CN104109236B - Fatty ring half aromatics polyarylether amide and preparation method thereof - Google Patents
Fatty ring half aromatics polyarylether amide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of fatty ring half aromatics polyarylether amide and preparation method thereof, be characterized in fatty ring half aromatics dihalo diamide 358 ~ 447 parts, catalyzer 5 ~ 300 parts, dewatering agent 1 ~ 200 part, diphenol 110 ~ 290 parts and solvent 150 ~ 3000 parts add in reactor, under nitrogen protection, in temperature 130 ~ 200 DEG C of dehydration reaction 0.5 ~ 5h, again at temperature 160 ~ 240 DEG C reaction 0.5 ~ 12h, obtain the polymers soln of thickness, 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, thick product, through water, washing with alcohol, in temperature 50 ~ 200 DEG C of drying 2 ~ 8h, is pulverized, then purifies with deionized water, acetone respectively, in temperature 80 ~ 200 DEG C of drying 1 ~ 20h, obtains purifying fatty ring half aromatics polyarylether amide resin.It has, and molecular weight is high, yield is high, purity is high, small pollution and easy processing, the advantage that its made membrane transparence is high.
Description
Technical field
The present invention relates to a kind of fatty ring 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 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 with 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 closely, thus cause its process window smaller), overcome the shortcoming of the resistance to strong acid of polymeric amide, highly basic; We devise fatty this base polymer of ring half aromatics polyarylether amide, and we also find that gained fatty ring half aromatics polyarylether amide has excellent transmittance simultaneously, are expected for high temperature resistant optical material.
Summary of the invention
The object of the invention is to provide a kind of fatty ring half aromatics polyarylether amide polymkeric substance 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 polymkeric substance by the method for solution polycondensation, it has, and molecular weight be high, yield is high, purity is high, small pollution and easy processing and by the high advantage of its made membrane transparence.
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 fatty ring half aromatics polyarylether amide is made up of following component:
Wherein, diphenol is any one in two (4-the hydroxyphenyl)-1-diphenylphosphino ethane of Resorcinol, Resorcinol or 1,1-.
Described catalyzer is any one 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, any one in 3-dimethyl-2-imidazolinone, quinoline, isoquinoline 99.9, N, 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 amide comprises the following steps:
(1) preparation of fatty ring half aromatics dihalo diamide monomer
By fatty ring diamines 114 ~ 170 parts, NaOH80 ~ 150 part, 1 ~ 50 part, tensio-active agent joins in the deionized water of 500 ~ 2000 parts successively, dissolves under room temperature; By parachlorobenzoyl chloride 348 parts or join in three-necked flask after mixing with 300 ~ 3500 parts of organic solvents fluorobenzoyl chloride 317 parts, then above-mentioned fatty ring two amine aqueous solution configured is 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 deionized water wash twice, removing water-soluble impurity, refilter, obtain the thick product of white powder, thick product is through recrystallization, filter, collect colourless acicular crystal, vacuum-drying, obtain the fatty ring half aromatics dihalo diamide of purifying, structural formula is as follows:
Wherein: X=F or Cl;
(3) preparation of fatty ring half aromatics polyarylether amide
By fatty ring half aromatics dihalo diamide 358 ~ 447 parts; catalyzer 5 ~ 300 parts; dewatering agent 1 ~ 200 part; diphenol 110 ~ 290 parts and solvent 150 ~ 3000 parts add in reactor; under nitrogen protection; in temperature 130 ~ 200 DEG C of dehydration reaction 0.5 ~ 5h; reaction 0.5 ~ 12h is continued temperature 160 ~ 240 DEG C; 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 one;
(4). the purifying of fatty ring 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 fatty ring half aromatics polyarylether amide resin.
Described aliphatie diamine is any one in isophorone diamine or trans-cyclohexanediamine.
Described tensio-active agent be sodium laurate, sodium stearate, trolamine, sodium lauryl sulphate, dioctyl succinate disulfonate acid, Sodium glycocholate, Sodium sulfanilate, Tetrabutyl amonium bromide, sodium alginate or lipid acid sorb smooth at least one.
Described organic solvent is any one 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 obtains confirmation, as shown in Figure 1, Figure 2, Figure 3 shows.
The structure of 2 fatty ring half aromatics polyarylether amide respectively through infrared spectra, nucleus magnetic resonance (
1h-NMR) test obtains confirmation, as shown in, Fig. 4, Fig. 5 ~ 8.
