WO2022188597A1 - Low-hygroscopicity pa10t and synthesis method therefor - Google Patents
Low-hygroscopicity pa10t and synthesis method therefor Download PDFInfo
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- WO2022188597A1 WO2022188597A1 PCT/CN2022/076302 CN2022076302W WO2022188597A1 WO 2022188597 A1 WO2022188597 A1 WO 2022188597A1 CN 2022076302 W CN2022076302 W CN 2022076302W WO 2022188597 A1 WO2022188597 A1 WO 2022188597A1
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- Prior art keywords
- pa10t
- hypophosphite
- low hygroscopicity
- acid
- synthesizing
- Prior art date
Links
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- 229920006119 nylon 10T Polymers 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- LWKOWFVDUSZDRA-UHFFFAOYSA-N 2,5-difluoroterephthalic acid Chemical compound OC(=O)C1=CC(F)=C(C(O)=O)C=C1F LWKOWFVDUSZDRA-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 5
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 3
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 3
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 claims description 3
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical group C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical group O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- 229910000160 potassium phosphate Inorganic materials 0.000 claims 1
- 235000011009 potassium phosphates Nutrition 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 125000003368 amide group Chemical group 0.000 abstract 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 230000003335 steric effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- WFNRNCNCXRGUKN-UHFFFAOYSA-N 2,3,5,6-tetrafluoroterephthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(C(O)=O)C(F)=C1F WFNRNCNCXRGUKN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HSASJEUDAQEILE-UHFFFAOYSA-N 2,3-difluoroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(F)=C1F HSASJEUDAQEILE-UHFFFAOYSA-N 0.000 description 1
- VILUXUCAKGZKCA-UHFFFAOYSA-N 2-(trifluoromethyl)terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C(C(F)(F)F)=C1 VILUXUCAKGZKCA-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
Definitions
- the invention belongs to the field of high temperature resistant materials, in particular to a high temperature resistant polyamide material with low hygroscopicity and a synthesis method thereof.
- the high temperature resistant polyamide based on decanediamine is polydecanediamine terephthalamide, referred to as PA10T. It is an aromatic polyamide resin with a special chemical structure based on castor oil.
- Genius HPN, or PA10T was launched by Jieshijie, which is the first high-temperature resistant nylon independently developed in my country. Low water absorption, excellent dimensional stability and chemical resistance and injection molding processability.
- Half of the raw materials of PA10T are derived from castor, with excellent comprehensive performance and excellent market competitiveness.
- PA10T has a very low water absorption rate, in the high-humidity environment of southern cities in my country, PA10T will still degrade the raw materials due to heating during processing after absorbing part of the water.
- the current common practice is to reduce the moisture content of PA10T material by drying the material, or set up a large dehumidifier in the processing workshop to remove the moisture in the air, so as to reduce the side effect of moisture in the processing process of PA10T.
- the present application aims at the water absorption effect of PA10T in the prior art, and provides a PA10T with low hygroscopicity, which can still be processed normally under high humidity conditions.
- the object of the present invention is to provide a kind of PA10T with low hygroscopicity and a synthesis method thereof, which is synthesized by using fluorine-containing terephthalic acid and decanediamine as raw materials, and introducing a certain amount of fluorine atoms at specific positions in PA10T can reduce PA10T High water absorption rate, so that PA10T can still be processed normally under high humidity conditions, reducing the investment of factory equipment.
- the low hygroscopicity PA10T of the present invention comprises the structure shown in formula (I):
- n is a positive integer greater than 1, preferably 10 to 20000, more preferably 100 to 10000, still more preferably 500 to 5000.
- the present invention also provides a method for synthesizing the PA10T with low hygroscopicity, which is formed by polycondensation of raw materials, and the raw materials include the following compounds:
- (A) 2,5-difluoroterephthalic acid and (B) decanediamine are fed in equal amounts, and the amounts of equal substances may include an error of less than 1%, preferably an error of less than 0.5%, and further An error of less than 0.1% is preferred. An excess of diamine is preferred.
- part (A) 2,5-difluoroterephthalic acid can be replaced with terephthalic acid.
- the above-mentioned raw materials can also be co-polycondensed with other diacids or diamines to ensure that n(NH 2 ) and n(COOH) are equal in quantity.
- the feedstock may also include a solvent.
- the solvent is one or a mixed solvent of water, methanol, ethanol, and N,N-dimethylformamide. Water is preferred.
- the raw materials may also include auxiliary agents such as surfactants, dispersants, nucleating agents, and antioxidants.
- auxiliary agents such as surfactants, dispersants, nucleating agents, and antioxidants.
- the catalyst is phosphorous acid, hypophosphite, hypophosphite; the hypophosphite is sodium hypophosphite, potassium hypophosphite; the hypophosphite is sodium hypophosphite, Potassium hypophosphite, magnesium hypophosphite, calcium hypophosphite.
- the present invention also provides a method for synthesizing PA10T with low hygroscopicity, comprising the following steps: (1) putting the amounts of 2,5-difluoroterephthalic acid and decanediamine into a polymerization reactor, adding catalyst, water , seal, stir, replace with non-reactive gas, set the air pressure to 10 ⁇ 100kPa. (2) Raise the temperature in the kettle to 100 ⁇ 150°C and keep the temperature for 1 ⁇ 3 hours until the raw material is completely salted.
