WO2018189016A1 - Stabilisants anti-oxydation organiques faiblement volatils pour systèmes polymères, production et utilisation associées - Google Patents

Stabilisants anti-oxydation organiques faiblement volatils pour systèmes polymères, production et utilisation associées Download PDF

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Publication number
WO2018189016A1
WO2018189016A1 PCT/EP2018/058685 EP2018058685W WO2018189016A1 WO 2018189016 A1 WO2018189016 A1 WO 2018189016A1 EP 2018058685 W EP2018058685 W EP 2018058685W WO 2018189016 A1 WO2018189016 A1 WO 2018189016A1
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WO
WIPO (PCT)
Prior art keywords
formula
process according
zerewitinoff
active compound
oxidation stabilizer
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PCT/EP2018/058685
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English (en)
Inventor
Frank THIELBEER
Christian Koenig
Thomas MATHIEU
Kai-Uwe Schoening
Original Assignee
Basf Se
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.)
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Priority to EP18714284.9A priority Critical patent/EP3609861A1/fr
Publication of WO2018189016A1 publication Critical patent/WO2018189016A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
    • C07C43/1785—Unsaturated ethers containing hydroxy or O-metal groups having more than one ether bound
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates

Definitions

  • the present invention deals with low volatile organic compound anti-oxidation stabilizers for polymeric systems, their production and use, in particular in polyurethane systems.
  • phenolic-based AO (antioxidant)-stabilizers are hydrolytically instable due to an ester bond modification (for example, commercial products Irganox® 1 135 & 1076, see also WO 2006/092636 A1 or WO 2017/037204). Cleavage of the ester bond leads to the release of volatile organic compounds, which is undesirable in most applications.
  • ester bond modification for example, commercial products Irganox® 1 135 & 1076, see also WO 2006/092636 A1 or WO 2017/037204
  • AO-stabilizers are solid (like some commercially available stabilizers of the Irganox® series, see also e.g., US 7,262,319 B2) at room temperature and cannot be readily used in PU (polyurethane) formulations.
  • Krysin et al. reports on the ⁇ -hydroxyal- kylation of sterically hindered phenols with epoxides in acid medium.
  • 2,6-di-tert-butylphenol was reacted with ethylene oxide (EO) under influence of SnCU, yielding 4-(2-hydroxy- ethyl)-2,6-di-tert-butylphenol.
  • EO ethylene oxide
  • alkoxylation can be effected mainly on the non-phenolic OH moiety.
  • alkoxylation can be effected mainly on the (non-phenolic) amine moiety.
  • the resulting products do not have ester bonds, but are linked through ether bonds. Therefore, the inventive stabilizers are not susceptible to ester bond cleavage and therefore show a high stability against hydrolysis.
  • inventive stabilizers can be used advantageously in PU formulations.
  • the in- ventive stabilizers can be used in other polymeric systems, for example in polyols (for example polyetherols, polyesterols, polymer polyols), polyolefins (for example polyethylene, polypropylene or polystyrene), polyamides, polyesters (for example polyethylene terephthalate or poly- butylene terephthalate), polyethers (for example polyoxymethylene), and/or polycarbonates.
  • polyols for example polyetherols, polyesterols, polymer polyols
  • polyolefins for example polyethylene, polypropylene or polystyrene
  • polyamides polyesters (for example polyethylene terephthalate or poly- butylene terephthalate), polyethers (for example polyoxymethylene), and/or polycarbonates.
  • one object of the present invention is an anti-oxidation stabilizer for polymeric systems.
  • R is -(CH 2 )n-X-[Y-0] P -H; X is selected from O, NR 1 ;
  • Y is selected from the group consisting of -CH 2 -CH 2 -, -CH(CH 3 )-CH 2 -, -CH 2 -CH(CH 3 )-, - CH(CH 2 -CH 3 )-CH 2 -, and -CH 2 -CH(CH 2 -CH 3 )- p is 3 to 50, preferably 3 to 30, more preferably 3 to 20, most preferably 3 to 10;
  • n is 1 , 2, 3 or 4, preferably 1 , 2 or 3;
  • R 1 is hydrogen, [Y-0]r-H or C1-C4 alkyl, preferably [Y-0]r-H or C1-C4 alkyl, more preferably [Y- 0]r-H alkyl, and
  • C1-C4 alk ly includes methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2- methylpropyl and 1 ,1 -dimethylethyl.
