CN101215379A - Polyarylene amide sulfides polymers and preparation method thereof - Google Patents
Polyarylene amide sulfides polymers and preparation method thereof Download PDFInfo
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- CN101215379A CN101215379A CNA2008100451138A CN200810045113A CN101215379A CN 101215379 A CN101215379 A CN 101215379A CN A2008100451138 A CNA2008100451138 A CN A2008100451138A CN 200810045113 A CN200810045113 A CN 200810045113A CN 101215379 A CN101215379 A CN 101215379A
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Abstract
The invention discloses a polythiamide amides polymerized substance and a process for preparation, which is characterized in that the process comprises adding 1-5 parts auxiliary agent, 2-8 parts catalyst, 0.1-6 parts alkali or strong base-weak acid salt, 100-500 parts organic solvent and 5-30 parts entrainer into autoclaves of an in-out pipe with nitrogen gas, a water separater, a stirrer and a thermometer, adding sodium sulfide 13 parts whose content is 60% after being evenly stirred, dewatering for 0.5 to 3 hours in 160-200 DEG C under the protection of nitrogen, adding 35.2 to 49.2 parts dihalogenated aromatic amide when the reaction temperature is lowered to 80-150 DEG C, keeping for 2-10 hours in 160-230 DEG C, pouring reaction liquid into water, separating out polymers, purifying with deionized water and acetone after washing and drying, at last obtaining high molecular weight polythiamide amides polymerized substance after drying for 24 hours in 120 DEGC in 0.09 MPa vacuum degree. The inherent viscosity eta=0.1-0.86( the density is 0.1g/dL, and the measuring temperature is 30+-0.1 DEG C), the glass transition temperature Tg is 150-300 DEG C, the initial heat decomposition temperature Td is 440-480 DEG C.
Description
Technical field
The present invention relates to a kind of polyarylene amide sulfides polymers and preparation method thereof, belong to the Polymer Synthesizing field.
Background technology
Poly arylidene thio-ester and polymeric amide all are special engineering plastics of excellent property, all have good mechanical performance and thermal characteristics, are the advantage of comprehensive two kinds of polymkeric substance, improve the second-order transition temperature and the fusing point of poly arylidene thio-ester, improve its toughness; Improve the polymeric amide erosion resistance, and give its flame retardant resistance.
The nineties people such as Wu Qixian once preliminary study novel aromatic polythioether amide resin synthetic, but the molecular resin amount that obtains is very low, does not have practical value; European patent EP 0162606A1 reported and used the synthetic aromatic polythioether amide of amino thiophenol, employing big to amino thiophenol toxicity, contaminate environment, in the polyreaction to the purity requirement harshness of solvent, complex process, the cost height is unfavorable for suitability for industrialized production.
Summary of the invention
The objective of the invention is provides a kind of polyaryl thioether sulfone acylamide polymer and preparation method thereof at the deficiencies in the prior art, be characterized in adopting symmetric dihalo aromatic amides and sodium sulphite have been synthesized the high molecular polyarylene amide sulfides polymers under normal pressure, use Na under the normal pressure
2The S method is introduced acid amides and sulfuryl or carbonyl or ehter bond on the poly arylidene thio-ester main chain simultaneously.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The chemical reaction structural formula of polyarylene amide sulfides polymers is:
N=2-200 wherein, Ar is:
The preparation method's of polyarylene amide sulfides polymers raw material comprises following component:
In 13 parts in the sodium sulphite of content 60%
Dihalo aromatic amides 35.2-49.2 part
Solvent 100-500 part
Auxiliary agent 1-5 part
Catalyzer 2-8 part
Alkali or strong base-weak acid salt 0.1-6 part
Entrainer 5-30 part
And by the preparation of following processing step and condition:
(1) the monomeric preparation of dihalo aromatic amides
A. the monomeric preparation of dihalo aromatic amides
