CN103739839A - Semi-aromatic polyarylether amide and preparation method thereof - Google Patents
Semi-aromatic polyarylether amide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses semi-aromatic polyarylether amide and a preparation method thereof. The method is characterized by comprising the following steps: adding 304-449 parts of semi-aromatic dihalogenated diamide, 10-200 parts of catalyst, 5-100 parts of dehydrating agent, 228-290 parts of aromatic diphenol and 200-2,000 parts of solvent into a reaction kettle; under nitrogen protection, performing a dehydration reaction for 0.5-3 hours at a temperature of 150-200 DEG C; reacting for 0.5-10 hours at a temperature of 180-230 DEG C to obtain a thick polymer liquid; cooling the polymer liquid to 50-160 DEG C and pouring water in the liquid while stirring to separate out a white strip crude product of polymer; washing the polymer with water and ethanol; drying for 2-8 hours at a temperature of 50-200 DEG C, and grinding; purifying with deionized water and acetone respectively; and drying for 1-20 hours at a temperature of 80-200 DEG C to obtain the purified semi-aromatic polyarylether amide resin. The semi-aromatic polyarylether amide has the characteristics of high molecular weight, high yield, high purity, little pollution and easiness in processing and is applied to special engineering plastics and heat-resistant and chemical corrosion-resistant high-molecular composite materials.
Description
Technical field
The present invention relates to a kind of half aromatics polyarylether acid amides 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, advantage for 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 used 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 very approaching, thereby cause its process window smaller), overcome the resistance to strong acid of polymeric amide, highly basic and chemical resistance are poor, hold incendive shortcoming, we have designed half this base polymer of aromatics polyarylether acid amides.
Summary of the invention
The object of the invention is provides a kind of half aromatics polyarylether amide polymer 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 polymer by the method for solution polycondensation, it has advantages of, and yield is high, molecular weight is high, easy processing, high temperature resistant, corrosion-resistant and fire-retardant.
Object of the present invention is realized by following technical measures, and wherein said raw material umber, except specified otherwise, is parts by weight.
The starting raw material of half aromatics polyarylether acid amides is made by following component, is by weight:
Wherein, aromatics diphenol is dihydroxyphenyl propane, 4, any in two (4-the hydroxyphenyl)-1-diphenylphosphino ethanes of 4 '-dihydroxy diphenylsulphone or 1,1-.
Described catalyzer is any 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 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 acid amides comprises the following steps:
The preparation of (1) half aromatics dihalo diamide
By 60～172 parts of aliphatie diamines, NaOH80～120 part, 1～30 part, tensio-active agent joins in the deionized water of 300～1000 parts successively, under room temperature, dissolves; After mixing with 500～3000 parts of organic solvents by 348 parts of parachlorobenzoyl chlorides or to 317 parts of fluorobenzoyl chlorides, join in three-necked flask, then the above-mentioned aliphatie diamine solution configuring 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 twice of deionized water wash, remove water-soluble impurity, refilter, obtain the thick product of white powder, thick product recrystallization in recrystallization solvent, filter, collect colourless acicular crystal, vacuum-drying, obtains half aromatics dihalo diamide of purifying, and 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 acid amides
By 304～449 parts of half aromatics dihalo diamide; 10～200 parts of catalyzer; 5～100 parts of dewatering agents; aromatics diphenol; 228～290 parts add in reactor with 200～2000 parts of solvents; under nitrogen protection; in 150～200 ℃ of dehydration reaction 0.5～3h of temperature; 180～230 ℃ of temperature, continue reaction 0.5～10h; obtain the polymers soln of thickness, more above-mentioned polymers soln is cooled to 50～160 ℃, be poured into water while stirring; separate out white fine strip shape polymer crude product, its structural formula is:
Wherein, n=10-300
(4). the purifying of half aromatics polyarylether acid amides
Above-mentioned polymer crude product, through water, washing with alcohol, in 50～200 ℃ of dry 2～8h of temperature, is pulverized, then with deionized water, acetone, purified respectively, in 80～200 ℃ of dry 1～20h of temperature, obtain purifying half aromatics polyarylether amide resins.
Described aliphatie diamine is any in quadrol, butanediamine, hexanediamine, octamethylenediamine or decamethylene diamine.
Described tensio-active agent is at least one in triethyl brometo de amonio, dodecyl triethyl 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 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 acid amides respectively through infrared spectra, nucleus magnetic resonance (
1h-NMR) test has obtained confirmation, as shown in Figure 1 and Figure 2.
