CN101768266B - Method for preparing semi-aromatic nylon - Google Patents

Abstract

The invention discloses a method for preparing semi-aromatic nylon and belongs to the technical field of macromolecular material synthesis. The method comprises the following steps: (1) uniformly mixing aliphatic diamine and water of which the weight is two to ten times that of the aliphatic diamine, heating the mixture to the temperature of between 50 and 90 DEG C, adding aromatic diacid into the mixture with stirring till a pH value of the solution reaches 7.0-7.7, continuously stirring for 1 to 5 hours, cooling the solution to room temperature, continuously stirring the solution for 1 to 5 hours again, and filtering and drying to obtain nylon salt for later use; and (2) adding the prepared nylon salt and a solvent to a polymerization kettle in a certain mixture ratio (0.5 to 3.0 g/mL), raising the temperature to between 190 and 230 DEG C under the protection of inert gas, keeping the pressure in the kettle between 2.0 and 3.0 MPa, discharging gas after 1 to 5 hours to make the pressure in the kettle reduced to normal pressure within 1 to 5 hours, raising the temperature to between 210 and 270 DEG C, and continuing to react for 1 to 5 hours, and discharging to obtain a powdery semi-aromatic nylon product. The method has mild reaction condition and low energy consumption; the product is easy to mold and machine; and the method solves the difficult problem of difficult discharging of the semi-aromatic nylon, and is applicable to industrialized production.

Description

A kind of preparation method of semi-aromatic nylon

Technical field

The present invention relates to a kind of preparation method of semiaromatic, belong to the macromolecular material synthesis technical field.Be particularly related to a kind of method of utilizing solvent-thermal method to prepare the semi-aromatic nylon powder.

Background technology

Along with the develop rapidly of contemporary science and technology, market is more and more higher to the demand of heat-resistant resin.In recent years, electronic industry is in order to adapt to product miniaturization, precise treatment and development trend cheaply, usually adopt on the unicircuit pole plate technology of carrying, connecting semi-conductor chip and electronic component, surperficial real packing technique (SMT) is popularized rapidly.And European Union implemented RoHS﹠amp on July 1st, 2006; [RoHS of European Union instructs introduction for WEEE instruction, power technology is used, 2007 (2), 65], this command request exports in the electronic product of European Union, lead content can not surpass 1000ppm, this just requires in the manufacturing processed of electronic and electrical equipment, especially in the implementation process of the real packing technique in surface, to use Pb-free solder, welding temperature is significantly improved than before, require matrix used material will under 270-280 ℃, keep indeformable [Li Xiaolan 45-75 second, be adapted to the PCB baseplate material of unleaded high heat-resisting low-k, copper-clad plate information, 2008 (5), 37], this new technology has proposed the requirement of higher thermotolerance and dimensional stability to the matrix resin material that uses.Simultaneously, some countries have put into effect the strict rules of some restricting vehicle oil consumption and exhaust emissions in succession in recent years, require car manufactures to improve motor efficiency, reduce automobile oil consumption and exhaust emissions amount.Addressing this problem one of important measures is to adopt light material to make the automobile lightweight, and plastics are most important light materials.The light-weighted emphasis of automobile is to replace metallic structural components with high performance plastics, and most important structure unit is the engine circumferential component, requires used plastics to have performances such as high temperature resistant, high strength, dimensional stabilizing and resistance to chemical reagents.Under this background, the semi-aromatic nylon material with good thermal stability, forming process, mechanical property and resistance to chemical reagents has obtained development faster.

Semi-aromatic nylon is by aliphatie diamine or diacid and is with aromatic diacid or diamines, makes through polycondensation.Owing in complete fragrant polymeric amide molecular backbone chain section, imported aliphatic chain, thereby improved forming process and solvability etc.Compare with aliphatics nylon, the characteristics of semi-aromatic nylon maximum are fine heat-resisting performance, second-order transition temperature is generally more than 100 ℃, fusing point is generally more than 250 ℃, all [Zhang Hongrong etc., the performance of high-performance semi-aromatic nylon engineering plastics and use progress, fine-chemical intermediate near 300 ℃ mostly, 2002 (6), 1].Heat aging property is good, and mechanical property is little to dependence on temperature, can keep more stable performance in wide temperature range.Water-intake rate is low, and the size and the mechanical property variation of goods is little after moisture absorption, and dimensional stability is good.Pharmaceutical chemicalss such as organic solvent-resistant and various vehicle fuel, oils, deicing fluid are good, and some has more good barrier properties for gases.Electrical insulation capability is good, also has outstanding arc resistance and tracking.Shrinkability, deformability, creep properties are very little, and rigidity and intensity generally are better than general aliphatics nylon.

