EP2576140A1 - Haftzusammensetzung mit einem wasserlöslichen oder in wasser dispergierbaren ungesättigten polyester und einem ethylengesättigten monomer und verwendungen davon - Google Patents

Haftzusammensetzung mit einem wasserlöslichen oder in wasser dispergierbaren ungesättigten polyester und einem ethylengesättigten monomer und verwendungen davon

Info

Publication number
EP2576140A1
EP2576140A1 EP11726913.4A EP11726913A EP2576140A1 EP 2576140 A1 EP2576140 A1 EP 2576140A1 EP 11726913 A EP11726913 A EP 11726913A EP 2576140 A1 EP2576140 A1 EP 2576140A1
Authority
EP
European Patent Office
Prior art keywords
acid
composition according
unsaturated
water
polyester
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Withdrawn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
EP11726913.4A
Other languages
English (en)
French (fr)
Inventor
Lidia Jasinska
Cornelis Eme Koning
Alix Arnaud
Clément HOUGA
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.)
Saint Gobain Recherche SA
Original Assignee
Saint Gobain Recherche SA
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 Saint Gobain Recherche SA filed Critical Saint Gobain Recherche SA
Publication of EP2576140A1 publication Critical patent/EP2576140A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D11/00—Constructional features of flexible abrasive materials; Special features in the manufacture of such materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
    • B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6858—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/126—Copolymers block

