[go: up one dir, main page]

WO2014158705A1 - Procédés de fabrication de compositions à faible retrait et expansibles et monomère expansibles - Google Patents

Procédés de fabrication de compositions à faible retrait et expansibles et monomère expansibles Download PDF

Info

Publication number
WO2014158705A1
WO2014158705A1 PCT/US2014/019419 US2014019419W WO2014158705A1 WO 2014158705 A1 WO2014158705 A1 WO 2014158705A1 US 2014019419 W US2014019419 W US 2014019419W WO 2014158705 A1 WO2014158705 A1 WO 2014158705A1
Authority
WO
WIPO (PCT)
Prior art keywords
expandable
monomer
carbonate
composition
epoxy resin
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.)
Ceased
Application number
PCT/US2014/019419
Other languages
English (en)
Inventor
Rama V. Rajagopal
Keizo Yamanaka
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.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
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 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of WO2014158705A1 publication Critical patent/WO2014158705A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • Another form of the present invention is a composition for a curing agent that is a compound containing two or more first carbamate linkages, where each first carbamate linkage is connected to a second carbamate linkage.
  • the ester side of the first carbamate linkages are connected to the ester side of corresponding second carbamate linkages.
  • Yet another form of the present invention is a method for preparing a curing agent by reacting a compound containing at least two carbamate linkages, where each carbamate linkage is connected to at least one carbonate, with an excess of a diamine.
  • a method of making a composition comprising providing an expandable monomer derived from reacting a cyclic compound comprising a carbonate group and a hydroxyl group with a hydroxyl-reactive compound; and combining the expandable monomer with an epoxy resin and a curing agent, wherein the curing agent concurrently reacts with the carbonate of the expandable monomer and epoxy groups of the epoxy resin.
  • a low shrinkage composition comprising an expandable monomer comprising at least two cyclic carbonate end groups; an epoxy resin; and a curing agent that concurrently reacts with the cyclic carbonate of the expandable monomer and epoxy groups of the epoxy resin.
  • an expandable composition comprising an expandable monomer comprising at least two cyclic carbonate end groups; an epoxy resin; and a curing agent that reacts with the cyclic carbonate of the expandable monomer and epoxy groups of the epoxy resin; wherein the expandable composition exhibits an increase in volume after curing.
  • favored expandable monomers are described comprising the reaction product of a cyclic compound having a hydroxyl group and a carbonate group and a polyisocyanate comprising at least two hexamethylene groups and at least one uretdione, biuret, and/or isocyanurate group.
  • the low shrinkage and expandable compositions and expandable monomers are suitable for various used such as (e.g. structural) adhesive wherein two substrates are bonded by the cured composition described herein.
  • the present invention pertains to expandable monomers.
  • the expandable monomer is derived from a cyclic compound comprising a carbonate group and a hydroxyl group.
  • the carbonate group forms a portion of the cyclic group.
  • the cyclic group may be considered a cyclic aliphatic carbonate.
  • the hydroxyl group of a cyclic carbonate compound can be reacted with an isocyanate compound to form an expandable monomer having urethane linkages.
  • the expandable monomer preferably comprises a residue of a polyisocyanate and urethane linkages terminating with a cyclic carbonate moiety.
  • a representative structure of the expandable monomers is as follows:
  • Ri (NHCOOR c ) n wherein Ri is a residue of a polyisocyanate
  • R c comprises a cyclic carbonate group
  • n averages greater than 1.
  • the total number of atoms that form the cyclic carbonate group is typically at least 4 or 5 and no greater than 8 or 6.
  • An alkylene (C 2 - C 6 ) spacer group is typically present between the terminal cyclic carbonate group and the oxygen atom of the urethane linkage. In some embodiments, n averages 2 to 4 or 2 to 3.