- the amount of the equivalent substances in the step (1) may include an error of less than 1%, preferably an error of less than 0.5%, and more preferably an error of less than 0.1%.
- An excess of diamine is preferred.
- the catalyst is phosphorous acid, hypophosphite, hypophosphite; the hypophosphite is sodium hypophosphite, potassium hypophosphite; the hypophosphite is Sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite, calcium hypophosphite.
- the non-reactive gas in the step (1) is one or more of nitrogen, carbon dioxide, helium, neon, and argon.
- the air pressure in the step (1) is preferably 10-50 kPa, more preferably 50 kPa.
- the temperature in the kettle is raised to 110-130°C, preferably 110-120°C, more preferably 120°C.
- the holding time in the step (2) is 1-2 hours, preferably 2 hours.
- the pressure setting value in the step (3) is 1-3 MPa, preferably 2-3 MPa, more preferably 3 MPa.
- the pressure holding time in the step (3) is 1-2 hours, preferably 1 hour.
- the temperature for the continued temperature increase in the step (3) is 280-310°C, preferably 290-310°C, and more preferably 310°C.
- the constant pressure time in the step (3) is 1-2 hours, preferably 1 hour.
- the present invention has the following beneficial effects.
- the present invention selects 2,5-difluoroterephthalic acid as the dibasic acid, and introduces a certain amount of fluorine atoms at specific positions in PA10T, which can further reduce the water absorption rate of PA10T compared with ordinary terephthalic acid, so that PA10T can still be processed normally under high humidity conditions, reducing the investment in factory equipment.
- the preparation method of the present invention is simple in process, adopts one-pot polymerization, does not need to spatially separate the steps of salt, prepolymerization, and solid-phase thickening, and can complete all steps with one polymer, which is convenient for production.
- Terephthalic acid, 2,5-difluoroterephthalic acid, 2,3,5,6-tetrafluoroterephthalic acid and decanediamine are salted in water or ethanol, and the specific steps are: take 300 mL of water Or add ethanol into a 500mL three-necked flask equipped with a stirring and thermometer, take an appropriate amount of decanediamine according to the solubility of decanediamine, add it to the three-necked flask, and heat to 90°C to form a saturated solution of decanediamine.
- Solubility measurement is carried out to the obtained 10T salt in water and ethanol, the solubility of the salt in water and ethanol is all very little, all less than 0.1g/100g, therefore, adopting water or ethanol as solvent can relatively obtain 1: 1 molar ratio of 10T salt.
- water is preferred as the solvent in the present invention.
- the temperature in the kettle was raised to 120° C. and kept for 2 hours until 2,5-difluoroterephthalic acid and decanediamine were completely formed into a salt.
- Example 1 was repeated, except that on the basis of Example 1, the 2,5-difluoroterephthalic acid was replaced with terephthalic acid, and other conditions remained unchanged.
- Example 1 was repeated, except that on the basis of Example 1, the 2,5-difluoroterephthalic acid was replaced with 2,3,5,6-tetrafluoroterephthalic acid, and other conditions remained unchanged. .
- Example 1 was repeated, except that on the basis of Example 1, the 2,5-difluoroterephthalic acid was replaced with 2-trifluoromethyl terephthalic acid, and other conditions remained unchanged.
- Example 1 The melting point and moisture absorption rate of the PA10T prepared in Example 1 and Comparative Examples 1-3 were measured. And it was injected into standard splines to measure its tensile strength.
- the melting point was measured by DCS method, the temperature range was 30-360° C., the heating rate was 10° C./min, and the protective gas was nitrogen.
- the moisture absorption rate measurement environment 23° C., 50% relative humidity, and equilibrated for 24 hours.
- the low hygroscopicity PA10T of the present invention has a lower hygroscopic rate, and compared with the PA10T prepared from terephthalic acid as a raw material, the hygroscopic rate is greatly reduced.
- a low hygroscopic rate It can ensure that the resin is processed smoothly in the humid area of southern my country, and will not absorb moisture due to contact with air during the drying process to the feeding process, and the amide bond will be broken during the processing process.
- Example 1 the melting point and moisture absorption rate of Example 1 are almost the same as those of Comparative Example 2, but the use of 2,5-difluoroterephthalic acid has better tensile strength.
- the inventors make the following conjecture: 2,5 - The content of fluorine atoms in difluoroterephthalic acid is less, there is only one fluorine atom next to each carboxyl group, the fluorine atom has less shielding effect on the carboxyl group, and the effect of hydrogen bonds formed between amides between different molecules is less, so The obtained material is stronger.
- Comparative Example 2 In the 2,3,5,6-tetrafluoroterephthalic acid used in Comparative Example 2, each carboxyl group is surrounded by two fluorine atoms, which has a great shielding effect on the carboxyl group and affects the formation of intermolecular hydrogen bonds.
- Comparative Example 3 also includes fluorine atoms, but due to its too large steric hindrance, it is obvious that the synthesis speed is slow during the synthesis process, the obtained material is an amorphous phase, and no melting is observed in the DSC heating curve. The tensile strength of the standard spline is also extremely low, which further verifies the aforementioned conjecture of the shielding effect of fluorine atoms on carboxyl groups.
