CN103739839B - Half aromatics polyarylether amide and preparation method thereof - Google Patents
Half aromatics polyarylether amide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of half aromatics polyarylether amide and preparation method thereof, be characterized in half aromatics dihalo diamide 304 ~ 449 parts, catalyzer 10 ~ 200 parts, dewatering agent 5 ~ 100 parts, aromatics diphenol 228 ~ 290 parts and solvent 200 ~ 2000 parts add in reactor, under nitrogen protection, in temperature 150 ~ 200 DEG C of dehydration reaction 0.5 ~ 3h, again at temperature 180 ~ 230 DEG C reaction 0.5 ~ 10h, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 50 ~ 160 DEG C, separate out white fine strip shape polymer crude product; By above-mentioned polymkeric substance through water, washing with alcohol, in temperature 50 ~ 200 DEG C of drying 2 ~ 8h, pulverize, then purify with deionized water, acetone respectively, in temperature 80 ~ 200 DEG C of drying 1 ~ 20h, namely obtain purifying half aromatics polyarylether amide resin.It has, and molecular weight is high, yield is high, purity is high, the advantage of small pollution and easy processing, and this half aromatics polyarylether amide is used for special engineering plastics and heat-resisting, resistance to chemical attack polymer composite.
Description
Technical field
The present invention relates to a kind of half aromatics polyarylether amide and preparation method thereof, belong to Polymer Synthesizing field.
Background technology
Polyarylether and partially aromatic polyamide are all engineering plastics of excellent property, there is good mechanics, thermal property, for the advantage of comprehensive two kinds of polymkeric substance, improve the mechanical property of polyarylether, improve its toughness and processing fluidity, improve the process window of partially aromatic polyamide (as with p-phthaloyl chloride simultaneously, 1, the partially aromatic polyamide that 6-hexanediamine etc. synthesizes is due to its high-density hydrogen bond, make its fusing point and decomposition temperature closely, thus cause its process window smaller), overcome the resistance to strong acid of polymeric amide, highly basic and chemical resistance poor, hold incendive shortcoming, we devise half this base polymer of aromatics polyarylether amide.
Summary of the invention
The object of the invention is to provide a kind of half aromatics polyarylether amide polymkeric substance and preparation method thereof for the deficiencies in the prior art, be characterized in half aromatics dihalo diamide and aromatics diphenol to prepare half aromatics polyarylether amide polymkeric substance by the method for solution polycondensation, it has, and yield be high, molecular weight is high, easy processing, high temperature resistant, corrosion-resistant and fire-retardant advantage.
Object of the present invention is realized by following technical measures, and wherein said raw material number, except specified otherwise, is parts by weight.
The starting raw material of half aromatics polyarylether amide is made up of following component, is by weight:
Wherein, aromatics diphenol is dihydroxyphenyl propane, 4, any one in two (4-the hydroxyphenyl)-1-diphenylphosphino ethane of 4 '-dihydroxy diphenylsulphone or 1,1-.
Described catalyzer is any one in lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrated barta, Quilonum Retard, sodium carbonate, salt of wormwood, calcium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, saleratus, Calcium hydrogen carbonate or barium bicarbonate.
Described dewatering agent is toluene or dimethylbenzene.
Described solvent is N-methyl caprolactam, N, N-dimethyl propylene thiazolinyl urea, 1, any one in 3-dimethyl-2-imidazolinone, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), HMPA, N-cyclohexyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, 1-methyl-3-propyl imidazole bromo salt, 1-methyl-3-isopropylimdazole bromo salt or 1,3-dipropyl imidazoles bromo salt.
