WO2010003277A1 - 半芳香族聚酰胺及其低废水排放量的制备方法 - Google Patents

半芳香族聚酰胺及其低废水排放量的制备方法 Download PDF

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WO2010003277A1
WO2010003277A1 PCT/CN2008/001306 CN2008001306W WO2010003277A1 WO 2010003277 A1 WO2010003277 A1 WO 2010003277A1 CN 2008001306 W CN2008001306 W CN 2008001306W WO 2010003277 A1 WO2010003277 A1 WO 2010003277A1
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acid
reaction
semi
diamine
mol
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PCT/CN2008/001306
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English (en)
French (fr)
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曹民
夏世勇
黄险波
蔡彤旻
曾祥斌
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金发科技股份有限公司
上海金发科技发展有限公司
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Priority to EP08783511A priority Critical patent/EP2301985A4/en
Priority to US12/743,452 priority patent/US8420772B2/en
Priority to PCT/CN2008/001306 priority patent/WO2010003277A1/zh
Priority to KR1020107002638A priority patent/KR101183393B1/ko
Priority to JP2010537231A priority patent/JP5174921B2/ja
Publication of WO2010003277A1 publication Critical patent/WO2010003277A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C08G69/30—Solid state polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/02—Recovery or working-up of waste materials of solvents, plasticisers or unreacted monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to the field of polyamide resin technology, and in particular to a method for preparing a semi-aromatic polyamide having a low wastewater discharge amount.
  • Aliphatic polyamides such as PA6, PA66, have excellent mechanical strength, heat resistance, chemical resistance, abrasion resistance and self-lubricity, and have low friction coefficient.
  • Applications include electronics, automotive parts, furniture. , building materials and fiber, has become one of the most important engineering plastics.
  • the semi-aromatic polyamide is a polyamide resin prepared by polycondensation of a diamine or a dicarboxylic acid having an aromatic ring and an aliphatic dicarboxylic acid or a diamine, and is one of aromatic polyamides. Since the aromatic ring is introduced into the main chain of the polyamide molecule, the heat resistance and mechanical properties are improved, the water absorption rate is lowered, and the suitable performance/price ratio is obtained, which is between the general engineering plastic nylon and the high temperature resistant engineering plastic. A resin with high heat resistance between PEEK, mainly used in the automotive and electrical electronics industries. With the rapid development of high technology, its applications have made new breakthroughs and progress, and market demand is on the rise. Semi-aromatic polyamide products currently mainly include polyamide MXD6, 6T/66, 6 ⁇ /6 ⁇ , 6 ⁇ /6 ⁇ /66. 6 ⁇ / ⁇ -5 ⁇ and 9 ⁇ .
  • EP1074585A1 disclose a process for the preparation of polyamide MXD6.
  • an aromatic diamine is added dropwise to a molten aliphatic dicarboxylic acid in a batch reactor while the temperature of the system is raised to remove the water formed by the condensation to carry out a polymerization reaction.
  • CN1451677A describes a solid phase thickening method for polyamide MXD6, which holds the polyamide under specific conditions, even if the starting polyamide is used for 20 days or more from the post-preparation to solid phase thickening. Amide MXD6 yellowness is also very low.
  • the polyamide 6T copolymer is obtained by polycondensation of a dicarboxylic acid component mainly composed of terephthalic acid and isophthalic acid or adipic acid, and a diamine component mainly composed of hexamethylenediamine.
  • the polyamide 6T copolymer has a high amide group concentration, which results in poor chemical resistance, water absorption resistance, and melt processing stability of the polymer.
  • the addition of a large amount of the third monomer reduces the crystallinity of the polymer, and also causes a decrease in heat resistance, chemical resistance, water absorption resistance, and dimensional stability of the polymer.
  • U.S. Patents 5,158,882, 5,981,692 and US 962,628 describe terephthalic acid, isophthalic acid, 1,6-hexanedioic acid, 1,6-hexanediamine and 2-methyl-1,5-pentanediamine as main raw materials.
  • Patent US 6,140,459 describes the synthesis of a polyamide 6T copolymer by melt polymerization using terephthalic acid, 1,6-hexanediamine and another aliphatic long chain dicarboxylic acid as starting materials.
  • the late polymerization temperature exceeds the melting point of the polymer, and the residence time is too long at high temperatures, and various side reactions and degradation reactions of the polymer are severe, which tends to cause the color tone of the polymer to change. Poor, mechanical strength is reduced and moldability is deteriorated.
  • No. 5,663,284 discloses a process for preparing a polyamide 6T/66 polymer by first carrying out primary polymerization in the presence of water at a reaction temperature below the melting point of the polymer, and maintaining it by replenishing water into the autoclave during discharge.
  • the pressure, prepolymer is melt-bonded through a vented twin-screw extruder to give a high viscosity polymer.
  • the prepolymerization temperature is close to the melting point of the polymer to increase the intrinsic viscosity of the prepolymer.
  • the patent US6133406 proposes a polymerization process of a semi-aromatic polyamide: firstly synthesizing a low-characteristic prepolymer at a lower temperature in the presence of water, and then solid-phase increasing The pre-polymer with higher intrinsic viscosity is prepared by viscous reaction, and then the product is highly viscous by double-screw melt extrusion to obtain a polymer with high intrinsic viscosity.
  • This route involves pre-polymerization Complex, solid phase viscosification, melt viscosification multi-step reactions require complex production steps and equipment.
  • the polyamide 9T resin after obtaining the prepolymer, can be obtained by long-term solid phase thickening, which requires the prepolymer to have a high intrinsic viscosity.
  • Polyamide 9T has high crystallinity, dimensional stability and low water absorption.
  • a semi-aromatic polyamide prepolymer having a higher intrinsic viscosity can be obtained by increasing the prepolymerization temperature or discharging water in the prepolymerization system.
  • Increasing the prepolymerization temperature leads to the occurrence of side reactions, as well as the reaction pressure, and the equipment requirements are also increased. Exhausting the water in the reaction system volatilizes the unreacted diamine, resulting in a large difference between the monomer unit ratio of the prepolymer and the starting monomer added to the reactor, and the monomeric dicarboxylic acid cannot be guaranteed.
  • the molar ratio of the diamine is balanced.
  • Patent US5663284 determines the end point of the salt formation reaction by measuring the pH value, and uses a salt to prepare a semi-aromatic polyamide.
  • the preparation method recycles the wastewater generated during the polymerization process, greatly reduces the discharge of the wastewater; and the original in the wastewater The material has been effectively recycled, which improves the utilization rate of raw materials.
  • the diamine in the wastewater compensates for the diamine lost with the discharge of water during the prepolymerization process, ensuring the monomeric dicarboxylic acid and the second The molar ratio of the amine is balanced.
  • Another object of the present invention is to provide a semiaromatic polyamide prepared by the above production method.
  • a method for preparing a semi-aromatic polyamide comprising the steps of:
  • the aliphatic diamine having 4 to 14 carbon atoms in the above step (1) includes a linear aliphatic diamine, a branched aliphatic diamine or an alicyclic diamine.
  • the linear aliphatic diamine includes 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecyldiamine or U2-dodecaamine.
  • Branched aliphatic diamines include 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,4-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine or 5 - Methyl-1,9-nonanediamine.
  • the alicyclic diamine includes cyclohexanediamine, methylcyclohexanediamine or 4,4,-diaminodicyclohexylformamidine.
  • the semi-aromatic polyamide may contain one or more types of these aliphatic diamines, and the preferred aliphatic diamines are 1,6-hexanediamine, 1,9-nonanediamine, 1,10-fluorene. Diamine, 2-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine or 5-methyl-1,9-decanediamine. The most preferred aliphatic diamine is 1,6-hexanediamine, 1,9-nonanediamine or 1,10-nonanediamine.
  • the aromatic dicarboxylic acid in the above step (1) includes terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 2,5-dichloroterephthalic acid, 2,6-naphthene Formic acid, 1,4-na Dicarboxylic acid, 4,4'-diphenyl phthalate or 2,2'-diphenyl phthalic acid.
  • Semi-aromatic polyamides may contain one or more types of these aromatic dicarboxylic acids.
  • Preferred aromatic dicarboxylic acids are terephthalic acid, isophthalic acid or 4,4'-diphenyl phthalic acid.
