Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds

Definitions

• the invention relates to thermoplastic, polymeric materials with high IR absorption, a process for their production and their use.
• thermoplastic polymeric materials
• PET polyethylene terephthalate
• PET compositions as packaging material in the form of foils, bottles and other container shapes may be mentioned as an example.
• the polymer is usually fed to the process in the form of granules to form PET bottles.
• the granules (“PET chips") are first melted in extruders and processed into so-called preforms using injection molding processes. In a further process step, these preforms are brought into the final bottle shape using the stretch blow molding process.
• preforms are brought into the final bottle shape using the stretch blow molding process.
• heating is typically to a temperature of 105 ° C. The heating can e.g.
• preforms are irradiated with the light of a black radiator (radiator temperature 500 ° K to 3000 ° K, e.g. from commercially available quartz IR lamp radiators).
• a black radiator radiation temperature 500 ° K to 3000 ° K, e.g. from commercially available quartz IR lamp radiators.
• Polyester polymers only absorb for certain specific wavelength ranges of the IR spectrum and therefore only a low absorption of the energy made available.
• US Pat. Nos. 4408004 and 4535118 cite graphite or carbon black as a suitable absorption additive with the additional requirement that the particle size as well as the maximum addition amount must be kept in a closely controlled range in order to maintain or maintain the optical clarity of the resulting bottles sufficiently not to cause an unacceptable gray color.
• carbon black has a significantly higher absorption in the visible wavelength range than in the range 700 to 1500 nm, which is disadvantageous with regard to the maximum amount that can be used from the point of view of discoloration.
• the object of the invention is to overcome the disadvantages of the prior art and in particular to provide thermoplastic, polymeric materials which can be heated in a simple and economical manner by irradiation with NIR and / or IR light to such an extent that further shaping processing is possible is.
• thermoplastic, polymeric materials with high IR absorption which contain at least one inorganic metal phosphate of the general formula Me x (P0) y (OH) z , where Me consists of one or more elements from the group Cu, Fe, Mn, Sb, Zn, Ti, Ni, Co, V, Mg, Bi, Be, AI, Ce, Ba, Sr, Na, K, Ge, Ga, Ca, Cr, In or Sn, and where x, y and z are and x has values from 1 to 18, y values from 1 to 12 and z values from 0.2 to 10 and the inorganic metal phosphate can optionally also contain water of crystallization.
• Me x (P0) y (OH) z where Me consists of one or more elements from the group Cu, Fe, Mn, Sb, Zn, Ti, Ni, Co, V, Mg, Bi, Be, AI, Ce, Ba, Sr, Na, K, Ge, Ga, Ca, Cr, In or Sn, and where x,
• thermoplastic, polymeric materials have a high IR absorption without the addition of organic or organometallic substances to the polymers.
• the purely inorganic compounds which are relatively easy to produce, or minerals of the general formula Me x (PO 4 ) y (OH) z which are easy to obtain, are able to bring about a high IR absorption in the polymers.
• “High” IR absorption means that the transparency in the visible wavelength range 400 to 700 nm is not noticeably impaired and the absorption in the wavelength range 700 to 1500 nm is significantly higher than in the visible range; For example, the absorption of such a polymer at a wavelength of 1100 nm is at least twice as high as the absorption at 600 nm.
• thermoplastic, polymeric materials polyester (such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN)), polyalkylenes (such as polyethylene (PE), polypropylene (PP)) , Vinyl polymers (such as polyvinyl chloride (PVC)), polyamides, polyacetals, polyacrylates (such as polymethyl methacrylate (PMMA)), polycarbonates, polystyrenes, polyurethanes, acrylonitrile-butadiene-styrene copolymers (ABS), halogen-containing polyalkylenes, polyarylene oxides or polyarylene sulfides.
• PET polyethylene terephthalate
• PTT polytrimethylene terephthalate
• PBT polybutylene terephthalate
• PEN polyethylene naphthalate
• polyalkylenes such as polyethylene (PE), polyprop
• Phosphate-containing compounds of the Dana classification VII - 41 and VII - 42 can be used as inorganic metal phosphates with the general formula Me x (P0) y (OH) z .
• the Dana classification is described in: Dana's New Mineralogy, Eighth Edition, by Richard V. Gaines, H. Catherine Skinner, Eugene E. Foord, Brian Mason, and Abraham Rosenzweig, with sections by Vandall T. King, illustrations by Eric Dowty , (ISBN: 047119310-0) Copyright ⁇ 1997, John Wiley & Sons, Inc.
• the inorganic metal phosphates preferably contain one or more of the elements Cu, Fe and Al.
• inorganic metal phosphates with the general Formula Me x (P0 4 ) y (OH) z are preferably used: Cu 2 P0 4 OH, Cu 3 (P0 4 ) (OH) 3 Cu 3 (P0 4 ) (OH) 3 , Cu 5 (PO 4 ) 2 (OH) 4 , CuFe 2 (P0 4 ) 2 (OH) 2 (Cu, Zn) 2 ZnPO 4 (OH) 3 -2 (H 2 0), (Cu, Zn) 5 Zn (P0 4 ) 2 (OH ) 6 (H 2 0), Cu 3 AI 4 (P0 4 ) 3 (OH) 9 -4 (H 2 0),
