TW201439209A - PA-MXDT/ZT copolymers - Google Patents

Abstract

The invention related to a process for the production of a PA-MXDT/ZT polyamide copolymer 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 amount of Z is from 5 to 40 mole % with respect to the total amount of MXD and Z units in the copolymer and wherein the MXDT/ZT salt is provided by dosing of liquid diamines MXD and Z to a powder of terephthalic acid; ii. heating the solid MXDT/ZT salt to a first condensation temperature (Tc1) thereby condensing the salt in solid state to produce a solid polyamide copolymer, wherein Tc1 is below the melting temperature (Tm-salt) of said salt. The invention further relates to a PA-MXDT/ZT polyamide copolymer, wherein MXD is meta-xylylenediamine, T is terephthalic acid, Z is a linear aliphatic diamine having from 2 to 12 carbon atom, Z is from 5 to 40 mole % with respect to the total of MXD and Z nits in the copolymer.

Description

PA-MXDT/ZT copolymer Field of invention

The present invention relates to a process for the manufacture of a PA-MXDT/ZT polydecylamine copolymer, wherein MXD is meta-xylylenediamine, T is p-nonanoic acid, and Z is one having from 2 to 12 carbon atoms. Linear aliphatic diamine.

Background of the invention

A process for the preparation of transparent polyamidamide copolymers comprising MXD, a straight chain diamine, a citric acid and an aliphatic saturated dicarboxylic acid is known from US Pat. No. 4,018,746. No. 4,018,746 describes a process in which the diamines and dicarboxylic acids are placed in an autoclave. The salts of these diamines and dicarboxylic acids can be prepared in advance. The components are heated in a stream of nitrogen while stirring to a temperature in the range of 200 to 250 °C. The nitrogen flow is then stopped and the temperature is increased to about 260 to 300 °C. The mixture was stirred in a stream of nitrogen at this temperature for about 30 minutes. The condensation reaction is carried out until the polymer has obtained the desired molecular weight.

It is preferred to replace the adipic acid with a less expensive opposite citric acid and maintain the amorphous transparency of the polyamine; however, the method of US 4,018,746 cannot be used to make MXDT/ZT for the following reasons:

1) a mixture comprising MXD, Z and T in a composition (wherein the number of Z is from 5 to 40 mol% relative to the total number of MXD and Z units) and A solid block that does not melt and becomes a sintered powder.

2) Due to the side reaction, heating 1,4-diaminobutane and/or 1,5-diaminopentane at a high temperature in the presence of an acid produces a 5- and 6-membered monofunctional ring. . These can react with RCO ₂ H and act as a chain stop agent which limits the molecular weight of the polyamine formed. Due to the side reaction, heating the longer chain linear aliphatic diamine at a high temperature in the presence of an acid produces a polyfunctional diamine. They can react with RCO ₂ H and act as a branching agent which can cause gelation.

3) When using the batch process described in US 4,018,746 on a large scale, it is necessary to granulate the liquid polyamine obtained at any stage of the process. It means that the resulting variation in residence time results in an undesired variation in the molecular weight of the polyamine and thus produces a non-uniform product. Attempts to manufacture PA-MXDT/ZT via other known polymerization methods for amorphous polyamines have also failed.

Summary of invention

It is an object of the present invention to provide a process for preparing the PA-MXDT/ZT copolymer which does not suffer from the above disadvantages.

According to the invention, this object is achieved by the nature of claim 1. Thus, as in the method of claim 1, a PA-MXDT/ZT copolymer having a viscosity value of more than 50 ml/g in H ₂ SO ₄ can be prepared, wherein the MXD and Z units are in the polymer. The total number of Z is from 5 to 40 mol%.

The statement "from x to y", where x and y are numerical values, for example in "from 2 "To 12 carbon atoms" and "from 0 to 40 mole %" are meant to encompass such values x and y. Thus "from x to y" should be interpreted as "from x up to and including y".

A Z concentration of less than 5 mol% and greater than 40 mol% relative to the total number of moles of MXD and Z units in the copolymer results in a semi-crystalline copolymer that is no longer amorphous.

Direct solid state polymerization (DSSP) process, that is, a method in which a polyamine salt is polymerized at a temperature below the melting temperature of the salt, and wherein the salt, the polymer formed, and the intermediate reaction mixture maintain a solid state It is known per se for polyamines, but only for semi-crystalline polyamines. It is not possible to use the method to produce an amorphous semi-aromatic polyamine because the material is liquid and becomes viscous in the absence of the glass transition temperature (Tg) and the reaction in the Tg. This will result in sintering of the material.

Unexpectedly, the present DSSP process can be used first to make amorphous PA-MXDT/ZT copolymers wherein Z is from 5 to 40 mole percent relative to the total number of MXD and Z units within the polymer. The invention is therefore also related to the PA-MXDT/ZT polyamidamide copolymer, wherein MXD is m-xylylenediamine, T is p-citric acid, and Z is a linear fat containing from 2 to 12 carbon atoms. The family diamine is present in an amount ranging from 5 to 40 mole %, relative to the total number of MXD and Z units in the polymer. Z is preferably a mixture (or composition) of 1,4-diaminobutane, 1,5-diaminopentane, hexamethylenediamine, or the like. Thus, if Z represents more than one diamine, the copolymer, which is the object of the invention, can be named 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 a mixture of diamines selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane and hexamethylenediamine.