  • the most preferred aromatic dicarboxylic acid is terephthalic acid.
  • the water in the above step (1) may also be the wastewater generated in the previous prepolymerization process.
  • the wastewater contains 0.1 to 5% by weight of an aliphatic diamine having 4 to 14 carbon atoms.
  • the prepolymerization in the above step (1) is carried out by adding an aromatic dicarboxylic acid, an aliphatic diamine having 4 to 14 carbon atoms, water, a blocking agent, and a catalyst to an autoclave, and prepolymerizing the reaction.
  • the temperature is 200 ⁇ 280°C
  • the reaction system pressure is l ⁇ 5MPa
  • the reaction time is .1 ⁇ 6 hours
  • the pressure is stabilized by discharging water in the system later in the reaction.
  • the prepolymer is dried and used, and the reaction is carried out.
  • the wastewater from the later discharge system and the wastewater separated from the drying of the prepolymer after the end of the reaction are collected for use in the next polymerization.
  • a preferred reaction temperature is 220 to 250 ° C; a preferred reaction time is 2 to 4 hours; and a preferred reaction system pressure is 1.5 to 3 MPa.
  • a prepolymer having an intrinsic viscosity [ ⁇ ] of from 0.06 to 0.3 dl/g, preferably from 0.08 to 0.2 dl/g, as measured in 96% sulfuric acid at 25 ° C can be obtained.
  • the catalyst includes phosphoric acid, succinic acid, hypophosphorous acid or a salt thereof or an ester thereof, preferably sodium phosphate, sodium phosphite, sodium hypophosphite, potassium phosphite.
  • the amount of the catalyst is 0.01 to 2% by weight of the raw material (the raw material refers to the total weight of the aromatic dicarboxylic acid, the aliphatic diamine having 4 to 14 carbon atoms, the blocking agent and the catalyst), preferably 0.05 to 1% by weight.
  • the blocking agent includes a monocarboxylic acid or a monoamine or a mixture thereof.
  • a monocarboxylic acid is preferred because the monocarboxylic acid is less toxic, less volatile, and easier to handle than the monoamine;
  • the blocking agent may be one or more of them.
  • the most preferred monocarboxylic acid is acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, benzoic acid or phenylacetic acid.
  • Monoamines include aliphatic monoamines such as ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine, n-pentylamine, n-decylamine, dodecylamine, stearylamine, etc.; A monoamine such as cyclohexylamine or the like; an aromatic monoamine such as aniline, p-toluidine, o-toluidine, 2,6-dimethylaniline, 3,4-dimethylaniline, o-ethylaniline or the like.
  • the blocking agent may be one or more of them.
  • the most preferred monoamine is ethylamine, n-propylamine, n-butylamine, aniline or p-toluidine.
  • the molar amount of the blocking agent is from 0.2 to 10%, preferably from 0.5 to 5%, based on the aromatic dicarboxylic acid. Because when the amount of the blocking agent is too high, the molecular weight of the polymer is too small; when the amount of the blocking agent is too low, the molecular weight of the polymer is too large or the active end group content of the polymer is too large.
  • the amount of water added in the initial stage of the prepolymerization in the above step (1) is 15 to 35% by weight. Because if the amount of water added is too small, the material will solidify during the polymerization process, the reaction will not proceed, and the product cannot be discharged from the reactor; if the amount of water added is too large, the polymerization rate will decrease, and the obtained prepolymerization will be obtained. The viscosity of the intrinsic property is also lowered, and the viscosity-increasing reaction cannot be smoothly performed. In order to increase the reaction speed and the intrinsic viscosity of the prepolymer, a large amount of water is discharged during the polymerization, which inevitably leads to serious loss of the diamine and destruction of the monomer. Molar ratio.
  • the water added in the above step (1) does not participate in the prepolymerization reaction, and a small amount of water is generated in the prepolymerization reaction, and after the prepolymerization process, a little more wastewater than the added amount is collected, and the wastewater can be further Add to the next prepolymerization.
  • the prepolymerization does not require the use of new water, and there is almost no discharge of wastewater. Since the waste water generated in the prepolymerization process contains a small amount of diamine, the discharge will cause the loss of the diamine, and the recycling of the waste water will increase the utilization rate of the raw material diamine. At the same time, the diamine in the wastewater added in the initial stage of prepolymerization compensates for the water in the prepolymerization process.
  • the removal of the lost diamine ensures a balance of the molar ratio of the monomeric dicarboxylic acid and the diamine, which facilitates the smooth progress of the polymerization reaction, and obtains a semi-aromatic polyamide having a high characteristic point.
  • the thickening of the prepolymer in the above step (2) can be achieved by a solid phase tackifying reaction or a melt thickening reaction, and among them, a solid phase thickening method is preferred.
  • the solid phase thickening is carried out below the melting point of the polymer, and the preferred reaction temperature is 220 to 280 ° C, and the solid phase viscosity increasing reaction time is 3 to 20 hours, preferably 5 to 15 hours; in order to prevent oxidation of the polymer, solid
  • the phase thickening reaction is carried out under a nitrogen atmosphere or under vacuum, preferably under a nitrogen atmosphere.
  • the advantage of solid phase thickening is that the reaction temperature is low, the degradation reaction is small, and the obtained polyamide has good color tone, dimensional stability, and heat resistance.
  • melt thickening is carried out on an extrusion device with a vent; the melt thickening temperature is higher than the melting point of the prepolymer, the preferred reaction temperature is 290 to 350 ° C ; the melt thickening reaction time is 1 to 8 minutes , preferably 2 to 6 minutes.
  • the advantage of melt thickening is that the reaction time is short. After the viscosity-increasing reaction, the final product semi-aromatic polyamide is obtained.
  • the semi-aromatic polyamide obtained by the invention has an intrinsic viscosity [ ⁇ ] of 0.8 to 2.5 dl/g, preferably 1.0 to 2.0 dl/g; a terminal carboxyl group content of 15 to 80 mol/t, preferably 15 to 50 mol/t; The amino group content is 15 to 80 mol/t, preferably 15 to 60 mol/t; and the melting point is 270 to 330 ° C, preferably 290 to 330 Torr.
  • the reason for this range is that when the melting point is too low, the heat resistance of the polyamide does not reach the requirements of the present invention; and when the melting point is too high, a degradation reaction occurs during hot working.
  • the semi-aromatic polyamide preparation method of the invention recycles the wastewater generated during the polymerization process, greatly reduces the discharge amount of the wastewater; The raw materials are effectively recycled, and the utilization rate of the raw material diamine is improved. Meanwhile, the diamine in the waste water added in the initial stage of the prepolymerization compensates for the diamine which is lost with the water discharge during the prepolymerization process, and is ensured. The molar ratio of the monomeric dicarboxylic acid to the diamine is balanced.
  • the semi-aromatic polyamide prepared by the invention has high crystallinity, intrinsic viscosity and heat-resistant temperature, good hue, low content of active end groups, good processing stability and no corrosion of the mold.
  • Antioxidant, lubricant, nucleation can be added as needed Agent, flame retardant, colorant, plasticizer, antistatic agent; can also be enhanced by adding glass fiber, carbon fiber, inorganic filler; at the same time, it can also be blended with other polymers to prepare polymer alloy.
  • the logarithmic specific viscosity ⁇ of a polyamide having a concentration of 0.05, 0.1, 0.3, and lg/dl was measured in 25 Torr of concentrated sulfuric acid.
  • riinh represents a logarithmic specific viscosity (dl/g), and to represents a solvent flow time. (see), indicating the flow time (sec) of the sample solution, and C indicates the concentration (g/dl) of the sample solution.
  • the data of riinh is extrapolated to a concentration of 0 to obtain the intrinsic viscosity [ ⁇ ] of the sample.
  • the amine content of the sample end was titrated by a fully automatic potentiometric titrator. 0.5 g of the polymer, 45 ml of phenol and 3 ml of anhydrous methanol were added, and the mixture was heated under reflux. After the sample was completely dissolved, it was cooled to room temperature, and the amine group content was titrated with a standard hydrochloric acid standard solution.
  • the carboxyl group content of the sample was titrated by a fully automatic potentiometric titrator. Take 0.5g of polymer, add 50ml of o-cresol, dissolve at reflux, quickly add 400 L of formaldehyde solution after cooling, and titrate the carboxyl group content with the calibrated KOH-ethanol solution.