The synthetic commonly used of semi-aromatic polyamide is High Temperature High Pressure solution polycondensation [Wang Peigang etc., semi-aromatic nylon synthesising process research progress, synthetic technology and application, 2006 (4), 29], general employing autoclave is a major equipment, with water is solvent, under High Temperature High Pressure, the nylon salt polymerization is generated the semi-aromatic polyamide prepolymer earlier, again with this prepolymer drying under reduced pressure, and pulverize and be carrying out solid phase polycondensation under high temperature and the vacuum condition or melt extruding to carry out melt phase polycondensation in the machine then by the particle of appropriate particle size, thereby acquisition semi-aromatic nylon product.This reaction was divided into for two steps, and synthetic route is longer, to having relatively high expectations of equipment.The major vendor of adopting this method to produce semi-aromatic nylon has French RhonePoulenc Chimie [the US Patent of company, US5109106, US5336754], Italy Eniricerche [the US Patent of company, US5070155, US5219953], Mitsui chemistry [US Patent, US6117942, US6130312, US6133406, US6319986], U.S. Amoco company [US Patent, US4603193, US5763561, US5962628], Belgium Solvay company [US Patent, US6518341], Holland DSM N. V. [US Patent, US6747120] etc.In addition, also has a kind of low-temperature solution polycondensation [US Patent, US6355769], with etc. aromatic dicarboxilic acid, aliphatic diamine and few stable agent (triphenyl phosphite) mixture of mole proportioning be dissolved in the mixed solvent of N-Methyl pyrrolidone (NMP) and pyridine, and add a small amount of CaCl of people ₂And LiCl; heating is about 2 hours under 100 ℃ and protection of inert gas condition; after the cooling with in the reaction mixture impouring methyl alcohol; filter the back methanol wash; place the vacuum drying oven drying to obtain the polyamide prepolymer polymers product that fusing point is higher, relative molecular mass is lower, will carry out solid state polymerization then equally and further improve molecular weight of product.The cryogenic fluid method is similarly two-step approach, has adopted the solvent system of the more expensive organic solvent of price as reaction simultaneously, and the hydrogen chloride gas that produces in the reaction process is dissolved in the solvent may produce corrosive nature to reactor, higher to equipment requirements.Adopt this method production cost higher, and can not operate by continuous production, therefore, the cryogenic fluid method also is not suitable for the large-scale industrialization production application.Japan Toyo Boseki K.K adopts the direct melt polycondensation method to develop MXD6 new variety [Tsuji well health people etc., the continuous preparation method of polymeric amide, Chinese patent, CN03820533.5], and design novel tubular polyamidation reaction unit at this reaction system, but this method scope of application is narrower, can only be applicable to this class fusing point of MXD6 relatively low product in semi-aromatic nylon, can't promote the use of.

The semi-aromatic nylon high melt point has caused its comparatively production process of difficulty, because high melt point is arranged, product is in the process of discharging, if fusion discharging, must be heated to more than the fusing point of product, thereby make product temperature when discharging too high, oxidation and decomposing phenomenon are serious, make jaundice of product color even blackening, influenced the performance and normal use of product.Simultaneously, can't be heated to too high temperature during owing to discharging, thereby cause the sticking still phenomenon of product serious, the yield of product is reduced greatly.And surpassed the product of its decomposition temperature for this class fusing point of PA6T, can't carry out the fusion discharging especially at all.So in the preparation process of semi-aromatic nylon, all can adopt two-step approach mostly, the lower prepolymer of synthetic molecular weight and fusing point at first, and then carrying out solid phase polycondensation under high temperature and the vacuum condition or melt extruding to carry out melt phase polycondensation in the machine, thus obtained performance meets the requirements of product.Such synthesis step, route is longer, to having relatively high expectations of equipment, carries out comparatively difficulty of continuous production, and energy consumption is also higher simultaneously.Therefore, demand exploring a kind of novel method of more efficiently preparation semi-aromatic nylon urgently.