Detailed description of the preferred embodiment

The method of the invention comprises at least two, optionally three steps.

In the first step (i), a solid MXDT/ZT salt is provided, wherein the MXD is m-xylylenediamine, T is p-citric acid, and Z is a linear fat having from 2 to 12 carbon atoms. a family diamine, and wherein Z is from 5 to 40 mole %, relative to the total number of MXD and Z units in the copolymer i, and wherein the MXDT/ZT salt is by dispensing liquid diamine MXD and Z to Provided for the powder of tannic acid. For the purposes of the present invention, this mole % is determined by ¹ H-NMR.

Any of the methods known in the art for preparing polyamine salts (e.g., a method wherein the MXDT/ZT salt is prepared from an aqueous solution of diamine MXD and Z and p-citric acid) A solid MXDT/ZT salt.

The solid MXDT/ZT salt is preferably provided by a novel process wherein the MXDT/ZT salt is prepared by dispensing liquid diamine MXD and Z to a stirred powder of citric acid. One of the advantages of the method is that the step of separating the salt formed from the solvent or dispersant can be omitted, thereby saving the cost of solvent treatment and recycling, and saving energy costs. The salt obtained in the step (i) is already a powder, and therefore, it is not necessary to crush and grind as the salt preparation 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 superheated steam, or in a complex controlled diamine atmosphere. A nitrogen purge can be used to carry out the method, which This will result in a faster removal rate of water from the neutralization reaction, thus reducing the risk of agglomeration of the reaction mixture. The salt prepared according to the process is preferably prepared from a mixture of MXD and a diamine wherein Z is a linear aliphatic diamine containing from 2 to 6 carbon atoms because it allows the diamine mixture to be confronted with The acid reacts more favorably to form the MXDT/ZT salt.

In the second step (ii), the solid MXDT/ZT salt is heated to a first condensation reaction temperature (Tc1) to condense the solid salt to produce a solid polyamine copolymer, wherein the Tc1 system is lower than the The melting temperature of the salt (Tm-salt). If all or almost all of the salt is converted to polyamine, the first condensation reaction step is considered complete. In the case of complete conversion, residual melting peaks from the salt are no longer found. If necessary, it can be confirmed by DSC assay using DSC methods and conditions as further described below.

Herein, the second step (ii) is also referred to as a first condensation reaction step. The method preferably includes one or more additional steps.

Preferably, the third step (iii) of the process of the present invention comprises condensing the solid state derived from the step (ii) at a second condensation reaction temperature (Tc2) below the melting temperature of the polyamidamide copolymer (Tm1). The polyamide copolymer is used to produce a polyamidamine copolymer having a higher degree of polymerization. This third step (iii) is also referred to herein as the second condensation reaction step.

The condensation reaction steps (ii) and (iii) can be carried out, for example, in a fixed bed reactor or in a stirred bed reactor in any manner suitable for the conventional DSSP process. The use of a stirred bed reactor, such as a rotating vessel or mechanically agitated reactor in which the solid MXDT/ZT salt and solid copolymer are stirred to produce and maintain a flowable powder, contributes to the following results: The polymer particulate material obtained by the method aids in forming a non-sticky powder material. For the second condensation reaction step (iii), a fixed bed can be a more economical alternative.

During the condensation reaction steps (ii) and (iii), it is preferred to use an inert gas purge to remove any water originally present in the MXDT/ZT salt and, more importantly, to remove the condensation reaction. Water. Alternatively, a portion of the water vapor pressure is reduced by applying a vacuum, or a combination of inert gas flushing and reduced pressure.

This method can be carried out, for example, as follows. The solid MXDT/ZT salt is prepared in a reactor or charged into the reactor and heated to a predetermined temperature (preferably about 130 ° C) in the range of 100-200 ° C to allow for the salt. Any water is removed by evaporation and carried away by the flushing gas while maintaining the temperature of the reactor wall and its internal devices at the same temperature or higher to avoid significant condensation phenomena on the surfaces. Preferably, the solid MXDT/ZT salt is staged at the predetermined temperature with the proviso that water in the salt must be removed. It can be checked, for example, by a water collector. Once the water removal step is complete, or almost complete, the solid MXDT/ZT salt is heated to a predetermined point equal to Tc1. The first condensation reaction step can be followed by the rate of formation of the condensate, which begins slowly and then increases as the temperature rises. This prepolymerization will typically proceed until the rate of collection of the condensate drops significantly. The degree of completion of the conversion of the salt can also be checked via DSC in the presence of residual enthalpy of enthalpy which can indicate the melting peak of the salt. For the second condensation step (iii), the solid prepolymer formed can be maintained at the same temperature, that is, Tc2 is equal to Tc1, or can be heated Up to a predetermined point equal to Tc2 and higher than Tc1, but below the melting temperature of the polyamidamide copolymer produced in step (ii). The polyamine is maintained at this temperature until the desired degree of polymerization is obtained. Once the polymerization is complete, the polymer is allowed to cool and drain from the reactor.