  • Glycerine carbonate One commercially available cyclic carbonate compound comprising a hydroxyl group is glycerine carbonate.
  • Glycerine carbonate depicted as follows, is commercially available from Hunstman under the trade designation "JEFFSOLTM GLYCERINE CARBONATE" and has been described as being readily biodegradable and having a renewable content of 76%.
  • the hydroxyl group of the cyclic carbonate is reacted with a polyisocyanate compound to form an expandable monomer.
  • Useful aliphatic polyisocyanates include, for example, bis(4-isocyanatocyclohexyl) methane, such as available from Bayer Corp., Pittsburgh, Pa. under the trade designation "Desmodur W";
  • IPDI isophorone diisocyanate
  • Huels America, Piscataway, N.J. hexamethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • trimethyl hexamethylene diisocyanate such as commercially available from
  • Vestanate TMDI m- tetramethylxylene diisocyanate
  • TMDI m- tetramethylxylene diisocyanate
  • TMXDI m- tetramethylxylene diisocyanate
  • aromatic isocyanates such as diphenylmethane diisocyanate (MDI) such as commercially available from Bayer Corp., Pittsburgh, Pa. under the trade designation "Mondur M”; toluene 2,4-diisocyanate (TDI) such as commercially available from Aldrich Chemical Co., Milwaukee, Wis., and 1 ,4-phenylene diisocyanate.
  • the polyisocyanates are derivatives of the above-listed monomeric polyisocyanates, such as derivatives of hexamethylene- 1 ,6-diisocyanate that comprise an uretdione, biuret, and/or isocyanurate.
  • the residue of the polyisocyanate typically comprises at least two or three hexamethylene groups and at least one uretdione, biuret, and/or isocyanurate.
  • These derivatives include, but are not limited to, biuret adducts of HDI, such as available from Bayer Corp. under the trade designation "Desmodur N 3200”; HDI uretdione polyisocyanates, such as available from Bayer Corporation under the trade designation “Desmodur N 3400”; HDI polyisocyanurates, such as available from Bayer Corp under the trade designation “Desmodur N 3300”; and polyisocyanate prepolymer resins based on HDI, such as available from Bayer Corp. under the trade designation "Desmodur XP 2599".
  • HDI uretdione polyisocyanates such as available from Bayer Corporation under the trade designation “Desmodur N 3400”
  • HDI polyisocyanurates such as available from Bayer Corp under the trade designation "Desmodur N 3300”
  • polyisocyanate prepolymer resins based on HDI such as available from Bayer Corp. under the trade designation "Desmodur XP
  • the expandable monomer prepared from derivatives of hexamethylene diisocyanate can be represented by the following formula:
  • Ri-CNHCOOR c wherein Ri is a residue of a hexamethylene polyisocyanate comprising least one uretdione, biuret, or isocyanurate group ;
  • R c comprises a cyclic carbonate group
  • n averages greater than 1 , as previously described.
  • Preferred aliphatic polyisocyanate are solvent- free and are substantially free of isocyanate (e.g. HDI) monomer, i.e. less than 0.5 % and more preferably no greater than 0.3 % as measured according to DIN EN ISO 10 283.
  • the polyisocyanate is selected such that the expandable monomer synthesized therefrom is compatible with the epoxy resin.
  • the epoxy resin is a diglycidyl ether of
  • Bisphenol A such as "EPON 828” it has been found that expandable monomers derived from aliphatic isocyanates, such as HDI derivative, can exhibit better compatibility than those derived from toluene diisocyanate or isophorone diisocyanate, particularly when the expandable monomer is present at a weight ratio of about 1 :3 or greater relative to the concentration of the epoxy resin.
  • One indication of poor compatibility is phase separation.
  • expandable monomers derived from aromatic polyisocyanates, such as toluene diisocyanate, or cyclic aliphatic polyisocyanates, such as isophorone diisocyanate may be sufficiently compatible with other types of epoxy resins.
  • epoxy resins can be utilized.
  • epoxides that are readily available include resins of octadecylene oxide, epichlorohydrin, styrene oxide, vinyl cyclohexene oxide, glycidol, glycidyl methacrylate, diglycidyl ethers of Bisphenol A (for example, EPON 828, EPON 825, EPON 1004, and EPON 1001 from Momentive Specialty Chemicals) as well as DER 221 , DER 332, and DER 334 from Dow Chemical Co., Midland, MI), vinylcyclohexene dioxide (for example, ERL 4206 from Union Carbide), 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexene carboxylate (for example, ERL 4221 , CYRACURE UVR 61 10, and CYRACURE UVR 6105 from Union Carbide), 3,4-epoxy-6-methylcyclohexylmethyl-3