The preparation method of half aromatics polyarylether amide comprises the following steps:
The preparation of (1) half aromatics dihalo diamide
By aliphatie diamine 60 ~ 172 parts, NaOH80 ~ 120 part, 1 ~ 30 part, tensio-active agent joins in the deionized water of 300 ~ 1000 parts successively, dissolves under room temperature; By parachlorobenzoyl chloride 348 parts or join in three-necked flask after mixing with 500 ~ 3000 parts of organic solvents fluorobenzoyl chloride 317 parts, then the above-mentioned aliphatie diamine solution configured is added dropwise in three-necked flask, after two amine aqueous solutions drip, at room temperature continue reaction 3 ~ 10h, generate half aromatics dihalo diamide;
The purifying of (2) half aromatics dihalo diamide
Organic solvent in above-mentioned half aromatics dihalo diamide is steamed, filter, collect filter cake, filter cake is through deionized water wash twice, removing water-soluble impurity, refilter, obtain the thick product of white powder, thick product recrystallization in recrystallization solvent, filter, collect colourless acicular crystal, vacuum-drying, obtain half aromatics dihalo diamide of purifying, structural formula is as follows:
Wherein: X=F or Cl, m=2 or 4 or 6 or 8 or 10;
The preparation of (3) half aromatics polyarylether amide
By half aromatics dihalo diamide 304 ~ 449 parts; catalyzer 10 ~ 200 parts; dewatering agent 5 ~ 100 parts; aromatics diphenol; 228 ~ 290 parts add in reactor with solvent 200 ~ 2000 parts; under nitrogen protection; in temperature 150 ~ 200 DEG C of dehydration reaction 0.5 ~ 3h; reaction 0.5 ~ 10h is continued temperature 180 ~ 230 DEG C; obtain the polymers soln of thickness, more above-mentioned polymers soln is cooled to 50 ~ 160 DEG C, be poured into water while stirring; separate out white fine strip shape polymer crude product, its structural formula is:
Wherein, n=10-300
in any one;
(4). the purifying of half aromatics polyarylether amide
By above-mentioned polymer crude product through water, washing with alcohol, in temperature 50 ~ 200 DEG C of drying 2 ~ 8h, pulverize, then purify with deionized water, acetone respectively, in temperature 80 ~ 200 DEG C of drying 1 ~ 20h, obtain purifying half aromatics polyarylether amide resin.
Described aliphatie diamine is any one in quadrol, butanediamine, hexanediamine, octamethylenediamine or decamethylene diamine.
Described tensio-active agent is at least one in triethylammonium bromide, dodecyltriethylammonium ammonium chloride, hexadecyldimethyl benzyl ammonium brometo de amonio, Sodium sulfanilate, Tetrabutyl amonium bromide, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, Sodium dodecylbenzene sulfonate, benzene sulfonic acid sodium salt, sodium alginate or sodium laurylsulfonate and sodium stearate.
Described organic solvent is any one in 1,2-ethylene dichloride, methylene dichloride, chloroform, hexanaphthene, sherwood oil or normal heptane.
Described recrystallization solvent is at least one in methyl alcohol, ethanol, Virahol, acetone, butanone, tetrahydrofuran (THF), methane amide, ethanamide, dimethyl formamide and N,N-DIMETHYLACETAMIDE.
Structural characterization and performance test
The structure of 1 half aromatics polyarylether amide respectively through infrared spectra, nucleus magnetic resonance (
1h-NMR) test obtains confirmation, as shown in Figure 1 and Figure 2.
2, by regulation and control reactant concn, material proportion and temperature of reaction, prepare half aromatics polyphenylene sulfide acid amides of different viscosity; And be solvent with NMP, the sample liquid of preparation 0.5g/dl, with the intrinsic viscosity=0.40 ~ 2.0dl/g of determination of ubbelohde viscometer polymkeric substance at temperature 30.0 ± 0.1 DEG C.
3 adopt NETZSCH DSC200PC to test the second-order transition temperature of half aromatics polyarylether amide, and temperature rise rate 10 DEG C/min, test result as shown in Figure 3.
4 adopt TGA to test the thermal weight loss temperature of half aromatics polyarylether amide, and test result as shown in Figure 4.
5 pairs of half aromatics polyarylether amide have carried out flame retardant properties test, respectively shown in 1.
Tool of the present invention has the following advantages:
1. adopt the diphenol containing aryl oxide structure as reaction monomers, introducing due to soft segment ehter bond can reduce the fusing point (Tm=300 DEG C ~ 404 DEG C of partially aromatic polyamide effectively, and poly-hexamethylene terephthalamide---the fusing point of PA6T is at 370 DEG C, but there is a small amount of decomposition at 330 DEG C in PA6T, cause its application limited, current business-like PA6T is its modification by copolymerization product mostly), thus improve its processing characteristics; The aliphatie diamine simultaneously adopted in monomer preparation process is easy to get, cheap.
2. what adopt in monomer preparation process is room temperature interfacial synthesis method, avoids the waste of high temperature to the energy, and it has, and technique is simple, and security is good, repeatability is strong, good stability, and product yield is high, purity is high, pollutes the advantages such as little and solvent easily reclaims.
3. half aromatics polyarylether amide has easy processing, high temperature resistant (its second-order transition temperature than polyphenylene sulfide and PPS fusing point---Tg=90 DEG C exceeds about 40 DEG C ~ 100 DEG C), the advantage such as fire-retardant.
4. this base polymer can be used for special engineering plastics and high performance polymer matrix material, and prepares parts and the goods of heat-resisting, resistance to chemical attack, also can be made into special fibre and film, has wide practical use.
