers and oxidative retardants, additives against thermal decomposition and decomposition by ultraviolet rays, lubricants and mold release agents, dyes, colorants, and plasticizers.

Viscosity value (VN)

The viscosity value (VN) was measured in accordance with ISO 307 (fourth edition). For this assay, a pre-dry polymer was used in a drying step at 80 ° C under high vacuum (i.e., less than 50 mbar) for 24 hours. The viscosity value was determined at a concentration of 96.00 ± 0.15% m/m of 0.5 g of the polymer in 100 ml of acid at 25.00 ± 0.05 °C. The flow time (t) of the solution and the flow time (to) of the solvent were determined using a DIN-Ubbelohde from Schott (Ref. No. 53020) at 25 °C. The definition of the VN is as follows:

Where: VN = viscosity value expressed in milliliters per gram

t = average flow time of the sample solution in seconds

t ₀ = average flow time of the solvent in seconds

C = concentration in grams per milliliter (=0.005)

The salt and the melting temperature (Tm) of the polymer, the glass transition temperature (Tg), and the melting enthalpy (ΔHm) were measured via DSC.

The term melting temperature (Tm) in the text means the temperature measured by the DSC method of ISO-11357-1/3 (2009) by using a heating and cooling rate of 20 ° C / min in a N ₂ atmosphere. The Tm1 and Tm2 systems are measured from the first heating cycle and the peak value of the highest melting peak in the second heating cycle after heating to 350 ° C and direct cooling.

The term "melting lanthanide" as used herein means enthalpy (ΔHm) determined according to the DSC method of ISO-11357-1/3 (2009) using a heating and cooling rate of 20 ° C / min in a N ₂ atmosphere. Here, ΔHm1 and ΔHm2 are respectively measured in the first heating cycle and in the second heating cycle after heating to 350 ° C and directly cooling.

The glass transition temperature (Tg) was measured in accordance with ISO 11357-1/2. This second heating cycle was used after heating at the above-described 20 ° C/min scan rate.

For these assays, a standard heat flux Mettler-Toledo DSC 823 was used and the following conditions were used. A sample of about 3 to 10 mg was weighed out using a precision balance and encapsulated (curled) in 40 microliters of known quality aluminum crucible. The aluminum crucible was sealed with a porous aluminum crucible cover. The perforations were mechanically made and consisted of a pore width of 50 microns. An identical open space was used as a control. Nitrogen flushing was carried out at a rate of 50 ml min ^-1 . A heating-cooling-heating cycle having a scan rate of 20 ° C/min in the range of 0 to 350 ° C was used to determine parameters that numerically represent the properties of the thermal properties of the polymers studied.

Determination of terminal group concentration and CH ₂ ratio (Y) by ¹ H NMR

PA-MXDT/ZT was dissolved in H ₂ SO ₄ in a 5 mm NMR tube. The 5 mm NMR tube placed in 10 mm NMR tube containing ₃ of CDCl3. The obtained ¹ H NMR spectrum was compared with the chloroform resonance (7.24 ppm). The concentration of the end groups is determined by the integration of the proton signals and the number of protons corrected as follows:

The area (spike 1) is the integral of the spike at a displacement of 4.17 ppm, the area (spike 2) is the integral of the spike at 3.04 ppm displacement, and the area (spike 3) is the peak at 8.23 ppm displacement. The integral of; and SUM is the total number of polyamines determined by the total number of all of the different units constituting the polyamine according to the following equation:

The area (spike 4) is the integral of the peak at a displacement of 4.79 ppm (combined MXD), and the area (spike 5) is the integral of the spike at 3.70 ppm displacement (combined diamine Z). The area (spike 6) is the integral of the spike at 7.85 ppm displacement (combined TPA), while the area (spike 7) is the integral of the spike at 8.23 ppm displacement; and MW _{diamine Z is} the diamine Z Molecular weight.

The concentration of the amine end groups is the total concentration of the MXD end groups and the concentration of the diamine end groups Z.

The weight ratio (g/) Y of all CH ₂ groups in the polyamine is determined according to the following equation with respect to the total weight of the polyamine:

Wherein cnst1 is the number of CH ₂ groups in the diamine Z, wherein if more than one diamine is present, cnst1 is the molar average of the CH ₂ groups present in the diamine and the area (spike 4) The area (spike 5) and SUM are as defined above.

raw material

experiment

S1. Preparation: MXDT/4T salt

223.35 grams (1.344 moles) of solid citric acid powder was loaded into a 2 liter baffle flask. The flask was attached to a rotary evaporator equipped with a heated diamine batching vessel and inerted by flushing with 5 grams of nitrogen per hour for 1 hour. The contents of the flask were mixed by rotating the flask at 60 rpm and maintained under a nitrogen atmosphere (5 g per hour). The rotary flask was partially immersed in an oil bath maintained at 65 ° C to allow the powder to reach the same temperature. The 13.5 g (0.157 mol) 1,4-diaminobutane and 164.8 g (1.21 mol) were prepared by melting and mixing the diamines at room temperature and heating to 65 ° C in a batching vessel. ) A liquid mixture of MXD. Then, the liquid mixture was added dropwise to the acid powder at a batch rate of 0.5 g ml/min under constant rotation. After the ingredients were completed, the reaction mixture was stirred by rotation and the flask was maintained at 65 ° C for 120 minutes. The flask was then cooled to room temperature and the salt was drained from the flask. The salt thus obtained is a free-flowing powder. Its melting point is 284 ° C.

