CN103435796A - Semi-aromatic transparent polyamide material and preparation method thereof - Google Patents
Semi-aromatic transparent polyamide material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a semi-aromatic transparent polyamide material and a preparation method thereof, belonging to the field of high-molecular materials. The material consists of a random copolymer of semi-aromatic amide salt and aliphatic amide salt and necessary auxiliaries; the intrinsic viscosity is 1.0-2.2dl/g, and the degree of crystallinity is less than 15%; the semi-aromatic amide salt is selected from amide salt 9T, amide salt 9I, amide salt 10T and amide salt 10I; and the aliphatic amide salt is selected from amide salt 610 and amide salt 1010. The preparation method comprises the following steps: adding the semi-aromatic amide salt, aliphatic amide salt and auxiliaries into a polymerization kettle; adding water which is 0.3-1.0 times the total mass of the semi-aromatic amide salt and aliphatic amide salt; in a protective gas atmosphere, stirring and heating to 160-210 DEG C within 1-2 hours, and performing constant-temperature pre-polymerization for 1-3 hours; heating to 240-300 DEG C, increasing pressure to 1-3MPa, and maintaining the pressure for reaction for 1-3 hours; slowly degassing to normal pressure within 1-4 hours; continuously stirring at constant temperature for 1-4 hours; and discharging after the reaction.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of semi-aromatic transparent polyamide material, also relate to the preparation method of this polyamide material simultaneously.
Background technology
Transparent polyamide is except transparent excellence, the performance that also there are many excellences, such as: Heat stability is good, physical strength is high, electrical insulating property good, wear-resisting, resistance to chemical attack, linear expansivity is little, molding shrinkage is low, good stability of the dimension, easily machine-shaping, nontoxic, odorless, barrier propterty and surface property superior etc., therefore in the fields such as wrapping material, frame, high-grade sports equipment and automobile component of precision optical instrument, measuring instrument, medication chemistry, all be widely used.
At present, about the research of transparent polyamide, have a lot, for example:
Patent US6943231 is with 4,4 '-diamino-cyclohexyl-methane (PACM) and 4,4 ' diamino-3, the mixture of 3 '-dimethyl-dicyclohexyl methyl hydride (MACM) reacts with aliphatic dicarboxylic acid and has made the transparent polyamide with excellent transparency, chemical resistant properties and high long-time fatigue strength.
Patent CN1092087A makes semicrystalline polyamides with aliphatic units, m-phthalic acid and the terephthalic acid (latter is main) and the ring grease diamines that contain at least 7 carbon atoms.
Patent CN103073717A discloses with terephthalic acid and 2,2, the long carbochain semi-aromatic transparent polyamide that 4 one trimethylammonium hexanediamines (TMD), 11 1 aminoundecanoic acids, nucleator and deionized water are raw material production, its melt temperature is lower than 260 ℃, elongation at break is greater than 120%, and transmittance is greater than 90%.
It is raw material that patent CN101372531A be take dimeracid, aromatic acid and the aliphatics straight chain diamine of domestic cheapness, and melt phase polycondensation obtains a kind of copolyamide, and transmittance reaches more than 90%, has higher resistance toheat and moulding processability simultaneously.
The transparent principle of the described polymeric amide of above patent is all to have destroyed the regularity of macromolecular chain due to the existence of complicated side group or phenyl ring in macromolecular chain, causes the non-crystallizable or crystallite of polymeric amide, thereby transparent.But raw material is all diacid or the diamines that contains many side chains or ring texture, technique for producing raw material is complicated, price is higher, causes the transparent polyamide cost higher.Though patent CN101372531A has introduced a kind of method of utilizing domestic cheap raw material to prepare transparent polyamide, its thermal characteristics and Materials Fracture elongation are difficult to meet the needs of some occasions.In addition, above-mentioned transparent polyamide generally has rigidity preferably, but toughness is difficult to meet some industry needs.In fact, the common rigidity of polymeric amide of existing good toughness is poor, and most price of mechanical property excellence is more expensive or transparent undesirable.
