CN104109236A - Fatty cyclosemi aromatic polyarylether amide and preparation method thereof - Google Patents
Fatty cyclosemi aromatic polyarylether amide and preparation method thereof Download PDFInfo
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- CN104109236A CN104109236A CN201410347679.1A CN201410347679A CN104109236A CN 104109236 A CN104109236 A CN 104109236A CN 201410347679 A CN201410347679 A CN 201410347679A CN 104109236 A CN104109236 A CN 104109236A
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Abstract
The invention discloses a fatty cyclosemi aromatic polyarylether amide and a preparation method thereof. The method is characterized by comprising the following steps: adding 358-447 parts of fatty cyclosemi aromatic dihalodiamide, 5-300 parts of catalyst, 1-200 parts of dehydrating agent, 110-290 parts of diphenol and 150-3000 parts of solvent into a reaction kettle; in a nitrogen protective atmosphere, carrying out dehydration reaction at 130-200 DEG C for 0.5-5 hours, and reacting at 160-240 DEG C for 0.5-12 hours to obtain a viscous polymer solution; cooling the polymer solution to 30-100 DEG C, and pouring into water while stirring to precipitate a white strip-shaped polymer crude product; and washing the crude product with water and ethanol, drying at 50-200 DEG C for 2-8 hours, pulverizing, respectively purifying with deionized water and acetone, and drying at 80-200 DEG C for 1-20 hours, thereby obtaining the purified fatty cyclosemi aromatic polyarylether amide. The fatty cyclosemi aromatic polyarylether amide has the advantages of high molecular weight, high yield, high purity, low pollution, high processability and high transmittance of the prepared film.
Description
Technical field
The present invention relates to a kind of fatty ring 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 etc., 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 used p-phthaloyl chloride, 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 shortcoming of the resistance to strong acid of polymeric amide, highly basic; We have designed fatty ring half this base polymer of aromatics polyarylether acid amides, and we also find that the fatty ring half aromatics polyarylether acid amides of gained has excellent transmittance, is expected for high temperature resistant optical material simultaneously.
Summary of the invention
The object of the invention is provides a kind of fatty ring half aromatics polyarylether amide polymer and preparation method thereof for the deficiencies in the prior art, be characterized in fatty ring half aromatics dihalo diamide and diphenol to prepare fatty ring half aromatics polyarylether amide polymer by the method for solution polycondensation, it has advantages of, and molecular weight is high, yield is high, purity is high, small pollution and easy processing and high by its made membrane transparence.
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 fatty ring half aromatics polyarylether acid amides is made up of following component:
Wherein, diphenol is any in two (4-the hydroxyphenyl)-1-diphenylphosphino ethanes of Resorcinol, Resorcinol or 1,1-.
Described catalyzer is any in sodium hydroxide, calcium hydroxide, Quilonum Retard, sodium carbonate, salt of wormwood, calcium carbonate, sodium bicarbonate, saleratus, sodium acetate, potassium acetate, lime acetate, caoxalate or sodium phosphate.
Described dewatering agent is toluene or dimethylbenzene.
Described solvent is N-Methyl pyrrolidone, 1,3-dimethyl-2-imidazolinone, quinoline, isoquinoline 99.9, N, any in N-dimethyl propylene thiazolinyl urea, dimethyl sulfoxide (DMSO), tetramethylene sulfone, N-methyl propanamide, HMPA, N-cyclohexyl pyrrolidone, methane amide, ethanamide or 2-Pyrrolidone.
