WO2008038532A1 - Procédé de production de particules sphériques de polyamide présentant une propriété de fusion améliorée - Google Patents

Procédé de production de particules sphériques de polyamide présentant une propriété de fusion améliorée Download PDF

Info

Publication number
WO2008038532A1
WO2008038532A1 PCT/JP2007/068010 JP2007068010W WO2008038532A1 WO 2008038532 A1 WO2008038532 A1 WO 2008038532A1 JP 2007068010 W JP2007068010 W JP 2007068010W WO 2008038532 A1 WO2008038532 A1 WO 2008038532A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamide particles
particles
spherical
producing
polyamide
Prior art date
Application number
PCT/JP2007/068010
Other languages
English (en)
Japanese (ja)
Inventor
Kenji Yamasaki
Original Assignee
Sumika Enviro-Science Company, Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP2006259907A external-priority patent/JP5288361B2/ja
Priority claimed from JP2007020364A external-priority patent/JP5334233B2/ja
Application filed by Sumika Enviro-Science Company, Limited filed Critical Sumika Enviro-Science Company, Limited
Publication of WO2008038532A1 publication Critical patent/WO2008038532A1/fr

Links

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
    • C08G69/46—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a method for producing spherical polyamide particles having improved meltability, and use of polyamide particles obtained by the production method for a laser sintered body.
  • a method of obtaining a molded body (laser-sintered body) by laser sintering of spherical polyamide particles is known.
  • spherical polyamide particles that can be used in this method Japanese Patent Application Laid-Open No. 2000-07096 discloses spherical polyamide particles having an average particle diameter of 10 to 100 / m, and their The manufacturing method is described. Disclosure of the invention
  • this polyamide particle is spherical and has a narrow particle size distribution, its meltability is insufficient, so that the density, hardness and toughness of the obtained laser sintered body are insufficient. Have the problem.
  • an object of the present invention is to provide a method for producing spherical polyamide particles having a narrow melting point width and a narrow particle size distribution and having improved meltability, and laser firing of polyamide particles obtained by the production method. It is to provide a use for ligation.
  • spherical polyamide particles having improved meltability can be obtained by hydrolyzing spherical polyamide particles in an aqueous medium while maintaining their shape to lower the melting point of the polyamide particles.
  • the present invention is a method for producing a polyamide particle having a melting point lower than that of the polyamide particle, comprising a step of hydrolyzing the spherical polyamide particle in an aqueous medium while maintaining its shape.
  • the present invention is also a laser-sintering powder containing the polyamide particles obtained by the above production method.
  • the present invention is further a method for producing a laser sintered body comprising the following steps: Step 1 Spherical polyamido particles are hydrolyzed in an aqueous medium while maintaining their shape, and are lower than the polyamido particles. Producing polyamide particles having a melting point; and
  • Step 2 A step of laser sintering the polyamide particles.
  • the spherical polyamide particles used in the present invention may be known polyamide particles.
  • the polyamide particles are disclosed in Japanese Patent Application Laid-Open Nos. 4-7-2 5 1 57, Japanese Patent Application Laid-Open No. 2 00 0-2 4 8 061 and Japanese Patent Application Laid-Open No. 2 05- 3 0 7 0 96. It can be obtained by a production method described in a document such as a publication.
  • a lactam having 6 to 12 carbon atoms preferably at least one lactam selected from the group consisting of laurolactam and a lactam having 6 to 8 carbon atoms is used.
  • polyamides applied to polyamide particles include polylaurolactam, polyheptolactam, polycaprolactam, copolymer of laurolactam and heptactam, copolymer of laurolactam and force prolactam, and copolymer of heptlactam and caprolactam. Examples thereof include a polymer and a copolymer of laurolactam, heptolactam, and caprolactam.
  • the particle size of the spherical polyamide particles used in the present invention is preferably Or 3 to 200 xm, particularly preferably 15 to L50 m, and the average particle diameter is 6 to 150 m, preferably 20 to 100 m.
  • 90% by weight or more of the particles constituting the polyamide particles have a particle size in the range of 1/2 to 2 times the average particle size.
  • the term “spherical” above does not mean a spherical shape at a mathematically exact level, but means a spherical shape at a level possessed by the spherical polyamide particles disclosed in each of the above patent publications.
  • the amount of water as a medium in the present invention is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight with respect to 1 part by weight of the polyamide particles used.