  • the content of diamine in the wastewater produced by the prepolymerization was titrated by a fully automatic potentiometric titrator. Take 100 ml of wastewater and titrate the diamine content with the calibrated hydrochloric acid standard solution.
  • the melting point and heat of fusion of the sample were tested using a Perkin Elmer DSC-6 analyzer.
  • the atmosphere has a flow rate of 40 mIJmin.
  • the endothermic peak temperature at the time is set to the melting point Tm, and the heat of fusion A Hm is calculated from the endothermic peak area at this time.
  • the crystallinity of the polymer was measured by X-ray diffraction.
  • the molten polymer was quenched with liquid nitrogen to prepare an amorphous sample.
  • the X-ray diffraction peak areas of the amorphous sample and the polymer sample were respectively S ⁇ PS 2 , and the crystallinity was calculated by the following formula.
  • x c represents crystallinity (%), showing the X-ray diffraction peak area of the amorphous sample
  • s 2 represents the X-ray diffraction peak area of the polymer sample.
  • the reaction was continued at a constant temperature of 230 ° C and a constant pressure of 2 MPa for 2 hours.
  • the pressure was kept constant by removing the formed water, and the reaction was completed, and the prepolymer was vacuum dried at 80 ° C for 24 hours.
  • a prepolymer having an intrinsic viscosity [ ⁇ ] of 0.14 dVg was obtained.
  • a total of 2,361 g of wastewater was collected during the prepolymerization, and the content of diamine in the wastewater was 1.7% by weight.
  • the prepolymer was solid phase viscosified for 10 hours under a nitrogen atmosphere of 26 CTC to obtain a PA10T resin having a melting point of 319 ⁇ , a heat of fusion of 67.5 J/g, an intrinsic viscosity [ ⁇ ] of 1.02 dl/g and a terminal amine group content of 14 mol/t.
  • the terminal carboxyl group content was 107 mol/t.
  • Table 1 The results are shown in Table 1.
  • the temperature was raised to 220 ° C in the next 2 hours, and the reaction mixture was stirred at 220 ° C for 1 hour, and then the temperature of the reactant was raised to 230 ° C under stirring.
  • the reaction was continued at a constant temperature of 230 ° C and a constant pressure of 2 MPa. After 2 hours, the pressure was kept constant by removing the formed water.
  • the mixture was discharged, and the polymer was vacuum dried at 80 ° C for 24 hours to obtain a prepolymer having an intrinsic viscosity [ ⁇ ] of 0.15 dl/g.
  • a total of 2339 g of wastewater was collected during the prepolymerization, and the content of diamine in the wastewater was 1.8% by weight.
  • the prepolymer was solid phase viscosified in 26 (TC nitrogen atmosphere for 10 hours to obtain PA10T resin, melting point of 320 ° C, melting Heat 73.5J/g, intrinsic viscosity [ ⁇ ] 1.38dl / g, an amine end content of 35mol / t, terminal carboxyl group content of 43mol / t.
  • Table 1 The results are shown in Table 1.
  • Example 1 The preparation procedure of Example 1 was repeated except that the wastewater added was the wastewater collected during the polymerization of Example 1. The results are shown in Table 1.
  • Example 1 The preparation procedure of Example 1 was repeated except that the wastewater added was the wastewater collected during the polymerization of Example 2. The results are shown in Table 1.
  • Example 1 The preparation procedure of Example 1 was repeated except that the wastewater added was the wastewater collected during the polymerization of Example 3. The results are shown in Table 1. Table 1
  • the temperature was raised to 220 ° C over 2 hours with stirring, and the reaction mixture was stirred at 22 CTC for 1 hour, and then the temperature of the reactant was raised to 230 ° C with stirring.
  • the reaction was continued at a constant temperature of 230 ° C and a constant pressure of 2 MPa for 2 hours, the pressure was kept constant by removing the formed water, and the reaction was completed, and the prepolymer was vacuum dried at 80 ° C for 24 hours.
  • a prepolymer having a characteristic salary [ ⁇ ] of 0.13 dl/g was obtained.
  • a total of 2356 g of wastewater was collected during the prepolymerization, and the content of diamine in the wastewater was 1.5% by weight.
  • the prepolymer was solid phase viscosified for 10 hours under a nitrogen atmosphere of 26 CTC to obtain a semi-aromatic polyamide resin having a melting point of 291 ° C, a heat of fusion of 38.7 J/g, a characteristic salary [ ⁇ ] of 0.97 dVg, and an amine group content. It was 19 mol/t and the terminal carboxyl group content was 112 mol/t. The results are shown in Table 2.
  • the temperature was raised to 220 ° C over 2 hours with stirring, and the reaction mixture was stirred at 220 ° C for 1 hour, and then the temperature of the reactant was raised to 230 ° C with stirring.
  • the reaction was continued at a constant temperature of 230 ° C and a constant pressure of 2 MPa for 2 hours, the pressure was kept constant by removing the formed water, and the reaction was completed, and the prepolymer was vacuum dried at 80 ° C for 24 hours.
  • a prepolymer having an intrinsic viscosity [ ⁇ ] of 0.15 dl/g was obtained.
  • a total of 2386 g of wastewater was collected during the prepolymerization, and the content of diamine in the wastewater was 1.8% by weight.
  • the prepolymer was solid phase viscosified for 10 hours under a nitrogen atmosphere of 26 CTC to obtain a semi-aromatic polyamide resin having a melting point of 292 ⁇ , a heat of fusion of 45.3 J/g, an intrinsic viscosity [ ⁇ ] of 1.27 dl/g, and a terminal amine group content of 43 mol/t, the terminal carboxyl group content was 51 mol/t.
  • Table 2 The results are shown in Table 2.
  • Example 5 The preparation procedure of Example 5 was repeated except that the wastewater added was the wastewater collected during the polymerization of Example 5. The results are shown in Table 2.
  • Example 5 The preparation procedure of Example 5 was repeated except that the wastewater added was the wastewater collected during the polymerization of Example 6. The results are shown in Table 2.
  • Example 5 The preparation procedure of Example 5 was repeated except that the wastewater added was the wastewater collected during the polymerization of Example 7. The results are shown in Table 2. Table 2 Comparative Example Embodiment Example 2 Example 5 Example 6 Example 7 Example 8 Terephthalic acid (mol) 17 17 17 17 17 Interphthalic acid (mol) 3 3 3 3 3 3
  • the temperature was raised to 220 ° C over 2 hours with stirring, and the reaction mixture was stirred at 220 ° C for 1 hour, and then the temperature of the reactant was raised to 230 ° C with stirring.
  • the reaction was continued at a constant temperature of 230 Torr and a constant pressure of 2 MPa for 2 hours. The pressure was kept constant by removing the formed water.
  • the prepolymer was vacuum dried at 80 Torr for 24 hours to obtain an intrinsic viscosity [ ⁇ ] is a prepolymer of 0.13 dl 7 g.
  • a total of 2317 g of wastewater was collected during the prepolymerization, and the content of diamine in the wastewater was 1.6% by weight.
  • the prepolymer was solid phase viscosified for 10 hours under a nitrogen atmosphere of 260 Torr to obtain a semi-aromatic polyamide resin having a melting point of 294 ° C, a heat of fusion of 41.2 J/g, and an intrinsic viscosity [ ⁇ ] of 1.07 dl/g.
  • the content was 16 mol/t, and the terminal carboxyl group content was 96 mol/t.
  • the results are shown in Table 3.
  • the temperature was raised to 220 ° C over 2 hours with stirring, and the reaction mixture was stirred at 220 ° C for 1 hour, and then the temperature of the reactant was raised to 230 ° C with stirring.
  • the reaction was continued at a constant temperature of 230 ° C and a constant pressure of 2 MPa for 2 hours. The pressure was kept constant by removing the formed water, and the reaction was completed, and the prepolymer was vacuum dried at 80 ° C for 24 hours.
  • a prepolymer having an intrinsic viscosity [ ⁇ ] of 0.15 dl/g was obtained.
  • a total of 2,395 g of wastewater was collected during the prepolymerization, and the content of diamine in the wastewater was 1.7% by weight.