- Example 1 the difference is that on the basis of Example 1, the 2,5-difluoroterephthalic acid is replaced with 2,5-difluoroterephthalic acid and terephthalic acid in a molar ratio of 1 :1 mixture, other conditions unchanged.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
Provided are a low-hygroscopicity PA10T and a synthesis method therefor. The low-hygroscopicity PA10T is synthesized by using fluorine-containing terephthalic acid and decamethylenediamine as raw materials, and by means of introducing a certain amount of fluorine atoms into the specific position of PA10T, the water absorption rate of PA10T can be reduced, such that PA10T can still be normally processed under high-humidity conditions and the investment of factory equipment is reduced. The introduced fluorine atoms are positioned beside carboxyl groups, and it is ensured that there is only one fluorine atom beside each carboxyl group. Such a small steric effect can both reduce the hygroscopicity of PA10T and avoid a shielding effect of the fluorine atoms toward an amide group, and thus, the mechanical properties of PA10T are retained.
Description
本申请要求于2021年03月09日提交中国专利局、申请号为202110254417.0、发明名称为“一种低吸湿性PA10T及其合成方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application with the application number 202110254417.0 and the invention titled "A kind of low hygroscopicity PA10T and its synthesis method", which was submitted to the China Patent Office on March 09, 2021, the entire contents of which are incorporated by reference in in this application.
本申请要求于2021年03月30日提交中国专利局、申请号为202110341952.X、发明名称为“一种低吸湿性PA10T及其合成方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application with the application number 202110341952.X and the invention title "A kind of low hygroscopicity PA10T and its synthesis method", which was submitted to the China Patent Office on March 30, 2021, the entire contents of which are by reference Incorporated in this application.
本发明属于耐高温材料领域，具体涉及一种具有低吸湿性耐高温聚酰胺材料及其合成方法。The invention belongs to the field of high temperature resistant materials, in particular to a high temperature resistant polyamide material with low hygroscopicity and a synthesis method thereof.
基于癸二胺的耐高温聚酰胺即聚对苯二甲酰癸二胺，简称PA10T。其是以蓖麻为原料，具有特殊化学构造的芳香族聚酰胺树脂。2006年，杰事杰推出的Genius HPN即PA10T，是我国首款自主研发的耐高温尼龙，其熔点约310℃，玻璃化转变温度在100～200℃之间，具有优异的耐热性、极低的吸水率、优秀的尺寸稳定性以及耐化学性能和注塑加工性能。PA10T有一半的原材料都源自蓖麻，综合性能优异，具有极佳的市场竞争力。The high temperature resistant polyamide based on decanediamine is polydecanediamine terephthalamide, referred to as PA10T. It is an aromatic polyamide resin with a special chemical structure based on castor oil. In 2006, Genius HPN, or PA10T, was launched by Jieshijie, which is the first high-temperature resistant nylon independently developed in my country. Low water absorption, excellent dimensional stability and chemical resistance and injection molding processability. Half of the raw materials of PA10T are derived from castor, with excellent comprehensive performance and excellent market competitiveness.
PA10T虽然具有极低的吸水率，但是在我国南方城市高湿环境下，PA10T的依然会因为吸收了部分水分后，在加工过程中因升温导致原料降解。当前普遍的做法是通过对物料的干燥降低PA10T料的含水率，或者在加工车间中设立大型除湿器以除去空气中的水分，以减少PA10T在加工过程中水分的副作用。Although PA10T has a very low water absorption rate, in the high-humidity environment of southern cities in my country, PA10T will still degrade the raw materials due to heating during processing after absorbing part of the water. The current common practice is to reduce the moisture content of PA10T material by drying the material, or set up a large dehumidifier in the processing workshop to remove the moisture in the air, so as to reduce the side effect of moisture in the processing process of PA10T.
对此，本申请针对现有技术中PA10T的吸水作用，提供一种具有低吸湿性PA10T，能够在高湿条件下依然正常加工。In this regard, the present application aims at the water absorption effect of PA10T in the prior art, and provides a PA10T with low hygroscopicity, which can still be processed normally under high humidity conditions.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种具有低吸湿性PA10T及其合成方法，其通过使用含氟的对苯二甲酸与癸二胺为原料合成，在PA10T中特定位置引入一定量的氟原子能够降低PA10T的吸水率，使PA10T在高湿条件下依然能正常加工，减少工厂设备投入。The object of the present invention is to provide a kind of PA10T with low hygroscopicity and a synthesis method thereof, which is synthesized by using fluorine-containing terephthalic acid and decanediamine as raw materials, and introducing a certain amount of fluorine atoms at specific positions in PA10T can reduce PA10T High water absorption rate, so that PA10T can still be processed normally under high humidity conditions, reducing the investment of factory equipment.
为实现上述目的，本发明所述低吸湿性PA10T包括式(I)所示结构：In order to achieve the above purpose, the low hygroscopicity PA10T of the present invention comprises the structure shown in formula (I):
其中，所述n为大于1的正整数，优选10～20000，进一步优选100～10000，更进一步优选500～5000。Among them, the n is a positive integer greater than 1, preferably 10 to 20000, more preferably 100 to 10000, still more preferably 500 to 5000.
