CN103435796B - A kind of Semi-aromatic transparent polyamide material and preparation method thereof - Google Patents
A kind of Semi-aromatic transparent polyamide material and preparation method thereof Download PDFInfo
- Publication number
- CN103435796B CN103435796B CN201310403079.8A CN201310403079A CN103435796B CN 103435796 B CN103435796 B CN 103435796B CN 201310403079 A CN201310403079 A CN 201310403079A CN 103435796 B CN103435796 B CN 103435796B
- Authority
- CN
- China
- Prior art keywords
- salt
- semi
- amide salt
- aromatic
- acid amides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
A kind of Semi-aromatic transparent polyamide material and preparation method thereof, belong to polymeric material field, this material is made up of semi-aromatic amide salt and the random copolymers of aliphatic amide salt and the auxiliary agent of necessity, 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; Its preparation process is: add in polymeric kettle by semi-aromatic amide salt, aliphatic amide salt and auxiliary agent; add the water of semi-aromatic amide salt and aliphatic amide salt total mass 0.3 ~ 1.0 times; under shielding gas atmosphere; stir in 1 ~ 2h and be warming up to 160 DEG C ~ 210 DEG C, constant temperature prepolymerization 1h ~ 3h; then be heated to 240 DEG C ~ 300 DEG C, boost to 1MPa ~ 3MPa; pressurize reaction 1h ~ 3h; slowly exit to normal pressure in 1h ~ 4h afterwards; continue constant temperature and stir 1h ~ 4h, reaction end, discharging.
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, also there is the performance of many excellences, such as: Heat stability is good, physical strength are 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 are superior, be therefore all widely used in fields such as the wrapping material of precision optical instrument, measuring instrument, medication chemistry, frame, high-grade sports equipment and automobile component.
At present, the research about transparent polyamide has a lot, such as:
Patent US6943231 is with 4,4 '-diamino-cyclohexyl-methane (PACM) and 4, mixture and the aliphatic dicarboxylic acid of 4 ' diamino-3,3 '-dimethyl-dicyclohexyl methyl hydride (MACM) react the transparent polyamide having obtained and had excellent transparency, chemical resistant properties and high long-time fatigue strength.
The aliphatic units of patent CN1092087A containing at least 7 carbon atoms, m-phthalic acid and terephthalic acid (the latter is main) and ring grease diamines obtain semicrystalline polyamides.
Patent CN103073717A discloses with terephthalic acid and 2,2,4 one trimethylhexane diamine (TMD), 11 1 aminoundecanoic acids, nucleator and deionized water are the PATMDT/11 of raw material production, its melt temperature is lower than 260 DEG C, elongation at break is greater than 120%, and transmittance is greater than 90%.
Patent CN101372531A is with the dimeracid of domestic cheapness, aromatic acid and acyclic straight diamine for raw material, 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 polymeric amide described in above patent is all because in macromolecular chain, the existence of complicated side base or phenyl ring destroys the regularity of macromolecular chain, causes the non-crystallizable or crystallite of polymeric amide, thus transparent.But raw material is all diacid containing many side chains or ring texture or diamines, and technique for producing raw material is complicated, price is higher, causes transparent polyamide cost higher.Though patent CN101372531A describes a kind of method utilizing domestic cheap raw material to prepare transparent polyamide, its thermal characteristics and Materials Fracture elongation are difficult to the needs meeting some occasions.In addition, above-mentioned transparent polyamide generally has good rigidity, but toughness is difficult to meet some industry needs.In fact, the usual rigidity of polymeric amide of existing good toughness is poor, and most price of excellent in mechanical performance is then 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, a series of high-performance transparent polyamide that can meet various occasion demand of exploitation synthesis certainly will have very important realistic meaning.
Summary of the invention
The object of the invention is the preparation method of Semi-aromatic transparent polyamide material in order to provide a kind of over-all properties good and this polyamide material.
Based on above-mentioned purpose, this invention takes following technical scheme:
A kind of Semi-aromatic transparent polyamide material, be made up of semi-aromatic amide salt and the random copolymers of aliphatic amide salt and the auxiliary agent of necessity, 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, and addition is 0.01 ~ 0.45wt% of semi-aromatic amide salt and aliphatic amide salt total amount.
Described auxiliary agent comprises antioxidant; antioxidant is selected from N; N'-pair-(3-(3; 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, addition is 0.1 ~ 1wt% of 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 of 2-or 3-(4-chloro-phenyl-)-1-(4-phenylbenzimidazole sulfonic acid), addition is 0.01 ~ 0.09wt% of 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 semi-aromatic amide salt, aliphatic amide salt and auxiliary agent add in polymeric kettle, add the water of semi-aromatic amide salt and aliphatic amide salt total mass 0.3 ~ 1.0 times, under shielding gas atmosphere, first stir in 1 ~ 2h and be warming up to 160 DEG C ~ 210 DEG C, constant temperature prepolymerization 1h ~ 3h, then 240 DEG C ~ 300 DEG C are heated to, boost to 1MPa ~ 3MPa, pressurize reaction 1h ~ 3h, slowly exit to normal pressure in 1h ~ 4h afterwards, continue constant temperature and stir 1h ~ 4h, reaction terminates, discharging.