The preparation method of fatty ring half aromatics polyarylether acid amides comprises the following steps:
(1) preparation of fatty ring half aromatics dihalo diamide monomer
By 114～170 parts of fatty ring diamines, NaOH80～150 part, 1～50 part, tensio-active agent joins in the deionized water of 500～2000 parts successively, under room temperature, dissolves; After mixing with 300～3500 parts of organic solvents by 348 parts of parachlorobenzoyl chlorides or to 317 parts of fluorobenzoyl chlorides, join in three-necked flask, then above-mentioned fatty ring two amine aqueous solutions that configure are added dropwise in three-necked flask, after two amine aqueous solutions drip, at room temperature continue reaction 3～10h, generate fatty ring half aromatics dihalo diamide monomer;
(2) purifying of fatty ring half aromatics dihalo diamide monomer
Organic solvent in above-mentioned fatty ring 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 is through recrystallization, filter, collect colourless acicular crystal, vacuum-drying, obtains the fatty ring half aromatics dihalo diamide of purifying, and structural formula is as follows:
Wherein: X=F or Cl;
(3) preparation of fatty ring half aromatics polyarylether acid amides
By 358～447 parts of fatty ring half aromatics dihalo diamide; 5～300 parts of catalyzer; 1～200 part of dewatering agent; 150～3000 parts of 110～290 parts of diphenol and solvents add in reactor; under nitrogen protection; in 130～200 DEG C of dehydration reaction 0.5～5h of temperature; continue reaction 0.5～12h 160～240 DEG C of temperature; obtain the polymers soln of thickness; again above-mentioned polymers soln is cooled to 30～100 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;
(4). the purifying of fatty ring half aromatics polyarylether acid amides
Above-mentioned polymer crude product, through water, washing with alcohol, in 50～200 DEG C of dry 2～8h of temperature, is pulverized, then purified with deionized water, acetone respectively, in 80～200 DEG C of dry 1～20h of temperature, obtain the fatty ring half aromatics polyarylether amide resins of purifying.
Described aliphatie diamine is any in isophorone diamine or trans-cyclohexanediamine.
Described tensio-active agent is at least one in smooth of sodium laurate, sodium stearate, trolamine, sodium lauryl sulphate, dioctyl sodium sulfosuccinate, Sodium glycocholate, Sodium sulfanilate, Tetrabutyl amonium bromide, sodium alginate or lipid acid sorb.
Described organic solvent is any in methylene dichloride, chloroform, tetracol phenixin, tetrachloroethane, hexanaphthene, sherwood oil, normal heptane, toluene or dimethylbenzene.
Described recrystallization solvent is at least one in methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), methane amide, ethanamide, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone or methyl-sulphoxide.
Structural characterization and performance test
The structure of 1 fatty ring half aramid monomer respectively through infrared spectra, nucleus magnetic resonance (
1h-NMR) test has obtained confirmation, as shown in Figure 1, Figure 2, Figure 3 shows.
The structure of 2 fatty ring half aromatics polyarylether acid amides respectively through infrared spectra, nucleus magnetic resonance (
1h-NMR) test has obtained confirmation, as shown in, Fig. 4, Fig. 5～8.
3 by regulation and control reactant concn, material proportion and temperature of reaction, prepares the fatty ring half aromatics polyphenylene sulfide acid amides of different viscosity; And taking NMP as solvent, the sample liquid of preparation 0.5g/dl, at 30.0 ± 0.1 DEG C of temperature with the intrinsic viscosity=0.60～1.3dl/g of determination of ubbelohde viscometer polymkeric substance.
4 second-order transition temperatures that adopt NETZSCH DSC200PC to test fatty ring half aromatics polyarylether acid amides, 10 DEG C/min of temperature rise rate, test result is as shown in Figure 9.
The 5 thermal weight loss temperature that adopt TGA to test fatty ring half aromatics polyarylether acid amides, test result as shown in figure 10.
6 pairs of fatty ring half aromatics polyarylether acid amides have carried out respectively transmittance test, and test result as shown in figure 11.
Tool of the present invention has the following advantages:
1. adopt diphenol as reaction monomers, because the introducing of soft segment ehter bond can reduce (Tm=300 DEG C～404 DEG C of the fusing points of partially aromatic polyamide effectively, and gather, 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 its processing characteristics improved.
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. fatty ring 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 DEG C exceeds approximately 100 DEG C), transmittance advantages of higher.
4. this base polymer can be used for special engineering plastics and high performance polymer material, and prepares parts and goods heat-resisting, resistance to chemical attack, also can be made into special fibre and high temperature resistant optical thin film, has wide practical use.
Brief description of the drawings:
Fig. 1 is the infrared spectrum of fatty ring half aromatics dihalo diamide
In its infared spectrum at 3320cm
-1near the absorption of vibrations of occurred-CONH-, 3060cm
-1near occurred phenyl ring C-H stretching vibration absorb, 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, 1530cm
-1, 1490cm
-1for the skeletal vibration absorption peak of phenyl ring.
Fig. 2 is the nuclear magnetic spectrogram of two (4-fluorobenzoyl) trans cyclohexanediamine
The ownership at its each peak marks in the drawings.
