IP Library › Granted Patent US 12,421,372
Granted Patent B2
US 12,421,372 · App. 17/287,079 · Granted Sep 23, 2025

Method of stabilizing virgin thermoplastic material and stabilized plastics compositions, moulding compounds and mouldings produced therefrom, stabilizer compositions and uses thereof

Inventors: Elke Metzsch-Zilligen (Darmstadt, DE); Rudolf Pfaendner (Darmstadt, DE)
Assignee: Fraunhofer-Gesellschaft zur förderung der angewandten Forschung e.V.
C08K5/005C08K5/053C08K5/13C08K5/1545
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Quick Facts
Patent No.
US 12,421,372
App. No.
17/287,079
Granted
Sep 23, 2025
Kind
B2
Abstract

The present invention relates to a method of stabilizing virgin thermoplastic material against oxidative, thermal and/or actinic degradation. In the method of the invention, at least one polyphenol and at least one alditol and/or cyclitol are introduced into a virgin thermoplastic material. The method of the invention can stabilize virgin thermoplastic material with high efficacy and in a very environmentally friendly and inexpensive manner against oxidative, thermal and/or actinic degradation. The present invention additionally also relates to correspondingly stabilized virgin thermoplastic material and to moulding compounds and mouldings produced therefrom. The present invention also further relates to stabilizer compositions and to the use thereof for stabilization of virgin thermoplastic material against oxidative, thermal and/or actinic degradation.

Claims (45)

1. A method for stabilizing virgin thermoplastic material against oxidative, thermal, and/or actinic degradation, comprising introducing

(A) 0.02 to 3.0% by weight of a compound selected from the group consisting of gallic acid, esters of gallic acid, hydroxytyrosol, chrysin, quercetin, hesperidin, neohesperidin, naringin, morin, caempherol, fisetin, anthocyanin, carnosic acid, carnosol, rosmarinic acid, resveratrol, tannins, silymarin, and a combination thereof and

(B) 0.02 to 3.0% by weight of at least one alditol and/or at least one cyclitol

into 94.0 to 99.96% by weight of a virgin thermoplastic material;

wherein graphene and carbon nanotubes are not introduced into the virgin thermoplastic material.

2. The method according to claim 1 , wherein the anthocyanin is selected from the group consisting of delphinidin, malvidin, and combinations thereof.

3. The method according to claim 1 , wherein the at least one alditol is of the empirical formula:

HOCH 2 -[CH (OH)] n -CH 2 OH,

R 1 -OCH 2 -[CH (OH)] n -CH 2 OH, or

HOCH 2 -[CH(OH)] n -[CH(OR 1 )]-CH 2 OH,

wherein n=2-5 and R 1 is an optionally substituted sugar residue.

4. The method according to claim 1 , wherein the at least one alditol is selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, and maltitol.

5. The method according to claim 1 , wherein the at least one cyclitol is selected from the group consisting of inositol, quercitol, viscumitol, bornesitol, conduritol, ononitol, pinitol, pinpollitol, quebrachitol, quinic acid, shikimic acid, and valienol.

6. The method according to claim 1 , wherein component (A) and component (B) are introduced into the virgin thermoplastic material in a % by weight ratio of from 5:95 to 90:10.

7. The method according to claim 1 , wherein components (A) and (B) are introduced into the virgin thermoplastic material by mixing the components (A) and (B) with the virgin thermoplastic material present as a solid, and the resultant mixture is melted and cooled.

8. The method according to claim 1 , wherein the virgin thermoplastic material is selected from the group consisting of:

(a) polymers of olefins and polymers of diolefins,

(b) polymers of styrene,

(c) halogen-containing polymers,

(d) polymers of unsaturated esters,

(e) polymers of unsaturated alcohols and derivatives thereof,

(f) polyacetals,

(g) polyphenylene oxides, blends of polyphenylene oxides with polystyrene or polyamides, and blends of polyphenylene oxides with polyamides,

(h) polymers of cyclic ethers,

(i) polyurethanes of hydroxy-terminated polyethers and aromatic isocyanates, polyurethanes of hydroxy-terminated polyethers and aliphatic isocyanates, polyurethanes of hydroxy-terminated polyesters and aromatic isocyanates, and polyurethanes of hydroxy-terminated polyesters and aliphatic isocyanates,

(j) polyamides,

(k) polyimides, polyamide-imides, polyether imides, polyester imides, poly (ether) ketones, polysulfones, polyether sulfones, polyaryl sulfones, polyphenylene sulfide, polybenzimidazoles, polyhydantoins, and blends thereof,

(l) polyesters of aliphatic dicarboxylic acids and diols, polyesters of hydroxy-carboxylic acids, and polyesters of aromatic dicarboxylic acids and diols,

(m) polycarbonates (PC), polyester carbonates, and blends thereof,

(n) cellulose derivatives,

(o) difunctional epoxy compounds in combination with curing agents, and polyfunctional epoxy compounds in combination with curing agents,

(p) phenol resins,

(q) polyester resins of unsaturated dicarboxylic acids and diols with vinyl compounds,

(r) silicones,

(s) natural polymers, and

(t) combinations of the aforementioned polymers.