In described preparation method, shielding gas is nitrogen or carbonic acid gas.
Commercial semi-aromatic amide salt and aliphatic amide salt are for raw material with domestic for Semi-aromatic transparent polyamide material provided by the invention, and its price is relatively low, significantly can reduce the production cost of the finished product.Meanwhile, this product selects semi-aromatic amide salt that the carbochains such as acid amides 9T salt, 9I salt, 10T salt or 10I salt are longer and Long carbon chain aliphatic amide salt to be raw material, will a large amount of-CH
2-Long carbon chain joint is introduced in polyamide molecule chain, can effectively reduce product flow temperature and water-intake rate, improve its processing characteristics and impelling strength.In addition, semi-aromatic amide salt and the copolymerization of Long carbon chain aliphatic amide salt can cause multipolymer macromolecular chain regularity to reduce, and cause its crystallizing power to decline; Adding of nucleator, can grain-size be effectively reduced, make crystalline size be less than visible wavelength, thus make copolyamide present the excellent transparency.Simultaneously, suitably, appropriate nucleator can improve the overall crystallization rate of polymeric amide, be conducive to the integrity and the stability that improve crystalline structure like this, reduce goods subsurface defect, make goods stress distribution under external force more even, thus improve its mechanical property, its Tc also can be made simultaneously to improve, 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 the product, the antioxidant property of product can be strengthened, improve outward appearance, thus expand the Application Areas of product.
Test confirms, transparent polyamide material transmissivity provided by the invention can reach more than 90%, and tensile strength can reach more than 90MPa, and elongation at break can reach more than 190%, 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 is reaction medium with water and adds nucleator crystal grain thinning, the good product performance produced and solvent-free pollution; Meanwhile, whole reaction process is simple to operate, environmental protection, contributes to reducing production cost.
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, 0.68gNP-508,1.02gN, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 0.68g inferior sodium phosphate, 0.10g4, two (5 methyl-2-benzoxazolyl) toluylene of 4-, 150 grams of distilled water join in polymeric kettle, pass into 0.1MPa nitrogen after charge and discharge nitrogen three times, start to heat up; In 2h, temperature is elevated to 200 DEG C, insulation 1h, be progressively warming up to 270 DEG C subsequently, pressure rises to 2.5MPa, maintains 2h, and in 1h, slowly venting is to normal pressure afterwards, and after continuation constant temperature stirs 4h, discharging, obtains 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-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 0.51g inferior sodium phosphate, 0.14g4, two (5 methyl-2-benzoxazolyl) toluylene of 4-, 200 grams of 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 DEG C, insulation 1.5h, be progressively warming up to 240 DEG C subsequently, pressure rises to 3.0MPa, maintains 2.5h, and in 2h, slowly venting is to normal pressure afterwards, and after continuation constant temperature stirs 1.5h, discharging, obtains 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 grams of distilled water join in polymeric kettle, charge and discharge nitrogen three times, then 0.1MPa nitrogen is passed into, start to heat up, in 2h, temperature is elevated to 200 DEG C, insulation 3h; Progressively be warming up to 290 DEG C subsequently, pressure rises to 1.5MPa, maintains 2h, and in 3h, slowly venting is to normal pressure afterwards, and after continuing constant temperature stirring 3h, discharging, obtains 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 grams of distilled water join in polymeric kettle, charge and discharge carbonic acid gas three times, then pass into 0.1MPa carbonic acid gas, start to heat up; In 2h, temperature is elevated to 210 DEG C, insulation 1.5h, be progressively warming up to 280 DEG C subsequently, pressure rises to 1.0MPa, maintains 2.5h, and in 3h, slowly venting is to normal pressure afterwards, and after continuation constant temperature stirs 1h, discharging, obtains 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-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 0.70g inferior sodium phosphate, 0.36g1, two (5-methyl-2-benzoxazoles) ethene of 2-, 200 grams of distilled water join in polymeric kettle, charge and discharge carbonic acid gas three times, then pass into 0.1MPa carbonic acid gas, start to heat up; In 1.5h, temperature is elevated to 180 DEG C, insulation 2.0h, be progressively warming up