Fig. 3 is the nuclear magnetic spectrogram of your ketone diamines of two (4-fluorobenzoyl) different fluorine
The ownership at its each peak marks in the drawings.
Fig. 4 is the infrared spectrum of fatty ring half aromatics polyarylether acid amides
In its infared spectrum at 3320cm
-1near the absorption of vibrations of occurred-CONH-, 3060cm
-1near occurred phenyl ring C-H stretching vibration absorb, 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, 1530cm
-1, 1490cm
-1for the skeletal vibration absorption peak of phenyl ring, 1100cm
-1there is the absorption of vibrations of ehter bond.
Fig. 5-8 are respectively the nuclear magnetic spectrogram of the poly-pair fragrant acid amides of (4-hydroxyphenyl)-1-diphenylphosphino ethane-cyclohexanediamine half, poly-Resorcinol-different fluorine that ketone diamines half fragrant acid amides, poly-two (4-hydroxyphenyl)-1-diphenylphosphino ethanes-different fluorine that ketone diamines half fragrant acid amides, poly-Resorcinol-different fluorine that ketone diamines half fragrant acid amides
The ownership at its each peak marks in the drawings.
Fig. 9 is the Differential scanning calorimetry curve (DSC) of fatty ring half aromatics polyarylether acid amides
Curve embodiment 1 is the DSC curve of poly-two (4-hydroxyphenyl)-1-diphenylphosphino ethane-cyclohexanediamine half fragrant acid amides, and result shows that its second-order transition temperature is 263.3 DEG C, shows that polymkeric substance has good thermal characteristics.
Curve embodiment 2 is the DSC curve of your ketone diamines half fragrant acid amides of poly-Resorcinol-different fluorine, and result shows that its second-order transition temperature is 215.4 DEG C, shows that polymkeric substance has good thermal characteristics.
Curve embodiment 3 is the DSC curve of poly-your ketone diamines half fragrant acid amides of two (4-hydroxyphenyl)-1-diphenylphosphino ethanes-different fluorine, and result shows that its second-order transition temperature is 220.4 DEG C, shows that polymkeric substance has good thermal characteristics.
Curve embodiment 4 is the DSC curve of your ketone diamines half fragrant acid amides of poly-Resorcinol-different fluorine, and result shows that its second-order transition temperature is 231.6 DEG C, shows that polymkeric substance has good thermal characteristics.
Figure 10 is the thermogravimetric curve (TGA) of fatty ring half aromatics polyarylether acid amides
Curve embodiment 1 is the TGA curve of poly-two (4-hydroxyphenyl)-1-diphenylphosphino ethane-cyclohexanediamine half fragrant acid amides, and result shows that its hot temperature of initial decomposition is 431.6 DEG C, shows that polymkeric substance has good thermal characteristics.
Curve embodiment 2 is the DSC curve of your ketone diamines half fragrant acid amides of poly-Resorcinol-different fluorine, and result shows that its hot temperature of initial decomposition is 424.7 DEG C, shows that polymkeric substance has good thermal characteristics.
Curve embodiment 3 is the TGA curve of poly-your ketone diamines half fragrant acid amides of two (4-hydroxyphenyl)-1-diphenylphosphino ethanes-different fluorine, and result shows that its hot temperature of initial decomposition is 434.8 DEG C, shows that polymkeric substance has good thermal characteristics.
Curve embodiment 4 is the TGA curve of your ketone diamines half fragrant acid amides of poly-Resorcinol-different fluorine, and result shows that its hot temperature of initial decomposition is 429.8 DEG C, shows that polymkeric substance has good thermal characteristics.
Figure 11 is the transmittance curve (UV-Vis) of fatty ring half aromatics polyarylether acid amides
Curve embodiment 2 is the UV-Vis curve of your ketone diamines half fragrant acid amides of poly-Resorcinol-different fluorine, and result shows that its transmitance at 450nm place is 85.8%, shows that polymkeric substance has excellent light transmission.
Curve embodiment 3 is the UV-Vis curve of poly-your ketone diamines half fragrant acid amides of two (4-hydroxyphenyl)-1-diphenylphosphino ethanes-different fluorine, and result shows that its transmitance at 450nm place is 85.2%, shows that polymkeric substance has excellent light transmission.