  • the amount exceeds 20 parts by weight the volumetric efficiency of the hydrolysis reactor is deteriorated, and the separation of water and the reaction product is troublesome.
  • the amount is less than 1 part by weight, it is difficult to stir the reactor.
  • the hydrolysis in the present invention is preferably carried out in the presence of a hydrolysis catalyst for promoting the hydrolysis reaction.
  • the catalyst may be a known catalyst.
  • the hydrolysis catalyst include hydrolase, organic acid and inorganic acid.
  • the organic acid is preferably an organic acid having 1 to 4 carbon atoms such as formic acid, acetic acid and propionic acid.
  • the inorganic acid is preferably sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid. Of these, sulfuric acid, hydrochloric acid or nitric acid is particularly preferred from the viewpoint of the activity of the hydrolysis reaction and economic efficiency.
  • These catalysts may be used in combination of two or more.
  • the amount of the catalyst used is usually preferably 0.1 to 10 equivalents, more preferably 0.3 to 5.0 equivalents, per mole of amide bond contained in the polyamide particles used.
  • Water as a medium in the present invention is preferably used in combination with an alcohol or a surfactant in order to improve the affinity with polyamide particles.
  • the alcohol include lower alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol. These alcohols may be used in combination of two or more.
  • surfactants include anionic surfactants, nonionic surfactants and cationic surfactants. Can do. Among these, nonionic surfactants are preferred from the viewpoint of improving the stability to hydrolysis catalysts and the wettability of the polyamide particles used.
  • Polyoxyethylene alkylphenols as nonionic surfactants Polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ether, and polyoxyethylene alkenyl ether. These surfactants may be used in combination of two or more.
  • the amount of alcohol used is preferably 5 to 20 parts by weight with respect to 100 parts by weight of water as a medium from the viewpoint of improving the wettability of the polyamide particles used.
  • the amount of the surfactant used is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of water as a medium, from the same viewpoint as the preparation of alcohol.
  • the amount used is less than 0.05 parts by weight, dispersion of the polyamide particles used in water may deteriorate, and when it exceeds 5 parts by weight, foaming during the hydrolysis reaction increases. There is a case.
  • the reaction temperature for hydrolysis is a temperature lower than the melting point of the polyamide particles obtained by the reaction.
  • the reaction temperature is preferably 80 to 15 O: from the viewpoint of easy reaction operation and reaction control. If the reaction temperature is lower than 80, the reaction time may take a long time. When the reaction temperature is higher at 150, the reaction becomes complicated under high pressure, and the reaction becomes difficult because the reaction is difficult to control, resulting in poor physical properties of the resulting polyamide particles.
  • the hydrolysis reaction time may be appropriately selected according to conditions such as the type and concentration of the catalyst and the reaction temperature, and is preferably 4 to 24 hours from the viewpoint of ease of control of the reaction and economical efficiency. It is.
  • the meltability that is, the melting point of the polyamide particles obtained by hydrolysis can be easily determined by the type and amount of the hydrolysis catalyst and the temperature and time of the hydrolysis reaction. Can be controlled.
  • polyamide particles By treating the hydrolysis reaction mixture with ordinary separation and purification operations such as filtration, neutralization and washing, it is possible to isolate polyamide particles with improved meltability and spherical particle size distribution.
  • the polyamide particles may be decolorized with a decolorizing agent such as hydrogen peroxide.
  • the resulting polyamide particles can be used in combination with additives such as heat-resistant agents, UV absorbers, weathering agents, antistatic agents, lubricants, colorants, stabilizers and dispersants, and other powdered resin. Also good.
  • the laser sintering method in the method for producing a laser-sintered body of the present invention may be a known method.
  • Spherical polyamide particles having a narrow melting point width and a narrow particle size distribution obtained by the production method of the present invention and having improved meltability are formed by laser sintering to have a high density and good hardness and toughness.
  • Example 1 of Japanese Patent Laid-Open No. 2000-248 0 61 90 mol parts of laurolactam and 10 mol parts of force prolactam are copolymerized to have a melting point of 200 to 238.
  • spherical polyamide particles having an average particle diameter of 8 m were produced. 90% by weight or more of the particles have a particle diameter in the range of 6.8 to 10.3 m, that is, 2 times 1 (4 z / m) of the average particle diameter of 8 m.
  • the particle size was in the range of up to 6 m), and the particle size distribution was very sharp.