9. A plastics composition comprising (A) at least one polyphenol, (B) at least one alditol and/or one cyclitol, and (C) at least one virgin thermoplastic material,

wherein:

(A) is present in an amount of 0.02 to 3.0% by weight of a polyphenol selected from the group consisting of gallic acid, esters of gallic acid, hydroxytyrosol, chrysin, quercetin, hesperidin, neohesperidin, naringin, morin, caempherol, fisetin, anthocyanin, carnosic acid, carnosol, rosmarinic acid, resveratrol, tannins, and silymarin;

(B) is present in an amount of 0.02 to 3.0% by weight of at least one alditol and/or one cyclitol; and

(C) is present in an amount of 94.0 to 99.96% by weight; and

wherein the plastics composition is free of graphene and carbon nanotubes.

10. The plastics composition according to claim 9 , which further contains

at least one additive selected from the group consisting of UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleation agents, antinucleation agents, impact modifiers, plasticizers, lubricants, rheology modifiers, thixotropy agents, chain extenders, processing aids, demolding aids, flame retardants, pigments, dyes, optical brighteners, antimicrobial active substances, antistatic agents, thermally and/or electrically conductive additives, slip agents, antiblocking agents, coupling means, crosslinking agents, anticrosslinking agents, hydrophilizing agents, hydrophobing agents, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, propellants, degradation additives, antifoaming agents, odor scavengers, markers, antifogging agents, fillers, and reinforcements.