S2. Preparation: MXDT/4T salt

In addition to 227.02 g (1.344 mol) of solid p-citric acid powder was charged into the baffled flask and added at a rate of 0.5 ml/min containing 148.9 g. The procedure of Example S1 was repeated except that the mixture of (1.093 mol) MXD and 26.1 g (0.296 mol) of 1,4-diaminobutane was used. The salt thus obtained was a free-flowing powder; the melting point was 283 °C.

S3. Salt preparation: MXDT salt

150 ml of water and 22.52 g of MXD were placed in a 250 ml 3-necked flask equipped with a reflux condenser, a temperature sensor and a magnetic stir bar. Within a minute, 27.46 grams of p-citric acid was added via a 2 cm neck funnel attached to the third neck. It raises the temperature from 23 to 32 ° C while vigorously stirring. During the addition of the PTA, the MXDT salt is formed as a white insoluble slurry. The reaction mixture was heated to reflux temperature (102 ° C) for 1 hour at which temperature the slurry did not dissolve and then allowed to cool. The cooled slurry was filtered using a Büchner funnel and the filter cake was washed with 50 mL of acetone. The product was dried by allowing air to pass through the filter cake over a period of 3 hours. The product had a melting point of 292 ° C as determined by DSC.

Polymerization experiment:

The polymerization was carried out in a Mettler-Toledo TGA/DSC instrument. Approximately 3 to 10 milligrams of mass is weighed out using a precision balance and encapsulated (curled) in a 40 microliter aluminum crucible of known quality. The aluminum crucible was sealed with a porous aluminum cover. This perforation is carried out by mechanical means. An identical open space was used as a control. Nitrogen flushing was carried out at a rate of 50 ml/min. Heating is carried out at a rate of 1 ° C/min from room temperature to a maximum temperature, followed by constant temperature treatment.

Comparative Experiment C1 Copolyamine PA-MXDT/4T

7.64 mg of the salt of Example S1 (MXDT/4T) was heated in a 0.04 ml aluminum reactor with a 1 mm hole lid to allow the condensate to leave the reaction. Device. It was heated to 260 ° C at a rate of 20 ° C / min in an inert atmosphere and maintained at 260 ° C, which took 3 hours. The polymer in powder is obtained. The results are shown in Table 1.

Example E1 Copolyamide PA-MXDT/4T

7.02 mg of the salt powder of Example S1 was heated in a 0.05 ml aluminum reactor with a lid of 0.05 mm holes to allow the condensate to leave the reactor. It was heated to 260 ° C at a rate of 20 ° C / min in an inert atmosphere and maintained at 260 ° C, which took 3 hours. The polymer in powder is obtained. The results are shown in Table 1.

Example E2 Copolyamide PA-MXDT/4T

6.6 mg of the salt powder of Example S1 and 0.4 mg of MXD were heated in a 0.05 ml aluminum reactor with a lid of 0.05 mm holes to allow the condensate to leave the reactor. It was heated to a temperature of 20 ° C / min to 260 ° C in an inert atmosphere and maintained at this temperature, which took 3 hours. The polymer in powder is obtained.

Comparative Experiment C2 Copolyamine PA-MXDT/4T

The procedure of Example E2 was repeated except that 6.45 mg of the salt powder of Example S1 and 6.45 mg of MXD were used as starting materials. The polymer in powder is obtained.

Example E3 Copolyamide PA-MXDT/4T

The procedure of Example E1 was repeated except that 7.05 mg of the salt powder of Example S2 was used. The polymer in powder is obtained.

Example E4 Copolyamide PA-MXDT/4T

In addition to using 8.59 mg of S2 salt powder and 0.77 mg Repeat step E2 for the difference in MXD. The polymer is obtained as a powder.

Example E5 Polyamine PA-MXDT in a stirred reactor

The polymerization is carried out in a double-walled 1-liter electrically heated metal reactor equipped with a spiral stirring device, an inert gas inlet, and an outlet for the inert gas and condensate gas leaving the reactor, and A thermometer for measuring the temperature of the reactor wall and the contents of the reactor. A salt powder was charged into the reactor. The salt powder was stirred and flushed with 5 grams of nitrogen per hour to inertize the reactor contents. The reactor wall is then heated using a programmed temperature profile to heat the reactor contents and monitor the temperature of the reactor contents within the powder bed while continuing the nitrogen purge and the contents of the reactor. Stir.