  • the prepolymer was solid phase viscosified for 10 hours under a nitrogen atmosphere of 260 Torr to obtain a semi-aromatic polyamide resin having a melting point of 294 ° C, a heat of fusion of 48.3 J/g, and an intrinsic viscosity [ ⁇ ] of 1.29 dl/g.
  • the content was 34 mol/t, and the terminal carboxyl group content was 50 mol/t.
  • Table 3 The results are shown in Table 3.
  • the temperature was raised to 220 ° within 2 hours with stirring (:, the reaction mixture was stirred at 220 ° C for 1 hour, and then the temperature of the reactant was raised to 230 ° C under stirring.
  • the reaction was at a constant temperature of 230 ° C and 2 Mpa
  • the pressure was continued for 2 hours under constant pressure, the pressure was kept constant by removing the formed water, and the reaction was completed, and the prepolymer was vacuum dried at 8 (TC for 24 hours to obtain an intrinsic viscosity [ ⁇ ]. It is a prepolymer of 0.14 dl/g. A total of 1960 g of wastewater was collected during the prepolymerization, and the content of diamine in the wastewater was 1.4% by weight.
  • the prepolymer was solid phase viscosified for 10 hours under a nitrogen atmosphere at 260 ° C to obtain a semi-aromatic polyamide resin having a melting point of 312 ° C, a heat of fusion of 34.8 J/g, and an intrinsic viscosity [ ⁇ ] of 0.96 dl/g.
  • the amine group content was 17 mol/t, and the terminal carboxyl group content was 92 mol/t.
  • the temperature was raised to 220 ° C over 2 hours with stirring, and the reaction mixture was stirred at 220 ° C for 1 hour, and then the temperature of the reactant was raised to 230 ° C with stirring.
  • the reaction was continued at a constant temperature of 230 Torr and a constant pressure of 2 MPa for 2 hours. The pressure was kept constant by removing the formed water, and the reaction was completed, and the prepolymer was vacuum dried at 80 ° C for 24 hours to obtain characteristics.
  • the prepolymer having a viscosity [ ⁇ ] of 0.15 dl/g. A total of 2053 g of wastewater was collected during the prepolymerization, and the content of diamine in the wastewater was 1.4% by weight.
  • the prepolymer was solid phase viscosified for 10 hours under a nitrogen atmosphere of 260 Torr to obtain a semi-aromatic polyamide resin having a melting point of 312 ° C, a heat of fusion of 33.4 J/g, and an intrinsic viscosity [ ⁇ ] of 1.32 dl/g.
  • the content was 33 mol/t, and the terminal carboxyl group content was 39 mol/t.
  • Table 3 The results are shown in Table 3.
  • the temperature was raised to 220 °C over 2 hours with stirring, and the reaction mixture was stirred at 220 ° C for 1 hour, and then the temperature of the reactant was raised to 230 ° C with stirring.
  • the reaction was continued at a constant temperature of 230 ° C and a constant pressure of 2 MPa for 2 hours. The pressure was kept constant by removing the formed water, and the reaction was completed, and the prepolymer was vacuum dried at 80 ° C for 24 hours.
  • a prepolymer having an intrinsic viscosity [ ⁇ ] of 0.15 d]/g was obtained.
  • a total of 2023 g of wastewater was collected during the prepolymerization, and the content of diamine in the wastewater was 1.3% by weight.
  • the prepolymer was solid phase viscosified for 10 hours under a nitrogen atmosphere at 260 ° C to obtain a semi-aromatic polyamide resin having a melting point of 316 ° (:, a heat of fusion of 34.2 J/g, and an intrinsic viscosity [ ⁇ ] of 1.1 JLdl/g.
  • the terminal amine group content was 19 mol/t, and the terminal carboxyl group content was 87 mol/t.
  • the temperature was raised to 220 ° C over 2 hours with stirring, and the reaction mixture was stirred at 220 ° C for 1 hour, and then the temperature of the reactant was raised to 230 ° C with stirring.
