IP Library Granted Patent US 10,544,277
Granted Patent B2
US 10,544,277 · App. 15/787,083 · Granted Jan 28, 2020

Process for making gray expanded polystyrene

Inventors: Paul Hanna (Sugar Land, TX); Hakim Hazaimeh (Richmond, TX); William Cottom (Richmond, TX); Jeff Brooks (Owasso, OK)
Assignee: Baker Hughes, a GE company, LLC
C08K3/04C08F2/18C08F12/08C08L25/06C09C1/48C08F2500/01C08F2500/04
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Quick Facts
Patent No.
US 10,544,277
App. No.
15/787,083
Granted
Jan 28, 2020
Kind
B2
Abstract

Gray expanded polystyrene achieving target molecular weight, bead size, bead distribution, and cell structure may be reproducibly prepared by suspension polymerization by introducing to the suspension polymerization an additive that is carbon black and/or graphite only after approximately 20 to 60 wt % of the styrene monomer has been converted to polystyrene. Introducing the additive at this point slows the polymerization rate, such as for an optimized period of time to allow for the droplet size to equilibrate to the desired target range. In one nonlimiting embodiment, the styrene polymerization rate has about 35 wt % to about 60 wt % styrene monomer remaining after about 3 hours from the beginning of polymerizing.

Claims (73)

1. A method for preparing gray expanded polystyrene (EPS), the method comprising:

polymerizing styrene monomer to polystyrene by suspension polymerization;

after approximately 20 to 60 wt % of the styrene monomer has been converted to polystyrene, introducing to the suspension polymerization an additive selected from the group consisting of carbon black, graphite, and combinations thereof; and after a period of polymerizing to allow droplet size to equilibrate to within a desired size range between about 0.1 mm and about 1.0 mm, then

continuing to polymerize the styrene monomer to polystyrene by suspension polymerization to produce gray EPS having:

a weight average molecular weight between about 50,000 and about 1,000,000 amu;

a bead size between about 50 and about 1500 microns;

a bead distribution where from about 10 to about 90 weight % of the beads are in the range of about 850 to about 1170 microns; and

a cell size between about 4 and about 20 cells per millimeter.

2. The method of claim 1 where the gray EPS has a density from about 5 to about 35 g/l.

3. The method of claim 1 where the additive is introduced by a method selected from the group consisting of:

introducing the additive predispersed as a masterbatch;

introducing the additive as fluff or powder grade; and

combinations thereof.

4. The method of claim 3 , where

when the additive is introduced predispersed as a masterbatch:

a primary free radical initiator is introduced which is activated at about 90° C. in an amount from about 0.3 wt % to about 0.5 wt % based on the styrene monomer, and

a secondary free radical initiator is introduced which is activated at about 130° C. in an amount from about 0.1 wt % to about 0.3 wt % based on the styrene monomer;

when the additive is introduced as fluff or powder grade:

a free radical initiator is introduced which is in an initial dose in an amount from about 0.3 wt % to about 0.5 wt % based on the styrene monomer, and

a free radical initiator is introduced which is in an additional dose in an amount from about 0.4 wt % to about 0.6 wt % based on the styrene monomer; and

when the additive is introduced as a combination of predispersed as a masterbatch and as fluff or powder grade:

a free radical initiator is introduced which is in an initial dose in an amount from about 0.3 wt % to about 0.5 wt % based on the styrene monomer, and

a free radical initiator is introduced which is in an additional dose in an amount from about 0.3 wt % to about 0.5 wt % based on the styrene monomer.

5. The method of claim 1 where the amount of additive introduced ranges from about 0.1 to about 10 wt %, based on the produced gray EPS.

6. A method for preparing gray expanded polystyrene (EPS), the method comprising:

polymerizing styrene monomer to polystyrene by suspension polymerization;

after approximately 20 to 60 wt % of the styrene monomer has been converted to polystyrene, introducing to the suspension polymerization an additive selected from the group consisting of carbon black, graphite, and combinations thereof; and after a period polymerizing to allow droplet size to equilibrate to within a desired size range between about 0.1 mm and about 1.0 mm; and

continuing to polymerize the styrene monomer to polystyrene by suspension polymerization to produce gray EPS having:

a density from about 5 to about 35 g/l;

a cell size between about 4 and about 20 cells per millimeter;

a weight average molecular weight between about 50,000 and about 1,000,000 amu;

a bead size between about 50 and about 1500 microns; and

a bead distribution where from about 10 to about 90 weight % of the beads are in the range of about 850 to about 1170 microns;

where the polymerizing has a polymerization rate, and where the polymerization rate has about 35 wt % to about 60 wt % styrene monomer remaining after about 3 hours from the beginning of polymerizing.

7. The method of claim 6 where the additive is introduced by a method selected from the group consisting of:

introducing the additive predispersed as a masterbatch;

introducing the additive as fluff or powder grade; and

combinations thereof.

8. The method of claim 7 introduced predispersed as a masterbatch:

a primary free radical initiator is introduced which is activated at about 90° C. in an amount from about 0.3wt % to about 0.5 wt % based on the styrene monomer, and

a secondary free radical initiator is introduced which is activated at about 130° C. in an amount from about 0.1 wt % to about 0.3 wt % based on the styrene monomer;

when the additive is introduced as fluff or powder grade:

a free radical initiator is introduced which is in an initial dose in an amount from about 0.3 wt % to about 0.5 wt % based on the styrene monomer, and

a free radical initiator is introduced which is in an additional dose in an amount from about 0.4 wt % to about 0.6 wt % based on the styrene monomer; and

when the additive is introduced as a combination of predispersed as a masterbatch and as fluff or powder grade:

a free radical initiator is introduced which is in an initial dose in an amount from about 0.3 wt % to about 0.5 wt % based on the styrene monomer, and

a free radical initiator is introduced which is in an additional dose in an amount from about 0.3 wt % to about 0.5 wt % based on the styrene monomer.