Accompanying drawing illustrates:
Fig. 1 is the infrared spectrum of half aromatics polyarylether amide
At 3320cm in its infared spectrum
-1near there is the absorption of vibrations of-CONH-, 3060cm
-1near occurred phenyl ring C-H stretching vibration absorb, at 2930cm
-1and 2850cm
-1near there is-CH
2-absorption of vibrations, at 1640cm
-1near there is the absorption of vibrations of amide Ⅰ, 1590cm
-1, 1540cm
-1, 1490cm
-1for the skeletal vibration absorption peak of phenyl ring, 1110cm
-1the neighbouring absorption of vibrations being absorbed as-O-key occurred.
Fig. 2 is the nuclear magnetic spectrogram of half aromatics polyarylether amide
It is wherein the chemical shift of the N-H in half aromatics polyarylether amide structure near 8.4ppm, 6.6-7.8ppm is the chemical shift of the C-H of phenyl ring in half aromatics polyarylether amide structure, be the chemical shift of methyl in half aromatics polyarylether amide structure near 2.1ppm, and 1.1-3.5ppm is the chemical shift of half aromatics polyarylether amide structure methylene.
Fig. 3 is the Differential scanning calorimetry curve (DSC) of half aromatics polyarylether amide
Curve Embodiment 5 is the DSC curve of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether oxalamide, and result shows that the second-order transition temperature of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether oxalamide is 195.6 DEG C, shows that polymkeric substance has good thermal characteristics.
Curve Embodiment 6 is the DSC curve of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether succinic diamide, result shows that the second-order transition temperature of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether succinic diamide and fusing point are respectively 170.4 DEG C, shows that polymkeric substance has good thermal characteristics.
Curve Embodiment 7 is the DSC curve of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether adipamide, result shows that the second-order transition temperature of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether adipamide and fusing point are respectively 156.5 DEG C, shows that polymkeric substance has good thermal characteristics.
Curve Embodiment 8 is the DSC curve of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether suberamide, result shows that the second-order transition temperature of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether suberamide and fusing point are respectively 145.6 DEG C, shows that polymkeric substance has good thermal characteristics.
Curve Embodiment 9 is the DSC curve of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether decanediamide, result shows that the second-order transition temperature of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether decanediamide and fusing point are respectively 134.4 DEG C, shows that polymkeric substance has good thermal characteristics.
Fig. 4 is the thermogravimetic analysis (TGA) curve (TGA) of half aromatics polyarylether amide
Curve Embodiment 5 is the TGA curve of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether oxalamide, result shows that the temperature of initial decomposition of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether oxalamide and carbon left are respectively 396 DEG C, 28.3%, show that polymkeric substance has good thermal characteristics.
Curve Embodiment 6 is the TGA curve of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether succinic diamide, result shows that the temperature of initial decomposition of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether succinic diamide and carbon left are respectively 405 DEG C, 7.5%, show that polymkeric substance has good thermal characteristics.
Curve Embodiment 7 is the TGA curve of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether adipamide, result shows that the temperature of initial decomposition of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether adipamide and carbon left are respectively 436 DEG C, 4.1%, show that polymkeric substance has good thermal characteristics.
Curve Embodiment 8 is the TGA curve of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether suberamide, result shows that the temperature of initial decomposition of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether suberamide and carbon left are respectively 436 DEG C, 2.3%, show that polymkeric substance has good thermal characteristics.
Curve Embodiment 9 is the TGA curve of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether decanediamide, result shows that the temperature of initial decomposition of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether decanediamide and carbon left are respectively 438 DEG C, 0.9%, show that polymkeric substance has good thermal characteristics.
Embodiment
Below by embodiment, the present invention is specifically described, what be necessary to herein means out is that the present embodiment is only used to further illustrate the present invention, can not be interpreted as the restriction to the present invention includes scope, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
(1), the preparation of two (4-fluorobenzoyl) quadrol
First by quadrol 60g, NaOH80g, triethylammonium bromide 1g joins in the deionized water of 300g successively, dissolves under room temperature; Again will to fluorobenzoyl chloride 317g and 500g1, join after 2-ethylene dichloride mixes in the three-necked flask of 5L, then above-mentioned two amine aqueous solutions configured are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 3h generate two (4-fluorobenzoyl) quadrol; By reacted 1,2-ethylene dichloride steams, again reaction solution is filtered, collect filter cake, by filter cake through deionized water wash twice, removing water-soluble impurity, filter, obtain the thick product of white powder, thicker product is carried out recrystallization in methyl alcohol, namely collecting by filtration colourless acicular crystal, vacuum-drying obtain two (4-fluorobenzoyl) quadrol monomers of purifying;
(2), the preparation of polyether sulphone oxalamide
By two (4-fluorobenzoyl) quadrol 304g, sodium hydroxide 10g, toluene 5g, 4,4 '-dihydroxy diphenylsulphone 250g and N-methyl caprolactam 200g add in reactor, under nitrogen protection, in temperature 150 DEG C of dehydration reaction 0.5h, then at temperature 180 DEG C reaction 10h, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 50 DEG C, separate out white fine strip shape polymer crude product; By above-mentioned polymkeric substance through water, washing with alcohol, in the dry 8h of temperature 50 C, pulverize, then purify with deionized water, acetone respectively, in temperature 80 DEG C of dry 1h, namely obtain purifying polyether sulphone oxalamide resin, productive rate is about 94%; With the solution of NMP to be solvent configuration concentration be 0.5g/dl, with Ubbelohde viscometer at temperature 30.0 ± 0.1 DEG C, measure intrinsic viscosity=0.92dl/g, flame retardant properties is as shown in Table 1 below.