3, by regulation and control reactant concn, material proportion and temperature of reaction, prepare the fatty ring 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=0.60 ~ 1.3dl/g of determination of ubbelohde viscometer polymkeric substance at temperature 30.0 ± 0.1 DEG C.
4 adopt NETZSCHDSC200PC to test the second-order transition temperature of fatty ring half aromatics polyarylether amide, and temperature rise rate 10 DEG C/min, test result as shown in Figure 9.
5 adopt TGA to test the thermal weight loss temperature of fatty ring half aromatics polyarylether amide, and test result as shown in Figure 10.
6 pairs of fatty ring half aromatics polyarylether amide have carried out transmittance test respectively, and test result as shown in figure 11.
Tool of the present invention has the following advantages:
1. adopt diphenol 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.
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. fatty ring 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 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 the goods of heat-resisting, resistance to chemical attack, also can be made into special fibre and high temperature resistant optical thin film, has wide practical use.
Accompanying drawing illustrates:
Fig. 1 is the infrared spectrum of fatty ring half aromatics dihalo diamide
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, 1530cm
-1, 1490cm
-1for the skeletal vibration absorption peak of phenyl ring.
Fig. 2 is the nuclear magnetic spectrogram of two (4-fluorobenzoyl) trans cvclohexvl diamines
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 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, 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 is respectively the nuclear magnetic spectrogram of poly-two fragrant acid amides of (4-hydroxyphenyl)-1-diphenylphosphino ethane-cyclohexanediamine half, poly-Resorcinol-fragrant acid amides of your ketone diamines half of different fluorine, poly-two (4-hydroxyphenyl)-1-diphenylphosphino ethane-fragrant acid amides of your ketone diamines half of different fluorine, poly-Resorcinol-fragrant acid amides of your ketone diamines half of different fluorine
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 amide
Curve Embodiment 1 is the DSC curve of poly-two fragrant acid amides of (4-hydroxyphenyl)-1-diphenylphosphino ethane-cyclohexanediamine half, 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 poly-Resorcinol-fragrant acid amides of your ketone diamines half of 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-two (4-hydroxyphenyl)-1-diphenylphosphino ethane-fragrant acid amides of your ketone diamines half of 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 poly-Resorcinol-fragrant acid amides of your ketone diamines half of 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 amide
Curve Embodiment 1 is the TGA curve of poly-two fragrant acid amides of (4-hydroxyphenyl)-1-diphenylphosphino ethane-cyclohexanediamine half, 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 poly-Resorcinol-fragrant acid amides of your ketone diamines half of 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-two (4-hydroxyphenyl)-1-diphenylphosphino ethane-fragrant acid amides of your ketone diamines half of 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 poly-Resorcinol-fragrant acid amides of your ketone diamines half of 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 amide
Curve Embodiment 2 is the UV-Vis curve of poly-Resorcinol-fragrant acid amides of your ketone diamines half of 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-two (4-hydroxyphenyl)-1-diphenylphosphino ethane-fragrant acid amides of your ketone diamines half of 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 poly-Resorcinol-fragrant acid amides of your ketone diamines half of 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, 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) preparation of two (4-fluorobenzoyl) trans cvclohexvl diamines
By Isosorbide-5-Nitrae-cyclohexanediamine 114g, NaOH150g, the smooth 50g of lipid acid sorb joins in the deionized water of 2000g successively, dissolves under room temperature; Join in three-necked flask after mixing with 3000g hexanaphthene fluorobenzoyl chloride 317g, then above-mentioned two amine aqueous solutions configured are added dropwise in three-necked flask, after two amine aqueous solutions drip, at room temperature continue reaction 10h, generate two (4-fluorobenzoyl) trans cvclohexvl diamine monomer;
(2) purifying of two (4-fluorobenzoyl) trans cvclohexvl diamines
Hexanaphthene in above-mentioned two (4-fluorobenzoyl) trans cvclohexvl diamines 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 is through ethanamide recrystallization, filter, collect colourless acicular crystal, vacuum-drying, obtain two (4-fluorobenzoyl) trans cvclohexvl diamines of purifying, structural formula is as follows:
infrared and nuclear-magnetism characterizes and refers to shown in Fig. 1,2;
(3) preparation of poly-two fragrant acid amides of (4-hydroxyphenyl)-1-diphenylphosphino ethane-cyclohexanediamine half