  • r is 3 to 50, preferably 3 to 30, more preferably 3 to 20, most preferably 3 to 10
  • one preferred embodiment of the anti-oxidation stabilizer comprises a 2,6-di-tert- butylphenol compound substituted by a residue R in 4-position wherein residue R is -(CH 2 ) n -X- [Y-0]p-H, wherein X is selected from oxygen (O) or nitrogen-group (NR 1 ), and Y is selected from the group consisting of -CH 2 -CH 2 -, -CH(CH 3 )-CH 2 -, -CH 2 -CH(CH 3 )- , -CH(CH 2 -CH 3 )-CH 2 -, and -CH 2 -CH(CH 2 -CH 3 )-, and n is selected from the range from 1 to 4, and p is preferably selected from 3 to 10.
  • n 1 , 2 or 3.
  • p is 3 to 50, preferably 3 to 30, more preferably 3 to 20, most preferably 3 to 10;
  • n is 1 , 2, 3 or 4, preferably 1 , 2 or 3;
  • compounds 1-1 1 to 1-15 r is 3 to 50, preferably 3 to 30, more preferably 3 to 20, most preferably 3 to 10
  • n 1 , 2 or 3;
  • p 3 to 20;
  • n 1 , 2 or 3;
  • p 3 to 10
  • n 1 , 2 or 3;
  • the invention comprises compounds 1-1 to I-5 of formula I of Table 1 , wherein
  • p 3 to 10
  • n 3.
  • the term "at least one compound of formula I" in the context of the present invention means that the stabilizer may not only comprise one defined compound of formula I, but also mixtures of mixtures of two or more structurally different compounds of formula I. Such mixtures can be easily produced by the processes as referred to below.
  • polymeric systems in the context of this invention refers in particular to synthetic polymers but also polymeric compounds to be used for preparing polymers such as polyols. Mac- romolecular compounds of biological origin, for example DNA, are not aimed at by this inven- tion.
  • Polymeric systems include, without limitation, polyurethanes, thermoplastic polyurethanes, poly- ols (for example polyetherols, polyesterols, polymer polyols), polyolefines (for example polyethylene, polypropylene or polystyrene), polyamides, polyesters (for example polyethylene tereph- thalate or polybutylene terephthalate), polyethers (for example polyoxymethylene), and polycarbonates.
  • polyurethanes thermoplastic polyurethanes
  • poly- ols for example polyetherols, polyesterols, polymer polyols
  • polyolefines for example polyethylene, polypropylene or polystyrene
  • polymeric systems in this invention comprise polyurethanes, thermoplastic polyurethanes, polyols, polyolefines, polyamides, polyesters, polyethers and/or polycarbonates.
  • polymeric systems contain, preferably consist of, polyole- fins.
  • polymeric systems contain, preferably consist of, polyols. In yet another embodiment of this invention, polymeric systems contain, preferably consist of, polyurethanes.
  • a further object of the present invention comprises a process for the production of an anti-oxidation stabilizer by reacting at least one Zerewitinoff-active compound Z1 of formula II
  • R a is (CH 2 ) k -R b
  • k is 1 , 2, 3 or 4, preferably 1 , 2 or 3
  • R b is OH or NR c R d ,
  • R c is H
  • R d is H or C1-C4 alkyl
  • alkylene oxide under basic catalysis or coordinative catalysis or Lewis acid catalysis.