  • the reaction was continued at a constant temperature of 230 ° C and a constant pressure of 2 MPa for 2 hours. The pressure was kept constant by removing the formed water, and the reaction was completed, and the prepolymer was vacuum dried at 80 ° C for 24 hours.
  • a prepolymer having an intrinsic viscosity [ ⁇ ] of 0.15 dl/g was obtained.
  • a total of 1987 g of wastewater was collected during the prepolymerization, and the content of diamine in the wastewater was 1.5% by weight.
  • the prepolymer was solid phase viscosified for 10 hours under a nitrogen atmosphere at 260 ° C to obtain a semi-aromatic polyamide resin having a melting point of 317 ° C, a heat of fusion of 35.7 J/g, and an intrinsic viscosity [ ⁇ ] of 1.43 dl/g.
  • the amine group content was 40 mol/t, and the terminal carboxyl group content was 49 mol/t.

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Description

半芳香族聚酰胺及其低废水排放量的制备方法. 技术领域
本发明涉及聚酰胺树脂技术领域， 具体地说，涉及一种低废水排 放量的半芳香族聚酰胺制备方法。
背景技术
脂肪族聚酰胺， 如 PA6、 PA66， 具有优异的机械强度、 耐热性、 耐化学药品性、耐磨损性和自润滑性， 且摩擦系数低， 其应用领域包 括电子电器、汽车部件、家具、建材和纤维， 已成为最重要的工程塑 料之一。
半芳香族聚酰胺是带芳香环的二胺或二羧酸与脂肪族二羧酸或 二胺， 经缩聚所制备的聚酰胺树脂， 是芳香族聚酰胺中的一种。 由于 在聚酰胺分子主链中导入了芳香环， 从而提高了耐热性和力学性能， 降低了吸水率， 并且有较合适的性能 /价格比， 是介于通用工程塑料 尼龙和耐高温工程塑料 PEEK之间的耐热性高的树脂，主要用于汽车 和电气电子行业。随着高科技的迅速发展，其应用有新的突破和进展， 市场需求呈上升趋势。 半芳香族聚酰胺产品目前主要有聚酰胺 MXD6、 6T/66、 6Τ/6Ι、 6Τ/6Ι/66. 6Τ/Μ-5Τ和 9Τ。
专利 JP57200420、 JP58111829. EP1074585A1、 CN1624021A公 开了聚酰胺 MXD6的制备方法。 所提出的方法中， 在间歇式反应器 中将芳香族二胺滴加到熔融的脂肪族二羧酸中，同时升高体系温度除 去缩合生成的水进行聚合反应。 CN1451677A描述了一种聚酰胺 MXD6的固相增粘方法，在特定条件下保存聚酰胺， 即使起始聚酰胺 从制备后到固相增粘间用去 20天或更长时间， 制得的聚酰胺 MXD6 黄度也很低。
由于聚酰胺 6T的熔点高过了其分解温度， 必须加入第三单体以 降低熔点。 聚酰胺 6T共聚物是通过主要由对苯二甲酸和间苯二甲酸 或己二酸组成的二羧酸组分和主要由 1 ,6-己二胺组成的二胺组分缩 聚得到的。 聚酰胺 6T共聚物的酰胺基浓度较高， 会导致聚合物的耐 化学药品性、耐吸水性、熔融加工稳定性较差。加入大量的第三单体 降低了聚合物的结晶度， 也会导致聚合物的耐热性、 耐化学药品性、 耐吸水性和尺寸稳定性下降。
专利 US5516882、US5981692和 US962628描述了以对苯二甲酸、 间苯二甲酸、 1,6-己二酸、 1,6-己二胺和 2-甲基 -1,5-戊二胺为主要原 料，通过 300 °C以上的高温熔融聚合来合成聚酰胺 6T共聚物的方法。 专利 US6140459描述了以对苯二甲酸、 1，6-己二胺和另一种脂肪族长 链二元羧酸为原料， 通过熔融聚合来合成聚酰胺 6T共聚物。 然而采 用熔融聚合制备半芳香族聚酰胺时，后期聚合反应温度会超过聚合物 的熔点，且在高温下停留时间过长，各种副反应以及聚合物的降解反 应剧烈，容易造成聚合物色调变差、机械强度降低和成型性变坏的现 象。
专利 US5663284公开了一种制备聚酰胺 6T/66聚合物的方法， 先在有水存在、反应温度低于聚合物熔点的条件下进行初级聚合，在 出料时通过往高压釜内补充水来维持压力，预聚物通过排气式双螺杆 挤出机熔融增粘得到高黏度聚合物。但是为了得到可满足熔融增粘要 求的预聚物，预聚合温度接近了聚合物的熔点， 以提高预聚物的特性 黏度。
在现有技术中， 专利 US6133406提出了一种半芳香族聚酰胺的 聚合工艺：先在有水存在的条件下，在较低的温度合成低特性薪度的 预聚物，然后经固相增粘反应制备较高特性黏度的预聚物，再经双螺 杆熔融挤出增粘得到高特性黏度的聚合物。 这一路线涉及预聚合反 应、 固相增粘、 熔融增粘多步反应， 要求复杂的生产步骤和设备。 专利 US6156869中， 在得到预聚物后， 可以通过长时间的固相 增粘来得到聚酰胺 9T树脂， 这一技术要求预聚物具有较高的特性黏 度。 聚酰胺 9T具有较高的结晶度、 尺寸稳定性和较低的吸水率。
在现有技术中，得到较高特性黏度的半芳香族聚酰胺预聚物，可 以通过提高预聚合温度或排出预聚合反应体系中的水来实现。提高预 聚合温度会导致副反应的发生，也会提高反应压力，对设备的要求也 相应提高。排出反应体系中的水会将未反应的二元胺挥发掉，结果导 致预聚物的单体单元比例和加入到反应器的起始单体比例大为不同， 不能保证单体二元羧酸和二元胺的摩尔比例平衡。
先把单体制成盐，再由盐通过缩聚合成半芳香族聚酰胺就可以避 免二元胺的流失。专利 US5663284通过测定 PH值来判断成盐反应的 终点， 使用盐来制备半芳香族聚酰胺。然而，现有技术中存在这样一 个问题： 以水或醇作为溶剂来制备半芳香族聚酰胺盐时， 由于芳香族 二元羧酸和半芳香族聚酰胺盐在这些溶剂中的溶解度非常小，提纯半 芳香族聚酰胺盐变得很困难，难以得到纯净的半芳香族聚酰胺盐，继 而不能准确地控制二元羧酸和二元胺的摩尔比，影响了终产物半芳香 族聚酰胺的品质； 以其它有机溶剂来制备半芳香族聚酰胺盐时，虽然 可以得到高纯度的半芳香族聚酰胺盐， 但是提高了溶剂回收的成本。
在以上所有的专利中，没有涉及到半芳香族聚酰胺合成过程中所 产生废水的处理方法。
发明内容
本发明的目的在于针对现有技术存在的问题，提供一种低废水排 放量的半芳香族聚酰胺的制备方法。该制备方法对聚合过程中产生的 废水进行了循环利用，大大降低了废水的排放量；并且对废水中的原 料进行了有效的回收利用， 提高了原料的利用率； 同时， 废水中的二 元胺补偿了预聚合过程中随着水的排出流失的二元胺，保证了单体二 元羧酸和二元胺的摩尔比例平衡。
本发明的另一个目的是提供利用上述制备方法制备得到的半芳 香族聚酰胺。
本发明的上述目的是通过以下技术方案解决的：
一种半芳香族聚酰胺的制备方法， 包括以下步骤：
(1 )将芳香族二元羧酸、含有 4至 14个碳原子的脂肪族二元胺和水 加入到压力釜中进行预聚合反应；
(2)将上述得到的预聚物通过固相增粘反应或熔融增粘反应即得 半芳香族聚酰胺。
上述步骤（1 )中的碳原子数为 4〜14的脂肪族二元胺包括直链脂 肪族二元胺、支链脂肪族二元胺或脂环族二元胺。其中， 直链脂肪族 二元胺包括 1,4-丁二胺、 1,6-己二胺、 1,8-辛二胺、 1,9-壬二胺、 1，10- 癸二胺、 1，11-十一碳二胺或 U2-十二碳二胺。支链脂肪族二元胺包括 2-甲基 -1，5-戊二胺、 3-甲基 -1,5-戊二胺、 2,4-二甲基 -1,6-己二胺、 2,2,4- 三甲基 -1，6-己二胺、 2,4,4-三甲基 -1,6-己二胺、 2-甲基 -1，8-辛二胺或 5- 甲基 -1，9-壬二胺。脂环族二元胺包括环己烷二胺、 甲基环己烷二胺或 4，4，-二氨基二环己基甲垸。半芳香族聚酰胺可以含有一种或多种类型 的这些脂肪族二元胺， 优选的脂肪族二元胺是 1，6-己二胺、 1,9-壬二 胺、 1，10-癸二胺、 2-甲基 -1,5-戊二胺、 2-甲基 -1，8-辛二胺或 5-甲基 -1,9- 壬二胺。 最佳的脂肪族二元胺是 1,6-己二胺、 1，9-壬二胺或 1,10-癸二 胺。