Instead of using 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 can be carried out by using a temperature rise method. The heating and cooling can be carried out by heating the inert gas for rinsing, or by heating any of the reactor walls or internal devices therein, 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 diamine MXD and Z to a stirred powder of citric acid. In the present process, it is typically at a low temperature in the absence of a liquid reaction medium, any solvent or dispersant, as in the conditions inherent in the agitated powder, and in the intrinsic conditions of the ingredient temperature, such as above the melting temperature of the diamine. The salt preparation is carried out in the absence of a coolant. It does not exclude the following steps: Liquid components may be added or formed during the course of the process. First, the diamines in liquid form are added for salt preparation. The liquid diamine can also be added later (for example during this step (ii) or step (iii)). Moreover, once the amine is reacted with the carboxylic acid group, water may form during the condensation steps (ii) and (iii) and the water may evaporate and coagulate.

During the preparation of the salt, a small amount of water may also be present in the starting material or formed during the compounding step. The presence of a small amount of water does not pose a problem as long as it maintains the form of a loose and flowable powder. The water can be removed later or during heating within the first DSSP step.

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

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

For the preparation of the salt, the temperature of the compound is preferably at least 40 ° C, more preferably at least 60 ° F below the melting temperature (Tm - salt) of the salt. Premature condensation of the diamine and dicarboxylic acid salts can be reduced by using a furnish temperature that is much lower than the Tm-salt.

The use of a lower batch temperature reduces the problem of the released gaseous water being condensed at the cold spot and the powder fouling at such cold spots.

The diamine is dispensed to the stirred powder to form a powdered reaction mixture while retaining the form of agitated powder. Therefore, the diamine is preferably not added to the agitated powder together with the dicarboxylic acid and mixed because it does not retain the form of the agitated powder and also causes agglomeration and non-wetting of the wetted portion. It does not completely neutralize the reaction. It can be severely complicated and even inhibits proper mixing of the reaction components. It is preferable to limit the rate of the ingredients to prevent local accumulation of liquid diamine, thereby preventing problems of excessive adhesion and excessive humidification, local overheating, and premature reaction with the released water which may cause excessive movement of the bed.

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 0.1mppm (16.7 hours) and 4mppm (25 minutes), for example between 0.2mppm (8.35 hours) and 2mppm (50 minutes), or between 0.25mppm (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 in parentheses indicates the corresponding ingredient time.

Long dosing times and low dosing rates can be used separately, which do not have a significant effect on the salt preparation itself, and can allow the diamines to react longer with the dicarboxylic acid without softening or melting the acid or Solid MXDT/ZT salt, but may make this method less economical. If appropriate, short dosing times and higher dosing rates can be used, respectively, however, in order to subject the dicarboxylic acid to good mechanical agitation of the reaction mixture to effectively disperse the diamines in the reaction mixture and remove them. The heat of the reaction between the diamines and the neutralization of the ruthenium acid is prevented to prevent severe adhesion and agglomeration of the reaction mixture. Need more energy. The preferred rate of compounding can depend on the manner in which the powder is agitated, the flow properties of the powder, the manner in which the liquid diamine is dispersed, the reaction components, the reaction rate, and the reaction conditions employed during dry mixing. In each case, the fastest ingredient rate can be determined by routine experimentation using different ingredient rates.

The MXDT/ZT salt is not necessarily a first-class molar salt. For example, if less than one equivalent of diamine is used, the MXDT/ZT salt may still contain small amounts of unreacted dicarboxylic acid. For example, if more than one equivalent of diamine is used, the salt may also Contains a small amount of unreacted diamine. It has been found that the MXDT/ZT salt can contain a small excess of diamine and still exhibit the characteristics of a dry solid powder.

It has further been found that, in the case of excess diamine, the molar balance is at least partially corrected by evaporation of the diamine during the first condensation step (ii), however, in the case of excess dicarboxylic acid, The molar balance is corrected during the second condensation step (iii) of the method by adding a diamine during this step. Accordingly, the solid MXDT/ZT salt in the process according to the invention preferably has a diamine/dicarboxyl group 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. Acid molar ratio.

The salt preparation step (i) can be carried out using different methods and different types of reactors. Preferably, the diamines are contacted with the bismuth acid by spraying or dipping the diamine onto the stirred counter-powder powder. Preferably, in a batch operation, the diamine is sprayed or immersed in the stirred citric acid powder, and after the diamine has been added, the diamine is sprayed onto the formed salt and tannic acid powder. On the stirred mixture. Suitable reactors in which the diamines and the para-citric acid can be contacted and mixed are, for example, drums or mixers, plowshare mixers, conical mixers, planetary screw mixers and fluidized bed reactors . These mixers are all low shear mixers. Information on these and other low-cut 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), more specifically, in Chapter 15, Part 15.4 And within 15.11. Can use hot The converter is adapted to remove the heat of neutralization reaction that occurs once the diamine is reacted with the paraxamic acid to form the MXDT/ZT salt.

