• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Process for preparing ether-ester-amide block polymers. It consists in the reaction, in the molten state of a dicarboxylic polyamide having COOH end groups with a polyoxyalkylene glycol having hydroxyl end groups in the presence of metallic tetraalkoxide(s) as catalysts. The tetraalkoxide(s) used are of the formula M(OR)4 where M is Zr or Hf and the radicals R, identical or different are linear or branched C1-C24 alkyl radicals.
    公开号:SU971104A3
    申请号:SU782657249
    申请日:1978-09-01
    公开日:1982-10-30
    发明作者:Делеен Жерар；Ферлампен Жак；Гонне Мишель
    申请人:Ато Шими(Фирма)；
    IPC主号:
    专利说明:

    397 zirconium and hafnium oxides are methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, decyl, dodecyl, hexadodecyl. Zirconium and hafnium tetraalkoxides, in which R-identical or different is alkyl, are preferred. Examples of catalysts are Zr () 4, Zr (0-H30 CjH), ZrCOC Hg) Zr (,) 4, Zr () 4, HfCOCjH.), Hf (OC4Hg), Hf (0-H30 CjH). The effect of the catalyst according to the invention is for the polycondensation reaction of polyamide with COOH-terminus and polyoxyalkylene glycol a number of advantages. At the beginning of the reaction there are two immiscible phases, one of which is slightly liquid polyamide and in the absence of a catalyst the reaction is only partial, the reactivity is negligible and the resulting product has a significant portion of unreacted polyoxyalkylene glycol, which makes the product fragile and unable to participate in technological operations - casting, roll extrusion evanie When using a polycondensation reaction in the melt and in the presence of zirconium tetraalkoxide or hafnium, a polymer is obtained that has satisfactory characteristics, suitable for molding, extrusion or rolling processes. The weight ratio of the catalyst is preferably 0.01-5% by weight of the reaction mixture, preferably 0, 05, 2 wt., O Polyamides containing terminal COOH-groups are prepared in a known manner by the Polymerization of lactams and / or amino acids, for example caprolactam, enantholactam, dodecolactam, undecanolactam, decanolactam, 1,1-aminoundecanoic acid, 12-aminododecanoic acid. Examples of polyamides obtained by polycondensation include the condensation products of hexamethylenediamine and adipic acid (nylon 6.6), azelaic acid (6, 9), sebacic acid (6.10) and also nonamethylenediamine and adipino acid (9.6), Medium Molecular weight is 300-15000, preferably 800-5000. Polysxyalkylene glycol is selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol polyoxyethylene methylene glycol, copolymers derived from these polyoxyalkylene glycol. Average molecular weight 100-6000, preferably 200-3000 ° C The weight ratio of polyoxyalkylene glycol to total weight of polyoxyalkylene glycol and dicarboxylic polyamide in the formation of polyether amide is 5-85%, preferably 10-50%. The polycondensation reaction between the dicarboxylic polyamide and polyoxyalkylene glycol interacts stirring in the melt, at a temperature above the melting point of the starting polymers. The reaction temperature is preferably 200-300 ° Co. The reaction time is from 10 minutes to 10 hours, preferably 1-5 hours. This depends on the nature of the polyoxyalkylene glycol and on the final viscosity of the product having properties that allow it to be used as plastic. during casting or extrusion Additives can be added to the resulting polycondensate, for example, stabilizers, light stabilizers, antioxidants, colorants, and Topbie are added before and during the polycondensation process. The methods for monitoring and identifying the characteristics of the products obtained are as follows: Vicat point in о С (according to ASTM D1 525 65Т standards), intrinsic viscosity when in solution of m -cresol), elongation at stretching (according to ASTM standard Db38 6A), torsion modulus (according to standard ASIM D1 0 (3 61Т according to the Klas and Berg method). EXAMPLE 1 2 liters reactor — 60 g of dicarboxylic polyamide 6 — average molecular weight 2300, obtained by polycondensation of E-caprolactam in the presence of adipic acid, are then loaded 80 g of dihydroxylated poly polyethylene of average weight 00, then 1.1 g (or 2.8-1 () Zr (OC4H3) 4 The mixture is placed in an inert atmosphere and heated to 2 ° C. The reactor is then set to vacuum with thorough stirring since the melting of the reactants continue at 2bO ° C at 1 Torr for 2 h. The resulting product has an intrinsic viscosity of 1.3, with differential thermal analysis it has a crystalline melting peak at 202 ° C. Determination of average molecular weight Mg by chromatography of gel penetration into hexamethylphostriamide at the display of rank conducted for polydispersity index equal to 2.8, a product jected molding to obtain samples for tensile testing and determining modulation torsion. For elongation under stretching, 11 were obtained at 155 kg / cm at the yield point and at 520 kg / cm at 46 fracture. The magnitude of the torsion modulus G is kg / cm at and the Vicat point at 5 kg at the heating rate. Examples 2-6o Example 1 is repeated, but without a catalyst (example 2) with either a titanium catalyst as described above (example 3) or using the catalysts of the invention (examples 6). The results obtained are presented in the table.