2 by regulation and control reactant concn, material proportion and temperature of reaction, prepares half aromatics polyphenylene sulfide acid amides of different viscosity; And take NMP as solvent, the sample liquid of preparation 0.5g/dl, at 30.0 ± 0.1 ℃ of temperature with the intrinsic viscosity=0.40～2.0dl/g of determination of ubbelohde viscometer polymkeric substance.
3 second-order transition temperatures that adopt NETZSCH DSC200PC to test half aromatics polyarylether acid amides, 10 ℃/min of temperature rise rate, test result is as shown in Figure 3.
The 4 thermal weight loss temperature that adopt TGA to test half aromatics polyarylether acid amides, test result as shown in Figure 4.
5 pairs of half aromatics polyarylether acid amides have carried out respectively flame retardant properties test, shown in 1.
Tool of the present invention has the following advantages:
1. adopt the diphenol that contains aryl oxide structure as reaction monomers, because the introducing of soft segment ehter bond can reduce (Tm=300 ℃～404 ℃ of the fusing points of partially aromatic polyamide effectively, and gather, hexamethylene terephthalamide---the fusing point of PA6T is at 370 ℃, but there is a small amount of decomposition at 330 ℃ in PA6T, cause its application limited, current business-like PA6T is its modification by copolymerization product mostly), thus its processing characteristics improved; The aliphatie diamine simultaneously adopting in monomer preparation process is easy to get, cheap.
2. what in monomer preparation process, adopt is room temperature interfacial synthesis method, has avoided the waste of high temperature to the energy, and it is simple that it has technique, and security is good, repeatability is strong, good stability, and product yield is high, purity is high, pollutes the advantages such as little and the easy recovery of solvent.
3. half aromatics polyarylether acid amides has easy processing, high temperature resistant (its second-order transition temperature is the fusing point of PPS than polyphenylene sulfide---Tg=90 ℃ exceeds approximately 40 ℃～100 ℃), 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 goods heat-resisting, resistance to chemical attack, also can be made into special fibre and film, has wide practical use.
Accompanying drawing explanation:
Fig. 1 is the infrared spectrum of half aromatics polyarylether acid amides
In its infared spectrum at 3320cm
-1near the absorption of vibrations of occurred-CONH-, 3060cm
-1near occurred that the C-H stretching vibration of phenyl ring absorbs, at 2930cm
-1and 2850cm
-1near occurred-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
-1near the absorption of vibrations of the be absorbed as-O-key occurring.
Fig. 2 is the nuclear magnetic spectrogram of half aromatics polyarylether acid amides
It near 8.4ppm, is wherein the chemical shift of the N-H in half aromatics polyarylether amide structure, 6.6-7.8ppm is the chemical shift of the C-H of phenyl ring in half aromatics polyarylether amide structure, near 2.1ppm, be the chemical shift of methyl in half aromatics polyarylether amide structure, and 1.1-3.5ppm is the chemical shift of methylene radical in half aromatics polyarylether amide structure.
Fig. 3 is the Differential scanning calorimetry curve (DSC) of half aromatics polyarylether acid amides
Curve embodiment 7 is the DSC curve of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether adipamides, result shows that second-order transition temperature and the fusing point of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether adipamides are respectively 156.5 ℃, show that polymkeric substance has good thermal characteristics.
Fig. 4 is the thermogravimetic analysis (TGA) curve (TGA) of half aromatics polyarylether acid amides
Curve embodiment 7 is the TGA curve of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether adipamides, result shows that temperature of initial decomposition and the carbon residue amount of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether adipamides are respectively 436 ℃, 4.1%, show that polymkeric substance has good thermal characteristics.