Embodiment 2
(1), the preparation of two (4-chlorobenzoyl) butanediamine
First by butanediamine 88g, NaOH100g, dodecyltriethylammonium ammonium chloride 10g and benzene sulfonic acid sodium salt 20g joins in the deionized water of 1000g successively, dissolves under room temperature; Join in the three-necked flask of 5L after again parachlorobenzoyl chloride 348g being mixed with 3000g methylene dichloride, then above-mentioned two amine aqueous solutions configured are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 10h generate two (4-chlorobenzoyl) butanediamine; Reacted methylene dichloride is steamed, again reaction solution is filtered, collect filter cake, by filter cake through deionized water wash twice, removing water-soluble impurity, filters, obtains the thick product of white powder, again thick product is carried out recrystallization in the mixed solvent of methyl alcohol and methane amide, namely collecting by filtration colourless acicular crystal, vacuum-drying obtain two (4-chlorobenzoyl) butanediamine monomers of purifying;
(2), the preparation of polymer with bis phenol A aryl oxide succinic diamide
By two (4-chlorobenzoyl) butanediamine 365g, salt of wormwood 200g, dimethylbenzene 100g, dihydroxyphenyl propane 228g and N, N-dimethyl propylene thiazolinyl urea 2000g adds in reactor, under nitrogen protection, in temperature 200 DEG C of dehydration reaction 3h, then at temperature 230 DEG C reaction 0.5h, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 160 DEG C, separate out white fine strip shape polymer crude product; By above-mentioned polymkeric substance through water, washing with alcohol, in temperature 200 DEG C of dry 2h, pulverize, then purify with deionized water, acetone respectively, in temperature 200 DEG C of dry 20h, namely obtain purifying polymer with bis phenol A aryl oxide succinic diamide resin, productive rate is about 93%; With the solution of NMP to be solvent configuration concentration be 0.5g/dl, with Ubbelohde viscometer at temperature 30.0 ± 0.1 DEG C, measure intrinsic viscosity=0.84dl/g, flame retardant properties is as shown in Table 1 below.
Embodiment 3
(1), the preparation of two (4-chlorobenzoyl) octamethylenediamine
First octamethylenediamine 144g, NaOH90g, sodium stearate 15g are joined in the deionized water of 600g successively, dissolve under room temperature; Join in the three-necked flask of 5L after again parachlorobenzoyl chloride 348g being mixed with 1500g hexanaphthene, then above-mentioned two amine aqueous solutions configured are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 6h generate two (4-chlorobenzoyl) octamethylenediamine; Reacted hexanaphthene is steamed, again reaction solution is filtered, collect filter cake, by filter cake through deionized water wash twice, removing water-soluble impurity, filters, obtains the thick product of white powder, again thick product is carried out recrystallization in methane amide, namely collecting by filtration colourless acicular crystal, vacuum-drying obtain two (4-chlorobenzoyl) octamethylenediamine monomers of purifying;
(2), the preparation of polyether sulphone suberamide
By two (4-chlorobenzoyl) octamethylenediamine 421g, hydrated barta 150g, dimethylbenzene 70g, 4,4 '-dihydroxy diphenylsulphone 250g and 1,3-dipropyl imidazoles bromo salt 1200g adds in reactor, under nitrogen protection, in temperature 175 DEG C of dehydration reaction 1.5h, again at temperature 200 DEG C reaction 6h, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 100 DEG C, separate out white fine strip shape polymer crude product; By above-mentioned polymkeric substance through water, washing with alcohol, in temperature 110 DEG C of dry 4h, pulverize, then purify with deionized water, acetone respectively, in temperature 120 DEG C of dry 6h, namely obtain purifying polyether sulphone suberamide resin, productive rate is about 91%; With the solution of NMP to be solvent configuration concentration be 0.5g/dl, with Ubbelohde viscometer at temperature 30.0 ± 0.1 DEG C, measure intrinsic viscosity=0.77dl/g, flame retardant properties is as shown in Table 1 below.