本发明还提供了所述低吸湿性PA10T的合成方法，将原料经缩聚而成，原料包括如下化合物：The present invention also provides a method for synthesizing the PA10T with low hygroscopicity, which is formed by polycondensation of raw materials, and the raw materials include the following compounds:
(A)2,5-二氟对苯二甲酸(A) 2,5-Difluoroterephthalic acid
(B)癸二胺(B) Decanediamine
(C)催化剂。(C) Catalyst.
其中(A)2,5-二氟对苯二甲酸与(B)癸二胺以等物质的量投料，所述等物质的量可以包括小于1％的误差，优选小于0.5％的误差，进一步优选小于0.1％的误差。以二胺过量为佳。Wherein (A) 2,5-difluoroterephthalic acid and (B) decanediamine are fed in equal amounts, and the amounts of equal substances may include an error of less than 1%, preferably an error of less than 0.5%, and further An error of less than 0.1% is preferred. An excess of diamine is preferred.
可选地，部分(A)2,5-二氟对苯二甲酸可以被替换成对苯二甲酸。Alternatively, part (A) 2,5-difluoroterephthalic acid can be replaced with terephthalic acid.
可选地，上述原料还可以与其他二元酸或二元胺进行共缩聚，保证n(NH
2)与n(COOH)为等物质的量。
Optionally, the above-mentioned raw materials can also be co-polycondensed with other diacids or diamines to ensure that n(NH 2 ) and n(COOH) are equal in quantity.
可选地，原料还可包括溶剂。所述溶剂为水、甲醇、乙醇、N,N-二甲基甲酰胺中的一种或混合溶剂。优选为水。Optionally, the feedstock may also include a solvent. The solvent is one or a mixed solvent of water, methanol, ethanol, and N,N-dimethylformamide. Water is preferred.
可选地，原料还可包括表面活性剂、分散剂、成核剂、抗氧化剂等助剂。Optionally, the raw materials may also include auxiliary agents such as surfactants, dispersants, nucleating agents, and antioxidants.
在一个优选的实施例中，所述催化剂为亚磷酸、次磷酸盐、次亚磷酸盐；所述次磷酸盐为次磷酸钠、次磷酸钾；所述次亚磷酸盐为次亚磷酸钠、次亚磷酸钾、次亚磷酸镁、次亚磷酸钙。In a preferred embodiment, the catalyst is phosphorous acid, hypophosphite, hypophosphite; the hypophosphite is sodium hypophosphite, potassium hypophosphite; the hypophosphite is sodium hypophosphite, Potassium hypophosphite, magnesium hypophosphite, calcium hypophosphite.
本发明还提供一种低吸湿性PA10T的合成方法，包括如下步骤：(1)将2,5-二氟对苯二甲酸与癸二胺等物质的量投入聚合反应釜中，加入催化剂、水，密封、搅拌，用非反应性气体置换，设定气压为10～100kPa。(2)将釜内温度升至100～150℃并保温1～3小时，至原料完全成盐。(3)继续加热聚合反应釜，当釜内压力达到设定值时释放水气，并保压1～3小时，随后继续升温至 280～320℃，恒压1～3小时，充气后出料，即得所述低吸湿性PA10T。The present invention also provides a method for synthesizing PA10T with low hygroscopicity, comprising the following steps: (1) putting the amounts of 2,5-difluoroterephthalic acid and decanediamine into a polymerization reactor, adding catalyst, water , seal, stir, replace with non-reactive gas, set the air pressure to 10 ~ 100kPa. (2) Raise the temperature in the kettle to 100～150℃ and keep the temperature for 1～3 hours until the raw material is completely salted. (3) Continue to heat the polymerization reaction kettle, release water vapor when the pressure in the kettle reaches the set value, and maintain the pressure for 1 to 3 hours, then continue to heat up to 280 to 320° C., maintain a constant pressure for 1 to 3 hours, and discharge after inflation , that is, the low hygroscopicity PA10T is obtained.
在一个优选的实施例中，所述步骤(1)中所述等物质的量可以包括小于1％的误差，优选小于0.5％的误差，进一步优选小于0.1％的误差。以二胺过量为佳。In a preferred embodiment, the amount of the equivalent substances in the step (1) may include an error of less than 1%, preferably an error of less than 0.5%, and more preferably an error of less than 0.1%. An excess of diamine is preferred.
在一个优选的实施例中，所述步骤(1)中催化剂为亚磷酸、次磷酸盐、次亚磷酸盐；所述次磷酸盐为次磷酸钠、次磷酸钾；所述次亚磷酸盐为次亚磷酸钠、次亚磷酸钾、次亚磷酸镁、次亚磷酸钙。In a preferred embodiment, in the step (1), the catalyst is phosphorous acid, hypophosphite, hypophosphite; the hypophosphite is sodium hypophosphite, potassium hypophosphite; the hypophosphite is Sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite, calcium hypophosphite.
在一个优选的实施例中，所述步骤(1)中非反应性气体为氮气、二氧化碳、氦气、氖气、氩气中的一种或多种。In a preferred embodiment, the non-reactive gas in the step (1) is one or more of nitrogen, carbon dioxide, helium, neon, and argon.
在一个优选的实施例中，所述步骤(1)中所述气压优选为10～50kPa，进一步优选为50kPa。In a preferred embodiment, the air pressure in the step (1) is preferably 10-50 kPa, more preferably 50 kPa.
