High strength polymeric networks derived from (meth) acrylate

35 Pages·2013·2.24 MB·English

US006184339B1
(12) United States Patent
(10) Patent N0.: US 6,184,339 B1
Stansbury et al. (45) Date of Patent: Feb. 6, 2001
(54) HIGH STRENGTH POLYMERIC NETWORKS 5,075,378 * 12/1991 Smierciak et al. ................. .. 525/109
DERIVED FROM (METH) ACRYLATE 5,380,901 1/1995 Antonucci et al. .
RESINS WITH ORGANOFLUORINE 5,406,641 4/1995 Bigley, Jr. et al. .
CONTENT AND PROCESS FOR PREPARING 574857541 1/1996 Bigley, Jr- e‘ ‘11- -
SAME 5,486,548 1/1996 PodsZun et a1. .
FOREIGN PATENT DOCUMENTS
(75) Inventors: Je?'rey W. Stansbury, Frederick;
Joseph M. Antonucci, Kensington; 1199937 8/1989 (JP) -
Kyllllg M. Choi, Gaithersburg, all Of OTHER PUBLICATIONS
MD (US)
Stansbury et al Polymer Preprints, 39(2), 878—879, 1998*
(73) Assignee: The United States of America as Choi et al Chem. Mater. 1996, 8, 2704—2707.*
represented by the Secretary of the Antonucci et al. Polymer Preprints, 1993, 34, 403—404.*
Commerce, Washington, DC (US) Stansbury et al, Polymer Preprints, 1995, 36(1), 831—832.*
Stansbury et al, Polymer Preprints, 1997, 38(2), 96—97.*
(*) NOIiCeI Under 35 U50 154(1)), the term Of this Stansbury, Macromolecules, 1991, 24, 2029—2035.*
patent Shall be eXtended for 0 days- Antonucci et al, Polymer Preprints, 1990, 31, 320—321.*
T. Maruno et al, Synthesis and properties of ?uorine—con
(21) Appl, N()_j 08/967,896 taining epoXy(meth)acrylate resins. J. Polym. Sci; Polym.
_ Chem. 1994, 32, 3211.
(22) Flled: NOV‘ 12’ 1997 O. Nuyken et al, Studies on neW non—shrinking, thermally
_ _ stable Araldite—type photopolymers With pendent aryl acry
_ _ Related U'_S‘ Apphcatlon Data loyl groups. Angew. Makromol. Chem. 1992, 199, 149.
(60) lljgggisional application No. 60/030,911, ?led on Nov. 14, 1M‘ Antonucci, J'VV~ stansbury, S~ VenZ, Synthesis and
' properties of a poly?uorinated prepolymer multifunctional
Int. (:1.7 ............................... .. urethane methacrylatg InjPrOgreSS Biomedicglpolymers,
C08K 2/00; C08G 65/00 C.G. Gebelein and R.L. Dunn, eds., Plenum Press, NeW
(52) US. Cl. .......................... .. 528/407; 522/90; 522/155; York, 1990.
522/156; 522/100; 522/908; 523/109; 523/116; * . .