With 4,4 '-248 parts of diaminodiphenylsulfone(DDS)s or 4,4 '-200 parts of diaminodiphenyl oxides or 4,4 '-108 parts of 212 parts of diaminobenzophenones or 108 parts of Ursol D or mphenylenediamines, solvent 100-900 part and triethylamine 150-300 part, add successively and be equipped with in the reactor of agitator, dropping funnel, when treating that its temperature is reduced to-5 ℃, begin to drip to fluorobenzoyl chloride 317-360 part, added in 1-3 hour, continue to keep 2-4 hour, at room temperature reacted again 4-6 hour, obtain dihalo aromatic amides monomer;
The monomeric purifying of b dihalo aromatic amides
Above-mentioned solution poured into make it precipitation in the cold water, precipitation is filtered with the deionized water wash that boils, removes the parafluorobenzoic acid that is attached to above the monomer, water-soluble impurities such as inorganic salt, in methyl alcohol backflow 0.5-1 hour, further removing parafluorobenzoic acid, and carry out recrystallization;
(2). the preparation of polyarylene amide sulfides polymers
With 1-5 part auxiliary agent; 2-8 part catalyzer; 0.1-6 part alkali or strong base-weak acid salt; 100-500 part organic solvent and 5-30 part entrainer add and have nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; the back that stirs adds in 13 parts in the sodium sulphite of content 60%; under nitrogen protection, in temperature 160-200 ℃ dehydration reaction 0.5-3 hour, the Na after obtaining dewatering
2S solution is treated above-mentioned Na
2When the S solution temperature is reduced to 80-150 ℃, add 35.2-49.2 part dihalo aromatic amides again, temperature 160-230 ℃ of reaction 2-10 hour, above-mentioned reactant is poured in the water while hot, separated out polymkeric substance, through washing, use deionized water after the drying more respectively, the acetone extracting in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa of temperature, obtains polyarylene amide sulfides polymers.
Solvent is any in N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), HMPA, N-cyclohexyl pyrrolidone, N,N-DIMETHYLACETAMIDE or the N-methyl caprolactam.
Auxiliary agent be in sodium formiate, lithium formate, sodium-acetate, Lithium Acetate, Sodium Benzoate, tertiary sodium phosphate or the lithium chloride any.
Catalyzer be in triphenylphosphine, stannous octoate, hydroxy acid sodium, hexanolactam, epsilon-amino caproic acid, para-aminotoluene or the Sodium sulfanilate any.
Alkali is sodium hydroxide or potassium hydroxide; Strong base-weak acid salt be in yellow soda ash, salt of wormwood, Quilonum Retard, sodium bicarbonate or the saleratus any.
Entrainer is toluene or dimethylbenzene.
By regulating the proportioning of sodium sulphite and dihalo aromatic amides, the conditioned reaction temperature, reaction times and feeding mode etc. can obtain the polyarylene amide sulfides polymers of the molecular weight of different viscosity, this polymer intrinsic viscosity η=0.1-0.86, its second-order transition temperature Tg is 150-300 ℃, initial heat decomposition temperature is 440-480 ℃, this base polymer can be used as special engineering plastics and high performance polymer matrix material resin base, the parts and the goods of, resistance to chemical attack heat-resisting in order to prepare, also can be made into special fibre and film, be with a wide range of applications.
The present invention has following advantage:
1. introduce two halogen atoms in the symmetrical dihalo aromatic amides monomer, made its unexpectedly poly-rate be complementary; Because the two ends halogen atom is a fluorine atom, the electrophilic carbonyl that its contraposition aryl links to each other can make reaction activity descend, and the easier high-molecular weight polymer that obtains has also been saved energy consumption.
2. in the process of the synthetic polyarylene amide sulfides polymers of symmetrical dihalo aromatic amides and sodium sulphite, employing be composite catalyst system, polymerization under normal pressure; Its security is good, cost is low, than environmental protection, repeatability is strong, molecular weight is high, yield is high and purity is high advantage.
3. this base polymer has the advantage of second-order transition temperature height, easily processing, high temperature resistant and erosion resistance.
