# US 11,993,691 B2 · Use of geopolymeric additive in combination with non-brominated flame retardant in polymer foams

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- Number: US 11,993,691 B2
- Document ID: US11993691B2
- Status: Granted
- Kind: B2
- Application number: 17/877,183
- Filed: 2022-07-29
- Published: 2023-02-16
- Granted: 2024-05-28
- Earliest claimed: 2016-07-20
- Assignees: Synthos S.A.
- Applicants: Synthos S.A.
- Inventors: Filip Lukasz Kondratowicz; Kamil Utrata
- Web page: https://patentgrep.com/patent/US11993691B2

## CPC

- C08J 9/18: by impregnating polymer particles with the blowing agent
- C04B 28/006: {containing mineral polymers, e.g. geopolymers of the Davidovits type}
- C08J 9/0038: {containing phosphorus}
- C08J 9/0066: {Use of inorganic compounding ingredients}
- C08J 9/0095: {Mixtures of at least two compounding ingredients belonging to different one-dot groups}
- C08J 9/141: {Hydrocarbons}
- C08J 9/16: Making expandable particles
- C08J 9/228: Forming foamed products
- C08K 3/32: Phosphorus-containing compounds
- C08K 3/34: Silicon-containing compounds
- C08K 5/5397: Phosphine oxides
- C04B 2103/63: Flame-proofing agents
- C04B 2111/28: Fire resistance, i.e. materials resistant to accidental fires or high temperatures
- C08J 2201/03: Extrusion of the foamable blend
- C08J 2203/14: Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J 2203/182: of physical blowing agents, e.g. acetone and butane
- C08J 2203/22: Expandable microspheres, e.g. Expancel®
- C08J 2325/04: Homopolymers or copolymers of styrene
- C08J 2325/06: Polystyrene
- C08J 2325/08: Copolymers of styrene (C08J2329/08, C08J2335/06, C08J2355/02 take precedence)
- C08K 2003/323: {Ammonium polyphosphate}
- C08K 2003/329: {Phosphorus containing acids}
- C08K 2201/005: Additives being defined by their particle size in general
- C08K 2201/006: Additives being defined by their surface area
- Y02P 40/10: Production of cement, e.g. improving or optimising the production methods; Cement grinding
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The invention relates to the use of i) geopolymer and ii) non-brominated, phosphorus- and/or nitrogen-based flame retardants for improving the self-extinguishing properties of a composition comprising polymer. The polymer may be a vinyl aromatic polymer, and may be in a granulate or foam.

## Claims

### Claim 1

A process for the production of expandable polymer granulate by an extrusion or a suspension process, the process comprising the addition of
i) one or more geopolymer additives, wherein the geopolymer additive is
a) a geopolymer;
b) a combination of a geopolymer with an athermanous additive; or
c) a geopolymer composite derived from geopolymer and comprising athermanous additive,
and
ii) one or more non-brominated flame retardants selected from
a) phosphorus-based flame retardants,
b) nitrogen-based flame retardants, and
c) phosphorus/nitrogen-based flame retardants;
wherein the polymer is a vinyl aromatic polymer, and
wherein the geopolymer or geopolymer composite has a particle size in the range of 0.1 μm to 200 μm.

### Claim 2

Composition comprising one or more vinyl aromatic polymers, the composition further comprising
i) one or more geopolymer additives, wherein the geopolymer additive is
a) a geopolymer;
b) a combination of a geopolymer with an athermanous additive; or
c) a geopolymer composite derived from geopolymer and comprising athermanous additive,
and
ii) one or more non-brominated flame retardants selected from
a) phosphorus-based flame retardants,
b) nitrogen-based flame retardants, and
c) phosphorus/nitrogen-based flame retardants,
wherein the composition is in the form of an expandable granulate,
wherein the polymer is a vinyl aromatic polymer, the granulate further comprising one or more propellants, and
wherein the geopolymer or geopolymer composite has a particle size in the range of 0.1 μm to 200 μm.

### Claim 3

Composition comprising one or more polymers, the composition further comprising
i) one or more geopolymer additives, wherein the geopolymer additive is
d) a geopolymer;
e) a combination of a geopolymer with an athermanous additive; or
f) a geopolymer composite derived from geopolymer and comprising athermanous additive,
and
ii) one or more non-brominated flame retardants selected from
d) phosphorus-based flame retardants,
e) nitrogen-based flame retardants, and
f) phosphorus/nitrogen-based flame retardants,
wherein the composition is in the form of expanded vinyl polymer foam, and the vinyl polymer is vinyl aromatic polymer,
the foam having
a density of from 8 to 30 kg/m3, and
a thermal conductivity (as measured according to ISO 8301) of from 25 to 35 mW/K·m,
wherein the geopolymer or geopolymer composite has a particle size in the range of 0.1 μm to 200 μm.