  • HELOXY MODIFIER 107 trimethylol ethane triglycidyl ether (for example, HELOXY MODIFIER 44), trimethylol propane triglycidyl ether (for example, HELOXY 48), polyglycidyl ether of an aliphatic polyol (for example, HELOXY MODIFIER 84), polyglycol diepoxide (for example, HELOXY MODIFIER 32), bisphenol F epoxides (for example, EPON 862 and Araldite GY-281 from Huntsman Advanced Materials), and 9,9-bis[4-(2,3-epoxypropoxy)-phenylfluorenone (for example, EPON 1079 from Momentive Specialty Chemicals).
  • HELOXY MODIFIER 44 trimethylol ethane triglycidyl ether
  • HELOXY 48 trimethylol propane triglycidyl ether
  • useful epoxy-containing materials include those that contain cyclohexene oxide groups such as epoxycyclohexanecarboxylates, typified by 3,4- epoxycyclohexylmethyl-3,4- epoxycyclohexanecarboxylate, 3,4-epoxy-2- methylcyclohexylmethyl-3,4-epoxy-2- methylcyclohexane carboxylate, and bis(3,4-epoxy- 6-methylcyclohexylmethyl) adipate.
  • cyclohexene oxide groups such as epoxycyclohexanecarboxylates, typified by 3,4- epoxycyclohexylmethyl-3,4- epoxycyclohexanecarboxylate, 3,4-epoxy-2- methylcyclohexylmethyl-3,4-epoxy-2- methylcyclohexane carboxylate, and bis(3,4-epoxy- 6-methylcyclohexylmethyl) adipate.
  • epoxy resins are well known and contain such epoxides as epichlorohydrins, alkylene oxides (for example, propylene oxide), styrene oxide, alkenyl oxides (for example, butadiene oxide), and glycidyl esters (for example, ethyl glycidate).
  • Still other useful epoxy resins include epoxy- functional silicones such as those described in U.S. 4,279,717 (Eckberg et al.), which are commercially available from the General Electric Company.
  • polydimethylsiloxanes in which 1 to 20 mole percent of the silicon atoms have been substituted with epoxyalkyl groups (preferably, epoxy cyclohexylethyl, as described in U.S. 5,753,346 (Leir et al.)).
  • epoxyalkyl groups preferably, epoxy cyclohexylethyl, as described in U.S. 5,753,346 (Leir et al.)
  • Blends of various epoxy-containing materials can also be utilized. Suitable blends can include two or more weight average molecular weight distributions of epoxy- containing compounds such as low molecular weight epoxides (e.g., having a weight average molecular weight below 200 g/mole), intermediate molecular weight epoxides (e.g., having a weight average molecular weight in the range of about 200 to 1000 g/mole), and higher molecular weight epoxides (e.g., having a weight average molecular weight above about 1000 g/mole).
  • the epoxy resin can contain a blend of epoxy-containing materials having different chemical natures such as aliphatic and aromatic or different functionalities such as polar and non-polar.
  • the method of making the composition comprises providing an expandable monomer derived from reacting a cyclic compound comprising a carbonate group and a hydroxyl group (e.g. glycerine carbonate) with a hydroxyl-reactive compound (e.g. a polyisocyanate); and combining the expandable monomer with an epoxy resin and a curing agent.
  • the curing agent reacts with the carbonate of the expandable monomer and epoxy groups of the epoxy resin.
  • the reaction of the curing agent with the carbonate results in ring-opening and an expansion in volume, whereas the reaction of the curing agent with the epoxy results in a contraction in volume, commonly known as "shrinkage".
  • the order of addition or synthesis is such that the curing agent concurrently reacts with the carbonate of the expandable monomer and epoxide groups of the epoxy resin. When concurrently reacted in this manner the expansion of the ring opened cyclic compound can offset or surpass the shrinkage.
  • the mixture can be a low shrinkage composition typically having a shrinkage of no greater than 0.5%, or 0.4%, or 0.3%, or 0.2%, 0.1%, or even 0 as measured according to the Shrinkage Test Method described in the forthcoming examples.
  • the concentration of expandable monomer increases, the expansion caused by the ring opening of the cyclic carbonate group surpasses the shrinkage and the resulting composition can exhibit an increase in volume, or in other words a positive shrinkage.