Curve embodiment 4 is the UV-Vis curve of your ketone diamines half fragrant acid amides of poly-Resorcinol-different fluorine, and result shows that its transmitance at 450nm place is 83.2%, shows that polymkeric substance has excellent light transmission.
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 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) preparation of two (4-fluorobenzoyl) trans cyclohexanediamine
By Isosorbide-5-Nitrae-cyclohexanediamine 114g, NaOH150g, the smooth 50g of lipid acid sorb joins in the deionized water of 2000g successively, under room temperature, dissolves; After mixing with 3000g hexanaphthene fluorobenzoyl chloride 317g, join in three-necked flask, then above-mentioned two amine aqueous solutions that configure are added dropwise in three-necked flask, after two amine aqueous solutions drip, at room temperature continue reaction 10h, generate two (4-fluorobenzoyl) trans cyclohexanediamine monomers;
(2) purifying of two (4-fluorobenzoyl) trans cyclohexanediamine
Hexanaphthene in above-mentioned two (4-fluorobenzoyl) trans cyclohexanediamine 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 is through ethanamide recrystallization, filter, collect colourless acicular crystal, vacuum-drying, obtains two (4-fluorobenzoyl) trans cyclohexanediamine of purifying, and structural formula is as follows:
infrared and nuclear-magnetism characterizes and refers to shown in Fig. 1,2;
(3) preparation of poly-two (4-hydroxyphenyl)-1-diphenylphosphino ethane-cyclohexanediamine half fragrant acid amides
By two (4-fluorobenzoyl) trans cyclohexanediamine 358g, sodium phosphate 200g, dimethylbenzene 200g, two (4-hydroxyphenyl)-1-diphenylphosphino ethane 290g and HMPA 3000g add in reactor, under nitrogen protection, in 170 DEG C of dehydration reaction 2h of temperature, continue reaction 10h 230 DEG C of temperature, obtain the polymers soln of thickness, more above-mentioned polymers soln is cooled to 30 DEG C, be poured into water while stirring, separate out white fine strip shape polymer crude product;
(4). the purifying of poly-two (4-hydroxyphenyl)-1-diphenylphosphino ethane-cyclohexanediamine half fragrant acid amides
By above-mentioned polymer crude product through water, washing with alcohol, in 130 DEG C of dry 5h of temperature, pulverize, purify with deionized water, acetone respectively again, in 160 DEG C of dry 12h of temperature, obtain the poly-two fragrant amide resinss of (4-hydroxyphenyl)-1-diphenylphosphino ethane-cyclohexanediamine half of purifying, productive rate is about 91%; Be that solvent configuration concentration is the solution of 0.5g/dl with NMP, at 30.0 ± 0.1 DEG C of temperature, with Ubbelohde viscometer, measure intrinsic viscosity=1.13dl/g, infrared and nuclear-magnetism characterizes respectively as shown in Figure 4,5, and its thermal performance test is respectively as shown in Fig. 9,10.
Embodiment 2
(1) preparation of your ketone diamines of two (4-fluorobenzoyl) different fluorine
By different fluorine that ketone diamines 170g, NaOH100g, Sodium glycocholate 10g joins in the deionized water of 1500g successively, under room temperature, dissolves; After mixing with 2000g methylene dichloride fluorobenzoyl chloride 317g, join in three-necked flask, then above-mentioned two amine aqueous solutions that configure are added dropwise in three-necked flask, after two amine aqueous solutions drip, at room temperature continue reaction 3h, generate two (4-fluorobenzoyl) different fluorine that ketone diamine monomer;
(2) purifying of your ketone diamines of two (4-fluorobenzoyl) different fluorine
Methylene dichloride in your ketone diamines of above-mentioned two (4-fluorobenzoyl) different fluorine 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 is through mixed solvent (ethanol+acetone) recrystallization, filter, collect colourless acicular crystal, vacuum-drying, obtains the tetrachloroethane of purifying, and structural formula is as follows:
infrared and nuclear-magnetism characterizes respectively as shown in Figure 1,3;
(3) preparation of your ketone diamines half fragrant acid amides of poly-Resorcinol-different fluorine
By different to two (4-fluorobenzoyl) fluorine that ketone diamines 414g, salt of wormwood 50g, dimethylbenzene 100g, Resorcinol 110g and N, N-dimethyl propylene thiazolinyl urea 2000g adds in reactor, under nitrogen protection, in 130 DEG C of dehydration reaction 5h of temperature, continue reaction 3h 200 DEG C of temperature, obtain the polymers soln of thickness, again above-mentioned polymers soln is cooled to 50 DEG C, is poured into water while stirring, separate out white fine strip shape polymer crude product;
(4). the purifying of your ketone diamines half fragrant acid amides of poly-Resorcinol-different fluorine
Above-mentioned polymer crude product, through water, washing with alcohol, in 100 DEG C of dry 4h of temperature, is pulverized, then purified with deionized water, acetone respectively, in 120 DEG C of dry 6h of temperature, obtain your ketone diamines half fragrant amide resins of purifying poly-Resorcinol-different fluorine, productive rate is about 92%; Be that solvent configuration concentration is the solution of 0.5g/dl with NMP, at 30.0 ± 0.1 DEG C of temperature, with Ubbelohde viscometer, measure intrinsic viscosity=0.90dl/g, infrared and nuclear-magnetism characterizes respectively as shown in Fig. 4,6, its thermal performance test is respectively as shown in Fig. 9,10, and film transmitance as shown in figure 11.