Embodiment 4
(1), the preparation of two (4-fluorobenzoyl) decamethylene diamine
First by decamethylene diamine 172g, NaOH85g, sodium laurylsulfonate 30g joins in the deionized water of 1000g successively, dissolves under room temperature; Join in the three-necked flask of 5L after fluorobenzoyl chloride 317g is mixed with 1200g sherwood oil again, then above-mentioned two amine aqueous solutions configured are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 7h generate two (4-fluorobenzoyl) decamethylene diamine; Reacted sherwood oil is steamed, again reaction solution is filtered, collect filter cake, by filter cake through deionized water wash twice, removing water-soluble impurity, filters, obtains the thick product of white powder, again thick product is carried out recrystallization in butanone and tetrahydrofuran (THF), namely collecting by filtration colourless acicular crystal, vacuum-drying obtain two (4-fluorobenzoyl) decamethylene diamine monomers of purifying;
(2), the preparation of polymer with bis phenol A aryl oxide decanediamide
By two (4-fluorobenzoyl) decamethylene diamine 416g, Calcium hydrogen carbonate 120g, toluene 50g, dihydroxyphenyl propane 228g and N-Methyl pyrrolidone 2000g adds in reactor, under nitrogen protection, in temperature 185 DEG C of dehydration reaction 1.5h, again at temperature 200 DEG C reaction 10h, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 100 DEG C, separate out white fine strip shape polymer crude product; By above-mentioned polymkeric substance through water, washing with alcohol, in temperature 130 DEG C of dry 3h, pulverize, then purify with deionized water, acetone respectively, in temperature 110 DEG C of dry 16h, namely obtain purifying polymer with bis phenol A aryl oxide decanediamide, productive rate is about 94%; With the solution of NMP to be solvent configuration concentration be 0.5g/dl, with Ubbelohde viscometer at temperature 30.0 ± 0.1 DEG C, measure intrinsic viscosity=0.83dl/g, flame retardant properties is as shown in Table 1 below.
Embodiment 5
(1), the preparation of two (4-fluorobenzoyl) quadrol
First by quadrol 60g, NaOH80g, triethylammonium bromide 1g joins in the deionized water of 300g successively, dissolves under room temperature; Again will to fluorobenzoyl chloride 317g and 500g1, join after 2-ethylene dichloride mixes in the three-necked flask of 5L, then above-mentioned two amine aqueous solutions configured are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 3h generate two (4-fluorobenzoyl) quadrol; By reacted 1,2-ethylene dichloride steams, again reaction solution is filtered, collect filter cake, by filter cake through deionized water wash twice, removing water-soluble impurity, filter, obtain the thick product of white powder, thicker product is carried out recrystallization in methyl alcohol, namely collecting by filtration colourless acicular crystal, vacuum-drying obtain two (4-fluorobenzoyl) quadrol monomers of purifying;
(2), the preparation of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether oxalamide
By two (4-fluorobenzoyl) quadrol 304g, sodium hydroxide 10g, two (4-the hydroxyphenyl)-1-diphenylphosphino ethane 290g and N-methyl caprolactam 200g of toluene 5g, 1,1-adds in reactor, under nitrogen protection, in temperature 150 DEG C of dehydration reaction 0.5h, then at temperature 180 DEG C reaction 10h, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 50 DEG C, separate out white fine strip shape polymer crude product; By above-mentioned polymkeric substance through water, washing with alcohol, in the dry 8h of temperature 50 C, pulverize, then purify with deionized water, acetone respectively, in temperature 80 DEG C of dry 1h, namely obtain purifying polyether sulphone oxalamide resin, productive rate is about 94%; With the solution of NMP to be solvent configuration concentration be 0.5g/dl, with Ubbelohde viscometer at temperature 30.0 ± 0.1 DEG C, measure intrinsic viscosity=0.63dl/g, flame retardant properties is as shown in Table 1 below, infrared, nuclear-magnetism characterizes and refers to respectively shown in Fig. 1, Fig. 2, DSC characterizes in detail as shown in Figure 3, and TGA characterizes in detail as shown in Figure 4.