  • the weight ratio of expandable monomer to epoxy resin is at least 1 :8, or 1 :7, or 1 :6, or 1 :5, or 1 :4, or 1 :3 or 1 :2.
  • the weight ratio of expandable monomer, to epoxy resin is typically no greater than 1 : 1. It is typically favored to utilize the minimum amount of expandable monomer that will provide the desired low shrinkage or expansion.
  • the amount of expandable monomer is least about 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt-% of the total polymerizable composition.
  • the amount of expandable monomer may range up to 15, 20 or 25 wt-% of the total polymerizable composition.
  • the thermal expansion of the epoxy resin does not significantly change by inclusion of up to 25 wt-% of expandable monomer.
  • the second heat may rise by about 10 - 15°C.
  • the glass transition temperature (Tg) of the epoxy resin is reduced by inclusion of up to 25 wt-% of expandable monomer.
  • the Tg may decrease by 30-35°C.
  • the curing agent is reactive with the epoxy groups of the epoxy resin and the cyclic carbonate group of the expandable monomer.
  • One class of curing agents having such reactivity are polyamines, such as diamines.
  • the polyamine crosslinker may be straight-chain, branched, and in some favored
  • the polyamine crosslinker is aliphatic. In other embodiments, the polyamine crosslinker is aromatic.
  • Useful polyamine are of the general formula R 5 -(NR ! R 2 )x wherein and R 2 are
  • R 5 is a polyvalent alkylene or arylene
  • x is at least two.
  • the alkyl groups of Ri and R 2 are typically Q to Qg alkyl and most typically methyl. Ri and R 2 may be taken together to form a cyclic amine.
  • x is two (i.e. diamine). In other embodiments, x is 3 (i.e. triamine). In yet other embodiments, x is 4.
  • Useful polyamines include diamines having at least two amino groups, wherein the two amino groups are primary, secondary, tertiary or a combination thereof.
  • Diamines may be represented by the general formula:
  • Ri, R 2 , R 3 and R4 are independently H or alkyl, and R5 is a divalent alkylene or arylene.
  • Ri, R 2 , R3 and R4 are each H and the diamine is a primary amine.
  • Ri and R4 are each H and R 2 , and R4 are each independently alkyl; and the diamine is a secondary amine.
  • Ri, R 2 , R3 and R4 are independently alkyl and the diamine is a tertiary amine.
  • primary and secondary amines are preferred.
  • Examples include hexamethylene diamine; 1, 10-diaminodecane; 1,12-diaminododecane; 2-(4- aminophenyl)ethylamine; isophorone diamine; 4,4'-diaminodicyclohexylmethane; and 1,3- bis(aminomethyl)cyclohexane.
  • Illustrative six member ring diamines include for example piperzine and l,4-diazabicyclo[2.2.2]octane ("DABCO").
  • polyamines having at least three amino groups include polyamines having at least three amino groups, wherein the three amino groups are primary, secondary, or a combination thereof. Examples include 3,3'- diaminobenzidine and hexamethylene triamine.
  • Polymeric polyamines can also be utilized; including for example poly(4-vinylpyridine) and branched polyethylenimine.
  • Polyamines that are solids at room temperature have low odor due to having low vapor pressures.
  • Polyamines having such property are straight-chain or branched polyamines having an alkylene group comprising at least 5 or 6 carbons. Cyclic polyamines are also favorably solids at room temperature.
  • the polyamine has a melting point of at least 100°C, 125°C, or 150°C. The melting point is typically no greater than 300°C, and in some embodiments no greater than 250°C, or 225°C, or 200°C, or 175°C.
  • the molecular weight of useful polyamines that are solids at room temperature is typically at least 100, 105, 1 10, or 1 15 g/mole.
  • the (weight average) molecular weight of the polyamine can range up 100,000 g/mole; yet is typically less than the molecular weight of the isobutylene copolymer.
  • the (weight average) molecular weight of the polyamine is no greater than 75.000 g/mole, 50,000 g/mole or 25,000 g/mole.
  • the molecular weight of the polyamine is typically no greater than 1500 g/mole and in some embodiments no greater than 1000 or 500 g/mole.
  • composition may further comprise optional additives such as antioxidants, inhibitors, (e.g. silane -treated) fillers, anti-sag additives, thixotropes, processing aids, waxes, and UV stabilizers.