Embodiment 3
(1) preparation of your ketone diamines of two (4-fluorobenzoyl) different fluorine
By different fluorine that ketone diamines 170g, NaOH100g, Sodium glycocholate 5g and sodium alginate 5g join in the deionized water of 1500g successively, under room temperature, dissolve; After mixing with 2000g methylene dichloride fluorobenzoyl chloride 317g, join in three-necked flask, then above-mentioned two amine aqueous solutions that configure are added dropwise in three-necked flask, after two amine aqueous solutions drip, at room temperature continue reaction 3h, generate two (4-fluorobenzoyl) different fluorine that ketone diamine monomer;
(2) purifying of your ketone diamines of two (4-fluorobenzoyl) different fluorine
Methylene dichloride in your ketone diamines of above-mentioned two (4-fluorobenzoyl) different fluorine 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 is through mixed solvent (ethanol+acetone) recrystallization, filter, collect colourless acicular crystal, vacuum-drying, obtains the tetrachloroethane of purifying, and structural formula is as follows:
(3) preparation of poly-your ketone diamines half fragrant acid amides of two (4-hydroxyphenyl)-1-diphenylphosphino ethane-different fluorine
By different to two (4-fluorobenzoyl) fluorine that ketone diamines 414g, sodium oxalate 160g, dimethylbenzene 80g, two (4-hydroxyphenyl)-1-diphenylphosphino ethane 290g and quinoline 2500g add in reactor, under nitrogen protection, in 165 DEG C of dehydration reaction 2h of temperature, continue reaction 4h 200 DEG C of temperature, obtain the polymers soln of thickness, more above-mentioned polymers soln is cooled to 30 DEG C, be poured into water while stirring, separate out white fine strip shape polymer crude product;
(4). the purifying of poly-your ketone diamines half fragrant acid amides of two (4-hydroxyphenyl)-1-diphenylphosphino ethanes-different fluorine
By above-mentioned polymer crude product through water, washing with alcohol, in 120 DEG C of dry 8h of temperature, pulverize, purify with deionized water, acetone respectively again, in 200 DEG C of dry 1h of temperature, obtain poly-two (4-the hydroxyphenyl)-1-diphenylphosphino ethanes of purifying-different fluorine that ketone diamines half fragrant amide resins, productive rate is about 92%; Be that solvent configuration concentration is the solution of 0.5g/dl with NMP, at 30.0 ± 0.1 DEG C of temperature, with Ubbelohde viscometer, measure intrinsic viscosity=1.26dl/g, infrared and nuclear-magnetism characterizes respectively as shown in Fig. 4,7, its thermal performance test is respectively as shown in Fig. 9,10, and film transmitance as shown in figure 11.