Embodiment 6
(1), the preparation of two (4-chlorobenzoyl) butanediamine
First by butanediamine 88g, NaOH100g, dodecyltriethylammonium ammonium chloride 10g and benzene sulfonic acid sodium salt 20g joins in the deionized water of 1000g successively, dissolves under room temperature; Join in the three-necked flask of 5L after again parachlorobenzoyl chloride 348g being mixed with 3000g methylene dichloride, then above-mentioned two amine aqueous solutions configured are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 10h generate two (4-chlorobenzoyl) butanediamine; Reacted methylene dichloride is steamed, again reaction solution is filtered, collect filter cake, by filter cake through deionized water wash twice, removing water-soluble impurity, filters, obtains the thick product of white powder, again thick product is carried out recrystallization in the mixed solvent of methyl alcohol and methane amide, namely collecting by filtration colourless acicular crystal, vacuum-drying obtain two (4-chlorobenzoyl) butanediamine monomers of purifying;
(2), the preparation of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether succinic diamide
By two (4-chlorobenzoyl) butanediamine 365g, salt of wormwood 200g, dimethylbenzene 100g, 1, two (4-hydroxyphenyl)-1-diphenylphosphino ethane 290g and N of 1-, N-dimethyl propylene thiazolinyl urea 2000g adds in reactor, under nitrogen protection, in temperature 200 DEG C of dehydration reaction 3h, again at temperature 230 DEG C reaction 0.5h, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 160 DEG C, separate out white fine strip shape polymer crude product; By above-mentioned polymkeric substance through water, washing with alcohol, in temperature 200 DEG C of dry 2h, pulverize, then purify with deionized water, acetone respectively, in temperature 200 DEG C of dry 20h, namely obtain purifying polymer with bis phenol A aryl oxide succinic diamide resin, productive rate is about 93%; With the solution of NMP to be solvent configuration concentration be 0.5g/dl, with Ubbelohde viscometer at temperature 30.0 ± 0.1 DEG C, measure intrinsic viscosity=0.68dl/g, flame retardant properties is as shown in Table 1 below, infrared, nuclear-magnetism characterizes and refers to respectively shown in Fig. 1, Fig. 2, DSC characterizes in detail as shown in Figure 3, and TGA characterizes in detail as shown in Figure 4.
Embodiment 7
(1), the preparation of two (4-fluorobenzoyl) hexanediamine
First by hexanediamine 116g, NaOH120g, sodium alginate 20g joins in the deionized water of 800g successively, dissolves under room temperature; Join in the three-necked flask of 5L after fluorobenzoyl chloride 317g is mixed with 2500g chloroform again, then above-mentioned two amine aqueous solutions configured are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 8h generate two (4-fluorobenzoyl) hexanediamine; Reacted chloroform is steamed, again reaction solution is filtered, collect filter cake, by filter cake through deionized water wash twice, removing water-soluble impurity, filters, obtains the thick product of white powder, again thick product is carried out recrystallization in acetone, namely collecting by filtration colourless acicular crystal, vacuum-drying obtain two (4-fluorobenzoyl) hexanediamine monomers of purifying;
(2), the preparation of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether adipamide
By two (4-fluorobenzoyl) hexanediamine 360g, lithium bicarbonate 100g, toluene 50g, 1, two (4-the hydroxyphenyl)-1-diphenylphosphino ethane 290g and 1 of 1-, 3-dimethyl-2-imidazolinone 1500g adds in reactor, under nitrogen protection, in temperature 190 DEG C of dehydration reaction 2.5h, again at temperature 210 DEG C reaction 8h, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 120 DEG C, separate out white fine strip shape polymer crude product; By above-mentioned polymkeric substance through water, washing with alcohol, in temperature 120 DEG C of dry 6h, pulverize, purify with deionized water, acetone respectively again, in temperature 100 DEG C of dry 5h, namely obtain two (4-the hydroxyphenyl)-1-diphenylphosphino ethane polyarylether adipamide resin of purifying, productive rate is about 96%; With the solution of NMP to be solvent configuration concentration be 0.5g/dl, with Ubbelohde viscometer at temperature 30.0 ± 0.1 DEG C, measure intrinsic viscosity=1.07dl/g, flame retardant properties is as shown in Table 1 below, infrared, nuclear-magnetism characterizes and refers to respectively shown in Fig. 1, Fig. 2, DSC characterizes in detail as shown in Figure 3, and TGA characterizes in detail as shown in Figure 4.
