US20100234549A1 - Radical polymerizable macrocyclic resin compositions with low polymerization stress - Google Patents

Radical polymerizable macrocyclic resin compositions with low polymerization stress Download PDF

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US20100234549A1
US20100234549A1 US12655028 US65502809A US20100234549A1 US 20100234549 A1 US20100234549 A1 US 20100234549A1 US 12655028 US12655028 US 12655028 US 65502809 A US65502809 A US 65502809A US 20100234549 A1 US20100234549 A1 US 20100234549A1
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polymerization
polymerizable
precursor
macrocyclic
activated
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US12655028
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Xiaoming Jin
Paul D. Hammesfahr
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Xiaoming Jin
Hammesfahr Paul D
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/1006Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylat
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/16Aliphatic-aromatic or araliphatic polycarbonates
    • C08G64/1691Aliphatic-aromatic or araliphatic polycarbonates unsaturated
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/34Oligomeric, e.g. cyclic oligomeric

Abstract

A composition of macrocyclic oligomer with at least one (meth)acrylate polymerizable group. A method includes preparing an activated precursor of an oligomer at pseudo high-dilution conditions. A method also includes preparing an activated precursor of an oligomer by reacting the precursor with an activated coupling agent, wherein the precursor is condensable and polymerizable.

Description

    RELATED APPLICATIONS
  • [0001]
    This is a Continuation Application which claims priority to pending U.S. Ser. No. 12/381,781 filed on Mar. 16, 2009, which claims priority to U.S. Ser. No. 12/079,525 filed on Mar. 27, 2008 which in turn claims priority to U.S. Ser. No. 11/153,090 filed on Jun. 15, 2005 which in turn claims priority to provisional patent application Ser. No. 60/579,836 (Case LDC-949A) filed on Jun. 15, 2004.
  • FIELD OF THE INVENTION
  • [0002]
    This invention relates to free radical polymerizable macrocyclic compounds and composition, which feature by their low shrinkage and low contraction stress upon polymerization. Such low shrinkage and low stress resin could find their wide range of applications, especially in microelectronic, special coating and restorative dentistry where the dimensional stability and contraction stress within cured materials are critical to the total performance.
  • BACKGROUND OF THE INVENTION
  • [0003]
    The polymerization shrinkage of curable material is referred to the dimensional contraction during polymerization or curing, because the formation of covalent bonding during polymerization bring the molecules closer each other than that while they are free in van der Walls distance. The origin of polymerization stress, on the other hand, comes from a restrained polymerization or shrinking during curing. Therefore, it is not only related to polymerization shrinkage, but also is dependent on the polymerization kinetics.
  • [0004]
    It is well known that with increasing molecular weight, the mobility of polymeric chain would be limited, the diffusion is becoming the rate control factor. In addition, such a limited mobility in a cross-linking system appear to come earlier in comparison with linear system, which means extra reaction would lead to an increasing polymerization stress. There are different ways to control the stress generation and development:
  • [0005]
    1. Slow down the polymerization rate;
      • Introducing a special rate controller like stable radicals;
      • Creating different polymerization zones from which the stress developed in a polymerized zone could be transferred to its adjacent unpolymerized zone and got relief like segmental polymerization technique;
      • Employing different polymerization groups;
      • Using large-size macromonomer to limited its reactivity at the early stage;
  • [0010]
    2. Reduce the conversion;
      • Pre-building a 2D or 3D structure like macrocyclics, dendrimers or hyperbranches; 3. Limiting the cross-link density to offer acceptable mechanical property.
  • [0012]
    To reduce polymerization shrinkage and stress in the specific dental restorative composite, all of above approaches are taking into account. In this invention, however, the objective is to present a general method to produce a macrocyclic oligomer which would be converted into 3D network via free radical polymerization.
  • [0013]
    U.S. Pat. No. 4,644,053, disclosed a method to synthesize single macrocyclic compounds. Then various macrocyclics oligomers, including carbonates, esters, amides, ethers, imides, sulfides, et al, have been prepared. However, high temperature ring-opening reaction has to be involved to convert these macrocyclics into high molecular weight polymers.
  • [0014]
    U.S. Pat. No. 5,047,261, disclosed a composition containing a five-member carbonate cyclic group for fast copolymerization with mathacrylate.
  • [0015]
    U.S. Pat. No. 5,792,821, disclosed polymerizable cyclidextrin (CD) derivatives, in which methacrylate was attached on CD.
  • [0016]
    U.S. Pat. No. 5,962,703, disclosed functionalized bicyclic methacrylate with norboneyl or norbonadienl group.
  • [0017]
    U.S. Pat. No. 6,043,361, disclosed polymerizable cyclic allylic sufides is used for low shrinkage materials.
  • APPROACH
  • [0018]
    The macrocyclic oligomers are prepared under pseudo-high-dilution condition via a condensation between a reactive and free radical polymerizable precursor and various coupling agents to afford carbonate, ester, siloxane, phosphonate, et al linkages to result in macrocyclic oligomers. To avoid the premature polymerization of methacrylate groups, the condensation groups usually have to be activated to assure a mild reaction for cyclization with the coupling monomers.
  • [0019]
    BisGMA is one of widely used dental resin and it contains two free radical polymerizable group, methacrylate and two hydroxyl groups. This turns BisGMA an ideal candidate for polymerizable macrocyclic oligomer, although the presence of BisGMA isomer would make more complicated to this approach. As shown in Scheme I, carbonyldiimidazol (CDI, 1), was used to selectively reacted with the secondary alcohol in BisGMA (2) to give an activated BisGMA, DIZ-BisGMA(3). It was isolated and the chemical structure of DIZ-BisGMA was fully characterized with FITR and NMR. Actually, according to the recent report by Davis et al of Courtlaulds, England, CDI and its intermediates could exhibit surprisingly specificity towards primary, secondary, tertiary functional groups, of the same type, during the controlled formation of various well-defined molecular sequence. Our idea is to adopt same chemistry of CDI and to activate the two secondary hydroxyl group. Furthermore, an activated precursor, DIZ-BisGMA, was made to react with various primary diols 1,10-decanediol, under a pseudo high-dilution condition, as shown in Scheme II. Both reactants were simultaneously charged into the system in a high-dilution condition via slowly, precisely controlled addition to ensure a favorable formation of cyclic product. Since the product, C10-CYCBGM (5), is accumulated with a final concentration of 0.02M, which is much higher than the classical high dilution condition (0.001M), this procedure is, therefore, referred as pseudo-high-dilution approach. Since imidazol is produced from both precursor and cyclization steps, a continuous process was successfully developed without direct separation of DIZ-BisGMA.
  • [0000]
    Figure US20100234549A1-20100916-C00001
  • [0000]
    Figure US20100234549A1-20100916-C00002
  • [0000]
    Figure US20100234549A1-20100916-C00003

Claims (7)

  1. 1. A dental composition comprising a macrocyclic oligomer with at least one (meth)acrylate polymerizable group.
  2. 2. A method of preparing a dental composition comprising a polymerizable macrocyclic oligomer, comprising the step of preparing an activated precursor of an oligomer at pseudo high-dilution conditions.
  3. 3. A method claimed in 2, wherein said activated precursor is liquid, crystalline solid or a combination of both.
  4. 4. A method as in claim 2, wherein said precursor itself is polymerizable.
  5. 5. A method as in claim 2, comprising the step of reacting said precursor with a coupling agent selected from the group consisting of primary diols, secondary amines, diacids and combinations thereof.
  6. 6. A method as in claim 5, wherein said coupling agent is aliphatic, aromatic or both.
  7. 7. A method of preparing a dental composition comprising a polymerizable macrocyclic oligomer, comprising the step of preparing an activated precursor of an oligomer by reacting said precursor with an activated coupling agent, wherein said precursor is condensable and polymerizable.
US12655028 2004-06-15 2009-12-22 Radical polymerizable macrocyclic resin compositions with low polymerization stress Abandoned US20100234549A1 (en)

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US57983604 true 2004-06-15 2004-06-15
US11153090 US20060287459A1 (en) 2004-06-15 2005-06-15 Radical polymerizable macrocyclic resin compositions with low polymerization stress
US12079525 US20080182997A1 (en) 2004-06-15 2008-03-27 Radical polymerizable macrocyclic resin compositions with low polymerization stress
US12381781 US20090182109A1 (en) 2004-06-15 2009-03-16 Radical polymerizable macrocyclic resin compositions with low polymerization stress
US12655028 US20100234549A1 (en) 2004-06-15 2009-12-22 Radical polymerizable macrocyclic resin compositions with low polymerization stress

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US12655028 US20100234549A1 (en) 2004-06-15 2009-12-22 Radical polymerizable macrocyclic resin compositions with low polymerization stress
US12912951 US8129446B2 (en) 2004-06-15 2010-10-27 Radical polymerizable macrocyclic resin compositions with low polymerization stress
US13300908 US20120108837A1 (en) 2004-06-15 2011-11-21 Radical polymerizable macrocyclic resin compositions with low polymerization stress

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US12079525 Abandoned US20080182997A1 (en) 2004-06-15 2008-03-27 Radical polymerizable macrocyclic resin compositions with low polymerization stress
US12381781 Abandoned US20090182109A1 (en) 2004-06-15 2009-03-16 Radical polymerizable macrocyclic resin compositions with low polymerization stress
US12655028 Abandoned US20100234549A1 (en) 2004-06-15 2009-12-22 Radical polymerizable macrocyclic resin compositions with low polymerization stress
US12912951 Active US8129446B2 (en) 2004-06-15 2010-10-27 Radical polymerizable macrocyclic resin compositions with low polymerization stress
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EP (1) EP1778164B1 (en)
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WO2013130488A1 (en) * 2012-02-28 2013-09-06 Dentsply International Inc. Acid-neutralizing resins and hardenable dental compositions thereof

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DE602005020806D1 (en) 2004-06-15 2010-06-02 Dentsply Int Inc Mensetzungen low polymerization strain
WO2006002086A1 (en) * 2004-06-15 2006-01-05 Dentsply International Inc. Low shrinkage and low stress dental compositions
JP6058482B2 (en) * 2013-06-26 2017-01-11 積水化成品工業株式会社 Cyclic macromonomer, the crosslinked polymer, the polymer gel, and a process for their preparation
CN105125415B (en) * 2015-06-30 2018-01-16 吉林省登泰克牙科材料有限公司 The method of preparing a dental composite resin material of low polymerization shrinkage

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CA2570341A1 (en) 2005-12-29 application
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US20090182109A1 (en) 2009-07-16 application
DE602005020806D1 (en) 2010-06-02 grant
US20080182997A1 (en) 2008-07-31 application
US20060287459A1 (en) 2006-12-21 application
US8129446B2 (en) 2012-03-06 grant
US20120108837A1 (en) 2012-05-03 application
JP5647176B2 (en) 2014-12-24 grant
WO2005123008A1 (en) 2005-12-29 application
JP2008502781A (en) 2008-01-31 application
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