Embodiment
Below by embodiment, the present invention is specifically described, be necessary to be pointed out that at this present embodiment is only used to further illustrate the present invention, can not be interpreted as that, to the present invention includes the restriction of 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, triethyl brometo de amonio 1g joins in the deionized water of 300g successively, under room temperature, dissolves; Again will be to fluorobenzoyl chloride 317g and 500g1, after mixing, 2-ethylene dichloride joins in the three-necked flask of 5L, then above-mentioned two amine aqueous solutions that configure are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 3h and generate two (4-fluorobenzoyl) quadrols; By reacted 1,2-ethylene dichloride steams, again reaction solution is filtered, collect filter cake, filter cake, through deionized water wash twice, is removed to water-soluble impurity, filter, obtain the thick product of white powder, thicker product is carried out to recrystallization in methyl alcohol, filtration collection 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 150 ℃ of dehydration reaction 0.5h of temperature, then at 180 ℃ of reaction 10h of temperature, obtain the polymers soln of thickness, after above-mentioned polymers soln is cooled to 50 ℃, be poured into water while stirring, separate out white fine strip shape polymer crude product; Above-mentioned polymkeric substance, through water, washing with alcohol, in the dry 8h of temperature 50 C, is pulverized, then with deionized water, acetone, purified respectively, in 80 ℃ of dry 1h of temperature, obtain purifying polyether sulphone oxalamide resin, productive rate is about 94%; With NMP, be that solvent configuration concentration is the solution of 0.5g/dl, at 30.0 ± 0.1 ℃ of temperature, with Ubbelohde viscometer, 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, dodecyl triethyl ammonium chloride 10g and benzene sulfonic acid sodium salt 20g join in the deionized water of 1000g successively, under room temperature, dissolve; After again parachlorobenzoyl chloride 348g being mixed with 3000g methylene dichloride, join in the three-necked flask of 5L, then above-mentioned two amine aqueous solutions that configure are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 10h and generate two (4-chlorobenzoyl) butanediamine; Reacted methylene dichloride is steamed, again reaction solution is filtered, collect filter cake, by filter cake through twice of deionized water wash, remove water-soluble impurity, filter, obtain the thick product of white powder, thick product is carried out in the mixed solvent of methyl alcohol and methane amide to recrystallization, filtration collection colourless acicular crystal, vacuum-drying obtain two (4-chlorobenzoyl) butanediamine monomers of purifying again;
(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 200 ℃ of dehydration reaction 3h of temperature, then at 230 ℃ of reaction 0.5h of temperature, obtain the polymers soln of thickness, after above-mentioned polymers soln is cooled to 160 ℃, be poured into water while stirring, separate out white fine strip shape polymer crude product; Above-mentioned polymkeric substance, through water, washing with alcohol, in 200 ℃ of dry 2h of temperature, is pulverized, then with deionized water, acetone, purified respectively, in 200 ℃ of dry 20h of temperature, obtain purifying polymer with bis phenol A aryl oxide succinic diamide resin, productive rate is about 93%; With NMP, be that solvent configuration concentration is the solution of 0.5g/dl, at 30.0 ± 0.1 ℃ of temperature, with Ubbelohde viscometer, 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 by octamethylenediamine 144g, NaOH90g, sodium stearate 15g joins in the deionized water of 600g successively, under room temperature, dissolves; After again parachlorobenzoyl chloride 348g being mixed with 1500g hexanaphthene, join in the three-necked flask of 5L, then above-mentioned two amine aqueous solutions that configure are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 6h and generate two (4-chlorobenzoyl) octamethylenediamines; Reacted hexanaphthene is steamed, again reaction solution is filtered, collect filter cake, by filter cake through twice of deionized water wash, remove water-soluble impurity, filter, obtain the thick product of white powder, thick product is carried out in methane amide to recrystallization, filtration collection colourless acicular crystal, vacuum-drying obtain two (4-chlorobenzoyl) octamethylenediamine monomers of purifying again;
(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 175 ℃ of dehydration reaction 1.5h of temperature, again at 200 ℃ of reaction 6h of temperature, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 100 ℃, separate out white fine strip shape polymer crude product; Above-mentioned polymkeric substance, through water, washing with alcohol, in 110 ℃ of dry 4h of temperature, is pulverized, then with deionized water, acetone, purified respectively, in 120 ℃ of dry 6h of temperature, obtain purifying polyether sulphone suberamide resin, productive rate is about 91%; With NMP, be that solvent configuration concentration is the solution of 0.5g/dl, at 30.0 ± 0.1 ℃ of temperature, with Ubbelohde viscometer, 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, under room temperature, dissolves; After being mixed with 1200g sherwood oil, fluorobenzoyl chloride 317g joins in the three-necked flask of 5L again, then above-mentioned two amine aqueous solutions that configure are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 7h and generate two (4-fluorobenzoyl) decamethylene diamines; Reacted sherwood oil is steamed, again reaction solution is filtered, collect filter cake, by filter cake through twice of deionized water wash, remove water-soluble impurity, filter, obtain the thick product of white powder, thick product is carried out in butanone and tetrahydrofuran (THF) to recrystallization, filtration collection colourless acicular crystal, vacuum-drying obtain two (4-fluorobenzoyl) decamethylene diamine monomers of purifying again;
(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 add in reactor, under nitrogen protection, in 185 ℃ of dehydration reaction 1.5h of temperature, again at 200 ℃ of reaction 10h of temperature, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 100 ℃, separate out white fine strip shape polymer crude product; Above-mentioned polymkeric substance, through water, washing with alcohol, in 130 ℃ of dry 3h of temperature, is pulverized, then with deionized water, acetone, purified respectively, in 110 ℃ of dry 16h of temperature, obtain purifying polymer with bis phenol A aryl oxide decanediamide, productive rate is about 94%; With NMP, be that solvent configuration concentration is the solution of 0.5g/dl, at 30.0 ± 0.1 ℃ of temperature, with Ubbelohde viscometer, measure intrinsic viscosity=0.83dl/g, flame retardant properties is as shown in Table 1 below.