  • the melting point was measured by a method consisting of the following procedure:
  • Micro melting point measuring device MP-S 3 type force burglar made by Yanagimoto Seisakusho Co., Ltd. (2) raising the temperature of the particles at 10 to 2 Ot: / min;
  • the melting point is from the temperature at which the particles begin to melt to the temperature at which the whole becomes uniformly transparent.
  • the above particle diameter and particle size distribution were measured with a laser diffraction particle size distribution measuring device SAL D-2000 manufactured by Shimadzu Corporation.
  • Reference example 2
  • the product name made by ExxonMobil Chemical Co., Ltd. becomes Pegasol AS-1100 in a 100-m1 four-necked flask with a thermometer, dropping funnel, stirrer and nitrogen gas inlet. 408 g of isoparaffin, 106 g of Laurora cupum, 6.8 g of strength prolactam, 2.5 g of potassium metal, and 3.5 g of stearic acid were added. The resulting mixture was heated to 1 75 t with stirring at 500 rpm under a nitrogen stream.
  • the obtained polyamide particles had a melting point of 188 to 226 t: and an average particle size of 19 m. 90% by weight or more of the particles have a particle size within the range of 19 to 34 m, that is, from 1/2 (9.5 m) to twice the average particle size of 19 ⁇ m (38 m ) In the range up to The degree distribution was very sharp.
  • Reference example 3
  • Seed Example 2 except that the seed was changed to Pegazol AS-1 100 isoparaffin slurry 31.4 g containing 34.4% by weight of the polyamide particles produced in Reference Example 2. In the same manner as above, spherical polyamide particles were obtained with a yield of 85%.
  • the resulting polyamide particles had a melting point of 1 85 to 230 t: and an average particle size of 44 m. 90% by weight or more of the particles have a particle size in the range of 42 to 77 m, that is, a particle size in the range of 1/2 (22 zm) to twice (88 zm) the average particle size 44 Therefore, the particle size distribution was extremely sharp.
  • Example 1
  • Example 2 The reaction mixture was filtered to separate polyamide particles, and the separated particles were neutralized with an aqueous sodium carbonate solution. The particles were then washed in the order of water and isopropyl alcohol. The washed particles were dried to obtain particles maintaining the shape of the polyamide particles obtained in Reference Example 3 having a melting point of 170 to 172 and an average particle size of 44 m. The results are summarized in Table 1.
  • Example 2 The results are summarized in Table 1.
  • Example 3 A 1 N sulfuric acid aqueous solution containing 10% by weight of isopropyl alcohol was changed to a 1 N hydrochloric acid aqueous solution containing 10% by weight of isopropyl alcohol, and the melting point was 1 Particles that retain the shape of the polyamide particles obtained in Reference Example 3, with 67 to 1 7 2 and an average particle size of 44 // m I got a child. The results are summarized in Table 1.
  • Example 4 A 1 N sulfuric acid aqueous solution containing 10% by weight of isopropyl alcohol was changed to a 0.5 N hydrochloric acid aqueous solution containing 10% of isopropyl alcohol, and the melting point was 1 Particles having the shape of the polyamide particles obtained in Reference Example 3 having an average particle diameter of 6 5 to 1 7 3 and 44 / zm were obtained. The results are summarized in Table 1.
  • Example 4 A 1 N sulfuric acid aqueous solution containing 10% by weight of isopropyl alcohol was changed to a 0.5 N hydrochloric acid aqueous solution containing 10% of isopropyl alcohol, and the melting point was 1 Particles having the shape of the polyamide particles obtained in Reference Example 3 having an average particle diameter of 6 5 to 1 7 3 and 44 / zm were obtained. The results are summarized in Table 1. Example 4
  • Example 5 The same procedure as in Example 1 was conducted except that the 1 N sulfuric acid aqueous solution containing 10% by weight of isopropyl alcohol was changed to the 1 N phosphoric acid aqueous solution containing 10% by weight of isopropyl alcohol. Particles having the shape of the polyamide particles obtained in Reference Example 3 having an average particle diameter of 7 3 to 1 78 and an average particle diameter of 44 m were obtained. The results are summarized in Table 1. Example 5
  • Example 6 10 g of spherical polyamide particles obtained in Reference Example 3 and 100 g of 1 N sulfuric acid aqueous solution containing 10% by weight of isopropyl alcohol were set in a 300 m 1 set with a thermometer and a stirrer. Placed in a one-necked flask. This was hydrolyzed by heating at 89 to 92 for 24 hours to obtain a reaction mixture. The reaction mixture was filtered to separate spherical polyamide particles, and the separated particles were neutralized with an aqueous sodium carbonate solution. The particles were then washed in the order of water and isopropyl alcohol, respectively. The washed particles are dried to obtain particles having the same average particle diameter and shape, lower melting point (168-174) and narrower width than the polyamide particles used as raw materials. It was. The results are summarized in Table 2.