11. The plastics composition according to claim 9 , which additionally contains at least one additive selected from the group consisting of acid scavengers, light stabilizers, dispersants, and filler deactivators.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 6, 2021
From: METZSCH-ZILLIGEN, ELKE; PFAENDNER, RUDOLF
To: FRAUNHOFER-GESELLSCHAFT ZUR FÖRDERUNG DER ANGEWANDTEN FORSCHUNG E.V.
Reel/Frame 056767/0100 →
Priority Claims (1)
DE 10 2018 218 120.9 · Oct 23, 2018 · national
Continuity (1)
Related Publication 20210388176A1 · Dec 16, 2021
References Cited (71)
US 10138354B2 · Groos et al. · 2018 [cited by applicant]
US 10214631B2 · Pfaendner et al. · 2019 [cited by applicant]
US 10323136B2 · Pfaendner et al. · 2019 [cited by applicant]
US 10364340B2 · Pfaendner et al. · 2019 [cited by applicant]
US 10370537B2 · Pfaendner et al. · 2019 [cited by applicant]
US 10450442B2 · Pfaendner et al. · 2019 [cited by applicant]
US 10544284B2 · Pfaendner et al. · 2020 [cited by applicant]
US 10781296B2 · Groos et al. · 2020 [cited by applicant]
US 10913743B2 · Pfaendner et al. · 2021 [cited by applicant]
US 20120091399A1 · Guntermann et al. · 2012 [cited by applicant]
US 20130041086A1 · Kimura et al. · 2013 [cited by applicant]
US 20140039066A1 · Grimadell et al. · 2014 [cited by applicant]
US 20160052927A1 · Pfaendner et al. · 2016 [cited by applicant]
US 20160068665A1 · Budhavaram et al. · 2016 [cited by applicant]
US 20160272789A1 · Pfaendner et al. · 2016 [cited by applicant]
US 20170107375A1 · Pfaendner et al. · 2017 [cited by applicant]
US 20170121499A1 · Pfaendner et al. · 2017 [cited by applicant]
US 20170260362A1 · Pfaendner et al. · 2017 [cited by applicant]
US 20170260363A1 · Pfaendner et al. · 2017 [cited by applicant]
US 20170260366A1 · Pfaendner et al. · 2017 [cited by applicant]
US 20170267835A1 · Groos et al. · 2017 [cited by applicant]
US 20180186970A1 · Groos et al. · 2018 [cited by applicant]
US 20190248927A1 · Klein et al. · 2019 [cited by applicant]
US 20200231783A1 · Pfaendner et al. · 2020 [cited by applicant]
US 20200317886A1 · Pfaendner et al. · 2020 [cited by applicant]
US 20200361879A1 · Fischer et al. · 2020 [cited by applicant]
US 20210130582A1 · Ciesielski et al. · 2021 [cited by applicant]
CN 102378785A · 2012 [cited by applicant]
CN 104448464B · 2015 [cited by applicant]
DE 102009014856A1 · 2010 [cited by applicant]
DE 102017217312A1 · 2019 [cited by applicant]
JP 2002060638A · 2002 [cited by applicant]
JP 2012522079A · 2012 [cited by applicant]
JP 2015523403A · 2015 [cited by applicant]
WO WO2011024399A1 · 2011 [cited by applicant]
WO WO2019063550A1 · 2019 [cited by applicant]
Encyclopedia of Human Nutrition (Third Edition). (Year: 2013). [cited by examiner]
U.S. Appl. No. 14/442,606, filed May 13, 2015. [cited by applicant]
U.S. Appl. No. 14/779,849, filed Sep. 24, 2015. [cited by applicant]
U.S. Appl. No. 15/311,674, filed Nov. 16, 2016. [cited by applicant]
U.S. Appl. No. 15/317,899, filed Dec. 9, 2016. [cited by applicant]
U.S. Appl. No. 15/511,410, filed Mar. 15, 2017. [cited by applicant]
U.S. Appl. No. 15/511,471, filed Mar. 15, 2017. [cited by applicant]
U.S. Appl. No. 15/511,445, filed Mar. 15, 2017. [cited by applicant]
U.S. Appl. No. 15/529,026, filed May 23, 2017. [cited by applicant]
U.S. Appl. No. 15/738,515, filed Dec. 20, 2017. [cited by applicant]
U.S. Appl. No. 16/344,830, filed Apr. 25, 2019. [cited by applicant]
U.S. Appl. No. 16/488,902, filed Aug. 26, 2019. [cited by applicant]
U.S. Appl. No. 16/633,645, filed Jan. 24, 2020. [cited by applicant]
U.S. Appl. No. 16/649,656, filed Mar. 22, 2020. [cited by applicant]
U.S. Appl. No. 16/764,291, filed May 14, 2020. [cited by applicant]
U.S. Appl. No. 17/423,800, filed Jul. 16, 2021. [cited by applicant]
U.S. Appl. No. 17/425,267, filed Jul. 22, 2021. [cited by applicant]
U.S. Appl. No. 17/441,626, filed Sep. 21, 2021. [cited by applicant]
Al-Malaika, “Learning from mother nature: exploiting a biological antioxidant for the melt stabilisation of polymers,” [cited by applicant]
Xiang, “Steel Mesh Skeleton Composite Pipe,” Chemical Abstracts Service Database accession No. 2015:527627 (May 30, 2015). [cited by applicant]
Iida et al., “Stabilization of poly(vinyl chloride). V. Synergism between metal soaps and polyols upon stabilization of poly(vinyl chloride),” [cited by applicant]
Krönke et al., “Antioxidants,” [cited by applicant]
Richaud et al., “Polyethylene stabilization against thermal oxidation by a trimethylquinoleine oligomer,” [cited by applicant]
Steenwijk et al., “The effect of (natural) polyols on the initial colour of heavy metal/ and zinc/free poly(vinyl chloride),” [cited by applicant]
Wirth et al., “The stabilization of PVC against heat and light,” [cited by applicant]
German Patent Office, Office Action in German Patent Application No. 10 2018 218 120.9 (Dec. 11, 2018). [cited by applicant]
German Patent Office, Office Action in German Patent Application No. 10 2018 218 120.9 (Mar. 23, 2021). [cited by applicant]
European Patent Office, International Search Report in International Application No. PCT/EP2019/078221 (Feb. 3, 2020). [cited by applicant]
European Patent Office, Written Opinion in International Application No. PCT/EP2019/078221 (Feb. 3, 2020). [cited by applicant]
International Bureau of WIPO, International Preliminary Report on Patentability—Chapter I in International Application No. PCT/EP2019/078221 (Apr. 27, 2021). [cited by applicant]
U.S. Appl. No. 17/625,387, filed Jan. 7, 2022. [cited by applicant]
“Antioxidants”, edited by Xingjun Hu, National Defense Industry Press, first edition, p. 162, Oct. 2009. [cited by applicant]
China National Intellectual Property Administration, Decision on Rejection in Chinese Patent Application No. 201980069843.8 (Jul. 6, 2023). [cited by applicant]
Japan Patent Office, Notification of Reasons for Refusal in Japanese Patent Application No. 2021-522045 (Jul. 18, 2023). [cited by applicant]
Japan Patent Office, Notification of Reasons for Refusal in Japanese Patent Application No. 2021-522045 (Mar. 12, 2024). [cited by applicant]