Solvent-thermal method is emerging a kind of synthetic method [Wei Mingzhen in the materials chemistry field in recent years, the progress of solvent-thermal method nano materials, the Sichuan chemical industry, 2007 (3), 22], be usually used in the synthetic of nano material, mainly be meant in airtight volume, with organism or non-water-soluble matchmaker is solvent, a kind of method of reacting under the autogenous pressure of certain temperature and solution.Under the solvent thermal condition, exist the quick convection current of solvent and effective diffusion of solute, eliminated the mass transport of material.Compare with additive method, the organic solvent thermal response has the advantage of reaction conditions gentleness, under pressurized conditions, alter a great deal under character of solvent (density, viscosity, dissemination) and the usual conditions, make the reaction that is difficult to carry out under the normal condition to be achieved, be " softening learning " method of a kind of energy-conserving and environment-protective, have application promise in clinical practice.Do not see at present this method is used for semi-aromatic nylon synthetic pertinent literature report.

Summary of the invention

At the present state of the art, the semi-aromatic nylon preparation method that the object of the invention is to provide a kind of discharging convenience, reaction times weak point, reactions steps simplification, molecular weight of product height and is suitable for suitability for industrialized production.

For realizing the object of the invention, we adopt solvent-thermal method, are that polymerizable raw material obtains synthesizing semi-aromatic nylon with aromatic acid and aliphatic diamine under comparatively gentle condition, simultaneously, the semi-aromatic nylon that synthesizes is Powdered, has solved semi-aromatic nylon discharging problem of difficult.

The preparation method of this semi-aromatic nylon specifically comprises the steps:

(1) synthetic nylon salt: aliphatic diamine and water are mixed, be heated to 50～90 ℃, under agitation add aromatic acid, reach 7.0～7.7 until the pH value of solution value, continue to stir after 1～5 hour, be cooled to room temperature and continued to stir 1～5 hour again, it is standby to obtain nylon salt behind the filtration drying; Aliphatic diamine is 1: 2～10 with the quality ratio.

(2) preparation semi-aromatic nylon: the nylon salt and the solvent that make are added polymeric kettle by 0.5～3.0g/mL solid-to-liquid ratio; be warming up to 190～230 ℃ under the protection of inert gas; keeping the still internal pressure is 2.0～3.0MPa; venting after 1～5 hour; make the still internal pressure in 1～5 hour, reduce to normal pressure; be warming up to 210～270 ℃ then and continue reaction 1～5 hour, discharging obtains pulverous semi-aromatic nylon product.

In the step (1), described aromatic acid is terephthalic acid, m-phthalic acid, 4,4 '-biphenyl dicarboxylic acid, 4,4 '-dicarboxylate biphenyl sulfone or 4, a kind of in 4 '-dicarboxylate biphenyl ether; In the step (1), described aliphatic diamine is to contain a kind of in the aliphatic diamine of 6-13 carbon atom in the molecular backbone chain.

In the step (2), described solvent is a kind of in methyl alcohol, ethanol or the acetone.In the step (2), described rare gas element is a kind of in carbonic acid gas, nitrogen, argon gas or the helium.Used nylon salt is one or more nylon salt mixtures that step (1) makes in the step (2).

The present invention compared with prior art has following advantage:

(1) temperature of reaction is lower, and the reaction conditions gentleness need not High Temperature High Pressure and higher vacuum tightness, and is not high to equipment requirements, and energy consumption is lower.

(2) reactions steps need not solid state polymerization equipment, has saved more equipment input.

(3) synthetic semi-aromatic nylon intrinsic viscosity is at 1.20-1.90dL/g, and product is Powdered, and discharging is convenient, need not further granulation, can be directly used in forming process, and the product last handling process is simple.Pulverous product oven dry is comparatively convenient, simultaneously, if particular requirement is arranged, need carry out further tackify to sample, pulverous product has bigger specific surface area and smaller particle size, and low-boiling-point substance removes easier, and tackify time and temperature all have respectively and certain shorten and reduce.