上述步骤（1 ) 中的芳香族二元羧酸包括对苯二甲酸、 间苯二甲 酸、 2-甲基对苯二甲酸、 2，5-二氯对苯二甲酸、 2,6-奈二甲酸、 1,4-奈 二甲酸、 4,4'-联苯二甲酸或 2,2'-联苯二甲酸。半芳香族聚酰胺可以含 有一种或多种类型的这些芳香族二元羧酸。优选的芳香族二元羧酸是 对苯二甲酸、 间苯二甲酸或 4,4'-联苯二甲酸。最优选的芳香族二元羧 酸是对苯二甲酸。
上述步骤（1 )中所述水也可以为上次预聚合过程中产生的废水。 废水中含有 0.1〜5重量％的含有 4至 14个碳原子的脂肪族二元胺。
上述步骤（1 )中的预聚合是把芳香族二元羧酸、含有 4至 14个碳 原子的脂肪族二元胺、水、封端剂、催化剂加入到高压釜中反应， 预 聚合的反应温度为 200〜280°C， 反应体系压力 l〜5MPa， 反应时间为 .1〜6小时，反应后期通过排出体系内的水来保持压力稳定，反应结束 后将预聚物干燥待用，将反应后期排出体系的废水和反应结束后干燥 预聚物时分离出来的废水收集在一起， 供下次聚合时使用。其中， 优 选的反应温度为 220〜250°C ;优选的反应时间为 2〜4小时；优选的反 应体系压力为 1.5〜3Mpa。 通过预聚合反应， 可得到在 25°C的 96%硫 酸中测定的特性黏度 [η]为 0.06〜0.3dl/g， 优选 0.08〜0.2dl/g范围内的 预聚物。
其中催化剂包括磷酸、亚憐酸、次磷酸或其盐或其酯，优选磷酸 纳、 亚磷酸钠、 次磷酸钠、 亚磷酸钾。 催化剂的量为原材料的 0.01〜 2重量％ (原材料指的是芳香族二元羧酸、 含有 4至 14个碳原子的脂肪 族二元胺、 封端剂和催化剂的总重量)， 优选 0.05〜1重量％。
封端剂包括一元羧酸或一元胺或其混合物。 其中优选一元羧酸， 因为相对于一元胺， 一元羧酸毒性小， 不易挥发， 便于处理； 一元羧 对甲基苯甲酸、邻甲基苯甲酸、对叔丁基苯甲酸、水杨酸、对甲氧基 苯甲酸、苯乙酸、 肉桂酸等。封端剂可以是它们中的一种或几种。其 中最佳的一元羧酸为乙酸、丙酸、丁酸、 月桂酸、硬脂酸、苯甲酸或 苯乙酸。一元胺包括脂肪族一元胺如乙胺、正丙胺、异丙胺、正丁胺、 仲丁胺、异丁胺、 正戊胺、 正癸胺、十二烷胺、硬脂胺等； 脂环族一 元胺如环己胺等； 芳香族一元胺如苯胺、 对甲苯胺、 邻甲苯胺、 2,6- 二甲基苯胺、 3,4-二甲基苯胺、 邻乙基苯胺等。 封端剂可以是它们中 的一种或几种。最佳的一元胺为乙胺、正丙胺、正丁胺、苯胺或对甲 苯胺。封端剂的摩尔量为芳香族二元羧酸的 0.2〜10%，优选 0.5〜5%。 因为当封端剂的量过高时，会导致聚合物的分子量偏小；封端剂的量 过低时， 会造成聚合物的分子量偏大或者聚合物的活性端基含量偏 大。
上述步骤 （1 ) 中预聚合初期加入的水量为 15〜35重量％。 因为 如果加入的水量过少，那么在聚合的过程中物料就会固化，反应无法 进行， 而且产物无法从反应釜内排出； 如果加入的水量过大，聚合反 应的速度会降低，得到的预聚物特性黏度也会降低，无法顺利进行增 粘反应，而为了提高反应速度和预聚物的特性黏度，在聚合过程中要 排出大量的水，必然会导致二元胺的严重流失，破坏单体的摩尔比例。
上述步骤 （1 ) 中所加入的水不会参加预聚合反应， 而且在预聚 合反应中会生成少量的水，在预聚合过程结束后会收集到比加入量略 多的废水，这些废水又可以加入到下次预聚合反应中。如此循环往复， 预聚合反应不需要使用新的水，而且几乎没有废水的排放。 由于预聚 合过程中产生的废水中含有少量的二元胺，排放的话会造成二元胺的 损失， 而对废水进行循环利用， 也就提高了原料二元胺的利用率。 同 时，预聚合初期所加入废水中的二元胺补偿了预聚合过程中随着水的 排出流失的二元胺， 保证了单体二元羧酸和二元胺的摩尔比例平衡， 有利于聚合反应的顺利进行， 得到高特性點度的半芳香族聚酰胺。
上述步骤（2) 中预聚物的增粘可以通过固相增粘反应或熔融增 粘反应来实现，其中优选的是固相增粘法。固相增粘是在聚合物熔点 以下来进行的，优选的反应温度为 220〜280°C， 固相增粘反应时间为 3〜20小时，优选 5〜15小时； 为了防止聚合物氧化， 固相增粘反应是 在氮气气氛下或真空条件下进行的，优选在氮气气氛下进行。固相增 粘的优点是反应温度低， 降解反应少， 得到的聚酰胺色调、尺寸稳定 性、耐热性较好。熔融增粘是在带排气口的挤出设备上进行的； 熔融 增粘温度高于预聚合物的熔点，优选的反应温度为 290〜350°C ;熔融 增粘反应时间为 1〜8分钟，优选 2〜6分钟。熔融增粘的优点是反应时 间较短。 通过增粘反应后， 得到终产物半芳香族聚酰胺。
本发明得到的半芳香族聚酰胺， 其特性黏度 [η]为 0.8〜2.5dl/g， 优选 1.0〜2.0dl/g; 端羧基含量为 15〜80mol/t， 优选 15〜50mol/t; 端 氨基含量为 15〜80mol/t， 优选 15〜60mol/t; 熔点为 270〜330°C， 优 选 290〜330Ό。优选此范围的原因是， 当熔点过低时， 聚酰胺的耐热 性达不到本发明的要求；而熔点过高时，在热加工时会发生降解反应。
与现有技术相比， 本发明具有如下有益效果： 1.本发明的半芳香 族聚酰胺制备方法对聚合过程中产生的废水进行了循环利用，大大降 低了废水的排放量；并且对废水中的原料进行了有效地回收利用，提 高了原料二元胺的利用率； 同时，预聚合初期所加入废水中的二元胺 补偿了预聚合过程中随着水的排出流失的二元胺，保证了单体二元羧 酸和二元胺的摩尔比例平衡。 2.本发明制备的半芳香族聚酰胺具有较 高的结晶度、特性黏度和耐热温度， 色相好， 活性端基含量低， 加工 稳定性好， 不腐蚀模具。根据需要， 可以添加抗氧剂、润滑剂、成核 剂、阻燃剂、着色剂、增塑剂、抗静电剂； 也可以通过加入玻璃纤维、 碳纤维、无机填料来进行增强； 同时还可以和其它聚合物共混来制备 聚合物合金。
具体实施方式
将通过实施例的方式对本发明进行描述，但不是对本发明进行限 制。 在实施例和对比例中诸特性， 均是按以下方法测定的。
1.特性黏度 [η]
在 25Ό的浓硫酸中测量浓度为 0.05、 0.1、 0.3和 lg/dl的聚酰胺的 对数比 黏度 ηω^ 其中， riinh表示对数比浓黏度 (dl/g)， to表示溶剂的流过时间 (see), 表示样品溶液的流过时间 (sec)， C表示样品溶液的浓度 (g/dl)。
将 riinh的数据外推到浓度为 0， 以得到样品的特性黏度 [η]。
2.端胺基含量
用全自动电位滴定仪滴定样品端胺基含量。取 0.5g聚合物， 加苯 酚 45ml及无水甲醇 3ml，加热回流，观察试样完全溶解后，冷至室温， 用已标定的盐酸标准溶液滴定端胺基含量。
3.端羧基含量
用全自动电位滴定仪滴定样品端羧基含量。取 0.5g聚合物， 加邻 甲酚 50ml， 回流溶解， 放冷后迅速加入 400 L甲醛溶液， 用已标定 的 KOH-乙醇溶液滴定端羧基含量。
4.废水中二元胺含量
用全自动电位滴定仪滴定预聚合产生的废水中二元胺含量。 取 100ml废水， 用已标定的盐酸标准溶液滴定二元胺含量。
5.瑢点和熔融热
采用 Perkin Elmer DSC-6分析仪测试样品的熔点和熔融热， 氮气 气氛，流速为 40mIJmin。测试时先以 10°C/min升温至 340°C， 在 34(TC 保持 2min， 然后以 10°C/min冷却到 50°C， 再以 10°C/min升温至 340°C， 将此时的吸热峰温度设为熔点 Tm， 通过此时的吸热峰面积计算熔融 热 A Hm。
6.结晶度
用 X射线衍射法测定聚合物的结晶度。将熔融的聚合物用液氮骤 冷来制备非晶样品， 非晶样品和聚合物样品的 X射线衍射峰面积分别 为 S^PS2， 通过下式计算结晶度。
Figure imgf000010_0001
其中， xc表示结晶度 (％)， 示非晶样品的 X射线衍射峰面积， s2表示聚合物样品的 X射线衍射峰面积。
对比例 1
在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的
20L压力釜中加入 3323g(20mol)对苯二甲酸、 3446g(20mol) 1，10-癸二 胺、 73.27g(0.6mol)苯甲酸、 6.85g (基于原材料的总重计为 0.1重量％) 次磷酸钠、 2283g (基于反应体系的总重计为 25重量％)去离子水， 氮气吹扫后升温。在搅拌下 2个小时内升温到 220 °C， 将反应混合物 在 220Ό搅拌 1小时， 然后在搅拌下使反应物的温度升高到 230°C。 反应在 230 °C的恒温和 2Mpa的恒压下继续进行 2小时， 通过移去所 形成的水而保持压力恒定， 反应完成后出料， 预聚物于 80°C下真空 干燥 24小时， 从而得到特性黏度 [η]为 0.14dVg的预聚物。 预聚合过 程中共收集到废水 2361g， 废水中的二元胺含量为 1.7重量％。 预聚 物在 26CTC氮气气氛下固相增粘 10小时， 得到 PA10T树脂， 熔点为 319Ό，熔融热 67.5J/g，特性黏度 [η]为 1.02dl/g，端胺基含量为 14mol/t， 端羧基含量为 107mol/t。 结果示于表 1中。 实施例 1
