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
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D211/56—Nitrogen atoms
  • C07D211/58—Nitrogen atoms attached in position 4

Definitions

• the invention relates to an additive having at least two condensable functionalities in combination with a Tetraalkyi-piperidinyl radical and a tertiary amine functionality.
• a universal additive can be provided, which on the one hand allows a narrower molecular weight distribution and at the same time improves the performance for spun polymers.
• likewise corresponding additized polyamide molding compositions and an additive solution are provided.
• the additives according to the invention are used in particular in the production of polyamide for textile applications.
• the threads must be well dyeable.
• Additives to achieve the desired performance must be available and applicable at an economic cost-benefit ratio.
• the use of multifunctional stabilizers has proven to have a narrowing effect on the molecular weight distribution.
• multifunctional carboxylic acids are used which at the same time keep the content of primary amine groups in the condensation equilibrium low and are thus favorable for a low monomer recovery during remelting.
• Examples of the use of multifunctional acids as additives for the production of polyamides are EP 0 818 491 A1 and EP 0 759 953 Al mentioned.
• the narrowing influence on the molecular weight distribution is e.g. the article by Z.-L Tang et al.
• Chain length regulator acting, but the molecular weight distribution non-modifying compounds possible, such. with said 4-amino-2,2,6,6-tetramethylpiperidine.
• it is important to minimize the number of reactive chain ends. This reduces the rate of postcondensation and monomer recovery, e.g. when remelting polyamide 6.
• the quantitative use of chain length controllers is limited by the process engineering possibilities and the consideration of economic factors.
• amino end groups are important for good staining, such as e.g. described in EP 0 818 491 AI, tertiary amines introduced into the polymer. These can not undergo amide bond and therefore remain for the
• R 1 independently of one another are H or C 1 -C 2 -alkyl
• R 2 H or CC 12 alkyl
• X and Y independently represent an aliphatic or unsaturated or aromatic carbon skeleton, linear or branched, having 1 to 12 carbon atoms, wherein X and Y each have at least one carboxy, an amine or an alcohol functionality.
• the additive according to the invention provides for a narrower molecular weight distribution compared to a partial or complete stabilization with monofunctional chain length regulators.
• the HALS compound as well as the tertiary amine are not bound to the chain end as usual, but are incorporated into the chain and, assuming the same process conditions, no longer reduce the potential for lowering the polydispersity. A performance gain in the field of high-speed spinning is therefore expected.
• the additive according to the invention makes it possible for the first time to be able to serve the stated requirements for textile polyamide with a single compound. This reduces dosing distances and storage tanks to a minimum and at the same time reduces the number of suppliers on which production depends.
• the structures are based on existing mass Chemicals can be produced and there are no additional costs to existing, comparable multi-component formulations expected.
• the structures mentioned make it possible for the first time to incorporate the HALS compound or the tertiary amine into the polymer chain. So far, only binding to the chain end is possible via quasi-monofunctional compounds, which limits the possibilities of modifying the molecular weight distribution. By gaining the potential to make the molecular weight distribution narrower, increases in performance in the area of high-speed spinning are possible because the melt strength is reduced, but the strength increases in the solidified state.
• a preferred additive according to the invention has the general formula II:
• R 1 and R 2 are each independently H or C 1 -C 2 -alkyl
• R 3 is independently H or an aliphatic or unsaturated or aromatic carbon skeleton, linear or branched, having 1 to 12 carbon atoms and
• n are each independently 0 to 10.
• At least one of R 3 has a carboxy functionality.
• at least one of R 3 is CH 2 COOH.
• an additive solution which contains the above-described additive together with caprolactam.
• Other additives may be included in this solution.
• the additive solution may additionally contain bifunctional carboxylic acids, such as terephthalic acid and / or adipic acid.
• bifunctional carboxylic acids such as terephthalic acid and / or adipic acid.
• a polyamide molding composition which has an additive, wherein the additive is covalently bound via at least two condensable functionalities in the polymer chain.
• units of general formula IV are incorporated into the polymer chain:
• Ri and 2 are each independently H or Ci- Ci2 alkyl
• R 3 is independently H or an aliphatic or unsaturated or aromatic carbon skeleton, linear or branched, having 1 to 12 carbon atoms and
• S and T are independently 0, NH or COO and
• n are each independently 0 to 10.
• R 2 are each independently H or CC i2 alkyl
• R 3 is independently H or an aliphatic or unsaturated or aromatic carbon skeleton, iinear or branched, having 1 to 12 carbon atoms and
• n are each independently 0 to 10.
• the polyamide molding compound has a polydispersity in the range in the range of 1.3 to 2.5, in particular 1.5 to 2.0.
• the additive according to the invention is used in the production of polycondensates, in particular of
• Caprolactam is polymerized at a constant water content of 300 mmol / kg (0.54 w%) at 245 ° C until the polycondensation equilibrium is reached. Subsequently, the polymer is granulated and hot
• Caprolactam and 41.7 mmol / kg of acetic acid are polymerized at a constant water content of 125 mmol / kg (0.225 w%) at 245 ° C until reaching the Poikkondensations Dermatheses.
• the further processing is analogous to Comparative Example 1.
• Triacetonediamine be at a constant water content of
• Caprolactam, 19.03 mmol / kg terephthalic acid and 17.5 mmol / kg compound II I are polymerized at a constant water content of 125 mmol / kg (0.225 w-%) at 245 ° C until the polycondensation equilibrium is reached.
• the further processing is analogous to Comparative Example 1.
• Table 1 compares the properties of the synthesized polymers of Comparative Beisptele 1 to 3 and Example 1 of the invention. All have the same relative viscosity, which can be used as a measure of processability in the molten state.
• Table 1 compares the properties of the synthesized polymers of Comparative Beisptele 1 to 3 and Example 1 of the invention. All have the same relative viscosity, which can be used as a measure of processability in the molten state.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Polyamides (AREA)
• Hydrogenated Pyridines (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

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Cited By (5)

Citations (13)

Family Cites Families (10)

• 2013
  • 2013-01-25 ES ES13152696.4T patent/ES2538802T3/es active Active
  • 2013-01-25 EP EP13152696.4A patent/EP2759534B1/de not_active Not-in-force
  • 2013-01-25 PL PL13152696T patent/PL2759534T3/pl unknown
• 2014
  • 2014-01-22 TW TW103102197A patent/TWI602877B/zh not_active IP Right Cessation
  • 2014-01-23 EA EA201591060A patent/EA029652B1/ru not_active IP Right Cessation
  • 2014-01-23 WO PCT/EP2014/051343 patent/WO2014114721A1/de not_active Ceased
  • 2014-01-23 KR KR1020157019718A patent/KR20150125645A/ko not_active Abandoned
  • 2014-01-23 CN CN201480006196.3A patent/CN105143184B/zh not_active Expired - Fee Related
  • 2014-01-23 JP JP2015554146A patent/JP6496249B2/ja not_active Expired - Fee Related
  • 2014-01-23 US US14/763,086 patent/US9908973B2/en not_active Expired - Fee Related

Patent Citations (13)

Non-Patent Citations (3)

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