  • Example 7 10 g of spherical polyamide particles obtained in Reference Example 3 and 100 g of 1 N sulfuric acid aqueous solution containing 10% by
  • Example 8 The reaction mixture was filtered to separate spherical polyamide particles, and the separated particles were neutralized with an aqueous sodium carbonate solution. The particles were then washed in the order of water and isopropyl alcohol, respectively. The washed particles were dried to obtain particles maintaining the shape of the polyamide particles obtained in Reference Example 3 having a melting point of 166 to 17 2 t: and an average particle size of 44 / zm. The results are summarized in Table 3.
  • Example 8 The results are summarized in Table 3.
  • Example 9 (1) 1N sulfuric acid aqueous solution containing 0.26% by weight of Naroacti HN 9 5 was changed to 2N sulfuric acid aqueous solution containing 0.26% by weight of Naroacti HN 9 5; and (2) Hydrolysis The reaction time of was changed to 4 hours Except for the above, the same procedure as in Example 7 was carried out, and the particles having the melting point of 16 7 to 1 7 3 t: and the average particle size of 4 4 // m and retaining the shape of the polyamide particles obtained in Reference Example 3 were obtained. Obtained. The results are summarized in Table 3. Example 9
  • Example 1 2 The same procedure as in Example 1 was performed except that the spherical polyamide particles obtained in Reference Example 3 were changed to the spherical polyamide particles obtained in Reference Example 1, and the average particle size was compared with the polyamide particles used as a raw material. And particles of the same shape, lower melting point (from 1 68 to 1 74) and narrower width. The results are summarized in Table 5.
  • Example 1 2 The same procedure as in Example 1 was performed except that the spherical polyamide particles obtained in Reference Example 3 were changed to the spherical polyamide particles obtained in Reference Example 1, and the average particle size was compared with the polyamide particles used as a raw material. And particles of the same shape, lower melting point (from 1 68 to 1 74) and narrower width. The results are summarized in Table 5.
  • Example 1 2 The same procedure as in Example 1 was performed except that the spherical polyamide particles obtained in Reference Example 3 were changed to the spherical polyamide particles obtained in Reference Example 1, and the average particle size was compared with
  • Example 1 3 The same procedure as in Example 1 was performed except that the spherical polyamide particles obtained in Reference Example 3 were changed to the spherical polyamide particles obtained in Reference Example 2, and the average particle size was compared with the polyamide particles used as a raw material. And particles having the same shape, a lower melting point (166-174t :) and a narrower width. The results are summarized in Table 6.
  • Example 1 3 The same procedure as in Example 1 was performed except that the spherical polyamide particles obtained in Reference Example 3 were changed to the spherical polyamide particles obtained in Reference Example 2, and the average particle size was compared with the polyamide particles used as a raw material. And particles having the same shape, a lower melting point (166-174t :) and a narrower width. The results are summarized in Table 6.
  • Example 1 3 The results are summarized in Table 6.
  • Example 1 4 The same procedure as in Example 6 was performed except that the spherical polyamide particles obtained in Reference Example 3 were changed to the spherical polyamide particles obtained in Reference Example 1, and the average particle diameter was compared with the polyamide particles used as a raw material. And particles of the same shape, melting point (lower than 1 68 8 to 1 7 4 0 and narrower). The results are summarized in Table 7.
  • Example 1 4 The same procedure as in Example 6 was performed except that the spherical polyamide particles obtained in Reference Example 3 were changed to the spherical polyamide particles obtained in Reference Example 1, and the average particle diameter was compared with the polyamide particles used as a raw material. And particles of the same shape, melting point (lower than 1 68 8 to 1 7 4 0 and narrower). The results are summarized in Table 7.
  • Example 1 4 The results are summarized in Table 7.
  • Example 1 5 Using the respective particles obtained in Reference Example 3, Example 6, Example 7 and Example 10 to the laser sinter equipment EO SI NT-P manufactured by ⁇ GS Gezelshaft Mit Beschlenktel. Thus, a rectangular parallelepiped shaped body (laser and sintered body) was produced.
  • the density of these sintered bodies was 0.60 gZcm 3 for the sintered bodies from the particles obtained in Reference Example 3, and 0.96 g no cm 3 for all the sintered bodies from the particles obtained in the examples. 7 hot.
  • the sintered bodies from the particles obtained in Reference Example 3 are “soft and brittle”, and the sintered bodies from the particles obtained in the examples are all “hard and tough”. there were.