(4) solvent for use toxicity is lower, and recyclable recycling, and environmental pollution is little.

Description of drawings

Fig. 1 is the infrared spectrogram of synthetic method synthetic semi-aromatic nylon PA12T of the present invention;

Fig. 2 is the infrared spectrogram of synthetic method synthetic semi-aromatic nylon PA13T of the present invention;

Fig. 3 is the infrared spectrogram of synthetic method synthetic semi-aromatic nylon PA6T of the present invention;

Fig. 4 is the nucleus magnetic hydrogen spectrum figure of synthetic method synthetic semi-aromatic nylon PA12I of the present invention; A, b, c, d, e represent the position of group shown in the structural formula respectively among the figure.

Fig. 5 is the infrared spectrogram of synthetic method synthetic semi-aromatic nylon PA11B of the present invention;

Fig. 6 is the nucleus magnetic hydrogen spectrum figure of synthetic method synthetic semi-aromatic nylon PA10S of the present invention; A, b, c, d, e represent the position of group shown in the structural formula respectively among the figure.

Fig. 7 is the infrared spectrogram of synthetic method synthetic semi-aromatic nylon PA9O of the present invention;

Fig. 8 is the infrared spectrogram of synthetic method synthetic PA12T/PA12I copolymerization product of the present invention;

Fig. 9 is the infrared spectrogram of synthetic method synthetic PA10O/PA10S copolymerization product of the present invention;

Figure 10 is the infrared spectrogram of synthetic method synthetic PA6T/PA12T copolymerization product of the present invention;

Figure 11 is the infrared spectrogram of synthetic method synthetic PA11B/PA9O copolymerization product of the present invention;

Figure 12 is the infrared spectrogram of synthetic method synthetic PA6T/PA12I/PA11B copolymerization product of the present invention;

Embodiment

Below in conjunction with embodiment the present invention is further described, but the present invention is not limited to this.

Embodiment 1

Mass ratio according to 12 carbon diamines and water is weighing in 1: 10, mix, be heated to 90 ℃, after treating the dissolving of 12 carbon diamines, under condition of stirring, add terephthalic acid, reach 7.2, continue afterwards to stir 3 hours until the pH of solution value, be cooled to room temperature again and keep stirring 2 hours, obtain the PA12T salt of white powder after suction filtration and the drying.

With the PA12T salt that makes and dehydrated alcohol proportioning by 1g/mL, add in the stainless steel polymeric kettle, behind air in the carbon dioxide replacement still 3 times, stir down progressively heat temperature raising to 205 ℃, control still internal pressure is at 2.8MPa, after the pressurize 1 hour, slowly venting made its still internal pressure reduce to normal pressure in 2 hours, was warming up to 215 ℃ then, continued reaction 3 hours, discharging obtains the PA12T product of white powder, and intrinsic viscosity is 1.72dL/g.The infrared spectrogram of product is seen Fig. 1, at 1630cm ^-1The place has formed the C=O key stretching vibration absorption peak on the strong amido linkage, has confirmed the synthetic of semi-aromatic nylon.Every physical and mechanical properties of product is listed in table 1, and chemical-resistant is listed in table 3, and by table 1 and table 3 as can be seen, PA12T has the good mechanical performance, and its tensile strength and flexural strength have in various degree raising than the aliphatics nylon 1212.Have good electrical properties and chemical-resistant, simultaneously, fusing point and second-order transition temperature are all far above corresponding aliphatics nylon.

Embodiment 2

Mass ratio according to 13 carbon diamines and water is weighing in 1: 5, mix, be heated to 70 ℃, after treating the dissolving of 13 carbon diamines, under condition of stirring, add terephthalic acid, reach 7.3, continue afterwards to stir 2 hours until the pH of solution value, be cooled to room temperature again and keep stirring 5 hours, obtain the PA13T salt of white powder after suction filtration and the drying.