在一个优选的实施例中，所述步骤(2)中所述釜内温度升至110～130℃，优选110～120℃，进一步优选120℃。In a preferred embodiment, in the step (2), the temperature in the kettle is raised to 110-130°C, preferably 110-120°C, more preferably 120°C.
在一个优选的实施例中，所述步骤(2)中保温时间为1～2小时，优选2小时。In a preferred embodiment, the holding time in the step (2) is 1-2 hours, preferably 2 hours.
在一个优选的实施例中，所述步骤(3)中所述压力设定值为1～3MPa，优选2～3MPa，进一步优选3MPa。In a preferred embodiment, the pressure setting value in the step (3) is 1-3 MPa, preferably 2-3 MPa, more preferably 3 MPa.
在一个优选的实施例中，所述步骤(3)中保压时间为1～2小时，优选1小时。In a preferred embodiment, the pressure holding time in the step (3) is 1-2 hours, preferably 1 hour.
在一个优选的实施例中，所述步骤(3)中继续升温的温度为280～310℃，优选290～310℃，进一步优选310℃。In a preferred embodiment, the temperature for the continued temperature increase in the step (3) is 280-310°C, preferably 290-310°C, and more preferably 310°C.
在一个优选的实施例中，所述步骤(3)中恒压时间为1～2小时，优选1小时。In a preferred embodiment, the constant pressure time in the step (3) is 1-2 hours, preferably 1 hour.
本发明同现有技术相比，具有以下有益效果。Compared with the prior art, the present invention has the following beneficial effects.
(1)本发明选用2,5-二氟对苯二甲酸作为二元酸，在PA10T中特定位置引入一定量的氟原子，相较于普通对苯二甲酸能够进一步降低PA10T的吸水率，使PA10T在高湿条件下依然能正常加工，减少工厂设备投入。(1) The present invention selects 2,5-difluoroterephthalic acid as the dibasic acid, and introduces a certain amount of fluorine atoms at specific positions in PA10T, which can further reduce the water absorption rate of PA10T compared with ordinary terephthalic acid, so that PA10T can still be processed normally under high humidity conditions, reducing the investment in factory equipment.
(2)本发明所述制备方法工艺简单，采用一锅法聚合，无需将盐、预聚、固相增粘步骤在空间上分离，采用一个聚合物即可完成全部步骤，方便生产。(2) The preparation method of the present invention is simple in process, adopts one-pot polymerization, does not need to spatially separate the steps of salt, prepolymerization, and solid-phase thickening, and can complete all steps with one polymer, which is convenient for production.
下面结合具体实施例对本发明的实施方式作进一步说明，熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效。The embodiments of the present invention will be further described below with reference to specific examples, and those who are familiar with the technology can easily understand other advantages and effects of the present invention from the contents disclosed in this specification.
在进一步描述本发明具体实施方式之前，应理解，本发明的保护范围包括但不限于以下特定的具体实施方案。一般地，本发明实施例中使用的术语是为了描述特定的具体实施方案，而不是为了限制本发明的保护范围。以下实施例中未注明具体条件的试验方法，通常按照常规条件，或者按照各制造商所建议的条件。Before further describing the specific embodiments of the present invention, it should be understood that the protection scope of the present invention includes but is not limited to the following specific specific embodiments. Generally, the terms used in the embodiments of the present invention are for describing specific specific embodiments, rather than for limiting the protection scope of the present invention. The test methods without specific conditions in the following examples are usually in accordance with conventional conditions, or in accordance with the conditions suggested by various manufacturers.
当实施例给出数值范围时，应理解，除非本发明另有说明，每个数值范围的两个端点以及两个端点之间任何一个数值均可选用。除非另外定义，本发明中使用的所有技术和科学术语与本技术领域技术人员通常理解的意义相同。除实施例中使用的具体方法、设备、材料外，根据本技术领域的技术人员对现有技术的掌握及本发明的记载，还可以使用与本发明实施例中所述的方法、设备、材料相似或等同的现有技术的任何方法、设备和材料来实现本发明。When numerical ranges are given in the examples, it is to be understood that, unless otherwise indicated herein, both endpoints of each numerical range and any number between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, equipment and materials used in the embodiments, according to the mastery of the prior art by those skilled in the art and the description of the present invention, the methods, equipment and materials described in the embodiments of the present invention can also be used Any methods, devices and materials similar or equivalent to those of the prior art can be used to implement the present invention.