Abstract

(1) L'invention concerne un procédé destiné à produire des particules de polyamide présentant un point de fusion inférieur à celui des particules sphériques de polyamide utilisées comme matière première, comprenant l'étape consistant à hydrolyser les particules sphériques de polyamide dans un milieu aqueux tout en préservant leur forme ; (2) un procédé destiné à produire un matériau fritté, comprenant l'étape consistant à fritter les particules de polyamide produites par le procédé (1) à l'aide d'un laser ; et (3) une poudre pour frittage laser, comprenant les particules de polyamide produites par le procédé (1).
PCT/JP2007/068010 2006-09-26 2007-09-10 Procédé de production de particules sphériques de polyamide présentant une propriété de fusion améliorée WO2008038532A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006259907A JP5288361B2 (ja) 2006-09-26 2006-09-26 球状ポリアミド粒子の製造方法
JP2006-259907 2006-09-26
JP2007020364A JP5334233B2 (ja) 2007-01-31 2007-01-31 レーザー焼結に使用される球状ポリアミド粉体およびそれを用いた成形体の製造方法およびレーザー焼結物品
JP2007-020364 2007-01-31

Publications (1)

Publication Number Publication Date
WO2008038532A1 true WO2008038532A1 (fr) 2008-04-03

Family

ID=39229968

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/068010 WO2008038532A1 (fr) 2006-09-26 2007-09-10 Procédé de production de particules sphériques de polyamide présentant une propriété de fusion améliorée

Country Status (1)

Country Link
WO (1) WO2008038532A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3199265A1 (fr) * 2016-01-27 2017-08-02 Ricoh Company, Ltd. Matériau en poudre de fabrication de forme libre solide, ensemble de matériau de fabrication de forme libre solide, procédé de fabrication d'un objet de fabrication de forme libre solide, procédé de fabrication d'élément compact fritté et dispositif de fabrication d'un objet de fabrication de forme libre solide

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS492100A (fr) * 1972-04-21 1974-01-09
JPS61233019A (ja) * 1985-04-10 1986-10-17 Toray Ind Inc ポリアミド微粒子
JPH0472329A (ja) * 1990-07-12 1992-03-06 Shinto Paint Co Ltd ポリアミド樹脂粉末の製造方法
JPH11216779A (ja) * 1997-10-27 1999-08-10 Huels Ag 粉末状材料の選択的レーザー焼結により成形体を製造する方法
JP2002080629A (ja) * 2000-06-14 2002-03-19 Ube Ind Ltd ポリアミド多孔質球状粒子およびその製造方法
JP2004143460A (ja) * 2002-10-23 2004-05-20 Atofina 水分処理によるポリアミドの融点および溶融エンタルピーの増加方法
WO2005082973A1 (fr) * 2004-02-27 2005-09-09 Degussa Ag Poudre polymere comportant un copolymere, utilisation de cette poudre polymere dans un procede de façonnage faisant appel a un apport d'energie non focalise, et corps moules produits a partir de ladite poudre polymere