523/118; 523/115; 523/300; 423/226; 528/406; ‘med by exammer
528/418; 528/59; 528/65; 528/87 Primary Examiner—James J. Seidleck
(58) Field Of Search .............................. .. 528/407, 59, 65, Assistant Examiner—SanZa L_ Mcclendon
528/418, 87, 406; 522/90, 96, 100, 155, (74) Attorney, Agent, or Firm—Stevens, Davis, Miller &
156; 523/109; 433/226, 228.1 Mosher, LLP
(56) References Cited (57) ABSTRACT
U_S_ PATENT DOCUMENTS Disclosed are ?uorinated materials for use in dental uses and
3 852 222 * 12/1974 Field et al 525/528 non-dental uses, e.g., aldhesives coatirégs. l\/(Iulti€1i;nctio1nal
’ ’ _ ' """"""""""""" " monomers an prepo ymers Wit pen ant met acry ate
4:356j296 10/1982 Grif?th et aL _ ................... Resins based on the ?uorinated monomers and prepolymers
473967377 8/1983 Roemer et a1_ _ With diluent comonomers, Were photocured as composites
4,396,476 8/1983 Roemer et a1_ _ With particulate ?llers. Fluorine contents of the prepolymers
4,514,342 4/1985 Billington et al. . ranged from 15 to 65%. Composites With high transverse
4,525,493 6/1985 Omura et a1. . strength (up to 120 MPa), loW Water sorption (as loW as 0.11
4,536,523 8/1985 Amonucci- mass %) and extremely loW polymerization shrinkage (as
475397382 * 9/1985 Omura “fil- - loW as 3.4% by volume) Were obtained. The ?uorinated
8231210521‘ """"""""""""" " 526/246 resins may be employed to produce hydrophobic dental
4:871j786 “V1989 Aasen et a1: compositte 'mkaterials With high strength and loW polymer
4,914,171 * 4/1990 Zwei ................................ .. 526/246 “anon S n“ age
5,004,790 * 4/1991 Harnigsh et al. .................... .. 526/242
5,061,184 10/1991 Yamazaki et al. . 17 Claims, 7 Drawing Sheets
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US 6,184,339 B1
1 2
HIGH STRENGTH POLYMERIC NETWORKS translucence of the cured composite that gives it the natural
DERIVED FROM (METH) ACRYLATE tooth-like appearance. Coloration incorporated during the
RESINS WITH ORGANOFLUORINE preparation of the ?ller can reproduce a broad spectrum of
CONTENT AND PROCESS FOR PREPARING natural tooth shades and this alloWs near perfect matching of
the composite to the adjacent tooth structure. The small
SAME
particle siZe of the ?llers used in the dental composites
means that the composites can be polished to produce an
The present application claims priority of US. Provi
excellent texture match With natural tooth.
sional Patent Application Ser. No. 60/030,911, ?led Nov. 14,
Typical conventional resins based on Bis-GMA and
1996 and incorporated herein by reference.
TEGDMA ranging from mass ratios of 50:50 to 80:20,
10
FIELD OF THE INVENTION depending on the particular dental application, provide
strong polymers. The cross-linked polymers are glasses
The present invention relates to high strength polymeric Whose degree of conversion of the available methacrylate
netWorks derived from (meth)acrylate resins With moderate groups is restricted by vitri?cation as the glass transition
to high organo?uorine contents and processes for making temperature of the developing polymer reaches the cure
15
same. In particular, these resins are useful for dental com temperature. The degree of conversion attained during ambi
posites.
ent temperature photopolymerZation is generally in the
range 60% to 70%. The conversion varies someWhat With
BACKGROUND OF THE INVENTION
the intensity of the curing light; a more intense irradiation
In dentistry, ?uoropolymers have been Widely utiliZed as results in a faster polymeriZation With a greater exotherm.
20
components of medical devices because of the advantageous The fully cured resin is characteriZed as a highly cross
blend of chemical inertness With generally good biocompat linked three dimensional polymeric netWork With many
ibility. As the demand for advanced ?uoropolymers With pendant methacrylate-terminated chains that lack suf?cient
speci?c physical properties has groWn, the molecular design mobility for further reaction.
of neW types of ?uorinated monomers has become an Polymers designed to permanently replace tissues in the
25
important area in synthetic polymer chemistry. Several prop human body lost to disease, trauma or simple deterioration
erties of ?uoropolymers, including their chemical inertness, must satisfy a number of criteria. Beyond the obvious
hydrophobicity and toughness, make ?uoropolymers inter requirement of biocompatibility, long-tem stability dictates
esting candidates for use in dental composites. HoWever, due the need for materials that are highly resistant to alteration
to loW cohesive energies, amorphous ?uorinated polymers or degradation upon exposure to aqueous environments and
30
tend to have unacceptably loW mechanical strength. resistant to a variety of chemical substances. In materials
In the area of aesthetic dental composite materials used under consideration for dental composite restorative
for restorative and cosmetic purposes, the critical advance applications, the need for inert polymer matrices is coupled
ment in polymer technology Was the introduction of 2,2-bis With the need for polymers that have adequate mechanical
[p-(2‘-hydroxy-3‘-methacrylpropoxy)phenyl]propane, com properties to minimiZe Wear and fracture in both load
35
monly referred to as Bis-GMA. This bulky dimethacrylate bearing and non-loadbearing situations. With an essentially
monomer is used With a loW viscosity diluent comonomer, limitless range of potential monomeric components
typically triethylene glycol dimethacrylate (TEGDMA), to available, advanced polymeric materials can be tailored to
prepare resins that form strong, densely cross-linked poly meet speci?c challenges such as these. Because of the
meric netWorks. More than 30 years after their introduction, excellent resistance displayed by ?uoropolymers used in
40
resins based on varying proportions of Bis-GMA/TEGDMA aqueous or other aggressive chemical environments, a vari
still constitute the majority of commercial dental composite ety of partially ?uorinated monomers have been investigated
?lling materials. Among other methacrylates utiliZed in previously as a means to achieve hydrophobic, chemically
commercial composite restoratives are urethane-containing stable dental polymers. HoWever, the use of signi?cant
monomers, such as urethane dimethacrylate (UDMA), and 45 proportions of ?uorinated mono- or di-methacrylate mono
oligomers, such as the linear poly(urethane) prepared from mers in dental resins typically produces polymers With
Bis-GMA and hexamethylene diisocyanate (Bis-GMA unacceptably loW mechanical strength properties primarily
HMDI). Additional components of dental composites due to the loW cohesive energies of amorphous ?uorinated
include a particulate ?ller, generally a barium, strontium or polymers.
