EP0925332A1 - Composition polymere comprenant un agent de modification - Google Patents

Composition polymere comprenant un agent de modification

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Publication number
EP0925332A1
EP0925332A1 EP97940998A EP97940998A EP0925332A1 EP 0925332 A1 EP0925332 A1 EP 0925332A1 EP 97940998 A EP97940998 A EP 97940998A EP 97940998 A EP97940998 A EP 97940998A EP 0925332 A1 EP0925332 A1 EP 0925332A1
Authority
EP
European Patent Office
Prior art keywords
matrix material
ingredient
modifying agent
polymeric
active chemical
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP97940998A
Other languages
German (de)
English (en)
Inventor
Steven P. Bitler
Ray F. Stewart
David A. Kamp
Paul A. Meyers
David A. Taft
Donald A. Schultz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lifecore Biomedical Inc
Original Assignee
Landec Corp
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 Landec Corp filed Critical Landec Corp
Publication of EP0925332A1 publication Critical patent/EP0925332A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • polymeric modifying agents which comprise (i) a crystalline polymeric moiety which melts over a relatively small temperature range and (ii) an active chemical moiety which is bonded to the polymeric moiety, preferably through a bond having a strength of at least 10 Kcal/mole;
  • compositions comprising (i) a matrix material and (ii) associated therewith, a polymeric modifying agent as defined in (A);
  • the polymeric modifying agents (A) are particularly useful for making compositions (B) which are stable for relatively long periods under storage conditions, but which will react rapidly when heated or otherwise treated to increase the contact between the matrix and the modifying agent.
  • One part of the present invention is our discovery that even when there is no chemical bond between the polymeric and active chemical ingredients of the modifier, and as a result the increase in stability is relatively small, this can be very valuable in situations in which storage stability is not desired or cannot be achieved in combination with acceptable activity at the reaction temperatures. Under these circumstances it is possible, and may be preferable, to make use of a modifying agent in which the active ingredient is bound to the polymeric ingredient physically but not chemically. Such modifying agents are referred to herein as "physically bound modifying agents.” This may produce a delay (as compared to the active chemical ingredient on its own) which is as short as a few seconds or as long as 12 hours or even more.
  • This delay may result in an increase in one or more of pot-life, cream time (time in hot mold prior to foaming) reaction time, or other reactivity indicator.
  • a physically bound modifying agent allows the active chemical ingredients to be released very rapidly, but provides sufficient delay to ensure that curing does not begin before the polymeric mixture is uniformly distributed throughout the mold.
  • Physically bound modifying agents are also useful when a coating is to be cured in place (e.g. with a hot wand) after being applied to a substrate.
  • the invention makes it possible to make up a "day batch" of the coating composition which can be used over a period of several hours.
  • a physically bound modifying agent the strength of the association between the ingredients can be influenced by hydrogen bonding and/or physical interaction between the groups on the ingredients, e.g. carboxyl, hydroxyl or other polar groups, or long chain alkyl groups.
  • this invention includes a composition which comprises (1) a matrix material; and
  • a polymeric ingredient which comprises a crystalline polymeric moiety having an onset of melting temperature T 0 and a peak melting temperature Tp such that Tp - T 0 is less than Tp 0-7, and (ii) an active chemical ingredient which is physically, but not chemically, bound to the polymeric ingredient, and which, when in contact with a matrix material under selected conditions, promotes a chemical reaction of the matrix material, and
  • (b) is in the form of a solid which, when exposed to a change in a variable selected from temperature, concentration of a solvent, electromagnetic radiation, ultrasonic radiation, and pH, undergoes a physical change which causes the modifying agent to lose its physical integrity and increases the extent to which the matrix material is contacted by the active chemical ingredient, said solid form being selected from
  • the physical association between the polymeric and active chemical ingredients can be of any kind which results (when the selected change in a variable takes place) in the desired increase in the contact between the matrix and the active ingredient.
  • the ingredients are intimately mixed together.
  • Such mixtures can be prepared, for example by dissolving the ingredients in a solvent and spray drying the resulting solution; or by emulsifying the ingredients in a heated liquid carrier and then cooling the emulsion while shearing.
  • the active ingredient is surrounded by a coating of the polymeric ingredient.
  • Such compositions can be prepared, for example, by spray drying the active chemical ingredient, suspending the spray-dried powder in a solution of the of the polymeric ingredient, and spray drying the suspension, or in solvent-free systems by forming particles through milling processes.
  • One of the situations in which it can be useful for at least part of the active ingredient to be present as part of a physically bound modifying agent, i.e. to be physically, but not chemically, bound to the polymeric ingredient, is when the active ingredient is the catalyst for the preparation of a polyurethane, polyurea or polyisocyanurate.
  • Such catalysts include for example compounds containing tin, lead, bismuth or another metal known to catalyze such reactions, e.g. tris(tributyltin) oxide, dibutyltin laurate, tributyl tin acetate, dibutyltin acetoacetate, or tributyl tin methacrylate.
  • catalysts for use in the curing of unsaturated polyesters provide the active chemical ingredient in the modifying agent.