Embodiment 4
(1) preparation of your ketone diamines of two (4-chlorobenzoyls) different fluorine
By different fluorine that ketone diamines 170g, NaOH120g, dioctyl sodium sulfosuccinate 50g joins in the deionized water of 1800g successively, under room temperature, dissolves; After being mixed with 3500g tetracol phenixin, parachlorobenzoyl chloride 348g joins in three-necked flask, then above-mentioned two amine aqueous solutions that configure are added dropwise in three-necked flask, after two amine aqueous solutions drip, at room temperature continue reaction 6h, generate two (4-chlorobenzoyl) different fluorine that ketone diamine monomer;
(2) purifying of your ketone diamines of two (4-chlorobenzoyls) different fluorine
Tetracol phenixin in your ketone diamines of above-mentioned two (4-chlorobenzoyl) different fluorine 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 is through mixed solvent (tetrahydrofuran (THF)+N-Methyl pyrrolidone) recrystallization, filter, collect colourless acicular crystal, vacuum-drying, obtains the tetrachloroethane of purifying, and structural formula is as follows:
(3) preparation of your ketone diamines half fragrant acid amides of poly-Resorcinol-1-diphenylphosphino ethane-different fluorine
By different to two (4-chlorobenzoyl) fluorine that ketone diamines 414g, sodium oxalate 300g, dimethylbenzene 80g, Resorcinol 110g and N-methyl propanamide 2500g add in reactor, under nitrogen protection, in 155 DEG C of dehydration reaction 2h of temperature, continue reaction 6h 210 DEG C of temperature, obtain the polymers soln of thickness, more above-mentioned polymers soln is cooled to 30 DEG C, be poured into water while stirring, separate out white fine strip shape polymer crude product;
(4). the purifying of your ketone diamines half fragrant acid amides of poly-Resorcinol-different fluorine
Above-mentioned polymer crude product, through water, washing with alcohol, in 130 DEG C of dry 2h of temperature, is pulverized, purify with deionized water, acetone respectively again, in 120 DEG C of dry 10h of temperature, obtain the poly-Resorcinol of purifying-different fluorine that ketone diamines half fragrant amide resins, productive rate is about 95%; Be that solvent configuration concentration is the solution of 0.5g/dl with NMP, at 30.0 ± 0.1 DEG C of temperature, with Ubbelohde viscometer, measure intrinsic viscosity=1.09dl/g, infrared and nuclear-magnetism characterizes respectively as shown in Fig. 4,8, its thermal performance test is respectively as shown in Fig. 9,10, and film transmitance as shown in figure 11.
Embodiment 5
(1) preparation of two (4-fluorobenzoyl) trans cyclohexanediamine
By Isosorbide-5-Nitrae-cyclohexanediamine 114g, NaOH80g, sodium stearate 1g joins in the deionized water of 500g successively, under room temperature, dissolves; After mixing with 300g tetrachloroethane fluorobenzoyl chloride 317g, join in three-necked flask, then above-mentioned two amine aqueous solutions that configure are added dropwise in three-necked flask, after two amine aqueous solutions drip, at room temperature continue reaction 3h, generate two (4-fluorobenzoyl) trans cyclohexanediamine monomers;
(2) purifying of two (4-fluorobenzoyl) trans cyclohexanediamine
Tetrachloroethane in above-mentioned two (4-fluorobenzoyl) trans cyclohexanediamine is steamed, filter, collect filter cake, filter cake, through deionized water wash twice, is removed water-soluble impurity, refilter, obtain the thick product of white powder, thick product, through ethanamide recrystallization, filters, collects colourless acicular crystal, vacuum-drying, obtains two (4-fluorobenzoyl) trans cyclohexanediamine of purifying;
(3) preparation of poly-Resorcinol-cyclohexanediamine half fragrant acid amides
By two (4-fluorobenzoyl) trans cyclohexanediamine 358g, Quilonum Retard 5g, toluene 1g, Resorcinol 110g and isoquinoline 99.9 150g add in reactor, under nitrogen protection, in 160 DEG C of dehydration reaction 0.5h of temperature, continue reaction 0.5h 180 DEG C of temperature, obtain the polymers soln of thickness, more above-mentioned polymers soln is cooled to 30 DEG C, be poured into water while stirring, separate out white fine strip shape polymer crude product;
(4). the purifying of poly-Resorcinol-cyclohexanediamine half fragrant acid amides
Above-mentioned polymer crude product, through water, washing with alcohol, in the dry 2h of temperature 50 C, is pulverized, then purified with deionized water, acetone respectively, in 80 DEG C of dry 10h of temperature, obtain the poly-fragrant amide resins of Resorcinol-cyclohexanediamine half of purifying, productive rate is about 94%; Be that solvent configuration concentration is the solution of 0.5g/dl with NMP, at 30.0 ± 0.1 DEG C of temperature, with Ubbelohde viscometer, measure intrinsic viscosity=0.87dl/g.