The fact that the salt preparation step in the process according to the invention can be carried out without the use of high shear and still achieves a high degree of conversion is surprising. In fact, low shear agitation can be used to produce a stirred powder so that the wear of the tannic acid powder can be avoided. In fact, the attrition can be so low, or even completely absent, and therefore the particle size distribution is hardly affected, unlike the fact that the particle size of the p-citric acid powder can even increase during the reaction with the diamine. This does not detract from the low shear agitation of the tannic acid powder because the amount of fine powder produced during the process is low, and the scale, dust, sagging of the weight when stored, and clogging due to fine powder The problem of reducing liquidity can be reduced.

In a preferred embodiment of the method according to the invention, the pair of decanoic acids used herein comprise a small amount of particles having a small particle size. A p-citric acid powder having a narrow particle size distribution is also provided. The advantage is that the MXDT/ZT salts thus produced also have smaller particles, a relatively narrow particle size distribution, and optionally even better flow properties. It is preferred to use a pair of citric acid powders having a small amount of small particles and/or a narrow particle size distribution and low shear agitation.

Preferably, the salt preparation step (i) and the condensation steps (ii) and (iii) in the process according to the invention are carried out in an inert gas atmosphere. As the inert gas atmosphere, a suitable gas conventionally known in the art for the polymerization of polyamide can be used. This inert gas is typically free of oxygen or substantially oxygen free and free of other oxidation reactive gases such as O ₃ , HNO ₃ , HClO ₄ and the like. A nitrogen gas is preferred as the inert gas. Preferably, the salt preparation and the polymerization steps are carried out under normal pressure or under a slight overpressure, for example in the range of between 1 and 5 bar, for example at about 1.5, or 2 or 3 bar. The advantage of using an overpressure is that the loss of diamine during salt preparation can be reduced, if any.

Another advantage of the process of the present invention is that the polymers produced by the process described in U.S. Patent No. 4,018,746 have fewer side reactions and degradation reactions. Thus, without sintering, a PA-MXDT/ZT copolymer according to the invention having a molecular weight expressed as a viscosity value of at least 50 ml/g in H ₂ SO ₄ can be produced. Another advantage of the process of the present invention as compared to the process described in U.S. Patent 4,018,746 is that the molecular weight variation of the PA-MXDT/ZT copolymer is substantially no greater than the variation of any condensation polymerization reaction because during this residence time, no Or almost no proliferation.

These PA-MXDT/ZT copolymers are novel copolymers in the latest technology, and it is a surprising fact that the DSSP process can be used to prepare these transparent amorphous copolymers. It is further surprising that within the first DSC heating profile, these copolymers have a melting point of at least 25, preferably at least 40, and most preferably at least 50 Joules per gram of melting enthalpy (ΔHm1). Higher melting enthalpy reduces the risk of reactor fouling or powder agglomeration during the polymerization reaction. The ΔHm1 system is calculated from the melting peak in the first heating cycle. Furthermore, according to the invention, the copolymers have a viscosity value (VN) of at least 50 ml/g which is at 25 ° C by means of the method ISO 307 (fourth edition) and in 96% H ₂ SO ₄ ( 0.005 g / ml) was measured.

Within the second heating profile of the DSC, the copolymers exhibit a low melting enthalpy, typically less than 25, or even less than 20 joules per gram. The advantage of the lower melting enthalpy within the second heating is in the injection forming or extrusion application, These materials are more transparent. The PA-MXDT/ZT polyamidamide copolymer in the form of a (almost) amorphous copolymer can be obtained by a melt processing such as injection molding or melt extrusion. When the copolyamide is processed at a cooling rate of more than 150 ° C / min, as found by the DSC experiment (where the simulated cooling from 350 ° C to room temperature does not show a crystallization reaction peak), the copolymer becomes completely non- Crystal form and even more transparent.

In the present application, an amorphous copolymer means one to 25 joules in a dynamic differential scanning calorimetry (DSC) according to ISO 1357-1/3 (2009) at a heating rate of 20 ° C/min. / gram of ruthenium 焓Hm2 polyamide.

Herein, the term melting temperature (Tm) means the temperature measured by a DSC method according to ISO-11357-1/3 (2009) 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 highest value of the highest melting peak in the second heating cycle after heating to 350 ° C and directly cooling.

The term "melting" in the text means enthalpy (ΔHm) measured by the DSC method of SO-11357-1/3 (2009) using a heating and cooling rate of 20 ° C / min in a N ₂ atmosphere. . The ΔHm1 and ΔHm2 in the text were measured in the first heating cycle and in the second heating cycle after heating to 350 ° C and directly cooling.

The invention further relates to a molding composition comprising the polyamine of the invention. The molding composition can include fillers (e.g., fibrous reinforcements), impact modifiers (e.g., elastomers), and other additives or processing adjuvants.

The preferred fibrous reinforcing material is carbon fiber, potassium titanate whisker, An aramid fiber, and particularly preferably a glass fiber. If glass fibers are used, they can be formulated with a coupling agent and are sized 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 ashstone (wollastonite) ).