  • Such catalysts include for example compounds containing cobalt, copper, vanadium, manganese, or another transition metal.
  • the catalyst-containing compound can contain carboxyl, hydroxyl or other polar groups which can interact with the same or similar groups on the polymer; and a catalyst- containing compound containing long chain alkyl groups can interact with similar groups on an SCC polymer.
  • a modifying agent comprising the SCC polymer and a metal compound containing polar groups.
  • the modifying agent may contain another active chemical ingredient, which may be another catalytic ingredient or a reactive ingredient.
  • a modifying agent containing a tin compound e.g. dibutyl tin dilaurate (DBTDL) and a tertiary amine, e.g. tetraethylene diamine (TEDA)
  • DBTDL dibutyl tin dilaurate
  • TMA tertiary amine
  • Such a modifying agent can also contain a blowing agent, e.g. BL from Air Products.
  • a typical modifying agent would contain 75% SCC polymer, 10% TEDA, 10% DBTDL and 5% BL.
  • the tin compound can be chosen so that it forms a chemical bond with the polymer, e.g. tributyl tin methacrylate.
  • the amine compound can be chosen so that it forms a chemical bond with the polymer, e.g. dimethylamino ethyl acryate.
  • the modifying agent and/or the matrix material preferably comprises enhancing groups, as described below in the fourth aspect of the invention.
  • this invention includes a composition which comprises
  • a modifying agent which (a) comprises (i) a polymeric ingredient which comprises a crystalline polymeric moiety having an onset of melting temperature To and a peak melting temperature Tp such that T p - T 0 is less than T p ° 7 , and (ii) an active chemical ingredient which contains a peroxy or an azo group, and (b) is in the form of solid particles which are dispersed in the matrix material and which, when heated, undergo a physical change which causes the modifying agent to lose its physical integrity and increases the extent to which the matrix material is contacted by the peroxide initiator, said solid particles having one or more of the following characteristics (i) an average particle size of 0.1 to 150 microns, (ii) a polymeric ingredient having a heat of fusion of at least
  • Another part of the present invention is our discovery of the valuable results which can be obtained, especially when preparing epoxy resins, through the use of various additives in conjunction with a modifying agent (in which the polymeric ingredient and the active ingredient can be bound together by a chemical bond only, by a physical bond only, or by both).
  • the coreactant preferably has one or more of the following features:
  • Preferred coreactants for epoxy resin cures are anhydrides, in particular, methyl tetrahydrophthalic anhydride (MeTHPA).
  • MeTHPA methyl tetrahydrophthalic anhydride
  • the anhydride also reduces the latency of the composition, e.g. to 30 days at 25 to 40° C. Such latency periods are sometimes desired because they indicate that curing will take place rapidly at cure temperatures.
  • low surface energy agents can be useful in improving at least the appearance of polymeric products obtained by reaction of the matrix material.
  • low surface energy agents prevent the cured resin from exhibiting a rippled surface. It is believed that the rippling occurs because the air-epoxy surface becomes rich in modifying agent and cures fastest, whereas the bulk epoxy phase cures more slowly and shrinks.
  • the low surface energy agents have a lower surface energy than the modifying agent, and are preferentially located at the air-epoxy resin interface. The low surface energy agents thus minimize the accumulation of the modifying agent at the air-epoxy interface and permit a more homogeneous curing process.
  • Preferred low surface energy agents are fluorocarbon surfactants, e.g. Fluorad FC-430 by 3M or Lodyne products from Ciba-Geigy.
  • coadditives for epoxy resins include alkenyl succinic anhydrides, e.g. nonenyl succinic anhydride available from Humphrey under the tradename K-9 and dodecenyl succinic anhydride.
  • the amount of coadditive is generally 0.5 to 10%, preferably 0.5 to 5%, e.g. 2% to 4%, based on the weight of the epoxy resin. In this weight range the coadditive often improves the uniformity and/or gloss of the cured resin.
  • the cured resin exhibited a minimal amount of chalking when used either as an adhesive or as a coating.
  • the latency of the modifying agent at ambient temperature was not affected.
  • Other preferred coadditives include dodecyl benzene sulphonic acid available under the tradename Nacure 5076, methyl tetra hydro phthalic anhydride, nonyl phenol and pentadec-1-yl phenol.
  • Other additives which we have found useful, especially for improving the surface gloss of highly filled epoxy and epoxy/anhydride systems include material such as phosphated polyesters (e.g.
  • the coadditive is added to the matrix material, before or after adding the modifying agent. However, on occasion it may be preferable for some or all of the coadditive to be embedded in the crystalline polymer ingredient, in which case, the coadditive is released therefrom when the modifying agent is heated above Tp.