Claims (9)
1. a fatty ring half aromatics polyarylether acid amides, is characterized in that the starting raw material of this fatty ring half aromatics polyarylether acid amides is made up of following component, is by weight:
Wherein, diphenol is any in two (4-the hydroxyphenyl)-1-diphenylphosphino ethanes of Resorcinol, Resorcinol or 1,1-.
2. fatty ring half aromatics polyarylether acid amides as claimed in claim 1, is characterized in that catalyzer is any in sodium hydroxide, calcium hydroxide, Quilonum Retard, sodium carbonate, salt of wormwood, calcium carbonate, sodium bicarbonate, saleratus, sodium acetate, potassium acetate, lime acetate, caoxalate or sodium phosphate.
3. fatty ring half aromatics polyarylether acid amides as claimed in claim 1, is characterized in that dewatering agent is toluene or dimethylbenzene.
4. fatty ring half aromatics polyarylether acid amides as claimed in claim 1, it is characterized in that solvent is N-Methyl pyrrolidone, 1,3-dimethyl-2-imidazolinone, quinoline, isoquinoline 99.9, N, any in N-dimethyl propylene thiazolinyl urea, dimethyl sulfoxide (DMSO), tetramethylene sulfone, N-methyl propanamide, HMPA, N-cyclohexyl pyrrolidone, methane amide, ethanamide or 2-Pyrrolidone.
5. the preparation method of fatty ring half aromatics polyarylether acid amides as described in one of claim 1～4, is characterized in that the method comprises the following steps:
(1) preparation of fatty ring half aromatics dihalo diamide monomer
By 114～170 parts of fatty ring diamines, NaOH80～150 part, 1～50 part, tensio-active agent joins in the deionized water of 500～2000 parts successively, under room temperature, dissolves; After mixing with 300～3500 parts of organic solvents by 348 parts of parachlorobenzoyl chlorides or to 317 parts of fluorobenzoyl chlorides, join in three-necked flask, then above-mentioned fatty ring two amine aqueous solutions that configure are added drop-wise in above-mentioned three-necked flask, after two amine aqueous solutions drip, at room temperature continue reaction 3～10h, generate fatty ring half aromatics dihalo diamide monomer;
(2) purifying of fatty ring half aromatics dihalo diamide monomer
Organic solvent in above-mentioned fatty ring 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 is through recrystallization, filter, collect colourless acicular crystal, vacuum-drying, obtains the fatty ring half aromatics dihalo diamide of purifying, and structural formula is as follows:
Wherein: X=F or Cl;
(3) preparation of fatty ring half aromatics polyarylether acid amides
By 358～447 parts of fatty ring half aromatics dihalo diamide; 5～300 parts of catalyzer; 1～200 part of dewatering agent; 150～3000 parts of 110～290 parts of diphenol and solvents add in reactor; under nitrogen protection; in 130～200 DEG C of dehydration reaction 0.5～5h of temperature; continue reaction 0.5～12h 160～240 DEG C of temperature; obtain the polymers soln of thickness; again above-mentioned polymers soln is cooled to 30～100 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;
(4). the purifying of fatty ring half aromatics polyarylether acid amides
Above-mentioned polymer crude product, through water, washing with alcohol, in 50～200 DEG C of dry 2～8h of temperature, is pulverized, then purified with deionized water, acetone respectively, in 80～200 DEG C of dry 1～20h of temperature, obtain the fatty ring half aromatics polyarylether amide resins of purifying.
6. the preparation method of fatty ring half aromatics polyarylether acid amides as claimed in claim 5, is characterized in that aliphatie diamine is any in isophorone diamine or trans-cyclohexanediamine.
7. the preparation method of fatty ring half aromatics polyarylether acid amides as claimed in claim 5, is characterized in that tensio-active agent is at least one in smooth of sodium laurate, sodium stearate, trolamine, sodium lauryl sulphate, dioctyl sodium sulfosuccinate, Sodium glycocholate, Sodium sulfanilate, Tetrabutyl amonium bromide, sodium alginate and lipid acid sorb.