  • R a is (CH 2 ) k -R b
  • k 1 , 2 or 3
  • R b is OH
  • R a is (CH 2 ) k -R b
  • k 1 , 2 or 3
  • R b is NR c R d ,
  • R c is H
  • R d is H
  • the Zerewitinoff-active compound Z1 is selected from the group consisting of 4-(Hydroxymethyl)-2,6-di-tert-butylphenol, 4-(2-Hydroxyethyl)-2,6-di-tert-butylphenol, 4-(2-Hy- droxypropyl)-2,6-di-tert-butylphenol, 4-(Aminomethyl)-2,6-di-tert-butylphenol, 4-(2-Aminoethyl)- 2,6-di-tert-butylphenol and 4-(2-Aminopropyl)-2,6-di-tert-butylphenol.
  • the invention comprises compounds of formula II, wherein R a is (CH 2 ) k -R b
  • R b is OH
  • R a is (CH 2 ) k -R b
  • R is NR c R d ,
  • R c is H
  • the coordinative catalyst is selected from the group containing, preferably consisting of, DMC (double metal cyanide) catalysts.
  • the DMC catalyst is selected from the group containing, preferably consisting of, crystalline and amorphous DMCs.
  • the DMC catalyst is non-crystalline.
  • the basic catalyst is selected from the group containing, preferably consisting of, alkaline earth metal hydroxides.
  • the basic catalyst is selected from KOH or CsOH, more preferably KOH.
  • the basic catalyst is selected from the group of phosphazenes.
  • the basic catalyst is selected from imidazole and/or dimethylaminoethylamine (DMEA), preferably imidazole.
  • DMEA dimethylaminoethylamine
  • a Lewie acid catalyst is used, wherein preferably the Lewis acid catalyst contains, more preferably consists of, BF3.
  • the alkylene oxide is preferably se- lected from ethylene oxide, propylene oxide and/or butylene oxide. More preferably, the alkylene oxide contains propylene oxide. In a further preferred embodiment, the alkylene oxide consists of propylene oxide.
  • one or more structurally different Zerewitinoff-active compound Z1 of formula II can be used.
  • a mixture of two or more structurally different Zerewitinoff-active compound Z1 of formula II can be used.
  • the at least one Zerewitinoff- active compound Z1 is selected from the group containing, preferably consisting of, 4-(Hy- droxymethyl)-2,6-di-tert-butylphenol, 4-(Hydroxyethyl)-2,6-di-tert-butylphenol and 4-(2-Hydrox- propyl)-2,6-di-tert-butylphenol.
  • the at least one Zerewitinoff-active compound Z1 is selected from the group containing, preferably consisting of, 4-(aminome- thyl)-2,6-di-tert-butylphenol, 4-(2-aminoethyl)-2,6-di-tert-butylphenol and 4-(2-aminopropyl)-2,6- di-tert-butylphenol.
  • the at least one Zerewitinoff-active compound Z1 is selected from the group containing, preferably consisting of, 4-(aminome- thyl)-2,6-di-tert-butylphenol, 4-(2-aminoethyl)-2,6-di-tert-butylphenol and 4-(2-aminopropyl)-2,6- di-tert-butylphenol.
  • only one Zerewitinoff-active compound Z1 of formula II is used.
  • This single Zerewitinoff-active compound Z1 is preferably selected from either 4-(Hydroxymethyl)-2,6-di-tert-butylphenol, 4-(Hydroxyethyl)-2,6-di-tert-butylphenol or 4-(2-Hy- droxpropyl)-2,6-di-tert-butylphenol.
  • the single Zerewitinoff-active compound Z1 is preferably selected from either 4-(Aminomethyl)-2,6-di-tert-butylphenol, 4-(2-Aminoethyl)-2,6-di- tert-butylphenol or 4-(2-Aminopropyl)-2,6-di-tert-butylphenol.
  • the temperature during the reaction is usually in the range of 80 to 180 °C, preferably 90 to 160 °C, more preferably 100 to 140 °C; the pressure during the reaction is usually in the range of 0.01 to 20 bar, preferably 2 to 15 bar, more preferably 3 to 10 bar; and the dosing of the alkylene oxide generally lasts less than 20 h, preferably less than 15 h.