  • the third aspect of the invention includes a composition which comprises
  • a polymeric ingredient which comprises a crystalline polymeric moiety having an onset of melting temperature T Q and a peak melting temperature Tp such that Tp - To is less than Tp 0 •
  • an active chemical ingredient which, when in contact with a matrix material under selected conditions, promotes formation of an epoxy resin from the matrix material, and (b) is in the form of solid particles which are dispersed in the main material and which, when heated, undergo a physical change which causes the modifying agent to lose its physical integrity and increases the extent to which the matrix material is contacted by the active chemical ingredient, said solid particles having one or more of the following characteristics (i) an average particle size of 0.1 to 150 microns,
  • (B3) 0.5 to 10% by weight, based on the weight of the epoxy resin precursor, of a coadditive which is an alkenyl succinic anhydride; dodecyl benzene sulphonic acid; methyl tetrahydro phthalic anhydride; nonyl phenol; pentadec-1-yl phenol; a phosphated polyester; a phosphated titanate; or a sulfonated titanate.
  • a coadditive which is an alkenyl succinic anhydride; dodecyl benzene sulphonic acid; methyl tetrahydro phthalic anhydride; nonyl phenol; pentadec-1-yl phenol; a phosphated polyester; a phosphated titanate; or a sulfonated titanate.
  • enhancing groups For example, it is possible to make use of (i) a modifying agent which includes, chemically bonded thereto, one or more enhancing groups which are compatible with the matrix or with a product of a chemical reaction of the matrix after the modifying agent has been exposed, and/or (ii) a matrix which includes, chemically bonded thereto, one or more enhancing groups which are compatible with the crystalline polymer ingredient of the modifying agent.
  • a particularly valuable use of enhancing groups is to introduce polar groups, particularly carboxyl groups, into the polymeric ingredient of a modifying agent which contains reactive chemical ingredients and which is to be used in making a cured epoxy resin.
  • polar groups particularly carboxyl groups
  • the cured epoxy resin will not have optimum properties unless the modifying agent is allowed to equilibrate with the matrix before curing takes place.
  • Such equilibration may be, for example, for 12-24 hours at 35-40°C. We have found that the need for such conditioning can be reduced or eliminated by introducing carboxyl groups into the crystalline polymer.
  • the crystalline polymer contains units derived from maleic anhydride, and the resulting anhydride group is reacted with an amino compound to form an amic acid.
  • the polymer can be for example a copolymer of one or more long chain ⁇ -olefins and maleic anhydride, e.g. Petrolite X8040, or a copolymer of one or more long chain alkyl acrylates, e.g. C22A, and maleic anhydride.
  • the amino compound may contain the reactive chemical moiety which, when exposed, will take part in the curing of the epoxy matrix, e.g. l-(2- aminoethyl)-2-methyl imidazole.
  • the residue of the amino compound can be further reacted to provide the active chemical moiety; for example ethanolamine can be reacted with the anhydride group and the resulting amic acid reacted with 2-ethyl-4-methyl imidazole or 2-methyl imidazole.
  • Enhancing groups of this type are particularly useful when the modifying agent is physically, but not chemically, bound to the matrix, since conditioning of such modifying agents is apt to cause reaction with the matrix.
  • a preferred embodiment of the fourth aspect of the invention is a composition which comprises
  • A a crystalline polymeric moiety having an onset of melting temperature T D and a peak melting temperature Tp such that Tp - T G is less than Tp °- 7
  • B polar groups which reduce the time needed to reach an equilibrium between the matrix material and the modifying agent after they have been mixed, and (ii) an active chemical ingredient which, when in contact with a matrix material under selected conditions, promotes formation of an epoxy resin from the matrix material
  • (b) is in the form of solid particles which are dispersed in the matrix material and which, when heated, undergo a physical change which causes the modifying agent to lose its physical integrity and increases the extent to which the matrix material is contacted by the active chemical ingredient, said solid particles having one or more of the following characteristics (i) an average particle size of 0.1 to 150 microns, (ii) a polymeric ingredient having a heat of fusion of at least
  • a polymeric ingredient in which the crystalline polymeric moiety is a side chain crystalline polymer;
  • Another way of overcoming the need to condition the modifying agent in the final mixture is to premix the modifying agent with an epoxy compound which has relatively low viscosity, so that it will accept a high concentration of the modifying agent.
  • the resulting concentrate can readily be dispersed in the final mix.
  • Preferred low viscosity epoxy compounds are cycloaliphatic epoxy resins, e.g.
  • matrix and “matrix material” are used in this specification to denote any material or mixture of materials with which the modifying agent is contacted.
  • the matrix often comprises at least one solid or liquid material which provides a continuous phase in which the modifying agent is distributed.
  • Such a matrix can include, in addition to the modifying agent, one or more other materials which are distributed in the continuous phase of the matrix, for example dissolved or dispersed in the form of particles in the continuous phase. Some such other materials are described in the sections below entitled_Coreactants and Coadditives.
  • the matrix can be in the form of particles, e.g.
  • a fine powder which is blended with particles of the modifying agent, or in the form of a liquid or gas or solid which is contacted with the modifying agent, for example with one or both surfaces of a film of the modifying agent (the term "film” is used herein to include a layer of the modifying agent which is supported on a substrate).
  • a matrix in the form of particles may melt at a temperature above or below the melting point of the modifying agent.
  • the invention is particularly useful for matrix materials which, alone or in combination with other ingredients, are polymerized and/or crosslinked when they are exposed to the active chemical moiety in the modifying agent.