With the PA13T salt that makes and acetone proportioning by 2g/mL, add in the stainless steel polymeric kettle, behind air in the high pure nitrogen displacement still 3 times, stir down progressively heat temperature raising to 190 ℃, control still internal pressure is at 2.0MPa, after the pressurize 3 hours, slowly venting made its still internal pressure reduce to normal pressure in 3 hours, was warming up to 220 ℃ then, continued reaction 5 hours, discharging obtains the PA13T product of white powder, and intrinsic viscosity is 1.85dL/g.The infrared spectrogram of product is seen Fig. 2, and every physical and mechanical properties of product is listed in table 2, and chemical-resistant is listed in table 3, and by table 2 and table 3 as can be seen, PA13T has shown mechanical property, electrical property and chemical-resistant preferably equally, and fusing point is a little less than PA12T.

Embodiment 3

Mass ratio according to hexanediamine and water is weighing in 1: 2, mix, be heated to 55 ℃, after treating own diamine dissolving, under condition of stirring, add terephthalic acid, reach 7.7, continue afterwards to stir 1 hour until the pH of solution value, be cooled to room temperature again and keep stirring 2 hours, obtain the PA6T salt of white powder after suction filtration and the drying.

With the PA6T salt that makes and methyl alcohol proportioning by 3g/mL, add in the stainless steel polymeric kettle, behind air in the high-purity argon gas displacement still 3 times, stir down progressively heat temperature raising to 230 ℃, control still internal pressure is at 3.0MPa, and pressurize is after 5 hours, slowly venting made its still internal pressure reduce to normal pressure in 2 hours, be warming up to 270 ℃ then, continue reaction 5 hours, discharging obtains the PA6T product of white powder.The intrinsic viscosity of product is 1.67dL/g, and fusing point is 372 ℃, and its infrared spectrogram is seen Fig. 3.

Embodiment 4

Mass ratio according to 12 carbon diamines and water is weighing in 1: 3, mix, be heated to 50 ℃, after treating the dissolving of 12 carbon diamines, under condition of stirring, add m-phthalic acid, reach 7.0, continue afterwards to stir 5 hours until the pH of solution value, be cooled to room temperature again and keep stirring 1 hour, obtain the PA12I salt of white powder after suction filtration and the drying.

With the PA12I salt that makes and methyl alcohol proportioning by 0.5g/mL, add in the stainless steel polymeric kettle, behind air in high-purity helium replacement still 3 times, stir down progressively heat temperature raising to 200 ℃, control still internal pressure is at 2.0MPa, and pressurize is after 1 hour, slowly venting made its still internal pressure reduce to normal pressure in 5 hours, be warming up to 210 ℃ then, continue reaction 1 hour, discharging obtains transparent pulverous PA12I product.The intrinsic viscosity of product is 1.65dL/g, and nucleus magnetic hydrogen spectrum figure sees Fig. 4.

Embodiment 5

Mass ratio according to 11 carbon diamines and water is weighing in 1: 8, mix, be heated to 90 ℃, after treating the dissolving of 11 carbon diamines, under condition of stirring, add 4,4 '-biphenyl dicarboxylic acid, reach 7.7 until the pH of solution value, continue afterwards to stir 5 hours, be cooled to room temperature again and keep stirring 5 hours, obtain pulverous PA11B salt after suction filtration and the drying.

With the PA11B salt that makes and ethanol proportioning by 1.0g/mL, add in the stainless steel polymeric kettle, behind air in the high pure nitrogen displacement still 3 times, stir down progressively heat temperature raising to 230 ℃, control still internal pressure is at 3.0MPa, and pressurize is after 5 hours, slowly venting made its still internal pressure reduce to normal pressure in 5 hours, be warming up to 270 ℃ then, continue reaction 5 hours, discharging obtains pulverous PA11B product.The intrinsic viscosity of product is 1.77dL/g, and fusing point is 360 ℃, and infrared spectra is seen Fig. 5.

