Process for preparing a functionalised polyHIPE polymer

(12) United States Patent Akay et a].

US007820729B2

US 7,820,729 B2 Oct. 26, 2010

(10) Patent N0.: (45) Date of Patent:

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PROCESS FOR PREPARING A FUNCTIONALISED POLYHIPE POLYMER

Inventors: Galip Akay, Newcastle Upon Tyne (GB); Zainura Zainon Noor, Newcastle Upon Tyne (GB); Omer Faruk Calkan, Newcastle Upon Tyne (GB); Teresa Manguangua Ndlovu, Newcastle Upon Tyne (GB); David Robert Burke, Newcastle Upone Tyne (GB)

Assignee: University of Newcastle Upon Tyne, c/o School of Chemical Engineering and Advanced Materials (GB)

Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 1231 days.

Appl. N0.: 11/403,996

Filed: Apr. 13, 2006

Prior Publication Data

US 2008/0281003 A1 Nov. 13, 2008

Int. Cl. C08F 2/00 (2006.01) C08F 2/24 (2006.01) C08F 2/22 (2006.01) C08F 2/46 (2006.01) US. Cl. ...................... .. 521/50.5; 521/64; 521/134;

521/135; 521/140; 521/143; 521/146; 521/149; 521/150; 521/915; 522/1; 522/84; 522/85;

522/86 Field of Classi?cation Search .............. .. 521/50.5,

521/64,134,135,140,143,146,149,150, 521/915; 522/1, 84, 85, 86

See application ?le for complete search history.

(56) References Cited

U.S. PATENT DOCUMENTS

4,522,953 A * 6/1985 Barby et al. ................ .. 521/64

4,606,958 A * 8/1986 Haq et al. ................... .. 428/68

4,611,014 A * 9/1986 Jomes et al. 521/146

4,612,334 A * 9/1986 Jones et al. ............... .. 521/146

4,775,655 A * 10/1988 Edwards et a1. ........... .. 502/416

4,788,225 A * 11/1988 Edwards et a1. 521/147

4,839,395 A * 6/1989 Masamizu et al. .......... .. 521/56

5,147,345 A * 9/1992 Young et al. .............. .. 604/378

5,149,720 A * 9/1992 DesMarais et a1. 521/63

5,198,472 A * 3/1993 DesMarais et a1. .......... .. 521/63

5,200,433 A * 4/1993 Beshouri 521/64

5,763,499 A * 6/1998 DesMarais . 521/64

5,795,921 A * 8/1998 Dyer etal. ................ .. 521/146

FOREIGN PATENT DOCUMENTS

EP 0060138 B1 * 9/1982

W0 W0 0034454 A2 * 6/2000

W0 WO 2004005355 A1 * 1/2004

* cited by examiner

Primary ExamineriSanza L McClendon (74) Attorney, Agent, or FirmiHarness, Dickey & Pierce, P.L.C.

(57) ABSTRACT

A process for preparing functionalised microporous poly mers (which are also known as micro-cellular polymers or polyHlPE polymers (PHPs)) using intensi?ed internal heat ing (for example by microwave irradiation).

38 Claims, 21 Drawing Sheets

US. Patent 0a. 26, 2010 Sheet 1 0f 21 US 7,820,729 B2



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US 7,820,729 B2 Sheet 10 0f 21 Oct. 26, 2010 US. Patent

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US. Patent 0a. 26, 2010 Sheet 11 0121 US 7,820,729 B2

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US. Patent 0a. 26, 2010 Sheet 12 of 21 US 7,820,729 B2

Sample X -1: Before sulphonation Surface area = 128. 6 ng" sample X-l with microwave for 8 minutes

Sample X-2: After sulphonation of

Surface area = 242. 7 ng‘l

Fig. 11B: Magnifiction

Fig. 11C: Magni?cation : 65000x(X1-6) Fi g. 11F: Magnification 65000x(X2-2)

US. Patent Oct. 26, 2010 Sheet 13 0f 21 US 7,820,729 B2

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Fig. 11: Sample x ag?cation = 1000x (XS-2)

Fig. 11H: Sample X3: Magni?ation = 10000:: (X3-3)

Fig. 11: Sample xs: Magnifiation :65000x (X3-5)

US 7,820,729 B2 Sheet 14 0f 21 Oct. 26, 2010 US. Patent

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Fig. 13A: Sample: A9A- 5: Fig. 14A: Sample A9A-l: Coalescence Pores dispersed into Coalescenee Pores dispersed into primary pores primary pores

Fig. 13B: Sample A9A-6: Fig. 14B: Sample A9B- 7: Two Coalescence pore coalescence pores

Fig. 13C: Sample: A9A-8: Primary pores Fig. 14C: Sample: A9B—4: Primary pores


Fig, 13D: Sample: A9A-2: Fracture Fig. 14D: Sample: A9B-4 Fracture surface of pore wall surface of pore wall

Fig. 13E: Sample A9A-l: Detail of Fig. 14E: Sample A9B-2: Fracture the fracture surface in A9A-2 surface detail

Fig. 13F: Sample A9A-7: Surface Fig. 14F: Sample: A9B-9: Surface appearance of coalescence pore in of coalesce pore showing ?ne cracks A9A-6 which are absent before irradiation.


Fig. 15A: A74A-7: Fig. 16A: A74B-5: Coalescence pores Coalesce pores

Fig. 15B: A74A-6: Fig. 16B: A74B: Wall structure Wall structure

Fig. 15C: Sample A74A-5: fracture Fig. 16C: Sample A74B-3: Fracture surface of wall surface of wall


Fig. 15D: Sample: A74A-2: Fracture Fig. 16D: Sample: A74B-1 Fracture surface of wall (Magni?cation: X surface of wall (Magnification: 100,000) X50,000)


Fig. 1515: Sample A74A-8: Surface of a Fig. 1615: Sample A74A-8: Surface of a coalescence pore at magnification X coalescence pore at magnification X 100,000. No sign of surface cracks. 20,000.

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Process for preparing a functionalised polyHIPE polymer

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