  • matrix materials include for example cyanoacrylates, epoxy resins, epoxy novolacs, unsaturated poly- esters, including vinyl esters, and precursors for polyurethanes, polyureas, polyisocyanurates, polycyanurates, polyacrylics and polyphenoiics.
  • cyanoacrylates for example cyanoacrylates, epoxy resins, epoxy novolacs, unsaturated poly- esters, including vinyl esters, and precursors for polyurethanes, polyureas, polyisocyanurates, polycyanurates, polyacrylics and polyphenoiics.
  • the matrix may be the sole material which takes part in the chemical reaction which is promoted or inhibited by the chemical moiety, or the chemical reaction can involve an additional material, including the coreactants and coadditives discussed below, which is added before or after the modifying agent is treated to change the extent to which the active chemical moiety is exposed to the matrix
  • the polymeric ingredient in the modifying agent can be (or be derived from) a single polymer or from a mixture of polymers, and the polymer can be a homopolymer, or a copolymer of two or more comonomers, including random copolymers, graft copolymers, block copolymers and thermoplastic elastomers.
  • Preferably at least part of the polymeric moiety is derived from a side chain crystallizable (SCC) polymer, but the invention includes the use of other crystalline polymers having the desired properties.
  • SCC side chain crystallizable
  • the molecular weight of the polymeric ingredient is an important factor in determining the rate at which the modifying agent diffuses through the matrix. A low molecular weight increases the availability of the reactive ingredient.
  • the number average molecular weight (M n ) of the polymeric ingredient is generally 1,000 to 100,000, preferably 1,000 to 50,000.
  • Other factors in determining the rate at which the modifying agent mixes with the matrix is the difference between the solubility parameters of the matrix and the modifying agent, and the crystallinity of the polymeric ingredient (the greater the crystallinity, the lower the rate).
  • an increase in crystallinity generally increases the stability of the composition at temperatures below Tp, but generally does not change the activity of the modifying agent at temperatures above Tp.
  • Another factor in determining the rate at which the modifying agent mixes with the matrix above and/or below Tp is the presence of compatibilizing groups on one or more of the matrix, the modifying agent and coadditives added to enhance the compatibility of ingredients of the composition.
  • Tp - T 0 is preferably less than TpO 7 , particularly less than TpO-6.
  • T 0 and Tp being in °C.
  • Tp can vary widely, e.g. from 10 to 150°C.
  • Tp is preferably at least 40°C, particularly at least 45°C, but not more than 100°C, particularly not more than 85°C, so that the modifying agent can be activated by moderate heating above room temperature.
  • Tp - T 0 is preferably less than 10°C, particularly less than 8°C, more particularly less than 6°C, especially less than 4°C.
  • the SCC polymers which are preferably used as polymeric ingredient in this invention include polymers derived from one or more monomers such as substituted and unsubstituted acrylates, methacrylates, fluoroacrylates, vinyl esters, acrylamides, methacrylamides, maleimides, ⁇ -olefins, p-alkyl styrenes, alkylvinyl ethers, alkylethylene oxides, alkyl phosphazenes and amino acids; polyisocyanates; polyurethanes; polysilanes; polysiloxanes; and polyethers; all of such polymers containing long chain crystal lizable groups.
  • Preferred SCC polymers comprise
  • Cy of the polymer backbone and Cy comprises a crystallizable moiety.
  • the crystallizable moiety may be connected to the polymer backbone directly or through a divalent organic or inorganic radical, e.g. an ester, carbonyl, amide, hydrocarbon (for example phenylene), amino, or ether link, or through an ionic salt linkage (for example a carboxyalkyl ammonium, sulfonium or phosphonium ion pair).
  • the radical Cy may be aliphatic or aromatic, for example containing alkyl of at least 10 carbons, fluoralkyl of at least 6 carbons or p-alkyl styrene wherein the alkyl contains 6 to 24 carbons, particularly linear polymethylene moieties containing 12 to 50, especially 14 to 22, carbon atoms, or linear perfluorinated or substantially perfluorinated polymethylene moieties containing 6 to 50 carbon atoms.
  • Polymers containing such side chains can be prepared by polymerizing one or more corresponding linear aliphatic acrylates or methacrylates, or equivalent monomers such as acrylamides or methacrylamides.
  • the polymers can optionally also contain units derived from one or more other comonomers preferably selected from other alkyl, hydroxyalkyl and alkoxyalkyl acrylates, methacrylates (e.g. glycidal methacrylate), acrylamides and methacrylamides; acrylic and methacryiic acids; acrylamide; methacrylamide; maleic anhydride; and comonomers containing amine groups.
  • Such other co-monomers are generally present in total amount less than 50%, particularly less than 35%, especially less than 25%, e.g. O to 15%.