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, 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; with 37.2g 4; 4 '-diaminodiphenylsulfone(DDS); 30g triethylamine and 200ml tetrahydrofuran (THF); add successively and have agitator; thermometer; in the reactor of dropping funnel; in dropping funnel, add fluorobenzoyl chloride 55g, when treating that its temperature is reduced to-5 ℃, begin to drip fluorobenzoyl chloride; in 1 hour, add; continue to keep 3 hours, at room temperature reacted again 6 hours, above-mentioned reaction solution is poured into made it precipitation in the cold water; precipitation is filtered with the deionized water wash that boils; removal is attached to the parafluorobenzoic acid above the monomer, and water-soluble impurities such as inorganic salt refluxed 0.5 hour in methyl alcohol; further to remove parafluorobenzoic acid; filtration obtains N through the pyridine recrystallization, N '-two (to fluoro benzoyl)-to sulfobenzide diamines 60.5g; productive rate is 82%, and purity is 99.1%.
With the 1g lithium chloride; the 2g epsilon-amino caproic acid; 1g salt of wormwood; 100gN-methyl-2-pyrrolidone and 10g dimethylbenzene add and have nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; add sodium sulphite 13g after stirring to contain 60%; under nitrogen protection,, treat above-mentioned Na in 160 ℃ of dehydration reactions of temperature 0.5 hour
2When the S solution temperature is reduced to 80 ℃, add 49.2gN again, N '-two (to fluoro benzoyl)-4; 4 '-diaminodiphenylsulfone(DDS); 200 ℃ of reactions of temperature 3 hours, reactant was poured in the boiling water while hot, separates out polymkeric substance; through pulverizing; deionized water, acetone extracting are used in washing more respectively after the drying; in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa of temperature, obtain polyphenylene sulfide sulfonamide acid amides virgin resin.Its productive rate is 90%.Intrinsic viscosity η=0.28.
Embodiment 2; with 37.2g 3; 3 '-diaminodiphenylsulfone(DDS); 30g triethylamine and 200ml tetrahydrofuran (THF); add successively and have agitator; thermometer; in the reactor of dropping funnel; in dropping funnel, add fluorobenzoyl chloride 55g, when treating that its temperature is reduced to-5 ℃, begin to drip fluorobenzoyl chloride; in 1 hour, add; continue to keep 3 hours, at room temperature reacted again 6 hours, above-mentioned reaction solution decompression is filtered; precipitation is filtered with the deionized water wash that boils; removal is attached to the parafluorobenzoic acid above the monomer, and water-soluble impurities such as inorganic salt refluxed 1 hour in methyl alcohol; further to remove parafluorobenzoic acid; filtration obtains N, and N '-two (to fluoro benzoyl)-sulfobenzide diamines 60g is through acetone recrystallization; productive rate is 81%, and purity is 99.3%.
With the 5g sodium-acetate; the 8g epsilon-amino caproic acid; 2g yellow soda ash; 100gN-methyl-2-pyrrolidone and 10g dimethylbenzene add band nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; add sodium sulphite 13g after stirring to contain 60%; under nitrogen protection,, treat above-mentioned Na in 180 ℃ of dehydration reactions of temperature 3 hours
2When the S solution temperature is reduced to 150 ℃; add 49.2g N again, N '-two (to fluoro benzoyl)-3,3 '-diaminodiphenylsulfone(DDS); 200 ℃ of reactions of temperature 10 hours; reactant is poured in the boiling water while hot, separates out polymkeric substance, through pulverizing; washing; use deionized water after the drying more respectively, acetone extracting, position polyphenylene sulfide sulfonamide acid amides virgin resin between 120 ℃ of vacuum tightness 0.09MPa of temperature obtained in dry 24 hours.Its productive rate is 89%, intrinsic viscosity η=0.42.
Embodiment 3; with the 16.2g mphenylenediamine; 25g triethylamine and 200ml tetrahydrofuran (THF); add successively and have agitator; thermometer; in the reactor of dropping funnel; in dropping funnel, add fluorobenzoyl chloride 47.5g; when treating that its temperature is reduced to-5 ℃; begin to drip to fluorobenzoyl chloride; in 1 hour, add; continue to keep 3 hours, at room temperature reacted again 6 hours, above-mentioned reaction solution is poured into made it precipitation in the cold water; precipitation is filtered with the deionized water wash that boils; removal is attached to the parafluorobenzoic acid above the monomer, and water-soluble impurities such as inorganic salt are through recrystallizing methanol; filtration obtains N; N '-two (to fluoro benzoyl)-mphenylenediamine 47g, productive rate are 89%, and purity is 99.3%.