在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的 20L压力釜中加入 3323g(20mol)对苯二甲酸、 3446g(20mol) 1,10-癸二 胺、 73.27g(0.6mol)苯甲酸、 6.85g (基于原材料的总重计为 0.1重量 次磷酸钠、 2283g (基于反应体系的总重计为 25重量％)对比例 1中 的废水， 氮气吹扫后升温。 在搅拌下 2个小时内升温到 220 °C， 将反 应混合物在 220Ό搅拌 1小时， 然后在搅拌下使反应物的温度升高到 230°C。反应在 230 °C的恒温和 2Mpa的恒压下继续进行 2小时，通过 移去所形成的水而保持压力恒定， 反应完成后出料， 聚物于 80°C 下真空干燥 24小时， 从而得到特性黏度 [η]为 0.15dl/g的预聚物。 预 聚合过程中共收集到废水 2339g，废水中的二元胺含量为 1.8重量％。 预聚物在 26(TC氮气气氛下固相增粘 10小时， 得到 PA10T树脂， 熔 点为 320°C， 熔融热 73.5J/g， 特性黏度 [η]为 1.38dl/g， 端胺基含量为 35mol/t, 端羧基含量为 43mol/t。 结果示于表 1中。
实施例 2
重复实施例 1的制备步骤，不同的是所加入的废水为实施例 1聚 合过程中收集到的废水。 结果示于表 1中。
实施例 3
重复实施例 1的制备步骤，不同的是所加入的废水为实施例 2聚 合过程中收集到的废水。 结果示于表 1中。
实施例 4
重复实施例 1的制备步骤，不同的是所加入的废水为实施例 3聚 合过程中收集到的废水。 结果示于表 1中。 表 1
Figure imgf000012_0001
对比例 2
在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的 20L压力釜中加入 2824g(17mol)对苯二甲酸、 498g(3mol)间苯二甲酸、 3446g(20mol) 1,10-癸二胺、 73.27g(0.6mol)苯甲酸、 6.85g (基于原材料 的总重计为 0 1重量％)次磷酸钠、 2283g (基于反应体系的总重计为 25重量％)去离子水， 氮气吹扫后升温。 在搅拌下 2个小时内升温 到 220°C， 将反应混合物在 22CTC搅拌 1小时， 然后在搅拌下使反应 物的温度升高到 230°C。 反应在 230°C的恒温和 2Mpa的恒压下继续 进行 2小时，通过移去所形成的水而保持压力恒定，反应完成后出料， 预聚物于 80°C下真空干燥 24小时， 从而得到特性薪度 [η]为 0.13dl/g 的预聚物。预聚合过程中共收集到废水 2356g， 废水中的二元胺含量 为 1.5重量％。预聚物在 26CTC氮气气氛下固相增粘 10小时， 得到半 芳香族聚酰胺树脂， 熔点为 291 °C， 熔融热 38.7J/g， 特性薪度 [η]为 0.97dVg, 端胺基含量为 19mol/t， 端羧基含量为 112mol/t。 结果示于 表 2中。 实施例 5
在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的 20L压力釜中加入 2824g(17mol)对苯二甲酸、 498g(3mol)间苯二甲酸、 3 6g(20mol) 1,10-癸二胺、 73.27g(0.6mol)苯甲酸、 6.85g (基于原材料 的总重计为 0.1重量％)次磷酸钠、 2283g (基于反应体系的总重计为 25重量％)对比例 2中的废水， 氮气吹扫后升温。 在搅拌下 2个小 时内升温到 220°C， 将反应混合物在 220°C搅拌 1小时， 然后在搅拌 下使反应物的温度升高到 230 °C。 反应在 230°C的恒温和 2Mpa的恒 压下继续进行 2小时，通过移去所形成的水而保持压力恒定，反应完 成后出料， 预聚物于 80°C下真空干燥 24小时， 从而得到特性黏度 [η] 为 0.15dl/g的预聚物。 预聚合过程中共收集到废水 2386g， 废水中的 二元胺含量为 1.8重量％。预聚物在 26CTC氮气气氛下固相增粘 10小 时， 得到半芳香族聚酰胺树脂， 熔点为 292Ό， 熔融热 45.3J/g， 特性 黏度 [η]为 1.27dl/g， 端胺基含量为 43mol/t， 端羧基含量为 51mol/t。 结果示于表 2中。
实施例 6
重复实施例 5的制备步骤，不同的是所加入的废水为实施例 5聚 合过程中收集到的废水。 结果示于表 2中。
实施例 7
重复实施例 5的制备步骤，不同的是所加入的废水为实施例 6聚 合过程中收集到的废水。 结果示于表 2中。
实施例 8
重复实施例 5的制备步骤，不同的是所加入的废水为实施例 7聚 合过程中收集到的废水。 结果示于表 2中。 表 2 对比 实施 实施 实施 实施 例 2 例 5 例 6 例 7 例 8 对苯二甲酸 (mol) 17 17 17 17 17 间苯二甲酸 (mol) 3 3 3 3 3
1，10-癸二胺 (mol) 20 20 20 20 20 去离子水加入量 (g) 2283
废水加入量 （g) 2283 2283 2283 2283 废水收集量 （g) 2356 2386 2325 2334 2406 废水中二元胺含量（重量％) 1.5 1.8 1.8 1.9 1.7 预聚物特性黏度 lKdl/g) 0.13 0.15 0.14 0.13 0.16 聚酰胺特性黏度 [Tl](dl/g) 0.97 1.27 1.36 1.32 1.43 端胺基含量 (mol/t) 19 43 36 35 44 端羧基含量 (mol/t) 112 51 47 39 54 熔点 (°c) 291 292 292 291 292
AHm(J/g) 38.7 45.3 39.6 42.9 47.2 结晶度 (％) 11 14 15 13 16 对比例 3
在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的 20L压力釜中加入 3323g(20mo〗.)对苯二甲酸、 2929g(17mol)l，10-癸二 胺、 517g (3mol) 5-甲基 -1,9-壬二胺、 73.27g(0.6mol)苯甲酸、 6.85g (基 于原材料的总重计为 0.1重量％)次磷酸钠、 2283g (基于反应体系的 总重计为 25重量％) 去离子水， 氮气吹扫后升温。 在搅拌下 2个小 时内升温到 220°C， 将反应混合物在 220°C搅拌 1小时， 然后在搅拌 下使反应物的温度升高到 230 °C。 反应在 230Ό的恒温和 2Mpa的恒 压下继续进行 2小时，通过移去所形成的水而保持压力恒定，反应完 成后出料，预聚物于 80Ό下真空干燥 24小时， 从而得到特性黏度 [η] 为 0.13dl7g的预聚物。 预聚合过程中共收集到废水 2317g， 废水中的 二元胺含量为 1.6重量％。预聚物在 260Ό氮气气氛下固相增粘 10小 时， 得到半芳香族聚酰胺树脂， 熔点为 294°C， 熔融热 41.2J/g， 特性 黏度 [η]为 1.07dl/g， 端胺基含量为 16mol/t， 端羧基含量为 96mol/t。 结果示于表 3中。 实施例 9
在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的 20L压力釜中加入 3323g(20mol)对苯二甲酸、 2929g(17mol)l,10-癸二 胺、， 517g (3mol) 5-甲基- 1,9-壬二胺、 73.27g(0.6mol)苯甲酸、 6,85g (基 于原材料的总重计为 0.1重量％)次磷酸钠、 2283g (基于反应体系的 总重计为 25重量％)对比例 3中的废水， 氮气吹扫后升温。 在搅拌 下 2个小时内升温到 220°C , 将反应混合物在 220°C搅拌 1小时， 然 后在搅拌下使反应物的温度升高到 230°C。 反应在 230°C的恒温和 2Mpa的恒压下继续进行 2小时， 通过移去所形成的水而保持压力恒 定， 反应完成后出料， 预聚物于 80°C下真空干燥 24小时， 从而得到 特性黏度 [η]为 0.15dl/g的预聚物。预聚合过程中共收集到废水 2395g， 废水中的二元胺含量为 1.7重量％。 预聚物在 260Ό氮气气氛下固相 增粘 10小时， 得到半芳香族聚酰胺树脂， 熔点为 294 °C， 熔融热 48.3J/g，特性黏度 [η]为 1.29dl/g， 端胺基含量为 34mol/t， 端羧基含量 为 50mol/t。 结果示于表 3中。