At present, the technology of preparing of high-performance transparent polyamide rests in external colleague's hand mostly.Therefore, if can using the relatively inexpensive monomer of domestic industrialization as raw material, the synthetic a series of high-performance transparent polyamides that can meet various occasion demands of exploitation certainly will have very important realistic meaning.
Summary of the invention
The objective of the invention is for the good semi-aromatic transparent polyamide material of a kind of over-all properties and the preparation method of this polyamide material are provided.
Based on above-mentioned purpose, the present invention has taked following technical scheme:
A kind of semi-aromatic transparent polyamide material, be comprised of the random copolymers of semi-aromatic amide salt and aliphatic amide salt and necessary auxiliary agent, and its intrinsic viscosity is 1.0～2.2dl/g, and degree of crystallinity is less than 15%; Described semi-aromatic amide salt is selected from acid amides 9T salt (paraphenylene terephthalamide's nonamethylene diamine salt), acid amides 9I salt (isophthaloyl nonamethylene diamine salt), acid amides 10T salt (paraphenylene terephthalamide's decamethylene diamine salt) or acid amides 10I salt (isophthaloyl decamethylene diamine salt), and aliphatic amide salt is selected from acid amides 610 salt or acid amides 1010 salt.
Described semi-aromatic amide salt and aliphatic amide salt mass ratio are 3:7～8:2.
Described auxiliary agent comprises nucleator, and nucleator is selected from NP-508, NP-509 or KM-1300,0.01～0.45wt% that addition is semi-aromatic amide salt and aliphatic amide salt total amount.
Described auxiliary agent comprises antioxidant; antioxidant is selected from N; N'-pair-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, thio-2 acid dibasic acid esters, two Lauryl Alcohol ester, two ten four carbon alcohols esters, sodium phosphate or inferior sodium phosphate, 0.1～1wt% that addition is semi-aromatic amide salt and aliphatic amide salt total amount.
Described auxiliary agent comprises whitening agent, whitening agent is selected from 4, two (5 methyl-2-benzoxazolyl) toluylene, 1 of 4-, two (5-methyl-2-benzoxazoles) ethene or the 3-(4-chloro-phenyl-s of 2-)-1-(4-phenylbenzimidazole sulfonic acid), 0.01～0.09wt% that addition is semi-aromatic amide salt and aliphatic amide salt total amount.
The preparation method of described semi-aromatic transparent polyamide material, comprise the following steps: by the semi-aromatic amide salt, aliphatic amide salt and auxiliary agent add in polymeric kettle, add the water of 0.3～1.0 times of semi-aromatic amide salt and aliphatic amide salt total mass, under the shielding gas atmosphere, first stir and be warming up to 160 ℃～210 ℃ in 1～2h, constant temperature prepolymerization 1h～3h, then be heated to 240 ℃～300 ℃, boost to 1MPa～3MPa, pressurize reaction 1h～3h, in 1h～4h, slowly exit to normal pressure afterwards, continue constant temperature and stir 1h～4h, reaction finishes, discharging.
In described preparation method, shielding gas is nitrogen or carbonic acid gas.
It is raw material that semi-aromatic transparent polyamide material provided by the invention be take domestic commercial semi-aromatic amide salt and aliphatic amide salt, and its price is relatively low, can significantly reduce the production cost of the finished product.Simultaneously, it is raw material that this product is selected semi-aromatic amide salt and the long carbochain aliphatic amide salt that the carbochains such as acid amides 9T salt, 9I salt, 10T salt or 10I salt are longer, will a large amount of-CH
2-long carbochain joint is introduced in the polymeric amide molecular chain, can effectively reduce product flow temperature and water-intake rate, improves its processing characteristics and impelling strength.In addition, semi-aromatic amide salt and long carbochain aliphatic amide salt copolymerization meeting cause multipolymer macromolecular chain regularity to reduce, and cause its crystallizing power to descend; Adding of nucleator can effectively reduce grain-size, makes crystalline size be less than visible wavelength, thereby makes copolyamide present the excellent transparency.Simultaneously, suitably, appropriate nucleator can improve the whole crystallization rate of polymeric amide, be conducive to like this improve integrity and the stability of crystalline structure, reduce the goods subsurface defect, make goods stress distribution under external force more even, thereby improve its mechanical property, also can make its Tc improve simultaneously, promote resistance toheat.The raising of crystallization rate also makes the shaping cycle of goods shorten, and can enhance productivity.