Embodiment 8
(1), the preparation of two (4-chlorobenzoyl) octamethylenediamine
First octamethylenediamine 144g, NaOH90g, sodium stearate 15g are joined in the deionized water of 600g successively, dissolve under room temperature; Join in the three-necked flask of 5L after again parachlorobenzoyl chloride 348g being mixed with 1500g hexanaphthene, then above-mentioned two amine aqueous solutions configured are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 6h generate two (4-chlorobenzoyl) octamethylenediamine; Reacted hexanaphthene is steamed, again reaction solution is filtered, collect filter cake, by filter cake through deionized water wash twice, removing water-soluble impurity, filters, obtains the thick product of white powder, again thick product is carried out recrystallization in methane amide, namely collecting by filtration colourless acicular crystal, vacuum-drying obtain two (4-chlorobenzoyl) octamethylenediamine monomers of purifying;
(2), the preparation of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether suberamide
By two (4-chlorobenzoyl) octamethylenediamine 421g, hydrated barta 150g, dimethylbenzene 70g, 1, two (4-the hydroxyphenyl)-1-diphenylphosphino ethane 290g and 1 of 1-, 3-dipropyl imidazoles bromo salt 1200g adds in reactor, under nitrogen protection, in temperature 175 DEG C of dehydration reaction 1.5h, again at temperature 200 DEG C reaction 6h, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 100 DEG C, separate out white fine strip shape polymer crude product; By above-mentioned polymkeric substance through water, washing with alcohol, in temperature 110 DEG C of dry 4h, pulverize, then purify with deionized water, acetone respectively, in temperature 120 DEG C of dry 6h, namely obtain purifying polyether sulphone suberamide resin, productive rate is about 91%; With the solution of NMP to be solvent configuration concentration be 0.5g/dl, with Ubbelohde viscometer at temperature 30.0 ± 0.1 DEG C, measure intrinsic viscosity=0.79dl/g, flame retardant properties is as shown in Table 1 below, infrared, nuclear-magnetism characterizes and refers to respectively shown in Fig. 1, Fig. 2, DSC characterizes in detail as shown in Figure 3, and TGA characterizes in detail as shown in Figure 4.
Embodiment 9
(1), the preparation of two (4-fluorobenzoyl) decamethylene diamine
First by decamethylene diamine 172g, NaOH85g, sodium laurylsulfonate 30g joins in the deionized water of 1000g successively, dissolves under room temperature; Join in the three-necked flask of 5L after fluorobenzoyl chloride 317g is mixed with 1200g sherwood oil again, then above-mentioned two amine aqueous solutions configured are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 7h generate two (4-fluorobenzoyl) decamethylene diamine; Reacted sherwood oil is steamed, again reaction solution is filtered, collect filter cake, by filter cake through deionized water wash twice, removing water-soluble impurity, filters, obtains the thick product of white powder, again thick product is carried out recrystallization in butanone and tetrahydrofuran (THF), namely collecting by filtration colourless acicular crystal, vacuum-drying obtain two (4-fluorobenzoyl) decamethylene diamine monomers of purifying;
(2), the preparation of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether decanediamide
By two (4-fluorobenzoyl) decamethylene diamine 416g, Calcium hydrogen carbonate 120g, two (4-the hydroxyphenyl)-1-diphenylphosphino ethane 290g and N-Methyl pyrrolidone 2000g of toluene 50g, 1,1-adds in reactor, under nitrogen protection, in temperature 185 DEG C of dehydration reaction 1.5h, then at temperature 200 DEG C reaction 10h, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 100 DEG C, separate out white fine strip shape polymer crude product; By above-mentioned polymkeric substance through water, washing with alcohol, in temperature 130 DEG C of dry 3h, pulverize, then purify with deionized water, acetone respectively, in temperature 110 DEG C of dry 16h, namely obtain purifying polymer with bis phenol A aryl oxide decanediamide, productive rate is about 94%; With the solution of NMP to be solvent configuration concentration be 0.5g/dl, with Ubbelohde viscometer at temperature 30.0 ± 0.1 DEG C, measure intrinsic viscosity=0.96dl/g, flame retardant properties is as shown in Table 1 below, infrared, nuclear-magnetism characterizes and refers to respectively shown in Fig. 1, Fig. 2, DSC characterizes in detail as shown in Figure 3, and TGA characterizes in detail as shown in Figure 4.
Table 1 is the flame retardant resistance experiment form of half aromatics polyarylether amide
Claims (9)
1. a half aromatics polyarylether amide, is characterized in that the starting raw material of this half aromatics polyarylether amide is made up of following component, is by weight:
Wherein, aromatics diphenol is dihydroxyphenyl propane, 4, any one in two (4-the hydroxyphenyl)-1-diphenylphosphino ethane of 4 '-dihydroxy diphenylsulphone or 1,1-, and half aromatics dihalo diamide is
x=F or Cl, m=2 or 4 or 6 or 8 or 10.
2. half aromatics polyarylether amide as claimed in claim 1, is characterized in that catalyzer is any one in lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrated barta, Quilonum Retard, sodium carbonate, salt of wormwood, calcium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, saleratus, Calcium hydrogen carbonate or barium bicarbonate.
3. half aromatics polyarylether amide as claimed in claim 1, is characterized in that dewatering agent is toluene or dimethylbenzene.