准备例Preparation example
将对苯二甲酸、2,5-二氟对苯二甲酸、2,3,5,6-四氟对苯二甲酸与癸二胺在水或乙醇中成盐，具体步骤为：取300mL水或乙醇加入配有搅拌、温度计的500mL三口烧瓶中，根据癸二胺的溶解度取适量的癸二胺，将其加入三口烧瓶中，加热至90℃，形成癸二胺的饱和溶液。然后分别称取与癸二胺等物质的量的对苯二甲酸、2,5-二氟对苯二甲酸、2,3,5,6-四氟对苯二甲酸加入三口烧瓶中，反应2小时。用少量单体调整pH至7.0，继续反应3小时，形成10T盐的悬浊液。降温至室温后放入冰箱冷冻，析出盐，趁冷过滤，用冰水或乙醇洗涤三次，烘干后得到白色的10T盐。Terephthalic acid, 2,5-difluoroterephthalic acid, 2,3,5,6-tetrafluoroterephthalic acid and decanediamine are salted in water or ethanol, and the specific steps are: take 300 mL of water Or add ethanol into a 500mL three-necked flask equipped with a stirring and thermometer, take an appropriate amount of decanediamine according to the solubility of decanediamine, add it to the three-necked flask, and heat to 90°C to form a saturated solution of decanediamine. Then weigh terephthalic acid, 2,5-difluoroterephthalic acid, and 2,3,5,6-tetrafluoroterephthalic acid in the amount of decanediamine and other substances respectively and add them to the three-necked flask, and react 2 Hour. The pH was adjusted to 7.0 with a small amount of monomer, and the reaction was continued for 3 hours to form a suspension of 10T salt. After cooling to room temperature, put it into the refrigerator to freeze, precipitate out the salt, filter while cold, wash with ice water or ethanol three times, and dry to obtain white 10T salt.
对得到的10T盐在水和乙醇中进行溶解度测定，所述盐在水和乙醇中的溶解度都极小，均小于0.1g/100g，因此，采用水或乙醇作为溶剂能够较纯净地得到1:1摩尔比的10T盐。但是乙醇经过高温高压反应釜后在泄压过程中容易引起火灾，因此本发明优选水作为溶剂。Solubility measurement is carried out to the obtained 10T salt in water and ethanol, the solubility of the salt in water and ethanol is all very little, all less than 0.1g/100g, therefore, adopting water or ethanol as solvent can relatively obtain 1: 1 molar ratio of 10T salt. However, after ethanol passes through the high temperature and high pressure reactor, it is easy to cause fire during the pressure relief process, so water is preferred as the solvent in the present invention.
实施例1Example 1
将2,5-二氟对苯二甲酸1mol，癸二胺1mol，催化剂次亚磷酸钠2×10
-3mol 混合均匀后倒入聚合反应釜中，注入100mL去离子水，密封聚合反应釜，开启搅拌，搅拌速度为100rpm，用N
2置换气体三次，将釜内气压设定为50kPa。
Mix 1 mol of 2,5-difluoroterephthalic acid, 1 mol of decanediamine, and 2 × 10 -3 mol of sodium hypophosphite as a catalyst and pour it into a polymerization reaction kettle, inject 100 mL of deionized water, and seal the polymerization reaction kettle. The stirring was turned on, the stirring speed was 100 rpm, the gas was replaced with N 2 three times, and the pressure in the kettle was set to 50 kPa.
将釜内温度升至120℃并保温2小时，至2,5-二氟对苯二甲酸和癸二胺完全成盐。The temperature in the kettle was raised to 120° C. and kept for 2 hours until 2,5-difluoroterephthalic acid and decanediamine were completely formed into a salt.
继续加热聚合反应釜，当釜内压力达到3MPa使开启泄压阀释放产生的水气，并保持釜内压力，恒压1小时，随后继续以5℃/min的速度升温至310℃，并恒压1小时，向釜内充入N
2后出料，即得所述低吸湿性PA10T。
Continue to heat the polymerization reaction kettle. When the pressure in the kettle reaches 3MPa, open the pressure relief valve to release the generated water vapor, and keep the pressure in the kettle at a constant pressure for 1 hour. Press for 1 hour, fill the kettle with N 2 and then discharge the material to obtain the low hygroscopicity PA10T.
对比例1Comparative Example 1
重复实施例1，不同的是，在实施例1的基础上将所述2,5-二氟对苯二甲酸替换成对苯二甲酸，其他条件不变。Example 1 was repeated, except that on the basis of Example 1, the 2,5-difluoroterephthalic acid was replaced with terephthalic acid, and other conditions remained unchanged.
对比例2Comparative Example 2
重复实施例1，不同的是，在实施例1的基础上将所述2,5-二氟对苯二甲酸替换成2,3,5,6-四氟对苯二甲酸，其他条件不变。Example 1 was repeated, except that on the basis of Example 1, the 2,5-difluoroterephthalic acid was replaced with 2,3,5,6-tetrafluoroterephthalic acid, and other conditions remained unchanged. .
对比例3Comparative Example 3
重复实施例1，不同的是，在实施例1的基础上将所述2,5-二氟对苯二甲酸替换成2-三氟甲基对苯二甲酸，其他条件不变。Example 1 was repeated, except that on the basis of Example 1, the 2,5-difluoroterephthalic acid was replaced with 2-trifluoromethyl terephthalic acid, and other conditions remained unchanged.
将实施例1和对比例1-3所制备得到的PA10T测定其熔点和吸湿率。并将其注塑成标准样条测定其拉伸强度。The melting point and moisture absorption rate of the PA10T prepared in Example 1 and Comparative Examples 1-3 were measured. And it was injected into standard splines to measure its tensile strength.
所述熔点采用DCS法测定，温度区间为30～360℃，升温速率10℃/min，保护气为氮气。The melting point was measured by DCS method, the temperature range was 30-360° C., the heating rate was 10° C./min, and the protective gas was nitrogen.
所述吸湿率测定环境：23℃，相对湿度50％，平衡24小时。The moisture absorption rate measurement environment: 23° C., 50% relative humidity, and equilibrated for 24 hours.