In addition, add oxidation inhibitor and whitening agent in product, can strengthen the antioxidant property of product, improve outward appearance, thereby expand the Application Areas of product.
The test confirmation, transparent polyamide material transmittance provided by the invention can reach more than 90%, and more than tensile strength can reach 90MPa, elongation at break can reach more than 190%, and the Izod notched Izod impact strength can reach 9.0kJ/m
2above, also there is good thermotolerance and moulding processability simultaneously.
On the other hand, preparation method provided by the invention be take water as reaction medium and is added the nucleator crystal grain thinning, the good product performance of producing and solvent-free pollution; Simultaneously, whole reaction process is simple to operate, environmental protection, contributes to reduce production costs.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
embodiment 1
By 135.2g acid amides 10T salt and 202.8g acid amides 610 salt, 0.68g NP-508,1.02g N, N'-pair-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 0.68g inferior sodium phosphate, 0.10g4, two (5 methyl-2-benzoxazolyl) toluylene of 4-, 150 gram distilled water join in polymeric kettle, pass into 0.1MPa nitrogen after charging and discharging nitrogen three times, start to heat up; In 2h, temperature is elevated to 200 ℃, insulation 1h, progressively be warming up to 270 ℃ subsequently, and pressure rises to 2.5MPa, maintains 2h, in 1h, slowly exits to normal pressure afterwards, and after continuing constant temperature stirring 4h, discharging, obtain semiaromatic transparent co-polyamide P10TA.
embodiment 2
By 169g acid amides 10T salt and 169g acid amides 1010 salt, 0.51gNP-508,1.02gN, N'-pair-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 0.51g inferior sodium phosphate, 0.14g4, two (5 methyl-2-benzoxazolyl) toluylene of 4-, 200 gram distilled water join in polymeric kettle, charge and discharge nitrogen three times, then pass into 0.1MPa nitrogen, start to heat up; In 1h, temperature is elevated to 190 ℃, insulation 1.5h, progressively be warming up to 240 ℃ subsequently, and pressure rises to 3.0MPa, maintains 2.5h, in 2h, slowly exits to normal pressure afterwards, and after continuing constant temperature stirring 1.5h, discharging, obtain semiaromatic transparent co-polyamide P10TS.
embodiment 3
By 240g acid amides 10I salt and 160g acid amides 610 salt, 0.60gNP-509,1.80g inferior sodium phosphate, 0.12g4, two (5 methyl-2-benzoxazolyl) toluylene of 4-, 300 gram distilled water join in polymeric kettle, charge and discharge nitrogen three times, then pass into 0.1MPa nitrogen, start to heat up, in 2h, temperature is elevated to 200 ℃, insulation 3h; Progressively be warming up to subsequently 290 ℃, pressure rises to 1.5MPa, maintains 2h, in 3h, slowly exits to normal pressure afterwards, and after continuing constant temperature stirring 3h, discharging, obtain semiaromatic transparent co-polyamide P10IA.
embodiment 4
By 280g acid amides 10I salt and 70g acid amides 1010 salt, 0.53gNP-509,1.75g inferior sodium phosphate, 0.10g4, two (5 methyl-2-benzoxazolyl) toluylene of 4-, 250 gram distilled water join in polymeric kettle, charge and discharge carbonic acid gas three times, then pass into the 0.1MPa carbonic acid gas, start to heat up; In 2h, temperature is elevated to 210 ℃, insulation 1.5h, progressively be warming up to 280 ℃ subsequently, and pressure rises to 1.0MPa, maintains 2.5h, in 3h, slowly exits to normal pressure afterwards, and after continuing constant temperature stirring 1h, discharging, obtain semiaromatic transparent co-polyamide P10IS.