  • the inventive process may be performed in a (additional) solvent and/or (additional) reagent.
  • the reaction is performed in another Zerewitinoff- active compound Z2.
  • the Zerewitinoff-active compound Z2 may be a polyetherol with an OH value of 15 to 6500 mg KOH/g, preferably 15 to 3000 mg KOH/g, more preferably 15 to 2000 mg.
  • the Zerewitinoff-active compound Z2 may also be selected from the list containing, preferably consisting of sugars such as sorbitol, sucrose or alcohols with a functionality between 2 to 8 such as glycerol, dipropylene glycol and diethylene glycole, ethylene glycole, propylene gly- cole, 1 ,1 ,1 -trimethylolpropane (TMP), or amines such as ethylendiamin, diethanolamin or tolu- oldiamine or trimethyl or mixtures thereof.
  • TMP trimethylolpropane
  • amines such as ethylendiamin, diethanolamin or tolu- oldiamine or trimethyl or mixtures thereof.
  • the term "in another Zerewitinoff-active compound Z2" in the context of the present invention means that the reagent may not only comprise one reagent Z2, but also mixtures of mixtures of two or more structurally different compounds Z2 can be used.
  • mixtures of sugars can be used in combination with glycerol.
  • the inventive process may also be performed in a different solvent, for example an ether bond- containing solvent and/or a solvent inert under the reaction conditions, preferentially polyeth- ylenglycol dimethylethers and/or polypropyleneglycol dimethylethers and/or polytetrahydrofu- rane dimethylethers.
  • a solvent for example an ether bond- containing solvent and/or a solvent inert under the reaction conditions, preferentially polyeth- ylenglycol dimethylethers and/or polypropyleneglycol dimethylethers and/or polytetrahydrofu- rane dimethylethers.
  • the reaction is performed in another component and the component is an alkoxylated phenol.
  • the reaction is performed in an inert solvent.
  • Another object of the present invention is the use of the inventive anti-oxidation stabilizer for the stabilization of a polymer, preferably polyolefines, polyols and/or polyurethanes; besides, an object of the present invention is also an anti-oxidation stabilizer, obtainable by the inventive process.
  • the inventive anti-oxidation stabilizer may serve to reduce emissions of volatile organic compounds (VOC) and medium volatile substances (FOG) in the stabilized products, compared to products stabilized with other stabilizers known from the prior art.
  • OH values were measured according to DIN 53240 and the viscosities in accordance with DIN 51550.
  • Compound A Synthesis of an ethylene oxide derivative of 3,5-di-tert-butyl-4-hydroxybenzylalco- hol using KOH as a catalyst A mixture of 43 g polyethylene glycol dimethyl ether 500, 98.5 g of 3,5-di-tert-butyl-4-hydroxyben- zylalcohol and 1 ,51 KOH g solution 50% in water were given in a 300 ml. autoclave. The mixture was dried for 60 min at 155° under full vacuum. The reactor was pressurized with 3.5 bar of nitrogen and 91 ,8 g of EO were added within 4 h at 155 °C.
  • the product had the following characteristics: OH value 151 ,56 mg KOH/g, viscosity 850 mPas at 25 °C.
  • a mixture of 64.2 g of a two-functional PPG polyol with an OH-value of 100 g/mol , 16,1 g of 3,5- di-tert-butyl-4-hydroxybenzylalcohol and 1 ,1 g DMC suspension (5,5% in a two-functional PPG polyol with an OH-value of 100 g/mol) were given in a 300 ml. autoclave.
  • the mixture was dried for 60 min at 1 10° under full vacuum. 1.95 g of propylene oxide were added at 1 10 °C temperature in one portion and stirred for 15 min. Now the remaining amount of 36,7 g of propylene oxide was added over 80 min at this temperature.
  • the reaction was stirred for another 6 h.
  • the reaction mixture was cooled to 100 °C and all volatile components were removed under full vacuum.
  • the product was cooled to temperature and analyzed. 1 16,1 g (96,7% yield) of yellow liquid were obtained.