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

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

raw material

For tannic acid: powder, industrial grade, melting temperature above 400 ° C

Adipic acid: powder, industrial grade

Isophthalic acid: powder, industrial grade

1,4-butanediamine butane: technical grade; up to 1% by weight water, impurities in the ppm range; melting temperature 27.5 ° C

Hexamethylenediamine: industrial grade; up to 1% by weight water, impurities in the ppm range; melting temperature 41 °C

m-Xylylenediamine: Industrial grade; up to 1% by weight water, in ppm Impurities in the circumference; melting temperature 14 ° C

Analytical method Viscosity value (VN)

The viscosity value (VN) was measured in accordance with ISO 307 (fourth edition). For this assay, a pre-dried polymer sample was used, the drying step of which was carried out at 80 ° C under high vacuum (i.e., less than 50 mbar) over 24 hours. The viscosity value was determined at a concentration of 0.5 g of the polymer in 100 ml of sulfuric acid (96.00 ± 0.15% m/m) at 25.00 ± 0.05 °C. The flow time (t) of the solution and the flow time (t ₀ ) of the solvent were measured at 25 ° C using a DIN-Ubbelohde from Schott (Ref. No. 53020). The definition of VN is Where: VN = viscosity value in millimeters 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 and the melting enthalpy (ΔHm) were determined by the DSC method.

The melting temperature (Tm) and the corresponding melting enthalpy (ΔHm) in the first and second heating of the polymer, and the melting temperature (Tm-salt) of the salt are by differential scanning calorimetry (DSC) was measured using the method according to ISO 11357-1/3 (2009). The Tm-salt was measured in this first heating. For these assays, a standard heat flux Mettler-Toledo is used. DSC 823 and uses the following conditions. A 3 to 10 milligram mass sample was weighed using a precision balance and encapsulated (curled) in 40 microliters of aluminum crucible containing known mass. The aluminum crucible is sealed by a porous aluminum crucible cover. The perforation is mechanically performed and consists of a 50 micron hole width. An identical open space was used as a control. Nitrogen flushing was performed at a rate of 50 ml/min. A heating-cooling-heating cycle was carried out at a scan rate of 20 ° C/min in the range of 0 to 350 ° C and immediately after cooling to 350 ° C.

Instance S1. Preparation: MXDT/4T salt

223.35 grams (1.344 moles) of solid p-citric acid powder was placed in a 2 liter baffle flask. The flask was attached to a rotary evaporator equipped with a heated diamine batching vessel and flushed with 5 grams of nitrogen per hour for 1 hour to be inerted. 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 spinner flask was partially immersed in an oil bath maintained at 65 ° C, thus allowing the powder to reach the same temperature. 13.85 g (0.157 mol) of 1,4-diaminobutane and 164.8 g (1.21 mol) of MXD were prepared by melting and mixing the diamines at room temperature and heating to 65 ° C in a batching vessel. . 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 in an oil bath 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 was a free-flowing powder having a melting point of 284 °C.

S2. Preparation: MXDT/4T salt

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

S3. Salt preparation: MXDT/6T salt

Repeated examples except that a mixture containing 146.1 grams (1.073 moles) of MXD and 35.16 grams (0.303 moles) of hexamethylenediamine was added at a rate of 0.5 grams per minute to 221.3 grams (1.341 moles) of solid versus citric acid. Steps of S1. The salt thus obtained was a free-flowing powder having a melting point Tm1 of 286 °C.

S4 salt preparation MXDT/4T salt The salt preparation was carried out in a double-layer 1 liter electrically heated metal reactor equipped with a spiral stirring device, an inert gas inlet and a gas for coagulating the inert gas. The liquid gas exits the outlet of the reactor and a thermometer that measures the temperature of the reactor wall and the contents of the reactor. 113.51 grams of solid p-citric acid powder was charged to the reactor. The pair of citric acid powders were stirred and flushed with 5 grams of nitrogen per hour for 3 hours to inertize the reactor contents. The nitrogen stream was then stopped and the reactor contents were heated to 180 °C by heating the reactor wall and lid within 1 hour. The diamine was mixed at room temperature and dispensed into the furnishing vessel at room temperature of 22 ° C to prepare 13.05 g of a liquid mixture containing 1,4-diaminobutane and 74.5 g of MXD. The liquid mixture was added dropwise to the acid powder in 4 hours at a batching rate of 0.25 ml/min under constant rotation. After the ingredients are completed, the reaction mixture is stirred by rotation At the same time, the reactor contents were maintained at a temperature of 180 ° C for a period of 120 minutes. The reactor was then cooled to room temperature and the salt was drained from the flask. The salt thus obtained was a powder having a melting point of 285 °C.

S5 salt preparation: MXDT/6T salt

Repeated examples except that a mixture containing 111.05 grams (0.815 moles) of MXD and 71.17 grams (0.613 moles) of hexamethylenediamine was added at a rate of 0.5 grams per minute to 225.78 grams (1.359 moles) of solid versus citric acid. Steps of S1. The salt thus obtained was a free-flowing powder having a melting point Tm1 of 271 °C.