(1), the preparation of two (4-fluorobenzoyl) quadrol
First by quadrol 60g, NaOH80g, triethyl brometo de amonio 1g joins in the deionized water of 300g successively, under room temperature, dissolves; Again will be to fluorobenzoyl chloride 317g and 500g1, after mixing, 2-ethylene dichloride joins in the three-necked flask of 5L, then above-mentioned two amine aqueous solutions that configure are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 3h and generate two (4-fluorobenzoyl) quadrols; By reacted 1,2-ethylene dichloride steams, again reaction solution is filtered, collect filter cake, filter cake, through deionized water wash twice, is removed to water-soluble impurity, filter, obtain the thick product of white powder, thicker product is carried out to recrystallization in methyl alcohol, filtration collection colourless acicular crystal, vacuum-drying obtain two (4-fluorobenzoyl) quadrol monomers of purifying;
(2), the preparation of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether oxalamides
By two (4-fluorobenzoyl) quadrol 304g, sodium hydroxide 10g, toluene 5g, two (4-the hydroxyphenyl)-1-diphenylphosphino ethane 290g of 1,1-and N-methyl caprolactam 200g add in reactor, under nitrogen protection, in 150 ℃ of dehydration reaction 0.5h of temperature, then at 180 ℃ of reaction 10h of temperature, obtain the polymers soln of thickness, after above-mentioned polymers soln is cooled to 50 ℃, be poured into water while stirring, separate out white fine strip shape polymer crude product; Above-mentioned polymkeric substance, through water, washing with alcohol, in the dry 8h of temperature 50 C, is pulverized, then with deionized water, acetone, purified respectively, in 80 ℃ of dry 1h of temperature, obtain purifying polyether sulphone oxalamide resin, productive rate is about 94%; With NMP, be that solvent configuration concentration is the solution of 0.5g/dl, at 30.0 ± 0.1 ℃ of temperature with Ubbelohde viscometer, 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.
(1), the preparation of two (4-chlorobenzoyl) butanediamine
First by butanediamine 88g, NaOH100g, dodecyl triethyl ammonium chloride 10g and benzene sulfonic acid sodium salt 20g join in the deionized water of 1000g successively, under room temperature, dissolve; After again parachlorobenzoyl chloride 348g being mixed with 3000g methylene dichloride, join in the three-necked flask of 5L, then above-mentioned two amine aqueous solutions that configure are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 10h and generate two (4-chlorobenzoyl) butanediamine; Reacted methylene dichloride is steamed, again reaction solution is filtered, collect filter cake, by filter cake through twice of deionized water wash, remove water-soluble impurity, filter, obtain the thick product of white powder, thick product is carried out in the mixed solvent of methyl alcohol and methane amide to recrystallization, filtration collection colourless acicular crystal, vacuum-drying obtain two (4-chlorobenzoyl) butanediamine monomers of purifying again;
(2), the preparation of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether succinic diamides
By two (4-chlorobenzoyl) butanediamine 365g, salt of wormwood 200g, dimethylbenzene 100g, 1, two (4-hydroxyphenyl)-1-diphenylphosphino ethane 290g and the N of 1-, N-dimethyl propylene thiazolinyl urea 2000g adds in reactor, under nitrogen protection, in 200 ℃ of dehydration reaction 3h of temperature, again at 230 ℃ of reaction 0.5h of temperature, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 160 ℃, separate out white fine strip shape polymer crude product; Above-mentioned polymkeric substance, through water, washing with alcohol, in 200 ℃ of dry 2h of temperature, is pulverized, then with deionized water, acetone, purified respectively, in 200 ℃ of dry 20h of