Definitions

  • the invention relates to the field of binders intended to bind together elements made of natural or synthetic material, in particular minerals, such as abrasive particles, glass or rock fibers, and glass threads.
  • the invention more particularly relates to an adhesive composition which contains at least one unsaturated polyester water-soluble or dispersible in water and at least one ethylenically unsaturated monomer.
  • thermosetting resins based on formaldehyde in particular urea-formaldehyde, melamine-formaldehyde and phenol-formaldehyde resins. These resins have good crosslinking ability, are water soluble, have good affinity for minerals and are relatively inexpensive.
  • the object of the present invention is to provide an adhesive composition containing no formaldehyde, capable of bonding together elements consisting of natural or synthetic materials, in particular mineral materials, in particular abrasive particles, glass or rock fibers and yarns. of glass.
  • the adhesive composition according to the present invention is an aqueous composition which contains at least one water-soluble or water-dispersible unsaturated polyester and at least one ethylenically unsaturated monomer, said unsaturated polyester being obtained by co-polymerization (A) of at least one monomeric or oligomeric polyol, (B) at least one unsaturated polycarboxylic acid or an unsaturated acid anhydride and (C) at least one polymer water-soluble composition containing at least two hydroxyl, amine and / or epoxy reactive functional groups.
  • aqueous composition is meant a composition which contains at least 20% by weight of water, preferably at most 70% and more preferably 40 to 60%.
  • part of the water may be substituted with an organic solvent, for example tetrahydrofuran (THF) or methyl tetrahydro rofuran. born .
  • THF tetrahydrofuran
  • methyl tetrahydro rofuran born .
  • the proportion of water replaced by the solvent is at most equal to 50% by weight, preferably at most 30% and advantageously at most 20%.
  • the polyol (A) according to the present invention comprises at least two hydroxyl functional groups capable of reacting with the carboxylic functions carried by the abovementioned unsaturated polycarboxylic acid or obtained by the hydrolysis of the unsaturated acid anhydride.
  • the polyol comprises at most 35 hydroxyl functions, and advantageously at most 15.
  • the polyol is a monomeric or oligomeric polyol, that is to say comprising at most 10 monomer residues polyols, preferably at most 4.
  • the polyol (A) is chosen from polyols originating from a renewable source, in particular obtained from plants, such as saccharides, or generated by fermentation of plant materials, such as 1,3-propanediol and 1,4-butanediol.
  • saccharides As an example of saccharides, mention may be made of monosaccharides, preferably containing 3 to 8 carbon atoms, in particular hexoses such as glucose, mannose, galactose, derivatives of these hexoses in the form of alcohols. alicyclics and derivatives of these alicyclic alcohols, such as isosorbide, and oligosaccharides such as maltose, cellobiose, lactose, sucrose, trehalose, raffinose, stachyose and dextrins.
  • the preferred saccharide is isosorbide.
  • the unsaturated polycarboxylic acid (B) comprises at least two carboxylic functions, preferably at most four, and advantageously at most three carboxylic functions, and at least one ethylenic unsaturation.
  • unsaturated polycarboxylic acid By way of examples of unsaturated polycarboxylic acid (B), mention may be made of linear or branched aliphatic acids, such as fumaric acid, itaconic acid, maleic acid, traumatic acid, and acid. metaconic acid, citraconic acid and aconitic acid, cyclic acids such as 2,5-furan dicarboxylic acid (dehydromucic acid) and aromatic acids such as phthalic acid, tetrahydrophthalic acid, isophthalic acid, terephthalic acid, trimesic acid or pyromellitic acid.
  • linear or branched aliphatic acids such as fumaric acid, itaconic acid, maleic acid, traumatic acid, and acid. metaconic acid, citraconic acid and aconitic acid, cyclic acids such as 2,5-furan dicarboxylic acid (dehydromucic acid) and aromatic acids such as phthalic acid, tetrahydrophthalic acid
  • the unsaturated polycarboxylic acid (B) can also be obtained from the corresponding unsaturated acid anhydride which, by hydrolysis, generates the carboxylic functions.
  • the unsaturated acid anhydride is, for example, maleic anhydride.
  • the unsaturated polycarboxylic acid (B) and the unsaturated acid anhydride are monomeric.
  • the polymer (C) is water-soluble and thus makes it possible to introduce hydrophilic segments in the co-polyester, which gives it a better solubility in polar solvents such as water.
  • the polymer (C) contains at least two hydroxyl, amine and / or epoxy functional groups.
  • the polymer (C) is chosen from the group consisting of poly (oxyalkylenes), for example polyethylene glycols and polyethylenepropylene glycols which may carry one or more additional amino functions, polyvinylpyrrolidones, polyethyleneimines and polyoxazolines.
  • the polymer (C) comprises at least 4 monomer units.
  • the polymer (C) is a polyol, it is necessarily different from the polyol (A).
  • the polyethylene glycol has a molar mass of less than or equal to 600 g / mol and advantageously greater than or equal to 200 g / mol.
  • the ratio of the number of hydroxyl, amine and epoxy functional equivalents to the number of carboxylic functional equivalents ranges from 1.01 / 1 to 2/1, preferably from 1.05 / 1 to 1.5 / 1 and better still 1, 10/1 to 1, 2/1.
  • the percentage of the number of monomer units of the polymer (C) to the total number of monomer units of the polyol (A) and the polymer (C) ranges from 70 to 95% and preferably 70 to 85%.