With the 1g tertiary sodium phosphate; the 2g triphenylphosphine; 0.1g potassium hydroxide; 300gN-methyl-2-pyrrolidone and 10g dimethylbenzene add band nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; add sodium sulphite 13g after stirring to contain 60%; under nitrogen protection,, treat above-mentioned Na in 160 ℃ of dehydration reactions of temperature 0.5 hour
2When the S solution temperature is reduced to 80 ℃; add 35.2g N again; N '-two (to fluoro benzoyl)-mphenylenediamine; 160 ℃ of reactions of temperature 2 hours, reactant was poured in the boiling water while hot, through washing; use deionized water after the drying more respectively; the acetone extracting, in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa of temperature, aromatic polythioether amide acid amides virgin resin in position between acquisition.Its productive rate is 91%.Intrinsic viscosity η=0.18.
Embodiment 4; with the 16.2g Ursol D; 25g triethylamine and 200ml tetrahydrofuran (THF); add successively and have agitator; thermometer; in the reactor of dropping funnel; in dropping funnel, add fluorobenzoyl chloride 47.5g; when treating that its temperature is reduced to-5 ℃; begin to drip, in 1 hour, add, continue to keep 3 hours fluorobenzoyl chloride; at room temperature reacted again 6 hours; above-mentioned reaction solution poured into make it precipitation in the cold water, precipitation is filtered with the deionized water wash that boils, removes the parafluorobenzoic acid that is attached to above the monomer; water-soluble impurities such as inorganic salt; in methyl alcohol, refluxed 0.5 hour,, filter and obtain N further to remove the parafluorobenzoic acid that adheres on the product; N '-two (to fluoro benzoyl)-Ursol D 43.8g; through the NMP recrystallization, productive rate is 83%, and purity is 99.2%.
With the 5g sodium formiate; the 8g stannous octoate; 6g sodium hydroxide; 500g HMPA and 10g dimethylbenzene add and have nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; add sodium sulphite 13g after stirring to contain 60%; under nitrogen protection,, treat above-mentioned Na in 200 ℃ of dehydration reactions of temperature 3 hours
2When the S solution temperature is reduced to 150 ℃; add 35.2g N again; N '-two (to fluoro benzoyl)-Ursol D, 230 ℃ of reactions of temperature 10 hours, reactant was poured in the water while hot; get polymer powder; through washing, use deionized water, acetone extracting after the drying more respectively; in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa of temperature, obtain the aromatic polythioether amide virgin resin.Its productive rate is 93%, intrinsic viscosity η=0.33.
Embodiment 5, with 30g to diaminobenzophenone, 30g triethylamine and 200ml tetrahydrofuran (THF) add successively and have in the reactor of agitator, thermometer, dropping funnel.In dropping funnel, add fluorobenzoyl chloride 55g; when treating that its temperature is reduced to-5 ℃; begin to drip to fluorobenzoyl chloride; in 1 hour, add; continue to keep 3 hours, at room temperature reacted again 6 hours, above-mentioned reaction solution is poured into made it precipitation in the cold water; deionized water wash through boiling filters; removal is attached to the parafluorobenzoic acid above the monomer, and water-soluble impurities such as inorganic salt refluxed 0.5 hour in methyl alcohol; further to remove parafluorobenzoic acid; through the NMP recrystallization, obtain N, N '-two (to fluoro benzoyl)-to benzophenone diamines 52.5g; productive rate is 81.3%, and purity is 99.0%.
With the 1g Sodium Benzoate; the 2g hydroxy acid sodium; 0.1g sodium bicarbonate; 100g HMPA and 30g toluene add band nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; add sodium sulphite 13g after stirring to contain 60%; under nitrogen protection,, treat above-mentioned Na in 160 ℃ of dehydration reactions of temperature 1 hour
2When the S solution temperature is reduced to 80 ℃; add 45.6g N again; N '-two (to fluoro benzoyl)-4,4 '-diaminobenzophenone was 160 ℃ of reactions of temperature 10 hours; reactant is poured in the water while hot; get polymer powder through washing, use deionized water, acetone extracting after the drying more respectively; in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa of temperature, obtain polyphenylene sulfide keto-amide acid amides virgin resin.Its productive rate is 91%, intrinsic viscosity η=0.30.