  • Preferred SCC polymers used in this invention comprise 30 to 100%, preferably 40 to 100%, of units derived from at least one monomer selected from the group consisting of alkyl acrylates, alkyl methacrylates, N-alkyl acrylamides, N-alkyl methacrylamides, alkyl oxazolines, alkyl vinyl ethers, alkyl vinyl esters, ⁇ -olefins, alkyl 1,2-epoxides and alkyl glycidyl ethers in which the alkyl groups are n-alkyl groups containing 12 to 50 carbon atoms, and the corresponding fluoroalkyl monomers in which the thermoalkyl groups are n-fluoroalkyl groups containing 6 to 50 carbon atoms; 0 to 20% of units derived from at least one monomer selected from the group consisting of alkyl acrylates, alkyl methacrylates, N-alkyl acrylamides, alkyl vinyl ethers, and alkyl
  • Such SCC moieties may also contain units derived from other monomers to change compatibility with the matrix, or to raise the modulus of a reaction product containing the modifying agent; such monomers include styrene, vinyl acetate, monoacrylic functional polystyrene and the like.
  • the selected active chemical ingredient can be a catalytic ingredient (including an initiator), a reactive ingredient, or an inhibiting ingredient.
  • the way in which an ingredient behaves may depend upon the matrix material: for example, an amine group may be catalytic in some circumstances and reactive in other circumstances.
  • the modifying agent preferably contains at least 1% of the active chemical ingredient.
  • the modifying agent can contain two or more different active chemical ingredients, in which case each can be a catalytic ingredient, or each can be a reactive ingredient, or one or more can be a catalytic ingredient and the other or others a reactive ingredient.
  • the active chemical ingredient can contain, for example, nitrogen, e.g.
  • phosphorus e.g. as a -PR3 group, where R is an organic radical
  • oxygen e.g. as a carboxyl, ester or amide group
  • metal or metal-containing group e.g. a transition metal such as rhodium, cobalt, vanadium or manganese, or a main group metal such as aluminum, bismuth tin, lead, or copper, or a metal alkoxide, for example attached to the polymeric moiety through one or more ligand groups
  • a peroxide initiator e.g. benzoyl peroxide, t-butyl perbenzoate or t-butyl peroctoate.
  • Chemical ingredients which are particularly useful in this invention include amines (including primary, secondary, tertiary and quaternary amines, and heterocyclic amines such as imidazoles); carboxyl groups; sulfonate groups; phosphines; main group metals, including lead, bismuth and tin; transition metals, including cobalt, copper, manganese, titanium and rhodium, e.g. as [(C2H4)2 RhCl]2, and acetylacetonate esters of transition metals; enzymes; superacids; metal alkoxides; UV- activated moieties, e.g. 4-vinylbenzophenone; Michler's ketone; and acetophenone; and groups which are converted into such groups when the modifying agent is used.
  • amines including primary, secondary, tertiary and quaternary amines, and heterocyclic amines such as imidazoles
  • carboxyl groups including lead,
  • the various parts of this invention can make use of any modifying agent in which an active chemical ingredient is bound (either chemically or physically or both, depending on the part of the invention in question) to a temperature-sensitive polymeric ingredient.
  • the active ingredient can be a catalyst, a reactant or an inhibitor.
  • Reactions which can be catalyzed include polymerizations, e.g. polymerization of one or more olefinically unsaturated monomers (particularly one or more olefins, optionally with one or more substituted olefins), and ring-opening polymerizations, hydrogenations, hydroformylation reactions, enzyme-catalyzed reactions (e.g. in the production of foods, including cheese, and pharmaceuticals, in medical diagnostic procedures, and in the treatment of waste products), oxidations, reductions, etc.
  • reactive chemical ingredients examples include isocyanato, anhydride, acyl halide, aldehyde, hydroxyl, alkyl or aryl halide, amide, amine, including saturated and unsaturated heterocyclic amine, carboxyl, amine, epoxide, mercaptan, azo and peroxy, and carbamate and urea.
  • isocyanato anhydride
  • acyl halide aldehyde
  • hydroxyl alkyl or aryl halide
  • amide amine, including saturated and unsaturated heterocyclic amine, carboxyl, amine, epoxide, mercaptan, azo and peroxy, and carbamate and urea.
  • the modifying agent is preferably in the form of solid particles which are uniformly dispersed in the matrix.
  • the matrix may be in the form of a solid or a liquid which provides a continuous phase including systems which are in the form of particles, with at least some of the particles, viewed individually, comprising a continuous phase of the matrix with particles of the modifying agent dispersed therein.
  • the matrix can also be in the form of particles. The smaller the particles, the easier they are to disperse and maintain in a uniformly dispersed state. On the other hand, the smaller the particles, the lower the ratio of active chemical moieties hidden within the particles to those exposed on the surface of the particles, and the less the potential storage stability of the composition.
  • This ratio decreases as the size of the particles decreases and also is higher for spherical particles than for particles of other shapes. It is, therefore, preferred to use substantially spherical particles having an average size of 0.1 to 150, more preferably 0.1 to 50, particularly 0.1 to 25, especially 0.1 to 10, microns. Preferably each of the particles is within these ranges. Suitable particles can be produced by known techniques, including spray drying, impact pulverizing, and agitation in a fluid followed by cooling to freeze the particle size.
  • the modifying agent may also be in the form of a film, which may be self- supporting or a layer on a support.
  • the relative amounts of modifying agent and matrix may vary widely, depending on the nature and concentration of the active chemical ingredient in the modifying agent, the conditions to which the composition is subjected, and the desired result. Generally the composition contains 0.01 to 50% of the modifying agent.
  • the modifying agent preferably contains 1 to 40% thereof, particularly 1 to 10% thereof
  • the modifying agent contains at least 5%, more preferably at least 15%, particularly at least 20%, e.g. 15 to 40%, especially 20 to 35%, thereof. .
  • the modifying agent can be contacted with the matrix in any desired way.
  • the resulting composition is then maintained at a temperature below Tp until the time comes to promote or inhibit the chemical reaction.
  • Heating and cooling are the preferred ways of changing the extent to which the matrix is contacted by the active chemical ingredient.
  • other measures can be used in addition to, or instead of, heating or cooling, as described in International Application No. PCT/US 96/03023.
  • compositions used in this invention which comprise the matrix material and the modifying agent, can contain one or more other ingredients which have a useful effect, and which are referred to herein as coadditives.
  • an ingredient can (a) help to achieve good distribution of the solid modifying agent in the matrix material and/or reduce the time needed to distribute the solid modifying agent in the matrix; (b) help to stabilize the composition before the treatment which exposes the active chemical ingredient; (c) have a desired effect on the manner or extent to which the active chemical ingredient is exposed by such treatment; (d) have a desired effect on a chemical reaction which takes place after such treatment, e.g.
  • a single coadditive can perform two or more of these functions.
  • the total amount of coadditive is preferably 0.05 to 50%, based on the "formula weight".
  • the term "formula weight” is used herein to denote the combined weight of the modifying agent and the matrix, but excluding any non-reactive, e.g. inorganic, fillers.
  • Examples 1-20 show the preparation of modifying agents
  • Examples A-F show the use of the modifying agents.
  • C22A is docosanyl acrylate
  • C18A is octadecyl acrylate
  • HE A is 2-hydroxyethylacrylate
  • C1M is methyl methacrylate
  • MA maleic anhydride
  • AA is acrylic acid
  • DMAEA is N,N- dimethylaminoethyl acrylate
  • AMZ is l-(2-aminoethyl)-2-methylimidazole
  • EMI 2- ethyl-4-methyl imidazole
  • 2EZ is 2-ethyl imidazole
  • AIBN is azo bis (isobutyronitrile)
  • TAP is t-amyl peroxy 2-ethyl hexanoate
  • BPB is t-butyl peroxybenzoate
  • C12SH is dodecane thiol
  • Petrolite is a copolymer of equal parts of maleic anhydride and a mixture of olefins containing
  • Pluracol is a hydroxy-terminated polyether available from BASF under the tradename Pluracol PI 010; Isonate is 4,4'- methylene bis(phenylisocyanate) available from Dow Chemical under the tradename Isonate 143L;
  • Ancamine 1110 is dimethylamino-methyl phenol available from Air Products Inc.;
  • DBU is diazobicycloundecene from Air Products;
  • D8 is a hydroxy terminated linear polyester polyol available from Bayer under the tradename Desmophen 800;
  • Dl 150 is a polyester polyol available from Bayer under the tradename Desmophen 1150;
  • Olin G36-272 is a trifunctional polyol available from Olin Corp.;
  • CB-60N is a polymeric toluene diisocyanate available from Bayer under the tradename Desmodur CB-60N;
  • MRS-4 is a polymeric diphenylmethane diisocyanate available from Bayer under the
  • the POMA and 4,4'-dimethylamino benzophenone (Michler's ketone) were mixed in a solvent in a ratio corresponding to 1 equivalent of POMA carboxyl group to 0.5 equivalent of the ketone.
  • the solvent was removed under vacuum, and the dried product formed into particles on an air mill, thus providing a modifying agent containing a photoactivatable group.
  • a physically bound polymeric modifying agent was made as follows. Petrolite (100 g) was heated to 65°C. Ethanolamine (13 g) was then added. After increasing the temperature to 95°C, EMI (28.06 g) was added with stirring.
  • a copolymer of C22A, AA, and C12SH (96/3/1) having an M w of 80,000- 100,000 was prepared.
  • a mixture of this copolymer (70 parts) and DBU (30 parts) was prepared at 80°C, cooled and formed into particles having an average size less than 20 micron.
  • a physically bound modifying agent was prepared by heating the C22A AA/C12SH polymer (400 g in 800 ml toluene) and DBTDL ( 100 g) with stirring until a homogeneous mixture resulted. The mixture was cooled to room temperature, and milled into a fine powder.
  • Examples 5-14 show the preparation of physically bound modifying agents.
  • Example 1 The ingredients used in these Examples, and the amounts thereof, are shown in Table 1.
  • an SCC polymer of C22A and AA in the proportions, and having To, Tp and ⁇ H values, shown in Table 1
  • Example 5-9 and 1 1-14 the resulting solution was heated and spray dried, using a Buchi laboratory spray drier under the conditions shown in Table 2 to yield particles of the size shown in Table 1.
  • Examples 5-7 the ingredients were simply mixed together before being spray dried.
  • Example 10 the SCC polymer (8g) and Ancamine (25 g) were mixed at 92°C to form an oil.
  • the oil was emulsified by adding it to stirred water (150 g) which contained 1% polyvinyl alcohol (Mowiol 18- 188) and was at 93°C. The mixture was sheared at 2500 rpm for 2 minutes, and then allowed to cool to room temperature while shearing at 1200 rpm. The resulting microcapsules of solidified oil had a particle size of about 30 microns and were collected by filtration. After washing with deionized water, the particles were dried in air for several days; they contained about 55% Ancamine and had a T 0 of 47°C, a Tp of 50°C and a ⁇ H of 45 J/G.
  • Example 11 When the product was collected by centrifugation instead of filtration, it contained about 27% Ancamine.
  • the SCC polymer was melt blended with the DABCO, then dissolved in the chloroform and spray dried.
  • Example 12 the ingredients were mixed and spray dried at 64°C.
  • 2EZ or AMI-2 was dissolved in water and spray dried to yield a fine powder.
  • This fine powder (10 g) was mixed with the SCC polymer (10 g) and heptane (180 ml) at 80°C, and the suspension spray dried to yield a powder in which the particles comprise the 2EZ or AMI-2 surrounded by a coating of the SCC polymer.
  • Examples A to D some of the modifying agents prepared in Examples 1 to 14 were used to prepare crosslinked polymeric resins.
  • POMA 20 parts, prepared in Example 1
  • C1M 50 parts
  • MA 10 parts
  • TPGDA 20 parts
  • the resin produced (10 parts) was dissolved in toluene (20 ml), coated onto a polyester film at a dry film thickness of 48 microns and subsequently covered with a 38 micron film of polyethylene, to produce a laminatable photoresist which could be activated by heat and light.
  • the modifying agents of Examples 6 and 7 were compared with each other and with the unmodified DBU catalyst, in experiments in which they were added to a polyurethane precursor containing D8 (70 parts) , Pluracol (30 parts) and MRS4 (38 parts) in an amount equivalent to about 0.3 parts of DBU or 0.3 part DMAEA per 100 parts of polyol.
  • the pot life in minutes at 25°C, measured on 25 ml samples, and the gel time in minutes, measured on 5 g samples on a hot plate, are given in Table 7 below.
  • a physically bound modifying agent containing 26% DBTDL was prepared as in Example 3 but replacing the DBU by DBTDL.
  • This modifying agent and DBTDL itself were used with various isocyanate/polyol combinations, in amount such that the mixture contained 0.5 phr of DBTDL versus polyol.
  • modifying agents identical or similar to the modifying agent of Example 4 i.e. agents prepared from different monomers and/or monomer ratios and/or different tin chelates
  • Pluracol 64 phr
  • Isonate 20 phr
  • G-36-232 16 phr
  • Table 5 shows the results.
  • Examples D1-D3 serve as controls.
  • Examples D4-D7 use modifying agents with tin covalently bound to the polymeric moiety.
  • Examples D8- D12 use modifying agents in which the tin is physically, but not chemically, bound to the crystalline polymer. Gel times at 20°C are slowest when the tin is covalently bound, but are still substantially slower than the control when the tin is physically bound. Other things being equal, the higher the ratio of AA to tin the longer, the higher the gel time at 20°C and the lower the gel time at 80°C.
  • a chemically bound modifying agent was made as follows. A solution of C22A (89.4 g), AA (6.7 g) and C12SH (3.8 g) in 100 g of toluene was sparged with nitrogen, and AIBN (0.1 g) was added. The mixture was heated at 60°C for 24 hours, and cooled to about 40°C. 500 ml of methyl alcohol was added with vigorous stirring. The precipitate was collected by filtration, and was dried in a vacuum oven at 50°C to 60°C for 15 hours. Analysis by GPC showed the molecular weight (M w ) to be 100,000.
  • the modifying agent made in this way was used to cure a mixture of 100 g of
  • Aropol 2036 unsaturated polyester resin and 1.25 g of methylethyl ketone peroxide (MEKP). 0.67 g of the modifying agent and the mixture were vigorously stirred for 5 min by hand to disperse the modifying agent. The gel time of the system at 20°C was 223 min.
  • Example F1-F4 the modifying agent (1.2 g) and Epon 828 (10 g) were placed in a 20 ml vial and mixed vigorously with a spatula. The samples were tested on a DSC at a heating rate of 10°C/min from 30° to 300°C.
  • the modifying agent or EMI-24 was hand mixed with the epoxy resin. DSC data were obtained in the same way. Viscosity was measured initially and after 2 days Lap shear values were obtained by spreading the mixture on 1 x 0.5 inch aluminum coupons with 0.5 inch overlap, heating the sample at 120°C, and measuring the lap shear strength on an Instron Tensile tester with a 1000 lb. load cell at 0.05 inch/min. after the times indicated. The viscosity profiles of the samples over time (rheometer, time sweep, 70°C, 25 rad/sec 20% strain) are shown in Table 7 below. TABLE 7
  • Examples F7-F10 the ingredients were mixed by hand.
  • Examples FI 1 and F12 the ingredients were mixed in amounts such that the NCO:OH ratio was 1 : 1.