Polymerization experiment

Example S6: Salt preparation: MXDT/6T/4T salt was added at a rate of 0.5 g/min containing 129.84 g (0.953 mol) MXD, 14.20 g (0.122 mol) hexamethylenediamine and 10.88 g (0.123 mol) The procedure of Example S1 was repeated except that the mixture of 1,4-diaminobutane was different from 221.3 g (1.341 mol) of solid to citric acid. The salt thus obtained was a free-flowing powder having a melting point Tm1 of 286 °C.

Example E1 Preparation of Copolyamine PA-MXDT/4T in a Stirred Reactor Using Salt from Example S1

The polymerization is carried out in a two-layer, one-liter electrically heated metal reactor equipped with a spiral stirring device, an inert gas inlet, and an outlet for the gas and condensate gas to exit the reactor. And a thermometer for measuring the temperature of the reactor wall and the contents of the reactor. The 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. Then borrow a program The reactor is heated to control the temperature profile and the reactor contents are heated and the temperature of the reactor contents in the powder bed is monitored while the nitrogen purge is continued and the reactor contents are agitated.

300 grams of the salt of Example S1 was used. The nitrogen purge was set and maintained at a gas volume of 5 grams per hour at room temperature. The reactor contents were inerted over 3 hours and then the heating profile was started. The reactor contents were heated from 25 to 220 ° C in 2 hours and maintained at 220 ° C for 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 to the closed reactor over 60 minutes, after which the nitrogen flush was reopened at a rate of 5 grams per hour and the temperature was maintained at 275 °C. The reactor contents were then cooled to <100 °C over 2 hours, which formed a free flowing powder. The yield was 260 g. The results are shown in Table 1.

Example E2 Preparation of Copolyamine PA-MXDT/4T in a Stirred Reactor Using Salt from S2

The procedure of Example E1 was repeated except that the salt powder was different using 300 grams of Example S2. The results of the analysis are shown in Table 1.

Example E3 Preparation of Copolyamine PA-MXDT/6T in a Stirred Reactor Using Salt from Example S3

The procedure of Example E1 was repeated except that the salt powder was different using 300 grams of Example S3. This heating profile is different from the example E1. 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 2 hours, and then maintained at 265 ° C Next, it takes 5 hours. Did not perform two during the polymerization After the amine is dispensed. The reactor contents were then cooled to <100 °C over 2 hours, which formed a free flowing polymer. The results of the analysis are shown in Table 1.

Example E4 Preparation of Copolyamine PA-MXDT/4T in a Stirred Reactor Using Salt from Example S4

The procedure of Example E1 was repeated except that the salt powder was different using 300 grams of Example S4. The results of the analysis are shown in Table 1.

Example E5 Preparation of Copolyamine PA-MXDT/6T in a Stirred Reactor Using Salt from Example S5

The procedure of Example E3 was repeated except that the powder salt was different using 300 grams of Example S5. This heating profile is different from E3. The reactor contents were heated from 25 to 220 ° C in 2 hours, heated to 223 ° C, and maintained at 223 ° C, which took 3 hours, heated to 238 ° C in 10 hours, and heated to 257 ° C in 2.5 hours. It is then maintained at 257 ° C and takes an hour. Dispensing after the diamine was not carried out during the polymerization. The reactor contents were then cooled to <100 °C over 2 hours to form a free flowing polymer. The results of the analysis are shown in Table 1.

Example E6 Preparation of Copolyamine PA-MXDT/6T/4T in a Stirred Reactor Using Salt S6

In addition to using 300 g of the salt powder of Example S6 and adding 15 g of a liquid mixture containing 7.5 g of hexamethylenediamine and 7.5 g of 1,4-diaminobutane in place of 15 g of 1,4-diaminobutane. Repeat the steps of instance E1. The results of the analysis are shown in Table 1.

Comparative Experiment A: Preparation of PA-MXDT/4T from a MXD/1,4-diaminobutane composition

A liquid mixture containing 1.47 g (0.017 mol) of 1,4-diaminobutane and 16.48 g (0.121 mol) of MXD was prepared by the following steps: mixing the diamines at room temperature and charging them A cylindrical 100 ml glass vessel for removing the volatile components of the distillation tube. 22.34 grams (0.134 moles) of solid p-citric acid powder was added and simultaneously mixed by a spatula. The tube is immersed in an electrically heated combination. The reactor was closed, inerted by evacuation and refilled with nitrogen and this step was repeated 3 times, then the thick slurry was heated from room temperature to 275 ° C over 90 minutes. At 195 ° C, the slurry becomes a solid block of sintered powder. The experiment was terminated by cooling. It is proved that, as with the monomer combination described in US 4,018,746, it is not possible to prepare the material in batches in a scientific manner.