  • additives such as antioxidants, inhibitors, (e.g. silane -treated) fillers, anti-sag additives, thixotropes, processing aids, waxes, and UV stabilizers.
  • typical fillers include glass bubbles, fumed silica, alumina, mica, feldspar, and wollastonite.
  • the low shrinkage or expandable composition is suitable for various uses such as for use as a (e.g. structural) adhesive.
  • the (e.g. adhesive) composition may take many forms, the composition is typically provided as multipack or two-part adhesive systems where one package or part contains the epoxy resin and expandable monomer and a second package or part contains the (e.g. amine) curing agent. The two parts are mixed together at the time of use in order to initiate the concurrent reaction of the epoxy and expandable monomer with the curing agent.
  • the typical means for dispensing the (e.g. adhesive) composition are two-chambered cartridges equipped with static mixers in the nozzle, and for larger scale application, meter mix dispensing equipment. After mixing the individual packages, one or both surfaces to be joined are coated with the mixed adhesive system and the surfaces are placed in contact with each other.
  • the (e.g. structural) adhesive may be used to bond metal surfaces, such as steel, aluminum and copper, to a variety of substrates, including metal, plastics, and other polymers, reinforced plastics, fibers, glass, ceramics, wood and the like.
  • the adhesive provides effective bond strength at room temperature, thus heat is not required either for applying the adhesive systems to the substrates or for developing handling strength and dimensional stability.
  • the (e.g. structural) adhesive may be brushed, rolled, sprayed, dotted, knifed, cartridge- applied, especially from a dual cartridge; or otherwise applied to one substrate or both substrates to desired thickness.
  • the liquid density (before curing) was measured by weighing a precise amount of liquid formulation.
  • the density of cured films (after curing) was measured by means of a Mettler Toledo Balance with density determination kit.
  • the Archimedes principle is applied for determining the specific gravity of a solid with this measuring device:
  • a solid immersed in a liquid is exposed to the force of buoyancy.
  • the value of this force is the same as that of the weight of the liquid displaced by the volume of the solid.
  • the Shrinkage during polymerization was calculated with the following formula:
  • the expanding monomers synthesized above was mixed with Epon 828 and cured with isophorone diamine (30 phr). To get a bubble-free sample for density measurements, the polymerization was carried out in silicon oil. The intimate mixture of monomer and hardener was placed in silicon oil and heated to 70°C for complete polymerization. After keeping for lh, the solidified sample was taken out and wiped thoroughly to remove the silicone oil. The volume shrinkage of the cured composition was determined as previously described. The test results are as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'une composition ainsi que des compositions à faible retrait et expansibles comprenant un monomère expansible comprenant au moins deux groupes terminaux carbonate cycliques ; une résine époxy ; et un agent de traitement qui réagit en même temps avec le carbonate cyclique du monomère expansible et les groupes époxy de la résine époxy. L'invention concerne également des monomères expansibles privilégiés comprenant le produit de la réaction d'un composé carbonate cyclique comportant un groupe hydroxyle et d'un polyisocyanate comprenant au moins deux groupes hexaméthylène et au moins une uretdione, un biuret, et/ou un groupe isocyanurate. Les compositions à faible retrait et expansibles et les monomères expansibles sont appropriés pour différentes utilisations telles qu'un adhésif (par exemple structurel) dans lequel deux substrats sont liés par la composition durcie selon la présente invention.
PCT/US2014/019419 2013-03-13 2014-02-28 Procédés de fabrication de compositions à faible retrait et expansibles et monomère expansibles Ceased WO2014158705A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361778651P 2013-03-13 2013-03-13
US61/778,651 2013-03-13