Embodiment 6; with 28.2g to diaminodiphenyl oxide; 26g triethylamine and 200ml tetrahydrofuran (THF); add successively and have agitator; thermometer; in the reactor of dropping funnel; in dropping funnel, add fluorobenzoyl chloride 60g; when treating that its temperature is reduced to-5 ℃, begin to drip, in 1 hour, add fluorobenzoyl chloride; continue to keep 3 hours; at room temperature reacted 6 hours again, and above-mentioned reaction solution was poured into made it precipitation in the cold water, precipitation is filtered with the deionized water wash that boils; removal is attached to the parafluorobenzoic acid above the monomer; water-soluble impurities such as inorganic salt refluxed 1 hour in methyl alcohol, further to remove parafluorobenzoic acid; filter; through the NMP recrystallization, obtain N, N '-two (to fluoro benzoyl)-to phenyl ether diamines 52.1g; productive rate is 83.6%, and purity is 98.9%.
With the 5g sodium-acetate; the 8g Sodium sulfanilate; 6g yellow soda ash; 500g dimethyl sulfoxide (DMSO) and 30g toluene add band nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; add sodium sulphite 13g after stirring to contain 60%; under nitrogen protection,, treat above-mentioned Na in 200 ℃ of dehydration reactions of temperature 3 hours
2When the S solution temperature is reduced to 150 ℃; add 44.4g N again; N '-two (to fluoro benzoyl)-4,4 '-diaminodiphenyl oxide was 190 ℃ of reactions of temperature 10 hours; reactant is poured in the water while hot; get polymer powder through washing, use deionized water, acetone extracting after the drying more respectively; in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa of temperature, obtain polyphenylene oxide sulfide acid amides acid amides virgin resin.Its productive rate is 89%, its intrinsic viscosity η=0.16.
Embodiment 7; with 74.4g 4; 4 '-diaminodiphenylsulfone(DDS); 60g triethylamine and 400ml tetrahydrofuran (THF); add successively and have agitator; thermometer; in the reactor of dropping funnel, in dropping funnel, add to fluorobenzoyl chloride 110g, when treating that its temperature is reduced to-5 ℃; begin to drip to fluorobenzoyl chloride; in 2 hours, add, continue to keep 3 hours, at room temperature reacted again 6 hours; with above-mentioned reaction solution pour into make it in the cold water precipitation; precipitation is filtered with the deionized water wash that boils, and removes the parafluorobenzoic acid that is attached to above the monomer, water-soluble impurities such as inorganic salt; in methyl alcohol, refluxed 0.5 hour; further to remove parafluorobenzoic acid, filter, through the pyridine recrystallization; obtain N; N '-two (to fluoro benzoyl)-to sulfobenzide diamines 124g, productive rate is 84%, and purity is 99.0%.
With the 1g tertiary sodium phosphate; the 2g para-aminotoluene; 8g salt of wormwood; 100g N,N-DIMETHYLACETAMIDE and 5g dimethylbenzene add and have nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; add sodium sulphite 13g after stirring to contain 60%; under nitrogen protection,, treat above-mentioned Na in 160 ℃ of dehydration reactions of temperature 0.5 hour
2When the S solution temperature is reduced to 120 ℃, add 49.2g N again, N '-two (to fluoro benzoyl)-4; 4 '-diaminodiphenylsulfone(DDS); 160 ℃ of reactions of temperature 6 hours, reactant was poured in the water while hot, separates out polymkeric substance; through pulverizing; deionized water, acetone extracting are used in washing more respectively after the drying; in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa, obtain poly arylidene thio-ester sulfonamide acid amides virgin resin.Its productive rate is 93%, intrinsic viscosity η=0.26.