Comparative Experiment B: Solution polymerization of MXDT/4T from a MXD/1,4-diaminobutane composition

13.85 g (0.157 mol) of 1,4-diaminobutane, 164.8 g (1.21 mol) MXD and 300 g of water were placed in a 2-liter capacity pressure vessel equipped with a stirrer, a A thermometer, a pressure gauge, a nitrogen inlet, a gas outlet for releasing evaporated water, and a polymer outlet. 223.35 grams (1.344 moles) of solid p-citric acid powder was added to form the solution to form a MXDT/4T salt slurry. The reactor contents were inerted with nitrogen. The material was heated to 200 ° C to form a clear solution. The 260 grams of water was then removed by evaporation over 30 minutes and maintained at 5 bar overpressure, allowing the temperature to rise. At the end of the distillation, the temperature was increased to 250 ° C for 10 minutes and maintained at this temperature, which took 15 minutes. The material is then removed from the reactor by releasing the reactor into a metal vessel at room temperature, allowing the metal vessel to be flushed with nitrogen to maintain inertness and an outlet to allow The gas escapes during this release. The material obtained was an amorphous glassy material at room temperature. Heating above the glass transition temperature causes the material to become a viscous material that inhibits the post-solids condensation reaction.

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

Comparative Example C: MXDT/4T/MXD6 from a MXDT/4T/MXD6 composition Salt salt preparation and polymerization Salt preparation

175.94 grams (1.059 moles) of solid p-citric acid powder and 27.31 grams (0.187 moles) of solid adipic acid powder were placed in a 2 liter baffle flask. Connecting the flask to a rotary evaporator equipped with a heated diamine batching vessel, It is flushed with 5 grams of nitrogen per hour and inerted 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 rotating flask was partially immersed in an oil bath maintained at 90 ° C, thus allowing the powder to reach the same temperature. A liquid containing 11.42 g (0.130 mol) of 1.4-diaminobutane and 136.56 g (1.003 mol) of MXD was prepared by melting and mixing the diamines at room temperature and heating to 65 ° C in a batching vessel. mixture. Then, the liquid mixture was added dropwise to the acid powder at a rate of 0.3 g ml/min under constant rotation. After the formulation was completed, the reaction mixture was stirred by rotation while maintaining the flask in the oil bath at a temperature of 90 ° 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.

Polymerization

The polymerization is carried out in a two-layer, one-liter electrically heated metal reactor equipped with a spiral stirring device, an inert gas inlet, and an outlet for the gas and condensate gas to exit the reactor. And a thermometer for measuring the temperature of the reactor wall and the contents of the reactor. The 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 is then heated by 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 agitating the reactor contents.

300 grams of this salt was used. The nitrogen purge was set and maintained at a gas volume of 5 grams per hour at room temperature. The reactor contents were made within 3 hours After inertization, the heating profile is then started. The reactor contents were heated from 25 to 210 ° C in 114 minutes. At 210 ° C, the torque increases and the agitation device is clogged and the reactor material becomes a solid block of sintered powder. The experiment was terminated by cooling. It is proved that in the case of the monomer combination according to the invention, it is not possible to manufacture the material in batches in a technical manner.

Comparative Example D: MXDT/4T/MXD from an MXDT/4T/MXDI composition Salt preparation and polymerization Salt equipment

166.12 grams (1.000 moles) of solid p-citric acid powder and 29.31 grams (0.176 moles) of solid isophthalic acid powder were placed in a 2 liter baffle flask. The flask was attached to a rotary evaporator equipped with a heated diamine batching vessel which was 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 rotating flask was partially immersed in an oil bath maintained at 65 ° C to allow the powder to reach the same temperature. A 10.81 g (0.123 mol) 1,4-diaminobutane and 145.00 g (1.065 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 completion of the batching, the reaction mixture was stirred by rotation while maintaining the flask in the oil bath at a temperature of 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.

Polymerization

The polymerization is carried out in a two-layer, one-liter electrically heated metal reactor equipped with a spiral stirring device, an inert gas inlet, and an outlet for the gas and condensate gas to exit the reactor. And a thermometer for measuring the temperature of the reactor wall and the contents of the reactor. The 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 is then heated by 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 agitating the reactor contents.

300 grams of this salt was used. The nitrogen purge was set and maintained at 5 grams of gas per hour at room temperature. The reactor contents were inerted over 3 hours and then the heating profile was started. The reactor contents were heated from 25 to 220 ° C in 120 minutes. The reactor contents were maintained at 220 ° C. After 20 minutes, the torque increased and the stirring device was blocked because the reactor material became a solid mass of sintered powder. The experiment was terminated by cooling. It is proved that in the case of the present monomer combination according to the present invention, batch production of the material cannot be carried out in a scientific manner.

Comparative Example E: Method for salt preparation and polymerization of PA-MXD6 Salt preparation

196.4 g (1.344 mol) of solid adipic acid powder was placed in a 2-liter baffled flask and 1.3 liters of ethanol was added. The flask was attached to a rotary evaporator equipped with a heated diamine batching vessel which was 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). Rotate the spin The bottle was partially immersed in an oil bath maintained at 65 ° C to allow the powder to reach the same temperature. The liquid 186.6 g (1.37 mol) of MXD 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 while maintaining the flask in the oil bath at a temperature of 65 ° C for 120 minutes. The flask was then cooled to room temperature and the salt slurry was drained from the flask. The MXD6 salt was isolated by filtration and dried under vacuum at 50 ° C under a vacuum of 50 mbar for 16 hours.

Polymerization

The polymerization is carried out in a two-layer, one-liter electrically heated metal reactor equipped with a spiral stirring device, an inert gas inlet, and an outlet for the gas and condensate gas to exit the reactor. And a thermometer for measuring the temperature of the reactor wall and the contents of the reactor. The 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 is then heated by 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 agitating the reactor contents.

