process for preparing a functionalised polyhipe polymer
TRANSCRIPT
(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
US. Patent 0a. 26, 2010 Sheet 2 0f 21 US 7,820,729 B2
US. Patent 0a. 26, 2010 Sheet 3 0f 21 US 7,820,729 B2
GA2S-2 Fig. 3A
GA3S -2(TI-ID-1) Fig. 31;
US. Patent 0a. 26, 2010 Sheet 4 0f 21 US 7,820,729 B2
GA4S-2 (THC-2)
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REQV Spot Magn Del WD }———1 10pm 70.00 l-IV 4 I] 2'30!le SE 100 Newcas-?e Uni
GA45-4 (THC-2) Fig. 4B
US. Patent 0a. 26, 2010 Sheet 5 0f 21 US 7,820,729 B2
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my Spot Magn Del WD 70.00 l-(V 5.0 500): SE 1|.3 0MB, Newcastle Uni
GAZS (MWD-7) Fig. 5A
Kiev “8‘00! Magn Der WD‘ 10 pm 70.00 IN ALI 2500* SE 11 3 Newcastle Uni
GA2S (MWD-7) Fig. 5B
US. Patent 0a. 26, 2010 Sheet 6 0f 21 US 7,820,729 B2
(ch-cz) Fig. 6A
(MWC-CS) Fig. 6B
US. Patent 0a. 26, 2010 Sheet 7 0f 21 US 7,820,729 B2
{claim-v30 sum SE 125
(MWC-DZ)
~"~.cc.V Spot Magn Del WEI 2 pm” "I ll] OD kV 3 D 15000! SE l2 5 (MA Newcastle Uni
(ch -D5) Fig. 712.
US. Patent 0a. 26, 2010 Sheet 8 0f 21 US 7,820,729 B2
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3.02M Spot Magn Del W0 }———| 50 pm T"10E! W 3 D SlJlIl'x SE ? :1 GM“, Newca?le Uni
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US. Patent 0a. 26, 2010 Sheet 9 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
00 nm Del W0 100000 X S E
ACQV Spot Magn 107 10.00 I-:\/ 2.0
Fig. 9C
Det WD SE 10.5 100000):
Spot Magn 10.00 kV 2.0
Fig. 9D (GA-3-9)
US. Patent 0a. 26, 2010 Sheet 11 0121 US 7,820,729 B2
ikccv Spot Magn [let WEI In?lle 3D ".1me SE 119 ELTIF
.cc,\/ Spot-Magn‘ we: WEI ~ £1ka 30 100cm: SE 119 SIS XLTIF
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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A“ V 5pm Inga Cel v.3 } ‘ - I I ' I l- '1] I
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
my, mu“. ‘
madam 2n SIS ILJW
: (X100,000) . 1213 Fig (X 1000) . 12A: Fig
(X100,000) lFig. 1211) : (X35,000) Fig. 12c
US. Patent 0a. 26, 2010 Sheet 15 0f 21 US 7,820,729 B2
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
US. Patent 0a. 26, 2010 Sheet 16 0f 21 US 7,820,729 B2
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.
US. Patent 0a. 26, 2010 Sheet 17 0f 21 US 7,820,729 B2
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
US. Patent 0a. 26, 2010 Sheet 18 0f 21 US 7,820,729 B2
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)
US. Patent 0a. 26, 2010 Sheet 19 0f 21 US 7,820,729 B2
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.