By two (4-fluorobenzoyl) trans cvclohexvl diamines 358g, sodium phosphate 200g, dimethylbenzene 200g, two (4-hydroxyphenyl)-1-diphenylphosphino ethane 290g and HMPA 3000g adds in reactor, under nitrogen protection, in temperature 170 DEG C of dehydration reaction 2h, continue reaction 10h temperature 230 DEG C, 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 fragrant acid amides of (4-hydroxyphenyl)-1-diphenylphosphino ethane-cyclohexanediamine half
By above-mentioned polymer crude product through water, washing with alcohol, in temperature 130 DEG C of dry 5h, pulverize, purify with deionized water, acetone respectively again, in temperature 160 DEG C of dry 12h, obtain the poly-two fragrant amide resins of (4-hydroxyphenyl)-1-diphenylphosphino ethane-cyclohexanediamine half of purifying, 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=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, dissolves under room temperature; Join in three-necked flask after mixing with 2000g methylene dichloride fluorobenzoyl chloride 317g, then above-mentioned two amine aqueous solutions configured 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 deionized water wash twice, removing 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, obtain the tetrachloroethane of purifying, structural formula is as follows:
infrared and nuclear-magnetism characterizes respectively as shown in Figure 1,3;
(3) preparation of poly-Resorcinol-fragrant acid amides of your ketone diamines half of 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 temperature 130 DEG C of dehydration reaction 5h, continue reaction 3h temperature 200 DEG C, 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 poly-Resorcinol-fragrant acid amides of your ketone diamines half of different fluorine
By above-mentioned polymer crude product through water, washing with alcohol, in temperature 100 DEG C of dry 4h, pulverize, then purify with deionized water, acetone respectively, in temperature 120 DEG C of dry 6h, obtain purifying and gather Resorcinol-fragrant amide resins of your ketone diamines half of different fluorine, productive rate is about 92%; 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=0.90dl/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 transmission rate 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, dissolve under room temperature; Join in three-necked flask after mixing with 2000g methylene dichloride fluorobenzoyl chloride 317g, then above-mentioned two amine aqueous solutions configured 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 deionized water wash twice, removing 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, obtain the tetrachloroethane of purifying, structural formula is as follows:
(3) preparation of poly-two (4-hydroxyphenyl)-1-diphenylphosphino ethane-fragrant acid amides of your ketone diamines half of 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 adds in reactor, under nitrogen protection, in temperature 165 DEG C of dehydration reaction 2h, continue reaction 4h temperature 200 DEG C, 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-fragrant acid amides of your ketone diamines half of different fluorine
By above-mentioned polymer crude product through water, washing with alcohol, in temperature 120 DEG C of dry 8h, pulverize, purify with deionized water, acetone respectively again, in temperature 200 DEG C of dry 1h, obtain poly-two (4-the hydroxyphenyl)-1-diphenylphosphino ethane of purifying-fragrant amide resins of your ketone diamines half of different fluorine, productive rate is about 92%; 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=1.26dl/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 transmission rate as shown in figure 11.
Embodiment 4
(1) preparation of your ketone diamines of two (4-chlorobenzoyl) different fluorine
By different fluorine that ketone diamines 170g, NaOH120g, dioctyl succinate disulfonate acid 50g joins in the deionized water of 1800g successively, dissolves under room temperature; Join in three-necked flask after parachlorobenzoyl chloride 348g is mixed with 3500g tetracol phenixin, then above-mentioned two amine aqueous solutions configured 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-chlorobenzoyl) 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 deionized water wash twice, removing 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, obtain the tetrachloroethane of purifying, structural formula is as follows:
(3) preparation of poly-Resorcinol-1-diphenylphosphino ethane-fragrant acid amides of your ketone diamines half of 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 temperature 155 DEG C of dehydration reaction 2h, continue reaction 6h temperature 210 DEG C, 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-fragrant acid amides of your ketone diamines half of different fluorine
By above-mentioned polymer crude product through water, washing with alcohol, in temperature 130 DEG C of dry 2h, pulverize, purify with deionized water, acetone respectively again, in temperature 120 DEG C of dry 10h, obtain purifying and gather Resorcinol-fragrant amide resins of your ketone diamines half of different fluorine, productive rate is about 95%; 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=1.09dl/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 transmission rate as shown in figure 11.