300 grams of this salt was used. The nitrogen purge was set and maintained at 5 grams of gas per hour at room temperature. The reactor contents were inerted over 3 hours and then the heating profile was started. The reactor contents were heated from 25 to 195 ° C over 2 hours. At 195 ° C, the material becomes a solid block of sintered powder. The experiment was terminated by cooling. It is proved that in the case of the monomer combination according to the invention, the material cannot be produced in a batchwise manner in a scientific manner.

From Comparative Example E it is understood that this method according to the invention is not a suitable method for obtaining the corresponding copolymer.

Comparative Example F: Method for salt preparation and polymerization of PA-MXDI/4I

A liquid mixture containing 1.47 g (0.017 mol) of 1,4-diaminobutane and 16.48 g (0.121 mol) of MXD was prepared by the following steps: mixing the diamines at room temperature and charging them A cylindrical 100 ml glass vessel for removing the volatile components of the distillation tube. 22.34 grams (0.134 moles) of solid p-citric acid powder was added and simultaneously mixed by a spatula. The tube is immersed in an electrically heated combination. The reactor was closed, inerted by evacuation and refilled with nitrogen and this step was repeated 3 times, then the thick slurry was heated from room temperature to 275 ° C over 90 minutes. At 195 ° C, the slurry becomes a solid block of sintered powder. The experiment was terminated by cooling. It is proved that, as with the monomer combination described in US 4,018,746, it is not possible to prepare the material in batches in a scientific manner.

As is apparent from Comparative Example F, this method is not a suitable method for obtaining the corresponding copolymer according to the present invention.

Claims (15)

A method for preparing a PA-MXDT/ZT polyamidamide copolymer, comprising the steps of: i. providing a solid MXDT/ZT salt, wherein MXD is m-xylylenediamine, 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 5 to 40 mol%, relative to the total number of MXD and Z units in the copolymer, and wherein the MXDT /ZT salt is provided by dispensing a liquid diamine MXD and Z to a powder of p-citric acid; ii. heating the solid MXDT/ZT salt to a first condensation temperature (Tc1) to condense the solid salt to produce a solid Polyamine copolymers in which the Tc1 system is below the melting temperature (Tm-salt) of the salt. The method of claim 1, which comprises the following step iii. further at a second condensation temperature (Tc2) below the melting temperature of the solid polyamine copolymer (Tm1) produced in step (ii) The solid polyamine copolymer obtained in the step (ii) is condensed to produce a polyamine copolymer having a higher degree of polymerization. The method of claim 1 or 2, wherein Tc1 is at least 210 °C. The method of any one of claims 1 to 3, wherein the MXDT/ZT salt is prepared by dispensing a liquid diamine MXD and Z to a stirred powder of a pair of citric acid. The method of claim 4, wherein the liquid diamine is at a compounding rate of up to 4 mol% diamine per minute, relative to the molar amount of the dicarboxylic acid. Match. The method of any one of claims 1 to 5, wherein the MXDT/ZT salt is prepared from an aqueous solution of citric acid and diamines MXD and Z. The method of any one of claims 1 to 6, wherein the diamine/dicarboxylic acid molar ratio in the solid MXDT/ZT salt is in the range of 1.10 to 0.90, preferably 1.05 to 0.95, and 1.02 to 0.98. . A PA-MXDT/ZT polyamidamide copolymer, wherein MXD is m-xylylenediamine, T is p-citric 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 copolymer, Z is from 5 to 40 mol%. The copolymer of any one of claims 8 to 10, wherein the Z system is selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane, and hexamethylenediamine. . 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 the amount of the MXD and the Z unit in the copolymer is From 5 to 40% by mole. A PA-MXDT/Z ¹ T/Z ² T/Z ³ T polyamidamide copolymer, wherein MXD is m-xylylenediamine, T is p-citric acid, Z ¹ , Z ² and Z ³ are selected from 1 a diamine of the group consisting of 4-diaminobutane, 1,5-diaminopentane, and hexamethylenediamine, and relative to the total number of MXD and Z units in the copolymer, They are present in amounts ranging from 5 to 40 mol%. The copolymer of any one of claims 8 to 11, wherein the copolymer has one Melting enthalpy ΔHm1 as determined by DSC at a scan rate of 20 ° C/min in a first DSC heating cycle having a melting enthalpy of at least 25 Joules per gram and determined according to the method of ISO 11357-1/3 . The copolymer of any one of claims 8 to 12, wherein the copolymer has a viscosity value (VN) of at least 50 ml/g, according to ISO 307, fourth edition, at 96 ° C at 96 ° H ₂ SO ₄ (0.005 g / ml) was measured. The copolymer of any one of claims 8-13, wherein the copolymer has from one to 25 joules per gram of lanthanide, which is heated to 350 ° C and cooled directly after 20 ° C in the second heating cycle. The DSC of the scan rate per minute was measured and determined by the method according to ISO 11357-1/3. A molding composition comprising the copolymer of any one of claims 8-14.