Embodiment 8; with 74.4g 3; 3 '-diaminodiphenylsulfone(DDS); 60g triethylamine and 400ml tetrahydrofuran (THF); add successively and have agitator; thermometer; in the reactor of dropping funnel; in dropping funnel, add fluorobenzoyl chloride 110g, when treating that its temperature is reduced to-5 ℃, begin to drip fluorobenzoyl chloride; in 2 hours, add; continue to keep 3 hours, at room temperature reacted again 6 hours, above-mentioned reaction solution decompression is filtered; deionized water wash through boiling filters; removal is attached to the parafluorobenzoic acid above the monomer, and water-soluble impurities such as inorganic salt refluxed 1 hour in methyl alcohol; further to remove parafluorobenzoic acid; filtration obtains N, and N '-two (to fluoro benzoyl)-sulfobenzide diamines 121g is through acetone recrystallization; productive rate is 82.0%, and purity is 99.3%.
With the 5g lithium chloride; the 8g epsilon-amino caproic acid; 0.1g Quilonum Retard; 200g N-Methyl pyrrolidone and 30g dimethylbenzene add and have nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; add sodium sulphite 13g after stirring to contain 60%; under nitrogen protection,, treat above-mentioned Na in dehydration reaction between 200 ℃ of temperature 3 hours
2When the S solution temperature is reduced to 150 ℃, add 49.2g N again, N '-two (to fluoro benzoyl)-3; 3 '-diaminodiphenylsulfone(DDS); 200 ℃ of reactions of temperature 10 hours, reactant was poured in the water while hot, separates out polymkeric substance; through pulverizing; deionized water, acetone extracting are used in washing more respectively after the drying; in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa of temperature, position polyphenylene sulfide sulfonamide acid amides virgin resin between acquisition.Its productive rate is 91%.Intrinsic viscosity η=0.38.
Embodiment 9; with the 16.2g mphenylenediamine; 25g triethylamine and 200ml tetrahydrofuran (THF); add belt stirrer successively; thermometer; in the reactor of dropping funnel; in dropping funnel, add fluorobenzoyl chloride 47.5g; when treating that its temperature is reduced to-5 ℃; begin to drip to fluorobenzoyl chloride; in 1 hour, add; continue to keep 3 hours, at room temperature reacted again 6 hours, above-mentioned reaction solution is poured into made it precipitation in the cold water; precipitation is filtered with the deionized water wash that boils; removal is attached to the parafluorobenzoic acid above the monomer, and water-soluble impurities such as inorganic salt are through recrystallizing methanol; filtration obtains N; N '-two (to fluoro benzoyl)-mphenylenediamine 44.9g, productive rate are 85%, and purity is 99.6%.
With the 1g sodium formiate; the 4g Sodium sulfanilate; 0.1g sodium hydroxide; 100g HMPA and 5g dimethylbenzene add and have nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; add sodium sulphite 13g after stirring to contain 60%; under nitrogen protection,, treat above-mentioned Na in 160 ℃ of dehydration reactions of temperature 0.5 hour
2When the S solution temperature is reduced to 80 ℃; add 35.2g N again; N '-two (to fluoro benzoyl)-mphenylenediamine; 230 ℃ of reactions of temperature 10 hours, reactant was poured in the water while hot, through washing; use deionized water after the drying more respectively; the acetone extracting in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa of temperature, obtains the aromatic polythioether amide virgin resin.Its productive rate is 93%, intrinsic viscosity η=0.21.
Embodiment 10; with the 16.2g Ursol D; 25g triethylamine and 200ml tetrahydrofuran (THF); add belt stirrer successively; thermometer; in the reactor of dropping funnel; in dropping funnel, add fluorobenzoyl chloride 47.5g; when treating that its temperature is reduced to-5 ℃; begin to drip, in 1 hour, add, continue to keep 3 hours fluorobenzoyl chloride; at room temperature reacted again 6 hours; above-mentioned reaction solution poured into make it precipitation in the cold water, precipitation is filtered with the deionized water wash that boils, removes the parafluorobenzoic acid that is attached to above the monomer; water-soluble impurities such as inorganic salt; in methyl alcohol, refluxed 1 hour, further to remove parafluorobenzoic acid, through the NMP recrystallization; filtration obtains N; N '-two (to fluoro benzoyl)-Ursol D 45.4g, productive rate are 86%, and purity is 99.3%.