Embodiment 5
(1) preparation of two (4-fluorobenzoyl) trans cvclohexvl diamines
Isosorbide-5-Nitrae-cyclohexanediamine 114g, NaOH80g, sodium stearate 1g is joined in the deionized water of 500g successively, dissolves under room temperature; Join in three-necked flask after mixing with 300g tetrachloroethane fluorobenzoyl chloride 317g, then above-mentioned two amine aqueous solutions configured are added dropwise in three-necked flask, after two amine aqueous solutions drip, at room temperature continue reaction 3h, generate two (4-fluorobenzoyl) trans cvclohexvl diamine monomer;
(2) purifying of two (4-fluorobenzoyl) trans cvclohexvl diamines
Tetrachloroethane in above-mentioned two (4-fluorobenzoyl) trans cvclohexvl diamines is steamed, filter, collect filter cake, filter cake, through deionized water wash twice, removes 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 cvclohexvl diamines of purifying;
(3) preparation of the poly-fragrant acid amides of Resorcinol-cyclohexanediamine half
By two (4-fluorobenzoyl) trans cvclohexvl diamines 358g, Quilonum Retard 5g, toluene 1g, Resorcinol 110g and isoquinoline 99.9 150g add in reactor, under nitrogen protection, in temperature 160 DEG C of dehydration reaction 0.5h, continue reaction 0.5h temperature 180 DEG C, 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 the poly-fragrant acid amides of Resorcinol-cyclohexanediamine half
By above-mentioned polymer crude product through water, washing with alcohol, in the dry 2h of temperature 50 C, pulverize, then purify with deionized water, acetone respectively, in temperature 80 DEG C of dry 10h, obtain purifying and gather the fragrant amide resins of Resorcinol-cyclohexanediamine half, 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=0.87dl/g.
Claims (8)
1. a preparation method for fatty ring half aromatics polyarylether amide, is characterized in that the starting raw material of this fatty ring half aromatics polyarylether amide is made up of following component, is by weight:
Wherein, diphenol is any one in two (4-the hydroxyphenyl)-1-diphenylphosphino ethane of Resorcinol, Resorcinol or 1,1-; And by following processing step and processing parameter preparation:
(1) preparation of fatty ring half aromatics dihalo diamide monomer
By fatty ring diamines 114 ~ 170 parts, NaOH80 ~ 150 part, 1 ~ 50 part, tensio-active agent joins in the deionized water of 500 ~ 2000 parts successively, dissolves under room temperature; By parachlorobenzoyl chloride 348 parts or join in three-necked flask after mixing with 300 ~ 3500 parts of organic solvents fluorobenzoyl chloride 317 parts, then above-mentioned fatty ring two amine aqueous solution configured is 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 deionized water wash twice, removing water-soluble impurity, refilter, obtain the thick product of white powder, thick product is through recrystallization, filter, collect colourless acicular crystal, vacuum-drying, obtain the fatty ring half aromatics dihalo diamide of purifying, structural formula is as follows:
Wherein: X=F or Cl;
(3) preparation of fatty ring half aromatics polyarylether amide
By fatty ring half aromatics dihalo diamide 358 ~ 447 parts; catalyzer 5 ~ 300 parts; dewatering agent 1 ~ 200 part; diphenol 110 ~ 290 parts and solvent 150 ~ 3000 parts add in reactor; under nitrogen protection; in temperature 130 ~ 200 DEG C of dehydration reaction 0.5 ~ 5h; reaction 0.5 ~ 12h is continued temperature 160 ~ 240 DEG C; 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 one;
(4). the purifying of fatty ring 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 fatty ring half aromatics polyarylether amide resin.
2. the preparation method of fatty ring half aromatics polyarylether amide as claimed in claim 1, is characterized in that catalyzer is any one 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. the preparation method of fatty ring half aromatics polyarylether amide as claimed in claim 1, is characterized in that dewatering agent is toluene or dimethylbenzene.
4. the preparation method of fatty ring half aromatics polyarylether amide as claimed in claim 1, it is characterized in that solvent is N-Methyl pyrrolidone, 1, any one in 3-dimethyl-2-imidazolinone, quinoline, isoquinoline 99.9, N, 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 amide as claimed in claim 1, is characterized in that aliphatie diamine is any one in isophorone diamine or trans-cyclohexanediamine.
6. the preparation method of fatty ring half aromatics polyarylether amide as claimed in claim 1, it is characterized in that tensio-active agent be sodium laurate, sodium stearate, trolamine, sodium lauryl sulphate, dioctyl succinate disulfonate acid, Sodium glycocholate, Sodium sulfanilate, Tetrabutyl amonium bromide, sodium alginate and lipid acid sorb smooth at least one.
7. the preparation method of fatty ring half aromatics polyarylether amide as claimed in claim 1, is characterized in that organic solvent is any one in methylene dichloride, chloroform, tetracol phenixin, tetrachloroethane, hexanaphthene, sherwood oil, normal heptane, toluene or dimethylbenzene.
8. the preparation method of fatty ring half aromatics polyarylether amide as claimed in claim 1, 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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