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS492100A (fr) * 1972-04-21 1974-01-09
JPS61233019A (ja) * 1985-04-10 1986-10-17 Toray Ind Inc ポリアミド微粒子
JPH0472329A (ja) * 1990-07-12 1992-03-06 Shinto Paint Co Ltd ポリアミド樹脂粉末の製造方法
JPH11216779A (ja) * 1997-10-27 1999-08-10 Huels Ag 粉末状材料の選択的レーザー焼結により成形体を製造する方法
JP2002080629A (ja) * 2000-06-14 2002-03-19 Ube Ind Ltd ポリアミド多孔質球状粒子およびその製造方法
JP2004143460A (ja) * 2002-10-23 2004-05-20 Atofina 水分処理によるポリアミドの融点および溶融エンタルピーの増加方法
WO2005082973A1 (fr) * 2004-02-27 2005-09-09 Degussa Ag Poudre polymere comportant un copolymere, utilisation de cette poudre polymere dans un procede de façonnage faisant appel a un apport d'energie non focalise, et corps moules produits a partir de ladite poudre polymere

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3199265A1 (fr) * 2016-01-27 2017-08-02 Ricoh Company, Ltd. Matériau en poudre de fabrication de forme libre solide, ensemble de matériau de fabrication de forme libre solide, procédé de fabrication d'un objet de fabrication de forme libre solide, procédé de fabrication d'élément compact fritté et dispositif de fabrication d'un objet de fabrication de forme libre solide

Similar Documents

Publication Publication Date Title
JP2780902B2 (ja) 新規ポリアミドと、それで作られた製品
KR102222160B1 (ko) 반-결정질 반-방향족 폴리아미드의 제조 방법
KR101349063B1 (ko) 고수율로 고분자량의 폴리아미드를 제조하는 방법
JPH04337325A (ja) ブロックポリエーテル−アミドの合成方法
JP2014506614A (ja) １，４−ブチレンジアミンのモノマー単位を含有するポリアミド
WO2008038532A1 (fr) Procédé de production de particules sphériques de polyamide présentant une propriété de fusion améliorée
JP5334233B2 (ja) レーザー焼結に使用される球状ポリアミド粉体およびそれを用いた成形体の製造方法およびレーザー焼結物品
KR20150114481A (ko) 폴리아미드의 제조 방법
JP4205354B2 (ja) ポリシラン系コポリマーの製造方法
JP7308818B2 (ja) 重合方法
JP6238988B2 (ja) 熱可塑性のプレセラミックポリマーの製造方法
CA1225511A (fr) Precurseurs a base de polysilahydrocarbures ramifies pour le carbure de silicium
CN105339415A (zh) 生产半芳族半结晶聚酰胺的方法
JPH1160664A (ja) 感圧熱自硬化性球状フェノール樹脂の製造方法
CN105837791B (zh) 一种海因环氧树脂的制备方法
KR20110109338A (ko) 특수 구조를 갖는 폴리아미드 ４ 및 이의 제조 방법
WO2014205358A1 (fr) Copolymères de polyamide contenant des motifs de 2,5-furane dicarboxamide
KR102307259B1 (ko) 폴리아미드의 시클릭 올리고머를 중합시키는 방법
KR101425173B1 (ko) 낮은 용융온도를 갖는 나일론 4의 제조방법
JP6991527B2 (ja) シリカ含有微粒子の製造方法、基材の表面に対するコーティング施工方法、及びゾルゲル反応用触媒
JP5207343B2 (ja) 生分解性ポリエステルアミド及びその製造方法
JP3674205B2 (ja) ポリシラン類の製造方法
JPS59145210A (ja) 高分子多糖グラフト共重合体の合成法
JP4911663B2 (ja) 球状ポリアミド粒子の製造方法
JP2874739B2 (ja) ２−ピロリドン重合体の製法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07807414

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07807414

Country of ref document: EP

Kind code of ref document: A1