Embodiment 6

Mass ratio according to decamethylene diamine and water is weighing in 1: 5, mix, be heated to 60 ℃, after treating the decamethylene diamine dissolving, under condition of stirring, add 4,4 '-dicarboxylate biphenyl sulfone, reach 7.3 until the pH of solution value, continue afterwards to stir 2 hours, be cooled to room temperature again and keep stirring 4 hours, obtain pulverous PA10S salt after suction filtration and the drying.

With the PA10S salt that makes and methyl alcohol proportioning by 0.5g/mL, add in the stainless steel polymeric kettle, behind air in the high-purity argon gas displacement still 3 times, stir down progressively heat temperature raising to 200 ℃, control still internal pressure is at 2.0MPa, and pressurize is after 3 hours, slowly venting made its still internal pressure reduce to normal pressure in 5 hours, be warming up to 250 ℃ then, continue reaction 3 hours, discharging obtains pulverous PA10S product.The intrinsic viscosity of product is 1.68dL/g, and fusing point is 295 ℃, and nucleus magnetic hydrogen spectrum figure sees Fig. 6.

Embodiment 7

Mass ratio according to nonamethylene diamine and water is weighing in 1: 2, mix, be heated to 50 ℃, after treating the nonamethylene diamine dissolving, under condition of stirring, add 4,4 '-dicarboxylate biphenyl ether, reach 7.5 until the pH of solution value, continue afterwards to stir 5 hours, be cooled to room temperature again and keep stirring 1 hour, obtain pulverous PA9O salt after suction filtration and the drying.

With the PA9O salt that makes and methyl alcohol proportioning by 3.0g/mL, add in the stainless steel polymeric kettle, behind air in high-purity helium replacement still 3 times, stir down progressively heat temperature raising to 220 ℃, control still internal pressure is at 2.5MPa, and pressurize is after 5 hours, slowly venting made its still internal pressure reduce to normal pressure in 3 hours, be warming up to 250 ℃ then, continue reaction 5 hours, discharging obtains pulverous PA9O product.The intrinsic viscosity of product is 1.73dL/g, and fusing point is 310 ℃, and infrared spectra is seen Fig. 7.

Embodiment 8

PA12T salt that embodiment 1 and embodiment 4 are prepared and PA12I salt are according to PA12T: the PA12I mass ratio is that 55: 45 ratio takes by weighing nylon salt and mixes, with mixed nylon salt and dehydrated alcohol proportioning with 1g/mL, add in the stainless steel polymeric kettle, behind air in the high pure nitrogen displacement still 3 times, stir down progressively heat temperature raising to 200 ℃, control still internal pressure is at 2.0MPa, after the pressurize 2 hours, slowly venting made its still internal pressure reduce to normal pressure in 3 hours, be warming up to 215 ℃ then, continue reaction 3 hours, discharging obtains translucent pulverous PA12T/PA12I copolymerization product.The intrinsic viscosity of product is 1.75dL/g, and fusing point is 250 ℃, and infrared spectrogram is seen Fig. 8.

Embodiment 9

Mass ratio according to decamethylene diamine and water is weighing in 1: 3, mix, be heated to 50 ℃, after treating decamethylene diamine dissolving, under condition of stirring 4,4 '-dicarboxylate biphenyl ether, reach 7.3 until the pH of solution value, continue afterwards to stir 2 hours, be cooled to room temperature again and keep stirring 2 hours, obtain pulverous PA10O salt after suction filtration and the drying.Take by weighing nylon salt PA10O, PA10S (the PA10S salt of embodiment 6 preparations), with PA10O: the PA10S mass ratio is that 3: 7 mixed is even, the proportioning that mixed nylon salt and dehydrated alcohol are pressed 0.5g/mL, add in the stainless steel polymeric kettle, behind air in the high-purity argon gas displacement still 3 times, stir down progressively heat temperature raising to 190 ℃, control still internal pressure is at 2.0MPa, after the pressurize 2 hours, slowly venting made its still internal pressure reduce to normal pressure in 5 hours, be warming up to 210 ℃ then, continue reaction 5 hours, discharging obtains pulverous PA10O/PA10S copolymerization product.The intrinsic viscosity of product is 1.67dL/g, and fusing point is 270 ℃, and infrared spectrogram is seen Fig. 9.