Zirconium-containing glass and/or a micro?ne silica, Whose 50 Fluorinated resins for use in dental materials and a variety
surface is modi?ed by attachment of a layer of a of other uses are disclosed by US. Pat. No. 4,616,073
methacrylate-functionaliZed silane coupling agent, (Antonucci); US. Pat. No. 4,914,171 (ZWeig); and US. Pat.
3-methacryloxypropyltrimethoxysilane. Avisible light acti No. 5,380,901 (Antonucci et al.) all of Which are incorpo
vated photoinitiator system, camphorquinone (CO) and an rated herein by reference in their entirety. Fluorinated resins
amine photoreductant, such as ethyl 4-N,N 55 for use in dental materials and a variety of other uses are also
dimethylaminobenZoate (EDMAB), alloWs the onset of disclosed by publications such as Douglas et al., J. Dent.
polymeriZation to be controlled and then the rapid develop Res. 58, 1981 (1979); Kurata et al., J. Dent. Res. 68, 481
ment of the cross-linked resin matrix to yield the cured (1989); Maruno et al., J. Polym. Sci. PartA: Polym. Chem.
composite under ambient conditions. 32, 3211 (1994); Cassidy et al., Eur Polym. J. 31, 353
The relatively high modulus ?llers used in dental com 60 (1995); and Stansbury et al., Amer. Chem. Soc., Polym.
posites serve to increase the strength, Wear resistance and Prepr. 36(1), 831 (1995) all of Which are incorporated herein
toughness of the resin matrix by reinforcement. The silane by reference in their entirety.
coupling agent plays a critical role in the development and Fluorinated polymers With moderate ?uorine contents are
maintenance of the reinforcing effect of the ?ller. Addition generally hydrophobic but lack good mechanical strength
of substantial amounts of ?ller also minimiZes the overall 65 properties due to the loW cohesive energies associated With
polymeriZation shrinkage associated With the continuous ?uorine-substituted amorphous polymers. A photocurable
matrix phase. The particulate ?ller is also responsible for the dimethacrylate monomer 2,2-bis(p-(2‘-hydroxy-3‘
US 6,184,339 B1
3 4
methacryloxy-propoxy)phenylene) propane (Bis-GMA) has The introduction of covalently bound organo?uorine into
been synthesized from the diglycidyl ether of bisphenol A dental resins offers a technique to dramatically reduce Water
and methacrylic acid. This reaction is shoWn by Reaction I. uptake, eliminate discoloration and improve the fracture
Bis-GMA has been used extensively as the basis of dental toughness of composites. Through appropriate design of the
composite ?lling materials as disclosed by BoWen, R. L., ?uoromonomers, materials achieving both loW polymeriZa
US. Pat. No. 3,066,112; BoWen, R. L., US. Pat. No. 20 tion shrinkage and excellent mechanical strength are
3,194,783; Venhoven, B. A. M., DeGee, A. J., Davidson, C. attained.