to 290 DEG C subsequently, pressure rises to 1.8MPa, maintains 1.5h, and in 2h, slowly venting is to normal pressure afterwards, and after continuation constant temperature stirs 2h, discharging, obtains 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-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 0.50g inferior sodium phosphate, 0.36g1, two (5-methyl-2-benzoxazoles) ethene of 2-, 250 grams of distilled water join in polymeric kettle, charge and discharge carbonic acid gas three times, then pass into 0.1MPa carbonic acid gas, start to heat up; In 2h, temperature is elevated to 210 DEG C, insulation 1.5h, be progressively warming up to 290 DEG C subsequently, pressure rises to 2.0MPa, maintains 2h, and in 4h, slowly venting is to normal pressure afterwards, and after continuation constant temperature stirs 1.5h, discharging, obtains 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-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 0.55g inferior sodium phosphate, 0.22g4, two (5 methyl-2-benzoxazolyl) toluylene of 4-, 200 grams of distilled water join in polymeric kettle, charge and discharge carbonic acid gas three times, then pass into 0.1MPa carbonic acid gas, start to heat up; In 2h, temperature is elevated to 210 DEG C, insulation 2.5h, be progressively warming up to 300 DEG C subsequently, pressure rises to 3.0MPa, maintains 1h, and in 3h, slowly venting is to normal pressure afterwards, and after continuation constant temperature stirs 1h, discharging, obtains 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 grams of 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 DEG C, insulation 2h, be progressively warming up to 300 DEG C subsequently, pressure rises to 2.0MPa, maintains 2h, and in 3h, slowly venting is to normal pressure afterwards, and after continuation constant temperature stirs 2h, discharging, obtains 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-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine, 0.80g inferior sodium phosphate, 0.16g4, two (5 methyl-2-benzoxazolyl) toluylene of 4-, 150 grams of 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 DEG C, insulation 2h, be progressively warming up to 300 DEG C subsequently, pressure rises to 2.0MPa, maintains 2h, and in 3h, slowly venting is to normal pressure afterwards, and after continuation constant temperature stirs 2h, discharging, obtains semiaromatic transparent co-polyamide P10ITS.
The semiaromatic transparent polyamide material obtained to embodiment 1-9 carries out performance test, and measurement result is in table 1.
The properties of semiaromatic transparent co-polyamide prepared by table 1 embodiment 1 ~ 9
As can be seen from Table 1, method of the present invention is utilized to prepare transparent co-polyamide, products obtained therefrom has excellent over-all properties, and raw material is domestic relatively inexpensive semi-aromatic amide salt and aliphatic amide salt, take water as medium, production technique is simple, and the shaping cycle of goods is short, production efficiency is high, greatly reduces production cost.
Claims (4)
1. a Semi-aromatic transparent polyamide material, is characterized in that, be made up of the random copolymers of semi-aromatic amide salt and aliphatic amide salt and nucleator, antioxidant, whitening agent, 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;
Nucleator is selected from NP-508, NP-509 or KM-1300, and addition is 0.01 ~ 0.45wt% of semi-aromatic amide salt and aliphatic amide salt total amount;
Antioxidant is selected from N, N'-pair-(3-(3,5-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, addition is 0.1 ~ 1wt% of semi-aromatic amide salt and aliphatic amide salt total amount;
Whitening agent is selected from 4, two (5 methyl-2-benzoxazolyl) toluylene, 1 of 4-, two (5-methyl-2-benzoxazoles) ethene of 2-or 3-(4-chloro-phenyl-)-1-(4-phenylbenzimidazole sulfonic acid), addition is 0.01 ~ 0.09wt% of semi-aromatic amide salt and aliphatic amide salt total amount.
2. Semi-aromatic transparent polyamide material as claimed in claim 1, it is characterized in that, described semi-aromatic amide salt and aliphatic amide salt mass ratio are 3:7 ~ 8:2.
3. the preparation method of Semi-aromatic transparent polyamide material described in claim 1 or 2, it is characterized in that, comprise the following steps: by semi-aromatic amide salt, aliphatic amide salt and auxiliary agent add in polymeric kettle, add the water of semi-aromatic amide salt and aliphatic amide salt total mass 0.3 ~ 1.0 times, under shielding gas atmosphere, stir in 1 ~ 2h and be warming up to 160 DEG C ~ 210 DEG C, constant temperature prepolymerization 1h ~ 3h, then 240 DEG C ~ 300 DEG C are heated to, boost to 1MPa ~ 3MPa, pressurize reaction 1h ~ 3h, slowly exit to normal pressure in 1h ~ 4h afterwards, continue constant temperature and stir 1h ~ 4h, reaction terminates, discharging.