实施例1和对比例1-3所述PA10T的熔点、吸湿率和拉伸强度结果如表1所示。The results of melting point, moisture absorption rate and tensile strength of PA10T described in Example 1 and Comparative Examples 1-3 are shown in Table 1.
表1Table 1
| 熔点(℃)Melting point(℃) | 吸湿率(％)Moisture absorption rate (%) | 拉伸强度(MPa)Tensile strength (MPa) | |
| 实施例1Example 1 | 313.7313.7 | 0.080.08 | 7474 |
| 对比例1Comparative Example 1 | 309.3309.3 | 0.720.72 | 7777 |
| 对比例2Comparative Example 2 | 318.4318.4 | 0.030.03 | 6262 |
| 对比例3Comparative Example 3 | —— | 0.030.03 | 1616 |
从表1中可以看出，本发明所述低吸湿性PA10T具有更低的吸湿率，其相较于对苯二甲酸为原料制备的PA10T在吸湿率方面有大幅的降低，这样低的吸湿率能够保证该种树脂在我国南方潮湿地区顺利加工，不会因为烘干至投料过程中与空气接触从而吸湿，并在加工过程中使酰胺键断裂。As can be seen from Table 1, the low hygroscopicity PA10T of the present invention has a lower hygroscopic rate, and compared with the PA10T prepared from terephthalic acid as a raw material, the hygroscopic rate is greatly reduced. Such a low hygroscopic rate It can ensure that the resin is processed smoothly in the humid area of southern my country, and will not absorb moisture due to contact with air during the drying process to the feeding process, and the amide bond will be broken during the processing process.
与此同时，实施例1相较于对比例2其熔点和吸湿率几乎相同，但是采用2,5-二氟对苯二甲酸具有更好的拉伸强度，发明人作出以下猜想：2,5-二氟对苯二甲酸中氟原子含量较少，每个羧基旁仅一个氟原子，所述氟原子对羧基的屏蔽作用较少，不同分子间的酰胺间形成的氢键影响较低，因此获得的材料强度更高。对比例2采用的2,3,5,6-四氟对苯二甲酸，每个羧基均被两个氟原子包围，其对羧基的屏蔽作用较大，影响分子间氢键的形成。作为补充的实验，对比例3同样包括氟原子，但是由于其位阻过大，在合成过程中明显能够观察到合成速度缓慢，获得的材料为非晶相，在DSC升温曲线中观察不到熔融峰，其标准样条的拉伸强度也极低，进一步验证了前述氟原子对羧基屏蔽作用的猜想。At the same time, the melting point and moisture absorption rate of Example 1 are almost the same as those of Comparative Example 2, but the use of 2,5-difluoroterephthalic acid has better tensile strength. The inventors make the following conjecture: 2,5 - The content of fluorine atoms in difluoroterephthalic acid is less, there is only one fluorine atom next to each carboxyl group, the fluorine atom has less shielding effect on the carboxyl group, and the effect of hydrogen bonds formed between amides between different molecules is less, so The obtained material is stronger. In the 2,3,5,6-tetrafluoroterephthalic acid used in Comparative Example 2, each carboxyl group is surrounded by two fluorine atoms, which has a great shielding effect on the carboxyl group and affects the formation of intermolecular hydrogen bonds. As a supplementary experiment, Comparative Example 3 also includes fluorine atoms, but due to its too large steric hindrance, it is obvious that the synthesis speed is slow during the synthesis process, the obtained material is an amorphous phase, and no melting is observed in the DSC heating curve. The tensile strength of the standard spline is also extremely low, which further verifies the aforementioned conjecture of the shielding effect of fluorine atoms on carboxyl groups.
实施例2Example 2
重复实施例1，不同的是，在实施例1的基础上将所述2,5-二氟对苯二甲酸替换成2,5-二氟对苯二甲酸与对苯二甲酸以摩尔比1:1的混合物，其他条件不变。Repeat Example 1, the difference is that on the basis of Example 1, the 2,5-difluoroterephthalic acid is replaced with 2,5-difluoroterephthalic acid and terephthalic acid in a molar ratio of 1 :1 mixture, other conditions unchanged.
实施例2所述PA10T的熔点、吸湿率和拉伸强度结果如表2所示。The results of melting point, moisture absorption rate and tensile strength of PA10T described in Example 2 are shown in Table 2.
表2Table 2
| 熔点(℃)Melting point(℃) | 吸湿率(％)Moisture absorption rate (%) | 拉伸强度(MPa)Tensile strength (MPa) | |
| 实施例1Example 1 | 313.7313.7 | 0.080.08 | 7474 |
| 实施例2Example 2 | 311.6311.6 | 0.330.33 | 7575 |
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。All documents mentioned herein are incorporated by reference in this application as if each document were individually incorporated by reference. In addition, it should be understood that after reading the above teaching content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
Claims (10)
- 一种低吸湿性PA10T，其特征在于，包括式(I)所示结构：A kind of low hygroscopicity PA10T is characterized in that, comprises the structure shown in formula (I):
其中，所述n为大于1的正整数，优选10～20000，进一步优选100～10000，更进一步优选500～5000。Among them, the n is a positive integer greater than 1, preferably 10 to 20000, more preferably 100 to 10000, still more preferably 500 to 5000. - 如权利要求1所述低吸湿性PA10T的合成方法，其特征在于，原料经缩聚而成，原料包括如下化合物：The synthetic method of PA10T with low hygroscopicity as claimed in claim 1, is characterized in that, raw material is formed through polycondensation, and raw material comprises following compound:(A)2,5-二氟对苯二甲酸(A) 2,5-Difluoroterephthalic acid(B)癸二胺(B) Decanediamine(C)催化剂。(C) Catalyst.