L., Biomaterials 1993, 14(11), 871; Stansbury, J. W., The initial objective of this investigation Which resulted in
Antonucci, J. M., Dent. Mater. 1992, 8, 270; VenZ, S.; the present invention Was the development of practical
Dickens, B., J. Biomed. Mater. Res. 1991,25,1231; synthetic routes to a variety of methacrylate monomers and
Antonucci, J. M., Scott, G. L., Polym. Prepr, 1995, 36 (1), 25 reactive oligomers With moderate to high organo?uorine
contents. PhotopolymeriZable dental resins that combine the
831; and Dulik, D., Bernier, R., Brauer, G. M.,]. Dent. Res.,
desirable properties of hydrophobicity, good mechanical
1981, 60 (6), 983. The photopolymeriZation of an un?lled
strength and loW polymeriZation shrinkage are sought for
resin based on Bis-GMA diluted With triethylene glycol
dental restorative applications. The oral environment pro
dimethylacrylate (TEGDMA) (7:3 by mass) produced a
vides signi?cant challenges for the survival of polymeric
volumetric shrinkage of 7.9%. The resulting crosslinked
materials. Dental restoratives experience continuous expo
polymer has a diametral tensile strength (DTS) and trans
sure to moisture, cyclic stresses and contact With a broad
verse strength (TS) of 42213.6 MPa and 75314.3 MPa,
range of chemicals introduced through food and drink. It is
respectively and a Water uptake of 3.8% as disclosed by
predicted that resins based on these neW ?uorinated mono
Venhoven, B. A. M., DeGee, A. J., Davidson, C. L., Bio mers Will produce more inert, stain-resistant dental compos
materials 1993, 14(11), 871; Stansbury, J. W., Antonucci, J. 35 ite materials With improved long-term durability compared
M., Dent. Mater 1992, 8, 270; and VenZ, S., Dickens, B. J. With existing hydrocarbon based resins. To aid in the selec
Biomed. Mater. Res. 1991, 25, 1231. tion of candidate ?uorinated materials With potential for use
HoWever, neW ?uorocompounds are needed to improve in dental composites, the refractive index, Water contact
the performance and durability of polymers used in chal angle, Water sorption, ?exural strength and polymeriZation
lenging environments, such as in biocompatible materials shrinkage of the photo-cured ?uorinated resins and their
for medical applications in the body. In dentistry, the composites Were evaluated. Although not measured here,
improvements in the fracture toughness of dental composites
requirements for durable ?uoropolymers as cavity ?lling
might also be expected for materials based on certain
materials include high hydrophobicity, chemical and physi
?uorinated resins. Due to the combination of loW refractive
cal resistance, mechanical strength and resilience along With
loW surface energy, polymeriZation shrinkage, toxicity, and 45 indices, dielectric constants and surface free energies asso
ciated With polymers With moderate to high organo?uorine
abrasion. It Would be desirable to provide dental composite
contents, the readily polymeriZable ?uorinated monomers
restoratives Which are less prone to excessive polymeriZa
and oligomers developed here also could be considered for
tion shrinkage, Water sorption, staining and brittle failure.
a variety of nonbiomaterial applications including structural
and optical adhesives, chemically resistant coatings, ?ber
SUMMARY OF THE INVENTION
optics, electronics and integrated circuits.
An object of the present invention is to provide (meth)
The polymeriZable ?uorinated acrylate and methacrylate
acrylate resins With moderate to high organo?uorine con
monomers and prepolymers of the present invention contain
tents Which are curable to form high strength polymeric
moderate to high ?uorine contents (15 to 65% by mass). The
netWorks.
55 monomers and prepolymers are designed to yield high
Another object of the present invention is to provide an strength, crosslinked polymers With loW surface energies,
inert dental composite that has loW shrinkage and signi?
loW Water sorption and loW polymeriZation shrinkage. The
cantly improved durability compared With existing dental
high strength properties available from the polymers of these
materials.
monomers and prepolymers are related to structural details
Another object of the present invention is to provide a incorporated in the monomers and prepolymers Which
process for producing the inert dental composite that has loW include: details to increase the crosslink density in polymers,
shrinkage and signi?cantly improved durability compared rigid backbones to enhance stiffness, and hydrogen bonding
With existing materials. via urethane (or other) linkages to reinforce the polymeric
Another object of the present invention is to provide a netWork. These structural aspects can be employed sepa
method of using the inert dental composite that has loW 65 rately or combined for greater effect. The potential exists to
shrinkage and signi?cantly improved durability compared use liquid crystalline side-chains to further enhance strength
With existing materials. of these materials.