对比例 4
在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的 20L压力釜中加入 1994g(12mol)对苯二甲酸、 1329g (8mol) 间苯二 甲酸、 2324g(20mol) 1，6-己二胺、 73.27g(0.6mol)苯甲酸、 5.73g (基于 原材料的总重计为 0.1重量％)次磷酸钠、 1909g (基于反应体系的总 重计为 25重量％) 去离子水， 氮气吹扫后升温。 在搅拌下 2个小时 内升温到 220° (：， 将反应混合物在 220°C搅拌 1小时， 然后在搅拌下 使反应物的温度升高到 230 °C。 反应在 230°C的恒温和 2Mpa的恒压 下继续进行 2小时，通过移去所形成的水而保持压力恒定，反应完成 后出料， 预聚物于 8(TC下真空干燥 24小时， 从而得到特性黏度 [η] 为 0.14dl/g的预聚物。 预聚合过程中共收集到废水 1960g， 废水中的 二元胺含量为 1.4重量％。预聚物在 260°C氮气气氛下固相增粘 10小 时， 得到半芳香族聚酰胺树脂， 熔点为 312°C， 熔融热 34.8J/g， 特性 黏度 [η]为 0.96dl/g， 端胺基含量为 17mol/t， 端羧基含量为 92mol/t。 结果示于表 3中。
实施例 10
在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的 20L压力釜中加入 1994g(12mol)对苯二甲酸、 1329g (8mol) 间苯二 甲酸、 24g(20mol) ϊ,6-己二胺、 73.27g(0.6mol)苯甲酸、 5.73g (基于 原材料的总重计为 0.1重量％)次磷酸钠、 1909g (基于反应体系的总 重计为 25重量％)对比例 4中的废水， 氮气吹扫后升温。 在搅拌下 2个小时内升温到 220°C， 将反应混合物在 220°C搅拌 1小时， 然后 在搅拌下使反应物的温度升高到 230 °C。反应在 230Ό的恒温和 2Mpa 的恒压下继续进行 2小时，通过移去所形成的水而保持压力恒定，反 应完成后出料， 预聚物于 80°C下真空干燥 24小时， 从而得到特性黏 度 [η]为 0.15dl/g的预聚物。 预聚合过程中共收集到废水 2053g， 废水 中的二元胺含量为 1.4重量％。 预聚物在 260Ό氮气气氛下固相增粘 10小时， 得到半芳香族聚酰胺树脂， 熔点为 312°C， 熔融热 33.4J/g， 特性黏度 [η]为 1.32dl/g，端胺基含量为 33mol/t，端羧基含量为 39mol/t。 结果示于表 3中。
对比例 5
在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的 20L压力釜中加入 3323g(20mol)对苯二甲酸、 1394g(12mol) 1,6-己二 胺、 930g (8mol) 2-甲基 -1,5-戊二胺、 73.27g(0.6mol)苯甲酸、 5.73g (基 于原材料的总重计为 0.1重量％)次磷酸钠、 1909g (基于反应体系的 总重计为 25重量％)去离子水， 氮气吹扫后升温。 在搅拌下 2个小 时内升温到 220Ό， 将反应混合物在 220 °C搅拌 1小时， 然后在搅拌 下使反应物的温度升高到 230°C。 反应在 230 °C的恒温和 2Mpa的恒 压下继续进行 2小时，通过移去所形成的水而保持压力恒定，反应完 成后出料，预聚物于 80 °C下真空干燥 24小时， 从而得到特性黏度 [η] 为 0.15d]/g的预聚物。 预聚合过程中共收集到废水 2023g， 废水中的 二元胺含量为 1.3重量％。预聚物在 260°C氮气气氛下固相增粘 10小 时， 得到半芳香族聚酰胺树脂， 熔点为 316° (：， 熔融热 34.2J/g， 特性 黏度 [η]为 l.lJLdl/g， 端胺基含量为 19mol/t， 端羧基含量为 87mol/t。 结果示于表 3中。
实施例 11
在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的 20L压力釜中加入 3323g(20mol)对苯二甲酸、 1394g(12mol) 1,6-己二 胺、 930g (8mol) 2-甲基 -1,5-戊二胺、 73.27g(0.6mol)苯甲酸、 5.73g (基 于原材料的总重计为 0.1重量％)次磷酸钠、 1909g (基于反应体系的 总重计为 25重量％)对比例 5中的废水， 氮气吹扫后升温。 在搅拌 下 2个小时内升温到 220°C， 将反应混合物在 220Ό搅拌 1小时， 然 后在搅拌下使反应物的温度升高到 230°C。 反应在 230°C的恒温和 2Mpa的恒压下继续进行 2小时， 通过移去所形成的水而保持压力恒 定， 反应完成后出料， 预聚物于 80 °C下真空干燥 24小时， 从而得到 特性黏度 [η]为 0.15dl/g的预聚物。预聚合过程中共收集到废水 1987g， 废水中的二元胺含量为 1.5重量％。 预聚物在 260°C氮气气氛下固相 增粘 10小时， 得到半芳香族聚酰胺树脂， 熔点为 317°C， 熔融热 35.7J/g, 特性黏度 [η]为 1.43dl/g， 端胺基含量为 40mol/t， 端羧基含量 为 49mol/t。 结果示于表 3中。 表 3
Figure imgf000018_0001

Claims

权 利 要 求 书
1、 一种低废水排放量的半芳香族聚酰胺的制备方法， 其特征在 于包括以下步骤：
( 1 )将芳香族二元羧酸、含有 4至 14个碳原子的脂肪族二元胺和水 加入到压力釜中进行预聚合反应；
(2)将上述得到的预聚物通过固相增粘反应或熔融增粘反应即得 半芳香族聚酰胺。
2、 根据权利要求 1所述的制备方法， 其特征在于步骤 (1)中所述 脂肪族二元胺为直链脂肪族二元胺、支链脂肪族二元胺或脂环族二元 胺中的一种或几种的混合物。
3、根据权利要求 2所述的制备方法，其特征在于所述直链脂肪族 二元胺为 1,4-丁二胺、 1,6-己二胺、 1，8-辛二胺、 1，9-壬二胺、 1,10-癸 二胺、 1,11-十一碳二胺或 1,12-十二碳二胺；所述支链脂肪族二元胺为 2-甲基- 1,5-戊二胺、 3-甲基- 1,5-戊二胺、 2，4-二甲基 -1,6-己二胺、 2，2，4- 三甲基 -1,6-己二胺、 2,4，4-三甲基 -1，6-己二胺、 2-甲基 -1,8-辛二胺或 5- 甲基 -1，9-壬二胺； 所述脂环族二元胺为环己垸二胺、 甲基环己烷二胺 或 4，4'-二氨基二环己基甲垸。
4、 根据权利要求 1所述的制备方法， 其特征在于步骤 (1)中所述 芳香族二元羧酸为对苯二甲酸、间苯二甲酸、 2-甲基对苯二甲酸、 2,5- 二氯对苯二甲酸、 2，6-奈二甲酸、 1,4-奈二甲酸、 4，4'-联苯二甲酸或 2，2'- 联苯二甲酸。
5、 根据权利要求 1所述的制备方法， 其特征在于步骤 (1)中所述 水为上次预聚合过程中产生的废水。
6、根据权利要求 5所述的制备方法，其特征在于所述废水中含有 0.1〜5重量％的含有 4至 14个碳原子的脂肪族二元胺。
7、 根据权利要求 1所述的制备方法， 其特征在于步骤 (1)中所述 的预聚合反应是把芳香族二元羧酸、 含有 4至 14个碳原子的脂肪族二 元胺、 水、 封端剂、 催化剂加入到高压釜中反应， 反应温度为 200〜 280 °C , 反应体系压力 l〜5Mpa， 反应时间为 1〜6小时， 反应后期排 出体系内的水来保持压力稳定，反应结束后将预聚物干燥待用；水加 入量为整个反应体系的 15〜35重量％，催化剂的量为原材料的 0.01〜2 重量％， 封端剂的摩尔量为芳香族二元羧酸的 0.2〜10%； 所述催化剂 为磷酸、亚磷酸、次磷酸或其盐或其酯； 所述封端剂为一元羧酸或一 元胺或其混合物。
8、根据权利要求 7所述的制备方法，其特征在于所述催化剂为磷 酸纳、亚磷酸钠、次磷酸钠、亚磷酸钾；所述一元羧酸为乙酸、丙酸、 丁酸、 月桂酸、硬脂酸、 苯甲酸或苯乙酸； 所述一元胺为乙胺、正丙 胺、 正丁胺、 苯胺或对甲苯胺。
9、 根据权利要求 1所述的制备方法， 其特征在于步骤 (2)中所述 的固相增粘反应是在氮气气氛下或真空条件下进行的， 反应温度为 220〜280°C， 反应时间为 3〜20小时； 熔融增粘反应是在带排气口的 挤出设备上进行的， 反应温度为 290〜350°C， 反应时间为 1〜8分钟。
10、 权利要求 1所述制备方法得到的半芳香族聚酰胺。
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