Publications (1)

Publication Number Publication Date
WO2014158705A1 true WO2014158705A1 (fr) 2014-10-02

Family

ID=50290293

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/019419 Ceased WO2014158705A1 (fr) 2013-03-13 2014-02-28 Procédés de fabrication de compositions à faible retrait et expansibles et monomère expansibles

Country Status (1)

Country Link
WO (1) WO2014158705A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106459728A (zh) * 2014-04-04 2017-02-22 汉高股份有限及两合公司 具有环碳酸酯基团和环氧基的双组分粘结剂体系
CN111909360A (zh) * 2020-08-11 2020-11-10 深圳飞扬兴业科技有限公司 一种高弹性环氧固化剂、制备方法以及环氧树脂
CN112961637A (zh) * 2021-04-14 2021-06-15 海泰纳鑫科技(成都)有限公司 低收缩率双组份环氧树脂胶黏剂及其制备方法和应用
CN113508151A (zh) * 2019-03-08 2021-10-15 聚合物技术中心莱奥本有限责任公司 新的膨胀共聚物
CN117384581A (zh) * 2023-11-06 2024-01-12 深圳市欣恒坤科技有限公司 一种低体积收缩率的光学胶及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3117099A (en) 1959-12-24 1964-01-07 Union Carbide Corp Curable mixtures comprising epoxide compositions and divalent tin salts
US4279717A (en) 1979-08-03 1981-07-21 General Electric Company Ultraviolet curable epoxy silicone coating compositions
US5753346A (en) 1992-10-02 1998-05-19 Minnesota Mining & Manufacturing Company Cationically co-curable polysiloxane release coatings
US20020183474A1 (en) 2001-03-30 2002-12-05 Klein Howard P. Multifunctional carbonates and derivatives
US20030050424A1 (en) * 1998-10-02 2003-03-13 Jean-Marie Bernard Modified isocyanates
US20030064227A1 (en) * 2001-09-12 2003-04-03 Allisa Gam Cathodic electrocoating compositions containing hydroxyl-carbonate blocked polyisocyanate crosslinking agent
US20100137507A1 (en) * 2007-03-27 2010-06-03 Perstorp France Composition Containing A Modified (Poly) Isocyanate And A Solvent Of The Acetal Or Aliphatic Ketone Type, And Use Of Said Composition For Producing Coatings

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3117099A (en) 1959-12-24 1964-01-07 Union Carbide Corp Curable mixtures comprising epoxide compositions and divalent tin salts
US4279717A (en) 1979-08-03 1981-07-21 General Electric Company Ultraviolet curable epoxy silicone coating compositions
US5753346A (en) 1992-10-02 1998-05-19 Minnesota Mining & Manufacturing Company Cationically co-curable polysiloxane release coatings
US20030050424A1 (en) * 1998-10-02 2003-03-13 Jean-Marie Bernard Modified isocyanates
US20020183474A1 (en) 2001-03-30 2002-12-05 Klein Howard P. Multifunctional carbonates and derivatives
US20030064227A1 (en) * 2001-09-12 2003-04-03 Allisa Gam Cathodic electrocoating compositions containing hydroxyl-carbonate blocked polyisocyanate crosslinking agent
US20100137507A1 (en) * 2007-03-27 2010-06-03 Perstorp France Composition Containing A Modified (Poly) Isocyanate And A Solvent Of The Acetal Or Aliphatic Ketone Type, And Use Of Said Composition For Producing Coatings