Embodiment 10

PA12T that embodiment 1 and embodiment 3 are prepared and PA6T salt are according to PA6T: the PA12T mass ratio is that 1: 4 ratio takes by weighing and mixes, the proportioning that mixed nylon salt and dehydrated alcohol are pressed 2g/mL, add in the stainless steel polymeric kettle, behind air in the carbon dioxide displacement still 3 times, stir down progressively heat temperature raising to 220 ℃, control still internal pressure is at 2.5MPa, after the pressurize 5 hours, slowly venting made its still internal pressure reduce to normal pressure in 3 hours, be warming up to 250 ℃ then, continue reaction 3 hours, discharging obtains the PA6T/PA12T copolymerization product of white powder.The intrinsic viscosity of product is 1.83dL/g, and fusing point is 305 ℃, and infrared spectrogram is seen Figure 10.

Embodiment 11

With the PA11B of embodiment 5 and embodiment 7 preparations and PA9O salt according to PA11B: the PA9O mass ratio is that 1: 9 ratio takes by weighing nylon salt and mixes, the proportioning that mixed nylon salt and dehydrated alcohol are pressed 2.0g/mL, add in the stainless steel polymeric kettle, behind air in high-purity helium replacement still 3 times, stir down progressively heat temperature raising to 220 ℃, control still internal pressure is at 2.5MPa, after the pressurize 5 hours, slowly venting made its still internal pressure reduce to normal pressure in 3 hours, be warming up to 245 ℃ then, continue reaction 3 hours, discharging obtains translucent pulverous PA11B/PA9O copolymerization product.The intrinsic viscosity of product is 1.66dL/g, and fusing point is 270 ℃, and infrared spectrogram is seen Figure 11.

Embodiment 12

With embodiment 3, the PA6T salt of embodiment 4 and embodiment 5 preparations, PA12I salt and PA11B salt, according to PA6T: PA12I: the PA11B mass ratio is that 1: 3: 1 ratio takes by weighing nylon salt and mixes, the proportioning that mixed nylon salt and dehydrated alcohol are pressed 0.5g/mL, add in the stainless steel polymeric kettle, behind air in the high pure nitrogen displacement still 3 times, stir down progressively heat temperature raising to 210 ℃, control still internal pressure is at 2.0MPa, after the pressurize 4 hours, slowly venting made its still internal pressure reduce to normal pressure in 3 hours, be warming up to 220 ℃ then, continue reaction 2 hours, discharging obtains pulverous PA6T/PA12I/PA11B copolymerization product.The intrinsic viscosity of product is 1.72dL/g, and fusing point is 255 ℃, and infrared spectrogram is seen Figure 12.

Adopt preparation method's products obtained therefrom of the present invention performance test as follows:

The physical and mechanical properties of table 1 semi-aromatic nylon PA12T

The physical and mechanical properties of table 2 semi-aromatic nylon PA13T

Measuring method about intrinsic viscosity [η] is as follows:

Polymers soln is different with small molecules solution, even under extremely rare situation, still has bigger viscosity.The measuring of internal friction when viscosity is molecular motion, because of strength of solution increases, intermolecular interaction increases, and resistance just increases during motion.We adopt Huggins formula and Kraemer formula can obtain intrinsic viscosity.

The Huggins formula:

$\frac{{\mathrm{\η}}_{\mathrm{sp}}}{C}=\left[\mathrm{\η}\right]+k{\left[\mathrm{\η}\right]}^{2}C---\left(1\right)$

C is the concentration of high polymeric solution in the formula, and [η] claims limiting viscosity, and it is and the irrelevant numerical value of concentration, therefore also claims intrinsic viscosity, η _SpBe called specific viscosity, if with η ₀The viscosity of expression solvent, η represents the viscosity of solution, then

${\mathrm{\η}}_{\mathrm{sp}}=\frac{\mathrm{\η}{-\mathrm{\η}}_0}{{\mathrm{\η}}_0}---\left(2\right)$

The Kraemer formula:

$\frac{\ln {\mathrm{\η}}_r}{C}=\left[\mathrm{\η}\right]-\mathrm{\β}{\left[\mathrm{\η}\right]}^{2}C---\left(3\right)$

K and β are constant in the formula, for flexible-chain polymer good solvent system, k+ β=1/2.η _rBe relative viscosity, η _r=η/η ₀, find out from formula (1) and formula (3), if use η _Sp/ C or ln η _r/ C is to the C mapping and be extrapolated to C → 0 (being infinite dilution), and two straight lines can meet on ordinate zou a bit, and its common intercept is limiting viscosity [η], and is as shown below:

The determination experiment step of semi-aromatic nylon intrinsic viscosity [η]:

Take by weighing 0.125g semi-aromatic nylon sample, pack in the 25mL volumetric flask, at room temperature add the 15mL mass percent concentration and be 98% the vitriol oil, after treating that sample dissolves fully, volumetric flask and the reagent bottle that fills the vitriol oil were placed 25 ± 0.05 ℃ of cleansing bath tub constant temperature 20 minutes, liquid level in the volumetric flask is added to the 25mL scale marks and shake up with the vitriol oil that is preheating to 25 ℃.

The solution for preparing is got 10mL add Ubbelohde viscometer, viscometer vertically is installed in 25 ± 0.05 ℃ the water bath with thermostatic control constant temperature and after 20 minutes solution stream is counted the elution time through the time of viscometer two scale markss.Each sample is surveyed (front and back error be no more than ± 0.1 second) 6 times, averages.In viscometer, add mass percent concentration successively more successively respectively and be 98% vitriol oil 5mL, 5mL, 10mL, 10mL, make strength of solution become 2/3,1/2,1/3,1/4 of initial concentration, measure the elution time respectively with quadrat method.

With being the elution time of 98% vitriol oil solvent with quadrat method quality measurement percentage concentration, by the following formula calculating of mapping, two straight lines meet at Y-axis, and intercept is [η].

$\underset{C\→0}{\lim }\frac{{\mathrm{\η}}_{\mathrm{sp}}}{C}=\underset{C\→0}{\lim }\frac{{\ln \mathrm{\η}}_r}{C}=\left[\mathrm{\η}\right]---\left(4\right)$

The chemical resistance of table 3 semi-aromatic nylon PA12T and PA13T

Institute's column data is that sample soaks the stretching strength retentivity after 7 days in 23 ℃ chemical (except the hot water) in the table.

Claims (4)

1. the preparation method of a semi-aromatic nylon is characterized in that, comprises the steps:

(1) synthetic nylon salt: aliphatic diamine and water are mixed, be heated to 50～90 ℃, under agitation add aromatic acid, reach 7.0～7.7 until the pH value of solution value, continue to stir after 1～5 hour, be cooled to room temperature and continued to stir 1～5 hour again, it is standby to obtain nylon salt behind the filtration drying; Aliphatic diamine is 1: 2～10 with the quality ratio;

(2) preparation semi-aromatic nylon: the nylon salt and the solvent that make are added polymeric kettle by 0.5～3.0g/mL solid-to-liquid ratio, be warming up to 190～230 ℃ under a kind of gas shield in carbonic acid gas, nitrogen, argon gas or helium, keeping the still internal pressure is 2.0～3.0MPa, venting after 1～5 hour, make the still internal pressure in 1～5 hour, reduce to normal pressure, be warming up to 210～270 ℃ then and continue reaction 1～5 hour, discharging obtains pulverous semi-aromatic nylon product; Described solvent is a kind of in methyl alcohol, ethanol or the acetone.

2. the preparation method of semi-aromatic nylon according to claim 1, it is characterized in that the aromatic acid described in the step (1) is terephthalic acid, m-phthalic acid, 4,4 '-biphenyl dicarboxylic acid, 4,4 '-dicarboxylate biphenyl sulfone or 4, a kind of in 4 '-dicarboxylate biphenyl ether.

3. the preparation method of semi-aromatic nylon according to claim 1 is characterized in that, the aliphatic diamine described in the step (1) is to contain a kind of in the aliphatic diamine of 6～13 carbon atoms in the molecular backbone chain.

4. the preparation method of semi-aromatic nylon according to claim 1 is characterized in that, used nylon salt is two or more a mixture of step (1) gained nylon salt in the step (2).

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