4. the preparation method of Semi-aromatic transparent polyamide material as claimed in claim 3, it is characterized in that, described shielding gas is nitrogen or carbonic acid gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310403079.8A CN103435796B (en) | 2013-09-06 | 2013-09-06 | A kind of Semi-aromatic transparent polyamide material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310403079.8A CN103435796B (en) | 2013-09-06 | 2013-09-06 | A kind of Semi-aromatic transparent polyamide material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103435796A CN103435796A (en) | 2013-12-11 |
| CN103435796B true CN103435796B (en) | 2015-12-09 |
Family
ID=49689523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310403079.8A Active CN103435796B (en) | 2013-09-06 | 2013-09-06 | A kind of Semi-aromatic transparent polyamide material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103435796B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105330843B (en) * | 2015-11-30 | 2017-12-05 | 江门市优巨新材料有限公司 | A kind of semi-aromatic transparent nylon and preparation method thereof |
| 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 |
| CN107337794B (en) * | 2017-07-07 | 2020-07-17 | 株洲时代新材料科技股份有限公司 | Copolymerized nylon containing six-membered 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284830B1 (en) * | 1997-07-21 | 2001-09-04 | Basf Aktiengesellschaft | Molding compositions comprising random copolyamides, their use, and process for their preparation |
| CN1537881A (en) * | 2003-04-18 | 2004-10-20 | 上海杰事杰新材料股份有限公司 | High-toughness semi-aromatic nylon and its preparation method |
| CN102477219A (en) * | 2010-11-29 | 2012-05-30 | 上海杰事杰新材料(集团)股份有限公司 | High-temperature resistant semi-aromatic nylon and its preparation method |
-
2013
- 2013-09-06 CN CN201310403079.8A patent/CN103435796B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284830B1 (en) * | 1997-07-21 | 2001-09-04 | Basf Aktiengesellschaft | Molding compositions comprising random copolyamides, their use, and process for their preparation |
| CN1537881A (en) * | 2003-04-18 | 2004-10-20 | 上海杰事杰新材料股份有限公司 | High-toughness semi-aromatic nylon and its preparation method |
| CN102477219A (en) * | 2010-11-29 | 2012-05-30 | 上海杰事杰新材料(集团)股份有限公司 | High-temperature resistant semi-aromatic nylon and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 多元共缩聚透明聚酞胺的制备、结构与性能;李巍;《中国优秀硕士学位论文全文数据库》;CNKI;20130415;第1.3.3节,第2.1节,第2.3.2节,第2.3.3节,第3.1.3节,第3.1.4节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103435796A (en) | 2013-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103435796B (en) | A kind of Semi-aromatic transparent polyamide material and preparation method thereof | |
| CN105330843B (en) | A kind of semi-aromatic transparent nylon and preparation method thereof | |
| TWI829632B (en) | Copolyamides containing dimeric fatty acid as monomer | |
| CN102666652B (en) | Semiaromatic polyamide, process for preparing same, composition comprising such a polyamide and uses thereof | |
| CN108047444B (en) | Semi-aromatic transparent copolymerized polyamide material and preparation method thereof | |
| CN105492537B (en) | Carbon-fiber reinforced resins composition, pellet, products formed and casting of electronic device | |
| EP2875063B1 (en) | Polyamide, method of its preparation and uses thereof | |
| CN103429657B (en) | Resin combination and molding thereof | |
| US9376535B2 (en) | Branched polyamide with different blocks | |
| CN104163918A (en) | High-temperature-resistant nylon PA66T material and preparation method thereof | |
| CN104774454B (en) | A kind of high temperature resistant nylon PA66T materials and preparation method thereof | |
| CN108424641A (en) | A kind of semiaromatic polyamide composition and preparation method thereof of random copolymerization toughening | |
| EP2749586B1 (en) | Crystalline polyamide ester resin, method for preparing the same, and article including the same | |
| EP2563840B1 (en) | Semi-aromatic polyamide | |
| CN113150269A (en) | Semi-aromatic polyamide copolymer and preparation thereof | |
| JP2015528521A (en) | Copolyamide, composition containing the copolyamide and use thereof | |
| CN113444241A (en) | Polyamide and preparation method thereof | |
| CN107446129A (en) | A kind of preparation method of anti-aging semi-aromatic nylon resin | |
| CN101560327A (en) | Method for preparing polyaniline/nylon 66 conductive composite material | |
| CN105330847A (en) | Synthetic method of high-fluidity transparent polyamide | |
| CN104098765A (en) | Synthesis method for biologically based transparent semi-aromatic poly-amide material | |
| CN103965467A (en) | Tough nylon and preparation method thereof | |
| CN103102647B (en) | Preparation method of polyester film with high heat shrinkage | |
| CN108264741A (en) | A kind of liquid crystal polyester/nylon composite materials and preparation method thereof | |
| KR101397703B1 (en) | Polyamide resin, a method for preparing the same, and an article comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |