WO1986005793A1 - Polymeres methacryliques et compositions ameliores - Google Patents

Polymeres methacryliques et compositions ameliores Download PDF

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Publication number
WO1986005793A1
WO1986005793A1 PCT/GB1986/000179 GB8600179W WO8605793A1 WO 1986005793 A1 WO1986005793 A1 WO 1986005793A1 GB 8600179 W GB8600179 W GB 8600179W WO 8605793 A1 WO8605793 A1 WO 8605793A1
Authority
WO
WIPO (PCT)
Prior art keywords
methylmethacrylate
polymer
polymerisation
powder
monomer
Prior art date
Application number
PCT/GB1986/000179
Other languages
English (en)
Inventor
Michael Braden
Alan Luxton
Rosemary Rodford
Laurence Gordon Wood
Original Assignee
Bonar Cole Polymers Limited
Revertex Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bonar Cole Polymers Limited, Revertex Limited filed Critical Bonar Cole Polymers Limited
Publication of WO1986005793A1 publication Critical patent/WO1986005793A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to improved methacrylate polymers and moulding compositions thereof primarily for use by dental technicians in moulding denture bases.
  • the dental technician will use a mould into which he will pack or pour a so-called acrylic doug consisting of a blend of finely divided preformed acrylic polymer together with methylmethacrylate monomer or methylmethacrylate containing a minor proportion of crosslinking monomer.
  • the invention is based upon the realisation that by forming a diene polymer having terminal groups which can co-polymerise witl; methylmethacrylate the dental technician can use a dough moulding procedure to make a dental base of improved properties, in particular impact strength.
  • polymer is to be construed to include the term “copolymer”, and the term “polydiene” to include the term “diene copolymer”.
  • a method of making a poly(methylmethacrylate) powder comprising, dissolving a diene polymer having terminal reactive groups in methylmethacrylate monomer and then carrying out polymerisation to form the polymer.
  • aqueous suspension polymerisation it is preferred to use aqueous suspension polymerisation.
  • a method of making a methylmethacrylate powder comprising,
  • the terminally reactive diene polymers preferably have an average molecular weight which is sufficiently low for the terminally o reactive diene polymer to dissolve readily in methylmethacrylate monomer to yield a solution of moderate viscosity. As a result, a subsequent aqueous suspension polymerisation will proceed without difficulty. Such a step would be inconvenient if the diene po ⁇ y er was of high molecular weight.
  • the average molecular weight is in within the range of about 10,000 to about 60,000 g/mole, most preferably about 25,000 to about 40,000.
  • the diene polymers carrying the terminal reactive group may be prepared by anionic polymerisation utilising organo-lithium or organo-sodium initiators.
  • the propagating species in this class of- polymerisation is the so-called "living" polymeric anion. It is possible to terminate the polymerisation, and at the* same time to introduce terminal groups such as acrylate terminal groups, by addition of suitable reagents capable of reaction with the polymeric carbanions.
  • Preferred 1,3-conjugated dienes which are amenable to anionic polymerisation to form elastomers are 1,3-butadiene, 1-methyl- l,3-butad!ene also known as * , piperylene, 2-methyl-l,3-butadiene also known as isoprene and 2,3-dimethyl-l,3-butadiene.
  • Particularly preferred are butadiene and/or Isoprene to form the dental compositions of the invention.
  • Preferred copolymers of dienes contain units derived from one or more vinyl aromatic monomers which are susceptible to copolymerisation with conjugated dienes by anionic polymerisation examples of which ar styrene, alpha-methyl styrene, nuclear substituted styrenes such as para-methyl styrene or mixed methyl styrenes, t-butyl styrene, vinyl naphthalene.
  • Suitable terminal reactive groups may be introduced Into the polydiene according to known techniques by terminating the anionic polymerisation with reagents such as acryloyl or methacryloyl or clnnamoyl chloride, allyl or methallyl chloride, malelc anhydride, vinyl chloroacetate or vinyl 2-chloroethyl ether.
  • reagents such as acryloyl or methacryloyl or clnnamoyl chloride, allyl or methallyl chloride, malelc anhydride, vinyl chloroacetate or vinyl 2-chloroethyl ether.
  • the terminal group be either acryloyl or methacryolyl.
  • the diene polymers formed by anionic polymerisation may be either random or block copolymers.
  • the diene polymer also contains units derived from one of more vinyl aromatic monomers, together with units derived from a conjugated diene., the proportion of units of the former class will not normally exceed about 50% by. weight of the copolymer.
  • terminally reactive diene polymers having comparatively low molecular weights are of relatively low viscosity and are also capable of enhancing the impact strength of polymethylmethacrylate. While we do not wish to be limited by this theory, we believe that these properties are because the terminal reactive groups of the diene polymer copolymerise with the methylmethacrylate, forming a polymer having a comblike structure, comprising a backbone of methylmethacrylate units with a plurality of branches derived from the diene polymer. If the diene polymer does not carry terminal reactive groups readily copolymerlsable with methylmethacrylate, a comparable enhancement of impact strength is not observed, as shown below.
  • the polymerisation of methylmethacrylate, or of a mixture of monomers comprising a major proportion of methyl methacrylate, together with the terminally reactive diene polymer may be carried out in mass, in aqueous dispersion, or in solution in organic solvent, using an appropriate free radical initiator. It is preferred to use aqueous suspension polymerisation, since this method is highly convenient, the polymer formed consisting of fine particles which are readily separated by filtration or centrifugation.
  • the proportion ' of diene polymer to methyl methacrylate in the mixture which is subjected to polymerisation to form one of the ingredients of compositions of the invention, designated ingredient A hereinafter, is normally in the range of about 5 to about 50 parts by weight of the total mixture.
  • the proportion will vary according to the nature of the polymer and the degree of desired toughening. If the terminally reactive polydiene is a homopolymer, the proportion used in the polymerisation mixture may be in the lower part of the range indicated. If the polydiene is a copolymer with a vinyl aromatic monomer, the proportion will be in the upper part of the range, depending on the proportion of vinyl aromatic monomer units in the terminally reactive polydiene.
  • the copolymer so formed is used to form a dough with methylmethacrylate monomer or methacrylate containing a polyfunctlonal methacrylate containing a polyfunctlonal methacrylate for crosslinking purposes as is well known In the art.
  • This monomeric component is hereinafter designated ingredient B and the ratio of A : B will typically be In the range of 2 : 1 to 1 : 1 by weight.
  • Ingredient B may optionally contain a polyfunctlonal monomer for the purpose of crosslinking such as ethylene glycol dimethacrylate, in the proportion of about 10. by weight.
  • suitable denture base physical properties can be realised without such a crosslinking monomer and since these substances are expensive, the ability to omit them represents a further advantage of the invention.
  • compositions of the invention exhibit excellent physical properties, in particular Impact strength while retaining flexural modulus. It is an advantage of the compositions of the invention that these enhanced physical properties are obtained together with retention of good doughlng behaviour, and that there are no drawbacks in the suspension polymerisation step.
  • the Invention provides as a new composition of matter, each of the ingredients A and B alone or in combination, optionally with ingredient C, and also includes products made thorefrom.
  • T' ⁇ e invention has been described in relation to moulding compositions primarily for use in making moulded dental bases.
  • the invention is not however limited to that purpose as mouldable or settable methylmethacrylate compositions are useful for other purposes e.g. as sealing or caulking compounds, car light covers, etc.
  • the polydiene prepared according to Example 1 was dissolved in methylmethacrylate monomer to form solutions of the following composition:
  • Methylmethacrylate (parts by weight) (100) 85 80 70
  • Example 2 The polymer beads of Example 2 were each made into a dough in the usual way with methylmethacrylate monomer (B), the proportion of A to B was 50/50 by weight of A plus B.
  • the doughs were processed to form test specimens appropriate to the tests, and the following data was obtained:
  • Powders * prepared according to Example III were mixed in the mould with preformed ' poly (methylmethacrylate) homopolymer (ingredient C) and properties were measured.
  • the glass transition temperature was over 100°C in each case.
  • the dough comprising 10. polydiene in the combined weight of A plus C yielded a high impact dental moulding composition and was readily workable.
  • Butadiene styrene copolymers with methacrylate end groups and formed from butadiene- and styrene in different proportions under, suitable conditions ' were each dissolved in methylmethacrylate together with benzoyl peroxide.
  • the solution was slurried with water and heat in a known suspension polymerisation technique to form polymer beads.
  • the beads were removed by centrifuging, washed, dried and sieved.
  • the product was mixed with some homo (polymethylmethacrylate) to form a denture base powder. This was then mixed with methylmethacrylate monomer to form a dough which was moulded and heat polymerised.
  • the products were tested for elastic modulus and impact, strength.
  • customary manufacturing techniques involving bead polymers i.e. suspension polymerisation, can be used.

Landscapes

  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dental Preparations (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Un polymère de diène finalement réactif est dissout dans du monomère méthylméthacrylique et la solution est polymérisée par une technique de suspension aqueuse de manière à produire des perles de polymère. Ces dernières peuvent être utilisées dans une pâte acrylique pour former une base dentaire moulée de plus grande résistance aux chocs tout en conservant le module de flexion.
PCT/GB1986/000179 1985-03-28 1986-03-26 Polymeres methacryliques et compositions ameliores WO1986005793A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8508094 1985-03-28
GB858508094A GB8508094D0 (en) 1985-03-28 1985-03-28 Modified methylmethacrylate polymers

Publications (1)

Publication Number Publication Date
WO1986005793A1 true WO1986005793A1 (fr) 1986-10-09

Family

ID=10576808

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1986/000179 WO1986005793A1 (fr) 1985-03-28 1986-03-26 Polymeres methacryliques et compositions ameliores

Country Status (3)

Country Link
EP (1) EP0215888A1 (fr)
GB (1) GB8508094D0 (fr)
WO (1) WO1986005793A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0411512A2 (fr) * 1989-08-02 1991-02-06 Mitsubishi Rayon Co., Ltd Composition dentaire
EP0505128A3 (en) * 1991-03-21 1992-12-23 Illinois Tool Works, Inc. Foamed acrylic polymer compositions
GB2347679A (en) * 1999-03-12 2000-09-13 Gc Kk Resin material for denture base
US6506815B2 (en) * 2000-09-26 2003-01-14 Gc Corporation Resin composition for denture base
US20060217488A1 (en) * 2005-03-17 2006-09-28 Heraeus Kulzer Gmbh High impact prosthetic plastics
EP1923037A2 (fr) * 2006-11-20 2008-05-21 Heraeus Kulzer GmbH Matériau dentaire polymérisable à base de méthylméthacrylates adapté à la fabrication de matière synthétique de prothèse
WO2015145175A1 (fr) * 2014-03-28 2015-10-01 Synthomer (Uk) Limited Polymère, procédé de production d'un polymère et utilisations dudit polymère

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862101A (en) * 1971-02-22 1975-01-21 Cpc International Inc Acrylate and methacrylate terminated polydiene macromolecular monomers having a substantially uniform molecular weight distribution
GB1400497A (en) * 1972-08-01 1975-07-16 Shell Int Research Polymerisation of conjugated dienes
US4033840A (en) * 1972-08-21 1977-07-05 Sony Corporation Thermosetting acryloyloxy-terminate butadiene polymers
JPS54144494A (en) * 1978-05-02 1979-11-10 Hitachi Ltd Heat-curable adhesive composition having improved plating property

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862101A (en) * 1971-02-22 1975-01-21 Cpc International Inc Acrylate and methacrylate terminated polydiene macromolecular monomers having a substantially uniform molecular weight distribution
GB1400497A (en) * 1972-08-01 1975-07-16 Shell Int Research Polymerisation of conjugated dienes
US4033840A (en) * 1972-08-21 1977-07-05 Sony Corporation Thermosetting acryloyloxy-terminate butadiene polymers
JPS54144494A (en) * 1978-05-02 1979-11-10 Hitachi Ltd Heat-curable adhesive composition having improved plating property

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Volume 92, No. 14, April 1980, Columbus, Ohio, (US), page 46, Abstract No. 111956k & JP, A, 79144494 (Hitachi) 10 November 1979 *
CHEMICAL ABSTRACTS, Volume 99, No. 14, 1983, Columbus, Ohio, (US) H. ISHIKAWA et al.: "A New Rubber-Modified Resin", see page 35, Abstract No. 106218m & Prog. Sci. Eng. Compos. Proc. Int. Conf. Compos. Mater., 4th 1982, 1, 129-36 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0411512A2 (fr) * 1989-08-02 1991-02-06 Mitsubishi Rayon Co., Ltd Composition dentaire
EP0411512A3 (en) * 1989-08-02 1991-09-25 Mitsubishi Rayon Co., Ltd Dental composition
AU619126B2 (en) * 1989-08-02 1992-01-16 Mitsubishi Rayon Company Limited Dental composition
US5182332A (en) * 1989-08-02 1993-01-26 Mitsubishi Rayon Co., Ltd. Dental composition
EP0505128A3 (en) * 1991-03-21 1992-12-23 Illinois Tool Works, Inc. Foamed acrylic polymer compositions
US5945461A (en) * 1991-03-21 1999-08-31 Illinois Tool Works Inc. Foamed acrylic polymer compositions
GB2347679A (en) * 1999-03-12 2000-09-13 Gc Kk Resin material for denture base
US6506815B2 (en) * 2000-09-26 2003-01-14 Gc Corporation Resin composition for denture base
US20060217488A1 (en) * 2005-03-17 2006-09-28 Heraeus Kulzer Gmbh High impact prosthetic plastics
EP1923037A2 (fr) * 2006-11-20 2008-05-21 Heraeus Kulzer GmbH Matériau dentaire polymérisable à base de méthylméthacrylates adapté à la fabrication de matière synthétique de prothèse
EP1923037A3 (fr) * 2006-11-20 2009-09-09 Heraeus Kulzer GmbH Matériau dentaire polymérisable à base de méthylméthacrylates adapté à la fabrication de matière synthétique de prothèse
WO2015145175A1 (fr) * 2014-03-28 2015-10-01 Synthomer (Uk) Limited Polymère, procédé de production d'un polymère et utilisations dudit polymère

Also Published As

Publication number Publication date
GB8508094D0 (en) 1985-05-01
EP0215888A1 (fr) 1987-04-01

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