With the 5g Lithium Acetate; the 8g hexanolactam; the 2g saleratus; 100g N-methyl caprolactam and 30g dimethylbenzene join and have nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; add sodium sulphite 13g after stirring to contain 60%; under nitrogen protection,, treat above-mentioned Na in 180 ℃ of dehydration reactions of temperature 1 hour
2When the S solution temperature is reduced to 150 ℃; add 35.2g N again; N '-two (to fluoro benzoyl)-Ursol D, 180 ℃ of reactions of temperature 10 hours, reactant was poured in the water while hot; separate out polymkeric substance; through washing, use deionized water, acetone extracting after the drying more respectively; in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa of temperature, obtain polyphenylene sulfide acid amides acid amides virgin resin.Its productive rate is 91%, intrinsic viscosity η=0.35.
Embodiment 11; with 30g to diaminobenzophenone; 30g triethylamine and 200ml tetrahydrofuran (THF); add successively and have agitator; thermometer; in the reactor of dropping funnel; in dropping funnel, add fluorobenzoyl chloride 55g; when treating that its temperature is reduced to-5 ℃; begin to drip, in 1 hour, add, continue to keep 3 hours fluorobenzoyl chloride; at room temperature reacted again 6 hours; above-mentioned reaction solution poured into make it precipitation in the cold water, precipitation is filtered with the deionized water wash that boils, removes the parafluorobenzoic acid that is attached to above the monomer; water-soluble impurities such as inorganic salt; in methyl alcohol, refluxed 0.5 hour, further to remove parafluorobenzoic acid, through the NMP recrystallization; filtration obtains N; N '-two (to fluoro benzoyl)-to benzophenone diamines 50.3g, productive rate is 78.0%, and purity is 99.3%.
With the 1g lithium formate; the 2g stannous octoate; the 5g Quilonum Retard; 100g HMPA and 10g toluene join and have nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; add sodium sulphite 13g after stirring to contain 60%; under nitrogen protection,, treat above-mentioned Na in 160 ℃ of dehydration reactions of temperature 0.5 hour
2When the S solution temperature is reduced to 80 ℃; add 45.6g N again, N '-two (to fluoro benzoyl)-4,4 '-diaminobenzophenone; 230 ℃ of reactions of temperature 10 hours; reactant is poured in the water while hot, gets polymkeric substance, through washing; use deionized water after the drying more respectively; the acetone extracting in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa of temperature, obtains the aromatic polythioether amide virgin resin.Its productive rate is 92%, intrinsic viscosity η=0.26.
Embodiment 12; with 28.2g to diaminodiphenyl oxide; 26g triethylamine and 200ml tetrahydrofuran (THF); add successively and have agitator; thermometer; in the reactor of dropping funnel; in dropping funnel, add fluorobenzoyl chloride 60g; when treating that its temperature is reduced to-5 ℃; begin to drip, in 1 hour, add, continue to keep 3 hours fluorobenzoyl chloride; at room temperature reacted again 6 hours; above-mentioned reaction solution poured into make it precipitation in the cold water, sink to the bottom with the deionized water wash that boils and filter, remove the parafluorobenzoic acid that is attached to above the monomer; water-soluble impurities such as inorganic salt; in methyl alcohol, refluxed 1 hour, further to remove parafluorobenzoic acid, NMP recrystallization after filtration; get N; N '-two (to fluoro benzoyl)-to phenyl ether diamines 50.5g, productive rate is 81%, and purity is 98.9%.
With the 5g sodium-acetate; the 8g triphenylphosphine; the 5g sodium bicarbonate; 500g N-cyclohexyl pyrrolidone and 30g toluene join and have nitrogen discrepancy pipe, and water trap is in the reactor of agitator and thermometer; add sodium sulphite 13g after stirring to contain 60%; under nitrogen protection,, treat above-mentioned Na in 200 ℃ of dehydration reactions of temperature 3 hours
2When the S solution temperature is reduced to 150 ℃; add 44.4g N again, N '-two (to fluoro benzoyl)-4,4 '-diaminodiphenyl oxide; 200 ℃ of reactions of temperature 10 hours; reactant is poured in the water while hot, separates out polymkeric substance, through washing; use deionized water after the drying more respectively; the acetone extracting in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa of temperature, obtains the aromatic polythioether amide virgin resin.Its productive rate is 87%, intrinsic viscosity η=0.10.