300 grams of the salt of Example S3 was used. The nitrogen purge was set and maintained at room temperature for a total of 5 grams of gas volume per hour. The reactor contents were inerted over a period of 3 hours and then the heating profile was started. The reactor contents were heated from 25 to 220 ° C in 2 hours, maintained at 220 ° C, took 3 hours, heated to 235 ° C in 5 hours, heated to 265 ° C in 1.5 hours, and then heated to 275 °C. The nitrogen flush is then discontinued. 15 grams of MXD was then dispensed into the closed reactor over 60 minutes, after which the nitrogen flush was restarted at 5 grams per hour and again at 275 °C for 2 hours. The reactor contents were then cooled to below 100 °C over 2 hours to form a free-flowing polymer. The yield was 260 g. The product had a solution viscosity (ISO 307) VN of 43.5 ml/g.

The values after Tg and Tm mean that they are determined in the first heating (1) or in the second heating (2).

Claims (12)

A method for preparing PA-MXDT/ZT polyamide, comprising the steps of: (i) providing a solid MXDT/ZT salt, wherein MXD is m-phenylenediamine, T is p-citric acid, and Z is one a linear aliphatic diamine of from 2 to 12 carbon atoms, and wherein the amount of Z is from 0 to 40 mol% in terms of the total number of MXD and Z units in the polymer; (ii) The MXDT/ZT salt is solid state polymerized to obtain the polyamine, wherein the solid state polymerization is carried out at least partially under a diamine atmosphere. The method of claim 1, wherein the MXDT/ZT salt is prepared by dispensing a liquid diamine MXD and optionally a stirring powder of Z to citric acid. The method of claim 1, wherein the MXDT/ZT salt is prepared from the diamine MXD and optionally Z in an aqueous solution. The method of any one of claims 1 to 3, wherein the diamines MXD and Z are distributed at a dispensing rate of up to 4 mol% per minute relative to the pair of citric acid. The method of any one of claims 1 to 4, wherein the diamine/p-quinic acid molar ratio in the solid MXDT/ZT salt is in the range of from 1.10 to 0.90. A PA-MXDT/ZT polyamidamide polymer, wherein MXD is m-xylylenediamine, T is p-nonanoic acid, and Z is a linear aliphatic diamine having from 2 to 12 carbon atoms, relative to the The total number of MXD and Z units in the polymer, Z is from 0 to 40 mol%, and the polymer has a glass transition temperature (Tg expressed in ° C) in accordance with the following relationship: Tg>226-475* Y, wherein Y is the weight ratio (g/g) of all CH ₂ groups in the polyamine, as measured by ¹ H-NMR in a solution of D ₂ SO ₄ , and relative to The total weight of the polyamine, wherein the Tg is determined by DSC at a scan rate of 20 ° C / min in the second heating cycle after heating to 350 ° C and directly cooled, and is based on ISO 11357-1 / Determined by the method of 2, wherein Y is at most 0.15. The polymer of claim 6, wherein the Z is selected from the group consisting of 1-4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane. A PA-MXDT/Z ¹ T/Z ² T polyamidamide copolymer, wherein MXD is m-xylylenediamine, T is p-citric acid, and Z ¹ and Z ² are selected from 1-4-diaminobutyl a diamine of the group consisting of alkane, 1,5-diaminopentane, and hexamethylenediamine, and is present in an amount ranging from the total number of MXD and Z units in the copolymer. From 5 to 40 mol%, and the copolymer has a glass transition temperature (Tg expressed in ° C) in accordance with the following relationship: Tg > 226 - 475 * Y, wherein Y is all CH in the polyamine a weight ratio of ₂ groups (g/g) as measured by ¹ H-NMR in a solution of D ₂ SO ₄ and based on the total weight of the polyamine, wherein the Tg is borrowed It was measured by DSC at a scan rate of 20 ° C/min during the second heating cycle, which was heated to 350 ° C and directly cooled, and was determined according to the method of ISO 11357-1/2, wherein Y was at most 0.15. A PA-MXDT/Z1T/Z2T/Z3T polyamido copolymer, MXD is m-xylylenediamine, T is p-citric acid, Z1 and Z2 and Z3 are 1-4-diaminobutane, 1,5 - diaminopentane, and hexamethylenediamine, and the amount thereof is in the range of from 5 to 40 mol%, based on the total number of MXD and Z units in the copolymer, and the copolymer Having a glass transition temperature (Tg expressed in ° C) in accordance with the following relationship: Tg > 226 - 475 * Y, wherein Y is the weight ratio (g / gram) of all CH ₂ groups in the polyamine, It is measured by ¹ H-NMR in a solution of D ₂ SO ₄ and based on the total weight of the polyamine, wherein the Tg is the second after heating to 350 ° C and directly cooling. The DSC was measured in a heating cycle at a scan rate of 20 ° C/min and was determined by the method according to ISO 11357-1/2, where Y was at most 0.15. The polymer of any one of clauses 6 to 9, wherein the polymer has a viscosity value of at least 40 ml/g, which is at 25 ° C in 96% sulfuric acid (0.005 g / ml) according to ISO 307 Determined by the method of the fourth edition. The polymer of any one of claims 6 to 10, wherein the polymer has a melting enthalpy of at least 40 J/g in the first heating cycle, by using the method according to ISO 11357-1/3, via use Measured by DSC at a scan rate of 20 ° C / min. A molding composition comprising the polymer of claims 6 to 11.