- 如权利要求2所述低吸湿性PA10T的合成方法，其特征在于，所述化合物(A)2,5-二氟对苯二甲酸与化合物(B)癸二胺以等物质的量投料，所述等物质的量可以包括小于1％的误差，优选小于0.5％的误差，进一步优选小于0.1％的误差；以化合物(B)过量为佳。The synthetic method of PA10T with low hygroscopicity as claimed in claim 2, is characterized in that, described compound (A) 2,5-difluoroterephthalic acid and compound (B) decanediamine are fed in the amount of equivalent material, so The amount of such substances may include an error of less than 1%, preferably an error of less than 0.5%, and more preferably an error of less than 0.1%; the compound (B) is preferably in excess.
- 如权利要求2所述低吸湿性PA10T的合成方法，其特征在于，部分(A)2,5-二氟对苯二甲酸被替换成对苯二甲酸。The method for synthesizing PA10T with low hygroscopicity according to claim 2, wherein part (A) 2,5-difluoroterephthalic acid is replaced by terephthalic acid.
- 如权利要求2～4任一项所述低吸湿性PA10T的合成方法，其特征在于，所述原料与其他二元酸或二元胺进行共缩聚。The method for synthesizing PA10T with low hygroscopicity according to any one of claims 2 to 4, characterized in that, the raw material is copolycondensed with other dibasic acid or dibasic amine.
- 如权利要求2～4任一项所述低吸湿性PA10T的合成方法，其特征在于，所述原料还包括溶剂，所述溶剂为水、甲醇、乙醇、N,N-二甲基甲酰胺中的一种或混合溶剂；优选为水。The method for synthesizing PA10T with low hygroscopicity according to any one of claims 2 to 4, wherein the raw material further comprises a solvent, and the solvent is water, methanol, ethanol, or N,N-dimethylformamide. one or mixed solvent; preferably water.
- 如权利要求2～4任一项所述低吸湿性PA10T的合成方法，其特征在于，所述原料还包括表面活性剂、分散剂、成核剂、抗氧化剂等助剂。The method for synthesizing PA10T with low hygroscopicity according to any one of claims 2 to 4, wherein the raw material further comprises auxiliary agents such as surfactants, dispersants, nucleating agents, and antioxidants.
- 如权利要求2～4任一项所述低吸湿性PA10T的合成方法，其特征在于， 所述催化剂为亚磷酸、次磷酸盐、次亚磷酸盐；所述次磷酸盐为次磷酸钠、次磷酸钾；所述次亚磷酸盐为次亚磷酸钠、次亚磷酸钾、次亚磷酸镁、次亚磷酸钙。The method for synthesizing PA10T with low hygroscopicity according to any one of claims 2 to 4, wherein the catalyst is phosphorous acid, hypophosphite, and hypophosphite; and the hypophosphite is sodium hypophosphite, hypophosphite, and hypophosphite. Potassium phosphate; the hypophosphite is sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite and calcium hypophosphite.
- 如权利要求2～4任一项所述低吸湿性PA10T的合成方法，其特征在于，包括如下步骤：(1)将2,5-二氟对苯二甲酸与癸二胺等物质的量投入聚合反应釜中，加入催化剂、水，密封、搅拌，用非反应性气体置换，设定气压为10～100kPa；(2)将釜内温度升至100～150℃并保温1～3小时，至原料完全成盐；(3)继续加热聚合反应釜，当釜内压力达到设定值时释放水气，并保压1～3小时，随后继续升温至280～320℃，恒压1～3小时，充气后出料，即得所述低吸湿性PA10T。The method for synthesizing PA10T with low hygroscopicity according to any one of claims 2 to 4, characterized in that it comprises the steps: (1) putting the amount of substances such as 2,5-difluoroterephthalic acid and decanediamine into In the polymerization reaction kettle, add catalyst and water, seal, stir, replace with non-reactive gas, and set the air pressure to be 10～100kPa; (2) the temperature in the kettle is raised to 100～150 ℃ and kept for 1～3 hours, until The raw material is completely salted; (3) continue to heat the polymerization reaction kettle, release water vapor when the pressure in the kettle reaches the set value, and maintain the pressure for 1 to 3 hours, then continue to heat up to 280 to 320 ° C, and maintain a constant pressure for 1 to 3 hours , the material is discharged after inflating to obtain the low hygroscopicity PA10T.
- 权利要求1所述一种低吸湿性PA10T或根据权利要求2～9任一项所述合成方法合成得到的PA10T作为低吸湿性材料的应用。Application of the low hygroscopicity PA10T described in claim 1 or the PA10T synthesized according to the synthesis method of any one of claims 2 to 9 as a low hygroscopicity material.
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| CN116355205A (en) * | 2023-03-29 | 2023-06-30 | 四川轻化工大学 | Bio-based polyamide and preparation method thereof |
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