  • Examples F13-F17 the ingredients were mixed by hand, and the results of DSC testing are given in Table 1 1 as the residual heat of reaction, expressed as a percentage of the initial heat of reaction (which was 300-350 J/g in Examples F13-F15 and 400- 600 J/g in Examples F16-F17).
  • a copolymer was prepared by heating C22A (75 g) DMAEA (25 g) and TAP (1%) at 110°C.
  • the copolymer had an M w of 15,000-25,000 and a T p of 63°C. It was formed into particles having an average size of 10 microns.
  • Example 4 a solution of the C22A AA/C12SH polymer prepared in Example 4 (400 g in 800 ml toluene) was warmed with stirring to dissolve the polymer. To the solution was added 324.3 g of BTBTO. The reaction mixture was distilled using a Dean-Stark water separator. Water was collected to indicate progress of the reaction.
  • the product had a tin content of 13.1%, a T c of 37.01°C, a T p of 49°C, and a ⁇ H of

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne de nouveaux agents de modification comprenant un composant polymère cristallin fondant rapidement, de préférence une fraction cristalline de chaîne latérale (SCC), et un composant chimique actif qui est lié physiquement (mais non pas chimiquement) au composant polymère. De tels agents de modification, notamment lorsqu'ils se présentent sous forme de particules, peuvent être mis en contact avec une matrice sans que celle-ci s'en trouve modifiée en dessous du point de fusion cristallin Tp, mais laquelle matrice sera rapidement modifiée au-dessus du point Tp. Le composant chimique actif peut réagir avec la matrice et catalyser ou inhiber une réaction de celle-ci. L'invention décrit également diverses compositions qui comprennent (1) une substance de matrice, p.ex. un précurseur de résine époxy; (2) un agent de modification comprenant un composant polymère cristallin fondant rapidement et un composant chimique actif (qui peut être lié physiquement ou chimiquement au composant polymère); et (3) un composant supplémentaire qui confère les propriétés désirées au mélange ou à un produit obtenu sur la base dudit mélange.
EP97940998A 1996-09-12 1997-09-10 Composition polymere comprenant un agent de modification Withdrawn EP0925332A1 (fr)

Applications Claiming Priority (3)

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US710161 1991-06-04
US71016196A 1996-09-12 1996-09-12
PCT/US1997/016019 WO1998011166A1 (fr) 1996-09-12 1997-09-10 Composition polymere comprenant un agent de modification

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JPH11256043A (ja) * 1998-01-16 1999-09-21 Landec Corp 架橋性樹脂のための低収縮剤
JP4647781B2 (ja) 1998-04-27 2011-03-09 エセックス スペシャリティ プロダクツ，リミティド ライアビリティ カンパニー シラン機能性接着剤組成物を用いて窓を基体に結合する方法
ATE259257T1 (de) 1998-04-27 2004-02-15 Dow Chemical Co Eingekapselte aktive materialien und herstellungsverfahren
JP2000044636A (ja) * 1998-05-27 2000-02-15 Hitachi Chem Co Ltd 熱硬化性樹脂組成物及びこれを用いたコイルの製造法
JP2000273323A (ja) * 1999-03-24 2000-10-03 Hitachi Chem Co Ltd 硬化剤組成物、熱硬化性樹脂組成物、これを用いた管ライニング材及び管ライニング工法
JP2001200021A (ja) * 2000-01-19 2001-07-24 Hitachi Chem Co Ltd 樹脂組成物
US6822058B1 (en) 2000-07-14 2004-11-23 The Sherwin-Williams Company Low-temperature in-mold coating composition
FI114237B (fi) 2003-05-23 2004-09-15 Metso Paper Inc Menetelmä telan pinnoitteen valmistamiseksi
US7842146B2 (en) 2007-01-26 2010-11-30 Dow Global Technologies Inc. Ultrasonic energy for adhesive bonding
US8114883B2 (en) * 2007-12-04 2012-02-14 Landec Corporation Polymer formulations for delivery of bioactive materials
WO2009154058A1 (fr) * 2008-06-20 2009-12-23 出光興産株式会社 Matériau de moulage en résine époxy pour l’étanchéification de semi-conducteurs, feuille en résine époxy pour l’étanchéification de semi-conducteurs et leur procédé de fabrication
WO2010068279A1 (fr) * 2008-12-11 2010-06-17 Landec Corporation Indicateur thermochromique
WO2010144755A2 (fr) * 2009-06-11 2010-12-16 Landec Corporation Compositions et procédés pour l'administration de matières
US9359499B2 (en) * 2011-05-05 2016-06-07 Stratasys, Inc. Radiation curable polymers

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GB1104274A (en) * 1965-10-12 1968-02-21 Plastic Coatings Ltd Improvements in or relating to fusible adhesive compositions
LU57906A1 (fr) * 1969-02-04 1970-08-04
US5665822A (en) * 1991-10-07 1997-09-09 Landec Corporation Thermoplastic Elastomers
JPH0786465A (ja) * 1993-09-16 1995-03-31 Toshiba Corp 半導体封止用エポキシ樹脂組成物
CA2214893A1 (fr) * 1995-03-07 1996-09-12 Stephen P. Bitler Composition polymere

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