4. half aromatics polyarylether amide as claimed in claim 1, it is characterized in that solvent is N-methyl caprolactam, N, N-dimethyl propylene thiazolinyl urea, 1, any one in 3-dimethyl-2-imidazolinone, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), HMPA, N-cyclohexyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, 1-methyl-3-propyl imidazole bromo salt, 1-methyl-3-isopropylimdazole bromo salt or 1,3-dipropyl imidazoles bromo salt.
5. the preparation method of half aromatics polyarylether amide as described in one of Claims 1 to 4, is characterized in that the method comprises the following steps:
The preparation of (1) half aromatics dihalo diamide
By aliphatie diamine 60 ~ 172 parts, NaOH 80 ~ 120 parts, 1 ~ 30 part, tensio-active agent joins in the deionized water of 300 ~ 1000 parts successively, dissolves under room temperature; By parachlorobenzoyl chloride 348 parts or join in three-necked flask after mixing with 500 ~ 3000 parts of organic solvents fluorobenzoyl chloride 317 parts, then the above-mentioned aliphatie diamine solution configured is added dropwise in three-necked flask, after two amine aqueous solutions drip, at room temperature continue reaction 3 ~ 10h, generate half aromatics dihalo diamide;
The purifying of (2) half aromatics dihalo diamide
Organic solvent in above-mentioned half aromatics dihalo diamide is steamed, filter, collect filter cake, filter cake is through deionized water wash twice, removing water-soluble impurity, refilter, obtain the thick product of white powder, thick product recrystallization in recrystallization solvent, filter, collect colourless acicular crystal, vacuum-drying, obtain half aromatics dihalo diamide of purifying, structural formula is as follows:
Wherein: X=F or Cl, m=2 or 4 or 6 or 8 or 10;
The preparation of (3) half aromatics polyarylether amide
By half aromatics dihalo diamide 304 ~ 449 parts; catalyzer 10 ~ 200 parts; dewatering agent 5 ~ 100 parts; aromatics diphenol; 228 ~ 290 parts add in reactor with solvent 200 ~ 2000 parts; under nitrogen protection; in temperature 150 ~ 200 DEG C of dehydration reaction 0.5 ~ 3h; reaction 0.5 ~ 10h is continued temperature 180 ~ 230 DEG C; obtain the polymers soln of thickness, more above-mentioned polymers soln is cooled to 50 ~ 160 DEG C, be poured into water while stirring; separate out white fine strip shape polymer crude product, its structural formula is:
Wherein, n=10-300
in any one;
(4). the purifying of half aromatics polyarylether amide
By above-mentioned polymer crude product through water, washing with alcohol, in temperature 50 ~ 200 DEG C of drying 2 ~ 8h, pulverize, then purify with deionized water, acetone respectively, in temperature 80 ~ 200 DEG C of drying 1 ~ 20h, obtain purifying half aromatics polyarylether amide resin.
6. the preparation method of half aromatics polyarylether amide as claimed in claim 5, is characterized in that aliphatie diamine is any one in quadrol, butanediamine, hexanediamine, octamethylenediamine or decamethylene diamine.
7. the preparation method of half aromatics polyarylether amide as claimed in claim 5, is characterized in that tensio-active agent is at least one in triethylammonium bromide, dodecyltriethylammonium ammonium chloride, hexadecyldimethyl benzyl ammonium brometo de amonio, Sodium sulfanilate, Tetrabutyl amonium bromide, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, Sodium dodecylbenzene sulfonate, benzene sulfonic acid sodium salt, sodium alginate or sodium laurylsulfonate and sodium stearate.
8. the preparation method of half aromatics polyarylether amide as claimed in claim 5, is characterized in that organic solvent is any one in 1,2-ethylene dichloride, methylene dichloride, chloroform, hexanaphthene, sherwood oil or normal heptane.
9. the preparation method of half aromatics polyarylether amide as claimed in claim 5, is characterized in that recrystallization solvent is at least one in methyl alcohol, ethanol, Virahol, acetone, butanone, tetrahydrofuran (THF), methane amide, ethanamide, dimethyl formamide and N,N-DIMETHYLACETAMIDE.
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| CN104387587B (en) * | 2014-11-07 | 2016-08-17 | 四川大学 | A kind of high fluidity polyether sulfone/amide copolymer and preparation method thereof |
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| CN114716664B (en) * | 2022-04-22 | 2023-02-28 | 四川大学 | Semi-aromatic copolymerized polyarylether amide, complex thereof and preparation method thereof |
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| US4958003A (en) * | 1987-12-25 | 1990-09-18 | Tosoh Corporation | Aromatic sulfideamide polymer and method for producing the same |
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