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106459728A (zh) * 2014-04-04 2017-02-22 汉高股份有限及两合公司 具有环碳酸酯基团和环氧基的双组分粘结剂体系
US10179871B2 (en) * 2014-04-04 2019-01-15 Henkel Ag & Co. Kgaa Two-component binder system with cyclocarbonate and epoxy groups
CN113508151A (zh) * 2019-03-08 2021-10-15 聚合物技术中心莱奥本有限责任公司 新的膨胀共聚物
CN113508151B (zh) * 2019-03-08 2023-10-31 聚合物技术中心莱奥本有限责任公司 新的膨胀共聚物
CN111909360A (zh) * 2020-08-11 2020-11-10 深圳飞扬兴业科技有限公司 一种高弹性环氧固化剂、制备方法以及环氧树脂
CN112961637A (zh) * 2021-04-14 2021-06-15 海泰纳鑫科技(成都)有限公司 低收缩率双组份环氧树脂胶黏剂及其制备方法和应用
CN117384581A (zh) * 2023-11-06 2024-01-12 深圳市欣恒坤科技有限公司 一种低体积收缩率的光学胶及其制备方法

Similar Documents

Publication Publication Date Title
JP5727369B2 (ja) ヘテロ原子を有する促進剤を含む熱硬化性エポキシ樹脂組成物
US7847034B2 (en) Adducts and curable compositions using same
US8729213B2 (en) Benzylated polyamine curing agents
US8076395B2 (en) Low temperature curable epoxy compositions containing urea curatives
AU2020281855A1 (en) Two-component composition with a high degree of strength
US4540750A (en) Diethyl toluene diamine hardener systems
WO2014158705A1 (fr) Procédés de fabrication de compositions à faible retrait et expansibles et monomère expansibles
US12018114B2 (en) Polymeric material including a uretdione-containing material and a thermally activatable amine, two-part compositions, and methods
KR20110057176A (ko) 에폭시드 수지 조성물용 고온활성 경화제로서의 실란/우레아 화합물
US20160083501A1 (en) Hardenable synthetic resin comprising considerable proportions of cyclic carbonate groups, as well as/and cyclocarbonate-resin-based fixing systems, the production and use thereof
US8632654B2 (en) Hardener for epoxy resins
JP2022145636A (ja) 水性エポキシ硬化剤
US20210340309A1 (en) Polymeric Material Including a Uretdione-Containing Material and an Epoxy Component, Two-Part Compositions, and Methods
EP2935441B1 (fr) Agents durcissants pour résines époxy à faible émission
JP7227960B2 (ja) エポキシ樹脂組成物および硬化物
WO2020121116A1 (fr) Matériau polymère comprenant un matériau contenant de l'uretdione, un composant époxy et un accélérateur, compositions à deux composants et procédés
JP5294387B2 (ja) ２液型硬化性組成物
EP3853278B1 (fr) Matériau polymère comprenant un matériau contenant de l'uretdione et un composant époxy, compositions en deux parties et procédés
JP2025501875A (ja) 一成分型湿分硬化性組成物
US20230365845A1 (en) One-component structural adhesive
EP4496787B1 (fr) Composés de thiol-oxamide et compositions
JPH11217488A (ja) エポキシ樹脂組成物
EP4493612A1 (fr) Adhésif époxyde à deux composants comprenant un indicateur de changement de couleur de durée de conservation en pot
WO2004003048A1 (fr) Monoépoxydes polyéther uréthanne contenant de l'isocyanato

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14711083

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14711083

Country of ref document: EP

Kind code of ref document: A1