Claims (7)
1. polyarylene amide sulfides polymers is characterized in that the chemical reaction structural formula of this polymkeric substance is:
N=2-200 wherein, Ar is:
2. the preparation method of an aromatic polythioether amide polymkeric substance is characterized in that the raw material of this polymkeric substance comprises that following component is by weight:
In 13 parts in the sodium sulphite of content 60%
Dihalo aromatic amides 35.2-49.2 part
Solvent 100-500 part
Auxiliary agent 1-5 part
Catalyzer 2-8 part
Alkali or strong base-weak acid salt 0.1-6 part
Entrainer 5-30 part
And by the preparation of following processing step and condition:
(1) the monomeric preparation of dihalo aromatic amides
A. the monomeric preparation of dihalo aromatic amides
With 4,4 '-248 parts of diaminodiphenylsulfone(DDS)s or 4,4 '-200 parts of diaminodiphenyl oxides or 4,4 '-108 parts of 212 parts of diaminobenzophenones or 108 parts of Ursol D or mphenylenediamines, solvent 100-900 part, add successively in the reactor that has agitator, dropping funnel with triethylamine 150-300 part, when treating that its temperature is reduced to-5 ℃, begin to drip to fluorobenzoyl chloride 317-360 part, added in 1-3 hour, continue to keep 2-4 hour, at room temperature reacted again 4-6 hour, obtain dihalo aromatic amides monomer;
The monomeric purifying of b dihalo aromatic amides
Above-mentioned solution poured into make it precipitation in the cold water, precipitation is filtered with the deionized water wash that boils, removes the parafluorobenzoic acid that is attached to above the monomer, the inorganic salt water-soluble impurity, in methyl alcohol backflow 0.5-1 hour, further removing parafluorobenzoic acid, and carry out recrystallization;
(2). the preparation of polyarylene amide sulfides polymers
With 1-5 part auxiliary agent; 2-8 part catalyzer; 0.1-6 adding, part alkali or strong base-weak acid salt, 100-500 part organic solvent and 5-30 part entrainer have nitrogen discrepancy pipe, water trap; in the reactor of agitator and thermometer; after stirring, add in 13 parts in the sodium sulphite of content 60%, under nitrogen protection; in temperature 160-200 ℃ dehydration reaction 0.5-3 hour, the Na after obtaining dewatering
2S solution is treated above-mentioned Na
2When the S solution temperature is reduced to 80-150 ℃, add 35.2-49.2 part dihalo aromatic amides again, temperature 160-230 ℃ of reaction 2-10 hour, above-mentioned reactant is poured in the water while hot, separated out polymkeric substance, through washing, use deionized water after the drying more respectively, the acetone extracting in dry 24 hours of 120 ℃ of vacuum tightness 0.09MPa of temperature, obtains polyarylene amide sulfides polymers.
3. according to the preparation method of the described polyarylene amide sulfides polymers of claim 2, it is characterized in that solvent is any in N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), HMPA, N-cyclohexyl pyrrolidone, N,N-DIMETHYLACETAMIDE or the N-methyl caprolactam.
4. according to the preparation method of the described polyarylene amide sulfides polymers of claim 2, it is characterized in that auxiliary agent is any in sodium formiate, lithium formate, sodium-acetate, Lithium Acetate, Sodium Benzoate, tertiary sodium phosphate or the lithium chloride.
5. according to the preparation method of the described polyarylene amide sulfides polymers of claim 2, it is characterized in that catalyzer be in triphenylphosphine, stannous octoate, hydroxy acid sodium, hexanolactam, epsilon-amino caproic acid, para-aminotoluene or the Sodium sulfanilate any.
6. according to the preparation method of the described polyarylene amide sulfides polymers of claim 2, it is characterized in that alkali is sodium hydroxide or potassium hydroxide; Strong base-weak acid salt is any in yellow soda ash, salt of wormwood, Quilonum Retard, sodium bicarbonate or the saleratus.
7. according to the preparation method of the described polyarylene amide sulfides polymers of claim 2, it is characterized in that entrainer is toluene or dimethylbenzene.
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