9. The method of claim 6 where the amount of additive introduced ranges from about 0.1 to about 10 wt %, based on the produced gray EPS.

10. A method for preparing gray expanded polystyrene (EPS), the method comprising:

polymerizing styrene monomer to polystyrene by suspension polymerization;

after approximately 20 to 60 wt % of the styrene monomer has been converted to polystyrene, introducing to the suspension polymerization an additive selected from the group consisting of carbon black, graphite, and combinations thereof, and after a period polymerizing to allow droplet size to equilibrate to within a desired size range, where the additive is introduced by a method selected from the group consisting of:

introducing the additive predispersed as a masterbatch;

introducing the additive as fluff or powder grade; and

combinations thereof;

when the additive is introduced predispersed as a masterbatch:

a primary free radical initiator is introduced which is activated at about 90° C. in an amount from about 0.3 wt % to about 0.5 wt % based on the styrene monomer, and

a secondary free radical initiator is introduced which is activated at about 130° C. in an amount from about 0.1 wt % to about 0.3 wt % based on the styrene monomer;

when the additive is introduced as fluff or powder grade:

a free radical initiator is introduced which is activated at about 90° C. in an initial dose in an amount from about 0.3 wt % to about 0.5 wt % based on the styrene monomer, and

a free radical initiator is introduced which is activated at about 130° C. in an additional dose in an amount from about 0.4 wt % to about 0.6wt % based on the styrene monomer; and

when the additive is introduced as a combination of predispersed as a masterbatch and as fluff or powder grade:

a free radical initiator is introduced which is activated at about 90° C. in an initial dose in an amount from about 0.3 wt % to about 0.5% wt % based on the styrene monomer, and

a free radical initiator is introduced which is activated at about 130° C. in an additional dose in an amount from about 0.3 wt % to about 0.5 wt % based on the styrene monomer; and

continuing to polymerize the styrene monomer to polystyrene by suspension polymerization to produce gray EPS.

11. The method of claim 10 where the desired droplet size ranges between about 0.1 mm and about 1.0 mm.

12. The method of claim 10 where the gray EPS:

has a weight average molecular weight between about 50,000 and about 1,000,000 amu;

has a bead size between about 50 and about 1500 microns;

has a bead distribution where from about 10 to about 90 weight % of the beads are in the range of about 850 to about 1170 microns; and

has a cell size between about 4 and about 20 cells per millimeter.

13. The method of claim 10 where the gray EPS has a density from about 5 to about 35 g/l.

14. The method of claim 10 where the amount of additive introduced ranges from about 0.1 to about 10 wt %, based on the produced gray EPS.

15. The method of claim 10 where the polymerizing has a polymerization rate, and where the polymerization rate has about 35 wt % to about 60 wt % styrene monomer remaining after about 3 hours from the beginning of polymerizing.

Assignments (8)
GRANT OF SECURITY INTEREST IN PATENT RIGHTS Recorded Apr 22, 2025
From: CHASE CORPORATION; NEPTCO INCORPORATED; NUCERA SOLUTIONS LLC; STEWART SUPERABSORBENTS, LLC
To: MORGAN STANLEY SENIOR FUNDING, INC., AS COLLATERAL AGENT
Reel/Frame 070909/0765 →
RELEASE OF SECURITY INTEREST IN PATENT COLLATERAL, RECORDED ON NOVEMBER 17, 2023 AT REEL 065597, FRAME 0771 Recorded Apr 22, 2025
From: ANTARES CAPITAL LP, AS COLLATERAL AGENT
To: CHASE CORPORATION; NEPTCO INCORPORATED; NUCERA SOLUTIONS LLC; STEWART SUPERABSORBENTS, LLC
Reel/Frame 070906/0753 →
SECURITY INTEREST Recorded Nov 17, 2023
From: CHASE CORPORATION; NEPTCO INCORPORATED; NUCERA SOLUTIONS LLC; STEWART SUPERABSORBENTS, LLC
To: ANTARES CAPITAL LP, AS COLLATERAL AGENT
Reel/Frame 065597/0771 →
RELEASE OF SECURITY INTEREST IN PATENT COLLATERAL AT REEL/FRAME NO. 54571/0200 Recorded Sep 2, 2022
From: KEYBANK NATIONAL ASSOCIATION, AS ADMINISTRATIVE AGENT
To: NUCERA SOLUTIONS LLC
Reel/Frame 061372/0144 →
PATENT SECURITY AGREEMENT Recorded Dec 2, 2020
From: NUCERA SOLUTIONS LLC
To: KEYBANK NATIONAL ASSOCIATION, AS ADMINISTRATIVE AGENT
Reel/Frame 054571/0200 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 26, 2020
From: BAKER HUGHES HOLDINGS LLC
To: NUCERA SOLUTIONS LLC
Reel/Frame 054166/0108 →
CHANGE OF NAME Recorded Jun 19, 2020
From: BAKER HUGHES A GE COMPANY, LLC
To: BAKER HUGHES HOLDINGS LLC
Reel/Frame 052989/0256 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 27, 2018
From: HANNA, PAUL; HAZAIMEH, HAKIM; COTTOM, WILLIAM; BROOKS, JEFF
To: BAKER HUGHES, A GE COMPANY, LLC
Reel/Frame 045053/0812 →
Continuity (1)
Related Publication 20190112447A1 · Apr 18, 2019