  • the product had the following characteristics: OH value 86.57 mg KOH/g, viscosity 340 mPas at 25 °C. Further Example: Stabilization of polypropylene
  • the employed mini-extruder which is commercially available from DSM, enables a flow of the melted polymer in a circle, i.e. two screws in a twin-screw arrangement press the melted polymer to the outlet, which is connected to the inlet zone of the extruder.
  • the temperature of the steel barrel of the mini-extruder can be regulated and the inlet zone of the extruder can be purged with a gas, which allows the removal of entrapped air originating from the loading of the polymer sample.
  • a sensor determines the force, which is exerted by the melted polymer onto the barrel during rotation of the two screws. A change in the viscosity of the melted polymer leads to a change of the force.
  • the steel housing of the extruder is set at a temperature of 240°C and the inlet zone is set under a nitrogen flow of 20 ml. / min.
  • 9 g of a mixture which consists of 8.955 g of a non pelletized, unstabilized polypropylene homopolymer (Moplen HF 501 N, LyondellBasell Industries; 99.75% by weight of the overall mixture), and 0.1 % by weight of Irgafos® 168FF (phosphor-based antioxidant) and 0.05 % by weight calcium stearate, and 0.1 % or 0.2 % by weight of a compound according to the invention (compound A or B as described above are loaded.
  • a compound according to the invention is not added.
  • the screw speed is set to 100 rpm and the force exerted on the barrel is recorded.
  • the test is conducted for 5 min under nitrogen at a flow rate of 20 mL / min. After a short period, a steady decrease of the force is recorded.
  • the decrease of the force is quantified as slope of the force-to-time curve, wherein the slope is calculated between the time period of 150 and 280 seconds (method A). The curve is rather linear during said period.
  • the decrease of the force with time is taken as degree of melt-degradation of the polymer sample.
  • the polymer sample if exposed to air to induce polymer oxidation.
  • the decrease of the force is quantified as slope of the force-to-time curve, wherein the slope is calculated between the time period of 530 and 650 seconds (method B).
  • Desired is a minimum of degradation, which is expressed by a small value for the slope of the curve. No degradation would mean zero slope.
  • Irgafos® 168 by weight Irgafos® 168
  • inventive compounds may be used to stabilize polymeric systems, like, for example, polypropylene.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyethers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne des stabilisants anti-oxydation de composés organiques faiblement volatils pour des systèmes polymères, leur production et leur utilisation.
PCT/EP2018/058685 2017-04-10 2018-04-05 Stabilisants anti-oxydation organiques faiblement volatils pour systèmes polymères, production et utilisation associées WO2018189016A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP18714284.9A EP3609861A1 (fr) 2017-04-10 2018-04-05 Stabilisants anti-oxydation organiques faiblement volatils pour systèmes polymères, production et utilisation associées

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Application Number Priority Date Filing Date Title
EP17165659.8 2017-04-10
EP17165659 2017-04-10

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WO2018189016A1 true WO2018189016A1 (fr) 2018-10-18

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112011047A (zh) * 2020-09-09 2020-12-01 江苏极易新材料有限公司 一种聚醚类受阻酚抗氧剂及其制备方法
US11041040B2 (en) 2017-05-05 2021-06-22 Basf Se Storage-stable polyurethane potting compound for embedding of hollow fibres in the production of filter elements
CN114316246A (zh) * 2020-09-29 2022-04-12 上海抚佳精细化工有限公司 一种抗氧剂及其制备方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11041040B2 (en) 2017-05-05 2021-06-22 Basf Se Storage-stable polyurethane potting compound for embedding of hollow fibres in the production of filter elements
CN112011047A (zh) * 2020-09-09 2020-12-01 江苏极易新材料有限公司 一种聚醚类受阻酚抗氧剂及其制备方法
CN114316246A (zh) * 2020-09-29 2022-04-12 上海抚佳精细化工有限公司 一种抗氧剂及其制备方法

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