### Claim 4 (depends on 3)

The expanded vinyl polymer foam of claim 3, obtainable by expansion of a granulate, comprising a composition comprising one or more polymers, the composition further comprising
i) one or more geopolymer additives, wherein the geopolymer additive is
a) a geopolymer;
b) a combination of a geopolymer with an athermanous additive; or
c) a geopolymer composite derived from geopolymer and comprising athermanous additive,
and
ii) one or more non-brominated flame retardants selected from
a) phosphorus-based flame retardants,
b) nitrogen-based flame retardants, and
c) phosphorus/nitrogen-based flame retardants,
wherein the composition is in the form of an expandable granulate, wherein the polymer is a vinyl aromatic polymer, the granulate further comprising one or more propellants.

### Claim 5 (depends on 2)

The composition of claim 2, which composition comprises
vinyl aromatic polymer prepared from styrene monomer with optional incorporation of one or more vinyl comonomers and
c) 0.01-50 wt. % (by polymer weight, including solid and, if any, liquid additives, but exclusive of propellant) of geopolymer composite in powder form, with a particle size in a range of from 0.1 μm to 200 μm and a BET surface in a range of from 0.01 to 10,000 m2/g.

### Claim 6 (depends on 2)

The composition of claim 2, wherein the composition does not comprise polymeric brominated flame retardant.

### Claim 7 (depends on 2)

The composition of claim 2, wherein the composition does not comprise brominated flame retardant.

### Claim 8 (depends on 2)

The composition of claim 2, wherein the composition does not comprise halogenated flame retardant.

### Claim 9 (depends on 2)

The composition of claim 2, wherein the athermanous additive is one or more selected from the group consisting of
(1) carbon-based athermanous additives,
(2) metal athermanous additives,
(3) metal oxide athermanous additives, and
(4) metal sulfide athermanous additives.

### Claim 10 (depends on 9)

The composition of claim 9, wherein the carbon-based athermanous additive is selected from carbon black, coke, graphitized carbon black, graphite, graphite oxides, anthracite, graphene, and graphene oxide.

### Claim 11 (depends on 9)

The composition of claim 9, wherein the metal athermanous additive is selected from copper, bismuth, nickel, iron, tungsten, silver, cadmium, cobalt, tin, and zinc.

### Claim 12 (depends on 9)

The composition of claim 9, wherein the metal oxide athermanous additive is selected from oxides of the metals of groups IIIB, IV-VIIIA, and I-VB of the periodic table.

### Claim 13 (depends on 2)

The composition of claim 2, wherein the phosphorus-based flame retardant a) is selected from red phosphorus, organic and inorganic phosphates, phosphon-ates, phosphinates, and phosphoramidates.

### Claim 14 (depends on 13)

The composition of claim 13, wherein
the organic phosphate is selected from triphenyl phosphate (TPP), resorcinol bis(diphenyl¬phosphate) (RDP), bisphenol A bis(diphenylphosphate) (BADP), tri¬cresyl phosphate (TCP), and resorcinol bis(2,6-dixylenyl¬¬phosphate) (RDX),
the phosphinate is selected from aluminium phosphinates, calcium phosphinates and zinc phosphinates, and
the phosphoramidate is 9,10-Dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO).

### Claim 15 (depends on 2)

The composition of claim 2, wherein the nitrogen-based flame retardant b) is selected from hindered amine stabilizer, ammonium octamolybdate, melamine octamolybdate, benzoguanamine, tris(hydroxy¬ethyl) isocyanurate, allantois, glycoluril, melamine, melamine cyanurate, dicyandiamide, guanidine, carbo¬diimides, condensation products of melamine, and derivatives thereof.

### Claim 16 (depends on 2)

The composition of claim 2, wherein the phosphorus/nitrogen-based flame retardant c) is selected from melamine phosphate, melamine pyrophosphate, melamine polyphosphate ammonium polyphosphate, and ethylene diamine phosphate.

### Claim 17 (depends on 2)

The composition of claim 2, wherein the non-brominated flame retardant is a non-halogenated flame retardant.

### Claim 18 (depends on 2)

The composition of claim 2, wherein the geopolymer or geopolymer composite has been modified with one or more water-soluble compounds.

### Claim 19 (depends on 18)

The composition of claim 18, wherein the water-soluble compound is selected from phosphorus compounds, nitrogen compounds, copper compounds, silver compounds, zinc compounds, tin compounds, and magnesium compounds.

### Claim 20 (depends on 19)

The composition of claim 19, wherein the modification is with a phosphorus compound.

### Claim 21 (depends on 20)

The composition of claim 20, wherein the modification is with a phosphorus compound selected from phosphoric acid and ammonium polyphosphate.

### Claim 22 (depends on 2)

The composition of claim 2, wherein the geopolymer or geopolymer composite has an average particle size (D50) in the range of 0.1 to 10 μm.