    Not
    Not
     The catalyst of this example is prepared in an anhydrous medium, a solution of 1 g of sodium in 99 g of n-butanol, then 16.7 tetra butoxide of zirconium is added, then the solution is poured into 200 ml of n-butanol. The analysis of the results of the table makes it possible to note the following. Polyesters obtained without a catalyst have a negligible characteristic viscosity, heterogeneous, friable, and are not suitable for casting, extruding or rolling, while the polyether amides obtained by using a catalyst are completely suitable for these processes. The products obtained in the presence of a catalyst according to the invention (examples 4-6) have a white color, and the product obtained in the presence of a titanium catalyst (example 3) has a residual yellow color. At the same molar amount of catalyst and duration of the reaction, use The catalysts according to the invention make it possible to obtain products with higher viscosity and Vicat-point in comparison with the products obtained using a titanium catalyst.
    0.4
    The product is heterogeneous, fragile. PRI meper 7. The technology of Example 1 is carried out, 390 g of dicarboxylic polyamide 6 has an average molecular weight of 1300 and 195 g of dihydroxypolyoxytetramethylene with an average molecular weight of 650 in the presence of 1 g of tetraiso, zirconium propoxide. (2g (o-isoc2, H), at 2 ° C and a pressure of 1 Torr for 2.5 hours. A very white polyetheramide is obtained with a characteristic viscosity of 1.55 and Topl, 192 ° C. The amount of elongation under stretching is em 12.5 at 110 kg / cm2 at the threshold of yield and 520% at kg / cm at 20 ° С and point В iC 163 C at 1 kg. Example 8. The technology of Example 1 is repeated and kO g of dicarboxylic polyamide 11 has an average molecular weight of 2000. 200 g of dihydroxy polyoxypropylene with an average molecular weight of 1000 and I, g of tetraethoxide 7 hafnium () at and Aakuu 1 Torr for k hours. The resulting product has the following characteristics: Bela stain with wrinkle Intrinsic viscosity Melting point, Torsion modulus G at 22 ° C, kg / cm Vicat point, at 1 kg, ° C Elongation,% i at UiO kg / cm at the threshold of yield at 1 O kg / cm at break When carrying out the same technology, but replacing the hafnium catalyst with the same molar amount of titanium tetraethoxide. (T iOC2H5-) 4 takes 6 hours to obtain a product with the same viscosity and, moreover, the product obtained in the presence of a titanium analyzer, has a residual yellowish color. of the invention. Method of producing polyether amides of pf by the action in the melt of polyamide containing terminal COOH groups and polyalkylene glycol in the presence of a catalyst, which is intended to intensify the process and also exclude shortening; vanities of the final product, in addition to: a catalyst, compounds of the formula M (OR) 4f are used in which f is added as zirconium or hafnium, and R is alkyl with 1–2 carbon atoms in an amount of 0.01–5% by weight of the –reaction mass with Sources of information taken into account in the examination 1, “Patent of Ifd 2273021, cl. From 08 g 23/00, (-pub. I97S (about
    权利要求:
    Claims (1)
    [1]
    5 claims
    A method for producing polyetheramides by melt reaction of a polyamide containing COOH end groups of the first polyalkid of sialkylene glycol in the presence of a catalyst, characterized in that, with the aim of intensifying the process and also eliminating the clipping of the final product, compounds of the formula M (0H) 4 are used as a catalyst , wherein !' is zirconium or hafnium, and R is alkyl with 1-24 carbon atoms in an amount of 0.01-5 wtL based on the weight of the reaction mass "
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    同族专利:
    公开号 | 公开日
    CS201502B2|1980-11-28|
    DE2837687A1|1979-03-15|
    GB2005283A|1979-04-19|
    GB2005283B|1982-03-24|
    FR2401947B1|1980-04-04|
    SE429134B|1983-08-15|
    US4252920A|1981-02-24|
    IT1099452B|1985-09-18|
    LU80180A1|1979-02-12|
    DE2837687C2|1986-02-13|
    CH635600A5|1983-04-15|
    JPS5447798A|1979-04-14|
    AR219126A1|1980-07-31|
    NL174837C|1984-08-16|
    BR7805715A|1979-04-17|
    JPS5811459B2|1983-03-03|
    NL7809006A|1979-03-06|
    BE870140A|1979-01-02|
    NL174837B|1984-03-16|
    SE7809203L|1979-03-03|
    DD138554A5|1979-11-07|
    IT7827181D0|1978-08-31|
    FR2401947A1|1979-03-30|
    引用文献:
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    US4417031A|1982-01-07|1983-11-22|Allied Corporation|Process for preparing graft and block copolymers|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7726678A|FR2401947B1|1977-09-02|1977-09-02|
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