temperature, obtain purifying polymer with bis phenol A aryl oxide succinic diamide resin, productive rate is about 93%; With NMP, be that solvent configuration concentration is the solution of 0.5g/dl, at 30.0 ± 0.1 ℃ of temperature with Ubbelohde viscometer, 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, under room temperature, dissolves; After being mixed with 2500g chloroform, fluorobenzoyl chloride 317g joins in the three-necked flask of 5L again, then above-mentioned two amine aqueous solutions that configure are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 8h and generate two (4-fluorobenzoyl) hexanediamines; Reacted chloroform is steamed, again reaction solution is filtered, collect filter cake, by filter cake through twice of deionized water wash, remove water-soluble impurity, filter, obtain the thick product of white powder, thick product is carried out in acetone to recrystallization, filtration collection colourless acicular crystal, vacuum-drying obtain two (4-fluorobenzoyl) hexanediamine monomers of purifying again;
(2), the preparation of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether adipamides
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 190 ℃ of dehydration reaction 2.5h of temperature, again at 210 ℃ of reaction 8h of temperature, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 120 ℃, separate out white fine strip shape polymer crude product; Above-mentioned polymkeric substance, through water, washing with alcohol, in 120 ℃ of dry 6h of temperature, is pulverized, with deionized water, acetone, purify respectively again, in 100 ℃ of dry 5h of temperature, obtain two (4-the hydroxyphenyl)-1-diphenylphosphino ethane polyarylether adipamide resins of purifying, productive rate is about 96%; With NMP, be that solvent configuration concentration is the solution of 0.5g/dl, at 30.0 ± 0.1 ℃ of temperature with Ubbelohde viscometer, 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.
(1), the preparation of two (4-chlorobenzoyl) octamethylenediamine
First by octamethylenediamine 144g, NaOH90g, sodium stearate 15g joins in the deionized water of 600g successively, under room temperature, dissolves; After again parachlorobenzoyl chloride 348g being mixed with 1500g hexanaphthene, join in the three-necked flask of 5L, then above-mentioned two amine aqueous solutions that configure are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 6h and generate two (4-chlorobenzoyl) octamethylenediamines; Reacted hexanaphthene is steamed, again reaction solution is filtered, collect filter cake, by filter cake through twice of deionized water wash, remove water-soluble impurity, filter, obtain the thick product of white powder, thick product is carried out in methane amide to recrystallization, filtration collection colourless acicular crystal, vacuum-drying obtain two (4-chlorobenzoyl) octamethylenediamine monomers of purifying again;
(2), the preparation of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether suberamides
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 175 ℃ of dehydration reaction 1.5h of temperature, again at 200 ℃ of reaction 6h of temperature, obtain the polymers soln of thickness, be poured into water while stirring after above-mentioned polymers soln is cooled to 100 ℃, separate out white fine strip shape polymer crude product; Above-mentioned polymkeric substance, through water, washing with alcohol, in 110 ℃ of dry 4h of temperature, is pulverized, then with deionized water, acetone, purified respectively, in 120 ℃ of dry 6h of temperature, obtain purifying polyether sulphone suberamide resin, productive rate is about 91%; With NMP, be that solvent configuration concentration is the solution of 0.5g/dl, at 30.0 ± 0.1 ℃ of temperature with Ubbelohde viscometer, 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.