• the addition amount of the inorganic metal phosphates depends on the absorption of the polymer produced therefrom in the range from 400 to 700 nm (the transparency should be impaired as little as possible) and the absorption in the range from 700 to 1500 nm (the higher the absorption, the lower the addition amount) and is to be determined in preliminary tests if necessary.
• addition quantities of 0.0002 to 2% by weight of inorganic metal phosphate, based on the finished thermoplastic, polymeric material have proven to be suitable.
• a preferred addition amount is in the range of 0.001 to 0.1% by weight.
• the inorganic metal phosphates are to be used in the form of naturally occurring minerals, these must first be ground up.
• the inorganic metal phosphate preferably has crystallite sizes (measured according to Scherrer) from 0.005 to 5 ⁇ m, particularly preferably from 0.001 to 2 ⁇ m.
• solutions of the metal ion (s) and a solution of the respective P0 component are precipitated in an aqueous medium.
• the pH value, temperature, rate of addition, addition concentrations and order of addition must be set in a known manner.
• Corresponding solutions of the sulfates, chlorides, nitrates, hydroxides or oxides can be used, for example, as metal ion solutions.
• Suitable solutions for the P0 4 component are, for example Phosphoric acid or its soluble salts (such as alkali or alkaline earth phosphates).
• the products can be treated hydrothermally (heating the aqueous precipitation suspension to temperatures> 100 ° C. at elevated pressure) and / or thermally treated in the dried state.
• the inorganic metal phosphate can be added to the polymer at various times during the production of the thermoplastic, namely before, during and after the polymerization reaction.
• the inorganic metal phosphate is preferably added in the form of a suspension (e.g. in an inert solvent or a reactant).
• a suspension of the inorganic metal phosphate in monoethylene glycol (or in propanediol or butanediol) can be added at different times in the reaction.
• thermoplastic polymer materials containing one or more inorganic metal phosphates are used wherever thermoplastic polymer materials are softened by heating by means of IR radiation and then subjected to shaping processing.
• the materials according to the invention are used in particular in the production of preforms, their heating with IR radiation and subsequent processing into articles for use (eg packaging).
• heating is typically carried out by means of IR radiation to a temperature of 90 to 120 ° C., preferably 100 to 110 ° C.
• thermoplastic polymers depending on the glass transition temperature and melting temperature, such heating temperatures are to be selected at which the subsequent shaping further processing of these polymers can be technically realized.
• the product obtained was filtered off and washed to a filtrate conductivity ⁇ 100 ⁇ S / cm.
• the filter cake was then dispersed in water using a dissolver and dried in a laboratory spray tower.
• the dry product had a well-developed crystal structure (see Figure 3).
• Example 3 Absorption spectrum of Cu 2 P0 4 OH
• Example 1 1.0 g of the copper phosphate Cu 2 P0 4 OH prepared in Example 1 was mixed with 1.0 I of an alkyd resin binder (DSM AD-9). An absorption spectrum in the wavelength range from 400 to 2000 nm was recorded from this mixture (see FIG. 1). The spectrum shows that the metal phosphate according to the invention has a significantly increased absorption with a maximum at 1150 nm in the range from 700 to 1600 nm relevant for IR radiation heating.
• Example 4 Energy consumption of Cu 2 P0 4 OH in PET when irradiated with an IR radiator compared to pure PET and PET with carbon black.
• Example 1 The copper phosphate produced in Example 1 was incorporated in a concentration of 0.01%, based on the plastic, in polyethylene terephthalate by means of an extruder. The melt was injection molded into platelets 9 mm thick. Transmission spectra of the platelets were recorded with a spectrometer in the range from 400 to 1600 nm.
• FIG. 2 shows on the one hand the energy emitted by an IR lamp at a radiation temperature of 2450 K (curve 1) and on the other hand the corresponding wavelength-dependent energy consumption of various test plates (curves 2 to 4) when irradiated with this radiation source.
• the formulation according to the invention (curve 4) has a significantly lower absorption in the visible range (400 to 700 nm) and thus a lower clouding or coloring potential than the comparative sample corresponding to the prior art (curve 3).
• the NIR range 800 to 1600 nm
• the clearly increased radiation absorption of the formulation according to the invention and thus better energy yield in the heating process in comparison to pure PET (curve 2) and to the comparison sample (curve 3) can be seen.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

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• 2003
  • 2003-11-28 DE DE10356334.2A patent/DE10356334B4/de not_active Expired - Fee Related
• 2004
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  • 2004-11-26 EP EP04798094A patent/EP1689810A1/de not_active Withdrawn
  • 2004-11-26 BR BRPI0417010-5A patent/BRPI0417010A/pt not_active IP Right Cessation
  • 2004-11-26 KR KR1020067012819A patent/KR20070009540A/ko active Search and Examination
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  • 2004-11-26 WO PCT/EP2004/013441 patent/WO2005052049A1/de active Application Filing
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