8. the preparation method of fatty ring half aromatics polyarylether acid amides as claimed in claim 5, is characterized in that organic solvent is any in methylene dichloride, chloroform, tetracol phenixin, tetrachloroethane, hexanaphthene, sherwood oil, normal heptane, toluene or dimethylbenzene.
9. the preparation method of fatty ring half aromatics polyarylether acid amides as claimed in claim 5, it is characterized in that recrystallization solvent is methyl alcohol, ethanol, acetone, tetrahydrofuran (THF), methane amide, ethanamide, N, at least one in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone and methyl-sulphoxide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387587A (en) * | 2014-11-07 | 2015-03-04 | 四川大学 | High-fluidity polyether sulfone/amide copolymer and preparation method thereof |
| CN113402706A (en) * | 2021-07-02 | 2021-09-17 | 天津师范大学 | Preparation method of polyaromatic ether |
| CN114716664A (en) * | 2022-04-22 | 2022-07-08 | 四川大学 | Semi-aromatic copolymerized polyarylether amide, complex thereof and preparation method thereof |
| CN114773602A (en) * | 2022-04-28 | 2022-07-22 | 四川大学 | Polyphenylene sulfide amide polymer and preparation and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215379A (en) * | 2008-01-04 | 2008-07-09 | 四川大学 | Polyarylene amide sulfides polymers and preparation method thereof |
| CN101820923A (en) * | 2007-10-12 | 2010-09-01 | 通用电气医疗集团股份有限公司 | Contrast medium |
| CN102532532A (en) * | 2011-12-21 | 2012-07-04 | 四川大学 | Thioether-containing semi-aromatic polyamide and preparation method thereof |
| CN102558544A (en) * | 2011-12-28 | 2012-07-11 | 吉林省聚科高新材料有限公司 | Soluble and ultraviolet crosslinking polyaryl ether nitrile and preparation method thereof |
| CN102796258A (en) * | 2012-07-25 | 2012-11-28 | 四川大学 | Preparation method for in-situ reinforced semi-aromatic polyamide composite material |
| CN103739839A (en) * | 2013-12-31 | 2014-04-23 | 四川大学 | Semi-aromatic polyarylether amide and preparation method thereof |
-
2014
- 2014-07-21 CN CN201410347679.1A patent/CN104109236B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101820923A (en) * | 2007-10-12 | 2010-09-01 | 通用电气医疗集团股份有限公司 | Contrast medium |
| CN101215379A (en) * | 2008-01-04 | 2008-07-09 | 四川大学 | Polyarylene amide sulfides polymers and preparation method thereof |
| CN102532532A (en) * | 2011-12-21 | 2012-07-04 | 四川大学 | Thioether-containing semi-aromatic polyamide and preparation method thereof |
| CN102558544A (en) * | 2011-12-28 | 2012-07-11 | 吉林省聚科高新材料有限公司 | Soluble and ultraviolet crosslinking polyaryl ether nitrile and preparation method thereof |
| CN102796258A (en) * | 2012-07-25 | 2012-11-28 | 四川大学 | Preparation method for in-situ reinforced semi-aromatic polyamide composite material |
| CN103739839A (en) * | 2013-12-31 | 2014-04-23 | 四川大学 | Semi-aromatic polyarylether amide and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387587A (en) * | 2014-11-07 | 2015-03-04 | 四川大学 | High-fluidity polyether sulfone/amide copolymer and preparation method thereof |
| 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 |
| CN113402706A (en) * | 2021-07-02 | 2021-09-17 | 天津师范大学 | Preparation method of polyaromatic ether |
| CN113402706B (en) * | 2021-07-02 | 2023-08-25 | 天津师范大学 | Preparation method of polyaromatic ether |
| CN114716664A (en) * | 2022-04-22 | 2022-07-08 | 四川大学 | Semi-aromatic copolymerized polyarylether amide, complex thereof and preparation method thereof |
| CN114716664B (en) * | 2022-04-22 | 2023-02-28 | 四川大学 | Semi-aromatic copolymerized polyarylether amide, complex thereof and preparation method thereof |
| CN114773602A (en) * | 2022-04-28 | 2022-07-22 | 四川大学 | Polyphenylene sulfide amide polymer and preparation and application thereof |
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