(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, under room temperature, dissolves; After being mixed with 1200g sherwood oil, fluorobenzoyl chloride 317g joins in the three-necked flask of 5L again, then above-mentioned two amine aqueous solutions that configure are added dropwise in flask, after two amine aqueous solutions drip, continue at room temperature to react 7h and generate two (4-fluorobenzoyl) decamethylene diamines; Reacted sherwood oil is steamed, again reaction solution is filtered, collect filter cake, by filter cake through twice of deionized water wash, remove water-soluble impurity, filter, obtain the thick product of white powder, thick product is carried out in butanone and tetrahydrofuran (THF) to recrystallization, filtration collection colourless acicular crystal, vacuum-drying obtain two (4-fluorobenzoyl) decamethylene diamine monomers of purifying again;
(2), the preparation of two (4-hydroxyphenyl)-1-diphenylphosphino ethane polyarylether decanediamides
By two (4-fluorobenzoyl) decamethylene diamine 416g, Calcium hydrogen carbonate 120g, toluene 50g, two (4-the hydroxyphenyl)-1-diphenylphosphino ethane 290g of 1,1-and N-Methyl pyrrolidone 2000g add in reactor, under nitrogen protection, in 185 ℃ of dehydration reaction 1.5h of temperature, then at 200 ℃ of reaction 10h of temperature, obtain the polymers soln of thickness, after above-mentioned polymers soln is cooled to 100 ℃, be poured into water while stirring, separate out white fine strip shape polymer crude product; Above-mentioned polymkeric substance, through water, washing with alcohol, in 130 ℃ of dry 3h of temperature, is pulverized, then with deionized water, acetone, purified respectively, in 110 ℃ of dry 16h of temperature, obtain purifying polymer with bis phenol A aryl oxide decanediamide, productive rate is about 94%; With NMP, be that solvent configuration concentration is the solution of 0.5g/dl, at 30.0 ± 0.1 ℃ of temperature with Ubbelohde viscometer, 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 acid amides
Claims (9)
1. a half aromatics polyarylether acid amides, is characterized in that the starting raw material of this half aromatics polyarylether acid amides is made by following component, is by weight:
Wherein, aromatics diphenol is dihydroxyphenyl propane, 4, any in two (4-the hydroxyphenyl)-1-diphenylphosphino ethanes of 4 '-dihydroxy diphenylsulphone or 1,1-.
2. half aromatics polyarylether acid amides as claimed in claim 1, is characterized in that catalyzer is any 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 acid amides as claimed in claim 1, is characterized in that dewatering agent is toluene or dimethylbenzene.
4. half aromatics polyarylether acid amides as claimed in claim 1, it is characterized in that solvent is N-methyl caprolactam, N, N-dimethyl propylene thiazolinyl urea, 1, any 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 acid amides as described in one of claim 1～4, is characterized in that the method comprises the following steps:
The preparation of (1) half aromatics dihalo diamide
By 60～172 parts of aliphatie diamines, NaOH80～120 part, 1～30 part, tensio-active agent joins in the deionized water of 300～1000 parts successively, under room temperature, dissolves; After mixing with 500～3000 parts of organic solvents by 348 parts of parachlorobenzoyl chlorides or to 317 parts of fluorobenzoyl chlorides, join in three-necked flask, then the above-mentioned aliphatie diamine solution configuring 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 twice of deionized water wash, remove water-soluble impurity, refilter, obtain the thick product of white powder, thick product recrystallization in recrystallization solvent, filter, collect colourless acicular crystal, vacuum-drying, obtains half aromatics dihalo diamide of purifying, and 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 acid amides
By 304～449 parts of half aromatics dihalo diamide; 10～200 parts of catalyzer; 5～100 parts of dewatering agents; aromatics diphenol; 228～290 parts add in reactor with 200～2000 parts of solvents; under nitrogen protection; in 150～200 ℃ of dehydration reaction 0.5～3h of temperature; 180～230 ℃ of temperature, continue reaction 0.5～10h; obtain the polymers soln of thickness, more above-mentioned polymers soln is cooled to 50～160 ℃, be poured into water while stirring; separate out white fine strip shape polymer crude product, its structural formula is:
Wherein, n=10-300
(4). the purifying of half aromatics polyarylether acid amides
Above-mentioned polymer crude product, through water, washing with alcohol, in 50～200 ℃ of dry 2～8h of temperature, is pulverized, then with deionized water, acetone, purified respectively, in 80～200 ℃ of dry 1～20h of temperature, obtain purifying half aromatics polyarylether amide resins.
6. the preparation method of half aromatics polyarylether acid amides as claimed in claim 5, is characterized in that aliphatie diamine is any in quadrol, butanediamine, hexanediamine, octamethylenediamine or decamethylene diamine.
7. the preparation method of half aromatics polyarylether acid amides as claimed in claim 5, is characterized in that tensio-active agent is at least one in triethyl brometo de amonio, dodecyl triethyl 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 acid amides as claimed in claim 5, is characterized in that organic solvent is any in 1,2-ethylene dichloride, methylene dichloride, chloroform, hexanaphthene, sherwood oil or normal heptane.
9. the preparation method of half aromatics polyarylether acid amides 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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| CN104109236B (en) * | 2014-07-21 | 2016-04-06 | 四川大学 | Fatty ring half aromatics polyarylether amide and preparation method thereof |
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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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