embodiment 5
By 200g acid amides 9T salt and 200g acid amides 610 salt, 1.80gKM-1300,3.3gN, N'-pair-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 0.70g inferior sodium phosphate, 0.36g1, two (5-methyl-2-benzoxazoles) ethene of 2-, 200 gram distilled water join in polymeric kettle, charge and discharge carbonic acid gas three times, then pass into the 0.1MPa carbonic acid gas, start to heat up; In 1.5h, temperature is elevated to 180 ℃, insulation 2.0h, progressively be warming up to 290 ℃ subsequently, and pressure rises to 1.8MPa, maintains 1.5h, in 2h, slowly exits to normal pressure afterwards, and after continuing constant temperature stirring 2h, discharging, obtain semiaromatic transparent co-polyamide P9TA.
embodiment 6
By 150g acid amides 9T salt and 350g acid amides 1010 salt, 0.50gKM-1300,3.0gN, N'-pair-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 0.50g inferior sodium phosphate, 0.36g1, two (5-methyl-2-benzoxazoles) ethene of 2-, 250 gram distilled water join in polymeric kettle, charge and discharge carbonic acid gas three times, then pass into the 0.1MPa carbonic acid gas, start to heat up; In 2h, temperature is elevated to 210 ℃, insulation 1.5h, progressively be warming up to 290 ℃ subsequently, and pressure rises to 2.0MPa, maintains 2h, in 4h, slowly exits to normal pressure afterwards, and after continuing constant temperature stirring 1.5h, discharging, obtain semiaromatic transparent co-polyamide P9TS.
embodiment 7
By 385g acid amides 9I salt and 165g acid amides 1010 salt, 1.65gNP-509,1.10gN, N'-pair-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 0.55g inferior sodium phosphate, 0.22g4, two (5 methyl-2-benzoxazolyl) toluylene of 4-, 200 gram distilled water join in polymeric kettle, charge and discharge carbonic acid gas three times, then pass into the 0.1MPa carbonic acid gas, start to heat up; In 2h, temperature is elevated to 210 ℃, insulation 2.5h, progressively be warming up to 300 ℃ subsequently, and pressure rises to 3.0MPa, maintains 1h, in 3h, slowly exits to normal pressure afterwards, and after continuing constant temperature stirring 1h, discharging, obtain semiaromatic transparent co-polyamide P9IS.
embodiment 8
By 120g acid amides 10T salt, 160g acid amides 10I salt and 120g acid amides 610 salt, 0.80gNP-508,2.0g inferior sodium phosphate, 0.12g1, two (5-methyl-2-benzoxazoles) ethene of 2-, 400 gram distilled water join in polymeric kettle, charge and discharge nitrogen three times, then pass into 0.1MPa nitrogen, start to heat up; In 1h, temperature is elevated to 200 ℃, insulation 2h, progressively be warming up to 300 ℃ subsequently, and pressure rises to 2.0MPa, maintains 2h, in 3h, slowly exits to normal pressure afterwards, and after continuing constant temperature stirring 2h, discharging, obtain semiaromatic transparent co-polyamide P10ITA.
embodiment 9
By 120g acid amides 10T salt, 160g acid amides 10I salt and 120g acid amides 1010 salt, 0.80gNP-508,1.20gN, N'-pair-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 0.80g inferior sodium phosphate, 0.16g4, two (5 methyl-2-benzoxazolyl) toluylene of 4-, 150 gram distilled water join in polymeric kettle, charge and discharge nitrogen three times, then pass into 0.1MPa nitrogen, start to heat up; In 1h, temperature is elevated to 160 ℃, insulation 2h, progressively be warming up to 300 ℃ subsequently, and pressure rises to 2.0MPa, maintains 2h, in 3h, slowly exits to normal pressure afterwards, and after continuing constant temperature stirring 2h, discharging, obtain semiaromatic transparent co-polyamide P10ITS.
The semiaromatic transparent polyamide material that embodiment 1-9 is made carries out performance test, and measurement result is in Table 1.
The properties of the prepared semiaromatic transparent co-polyamide of table 1 embodiment 1～9
As can be seen from Table 1, utilize method of the present invention to prepare transparent co-polyamide, products obtained therefrom has good over-all properties, and raw material is domestic relatively inexpensive semi-aromatic amide salt and aliphatic amide salt, take water as medium, and production technique is simple, and the shaping cycle of goods is short, production efficiency is high, greatly reduces production cost.
Claims (7)
1. a semi-aromatic transparent polyamide material, is characterized in that, the random copolymers of semi-aromatic amide salt and aliphatic amide salt and necessary auxiliary agent, consists of, and its intrinsic viscosity is 1.0～2.2dl/g, and degree of crystallinity is less than 15%; Described semi-aromatic amide salt is selected from acid amides 9T salt, acid amides 9I salt, acid amides 10T salt or acid amides 10I salt, and aliphatic amide salt is selected from acid amides 610 salt or acid amides 1010 salt.
2. semi-aromatic transparent polyamide material as claimed in claim 1, is characterized in that, described semi-aromatic amide salt and aliphatic amide salt mass ratio are 3:7～8:2.
3. semi-aromatic transparent polyamide material as claimed in claim 1, it is characterized in that, described auxiliary agent comprises nucleator, and nucleator is selected from NP-508, NP-509 or KM-1300,0.01～0.45wt% that addition is semi-aromatic amide salt and aliphatic amide salt total amount.
4. semi-aromatic transparent polyamide material as claimed in claim 1; it is characterized in that; described auxiliary agent comprises antioxidant; antioxidant is selected from N; N'-pair-(3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, thio-2 acid dibasic acid esters, two Lauryl Alcohol ester, two ten four carbon alcohols esters, sodium phosphate or inferior sodium phosphate, 0.1～1wt% that addition is semi-aromatic amide salt and aliphatic amide salt total amount.
5. semi-aromatic transparent polyamide material as claimed in claim 1, it is characterized in that, described auxiliary agent comprises whitening agent, whitening agent is selected from 4, two (5 methyl-2-benzoxazolyl) toluylene, 1 of 4-, two (5-methyl-2-benzoxazoles) ethene or the 3-(4-chloro-phenyl-s of 2-)-1-(4-phenylbenzimidazole sulfonic acid), 0.01～0.09wt% that addition is semi-aromatic amide salt and aliphatic amide salt total amount.
6. the preparation method of the arbitrary described semi-aromatic transparent polyamide material of claim 1-5, it is characterized in that, comprise the following steps: by the semi-aromatic amide salt, aliphatic amide salt and auxiliary agent add in polymeric kettle, add the water of 0.3～1.0 times of semi-aromatic amide salt and aliphatic amide salt total mass, under the shielding gas atmosphere, stir and be warming up to 160 ℃～210 ℃ in 1～2h, constant temperature prepolymerization 1h～3h, then be heated to 240 ℃～300 ℃, boost to 1MPa～3MPa, pressurize reaction 1h～3h, in 1h～4h, slowly exit to normal pressure afterwards, continue constant temperature and stir 1h～4h, reaction finishes, discharging.
7. the preparation method of semi-aromatic transparent polyamide material as claimed in claim 6, is characterized in that, described shielding gas is nitrogen or carbonic acid gas.
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| CN105330843A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | Semi-aromatic transparent nylon and preparing method thereof |
| CN105400190A (en) * | 2015-11-27 | 2016-03-16 | 昆山幻彩塑胶科技有限公司 | High-rigidity polyamide reinforced material |
| CN106928450A (en) * | 2015-12-30 | 2017-07-07 | 上海杰事杰新材料(集团)股份有限公司 | A kind of high temperature resistant bio-based PA10T copolymer materials and preparation method thereof |
| CN107337794A (en) * | 2017-07-07 | 2017-11-10 | 株洲时代新材料科技股份有限公司 | A kind of copolymer nylon containing hexatomic ring and preparation method thereof |
| CN109970970A (en) * | 2019-04-18 | 2019-07-05 | 东华大学 | A kind of high-strength and high ductility transparent nylon material and its preparation and application |
| CN112920400A (en) * | 2020-12-29 | 2021-06-08 | 深圳市华盈新材料有限公司 | Bio-based semi-aromatic polyamide copolymer and preparation method, composition and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112920400A (en) * | 2020-12-29 | 2021-06-08 | 深圳市华盈新材料有限公司 | Bio-based semi-aromatic polyamide copolymer and preparation method, composition and application thereof |
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