  • the co-polymerization reaction of the monomeric or oligomeric polyol (A), the unsaturated polycarboxylic acid or the unsaturated acid anhydride (B) and the water-soluble polymer (C) is preferably carried out in the presence of a catalyst.
  • a catalyst for example titanium n-butoxide (IV).
  • Said agent is generally added in an amount representing 0.005 to 4 mol% of the compound (B) and preferably 0.01 to 1%.
  • an antioxidant may be introduced into the polymerization medium, for example 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, an amount at most equal to 1% of the total weight of the unsaturated polycarboxylic acid and the unsaturated acid anhydride (B).
  • the co-polymerization is generally carried out at a temperature ranging from 140 to 230 ° C, preferably 150 to 220 ° C, and preferably 160 to 210 ° C.
  • the co-polymerization can be carried out in several steps, in particular according to the following thermal cycle: 160 ° C. for 1 to 15 hours, 210 ° C. for 2 to 10 hours at atmospheric pressure and 210 ° C. for 1 to 5 hours under a reduced pressure, of the order of 3 to 5 mbar.
  • the preferred heat cycle is 160 ° C for 1 to 10 hours, 210 ° C for 2 to 2 hours at atmospheric pressure and 210 ° C for 1 to 4 hours under reduced pressure.
  • the unsaturated co-polyester according to the invention is solid at ambient temperature (of the order of 20 ° C.) and can be easily solubilized or dispersed in water.
  • the co-polyester is also soluble in organic solvents, especially in chlororforme.
  • the preferred unsaturated co-polyester is a polymer obtained by co-polymerization of isosorbide, maleic anhydride and polyethylene glycol.
  • the adhesive composition according to the invention comprises at least one ethylenically unsaturated monomer used as crosslinking agent of the co-polyester.
  • the ethylenically unsaturated monomer used as the co-polyester crosslinking agent is generally selected from the group consisting of by (meth) acrylic acids and (meth) acrylates, in particular 2-hydroxyethyl methacrylate, methacrylamide, N-vinylpyrrolidone and unsaturated carboxylic acids, especially the unsaturated polycarboxylic acids mentioned above, in particular itaconic acid and citraconic acid, or their anhydrides, in particular maleic anhydride.
  • the ethylenically unsaturated monomer is preferably soluble in water.
  • the ethylenically unsaturated monomer is added to the aqueous adhesive composition in such proportions that the weight ratio of unsaturated monomer to co-polyester ranges from 1/10 to 1/1, preferably 1/3 to 1/1.
  • a free radical initiator may be introduced into the aqueous adhesive composition to initiate crosslinking.
  • peroxides especially 2-butanone peroxide, persulfates and azobisisobutyronitrile (AIBN).
  • AIBN azobisisobutyronitrile
  • the amount of said initiator generally represents 0.5 to 2% of the total weight of the unsaturated co-polyester and the ethylenically unsaturated monomer.
  • the crosslinking of the aqueous adhesive composition is carried out at a temperature ranging from 50 to 180 ° C, preferably 60 to 150 ° C, for a period which may vary from 5 minutes to 6 hours, preferably 15 minutes to 2 hours.
  • the crosslinked co-polyester is an amorphous polymer which, therefore, does not have a melting point.
  • the cross-linked co-polyester has sufficient thermal stability for the intended applications.
  • the aqueous adhesive composition according to the present invention can be used to bind any type of elements composed of natural or synthetic material, in particular mineral elements such as abrasive particles, glass or rock fibers and glass fibers, especially with a view to making sails and fabrics.
  • the aqueous adhesive composition according to the invention is particularly intended to be used for producing coated abrasive articles, in particular abrasives whose medium consists of paper or fabrics made from cotton, polyester or a blend of cotton and polyester. These abrasive articles constitute another object of the invention.
  • the molar mass (in g / mol) is determined by gel permeation chromatography using a modified silica column (PFG® marketed by PSS), 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as eluent and standards of polymethylmethacrylates of a given molar mass;
  • PFG® modified silica column
  • HFIP 1,1,1,3,3,3-hexafluoro-2-propanol
  • the polydispersity index is the ratio of the molar mass in mass (M m ) to the molar mass in number (M n );
  • the number of iodine (in gl 2/100 g of co-polyester) is measured by titration in N-methyl-pyrrolidone. It is representative of the level of unsaturation in the co-polyester;
  • the thermal stability of the crosslinked product is evaluated by measuring the temperature corresponding to a mass loss of 10%
  • Tg The glass transition temperature (Tg) is measured by DSC ("Differential Scanning Calorimetry) at a rate of 10 ° C / min under nitrogen.
  • the flask is heated to 160 ° C until a uniform reaction mixture is obtained. 3.3 mg of titanium n-butoxide (IV) are then added to 1.5 g of toluene.
  • the reaction mixture is placed under an argon atmosphere and heated at 210 ° C. for 3 hours. The reaction is continued for a further 3 hours at 210 ° C. under reduced pressure (3-5 mbar).
  • reaction mixture After cooling to room temperature, the reaction mixture is dissolved in chloroform and precipitated in methanol at about 10 ° C. The mixture is then filtered, washed several times and dried under vacuum at 85-90 ° C.
  • the co-polyester has a molar mass in number (Mn) equal to 4400 g / mol, a polydispersity index equal to 4.5, an iodine number equal to 50 g / 100 g and a glass transition temperature Tg equal to -17 ° C.
  • the weight ratio of the co-polyester to the ethylenically unsaturated monomer is 2/1.
  • the mixture is heated to 50 ° C and 0.2 g of 2-butanone peroxide is added. After complete homogenization of the mixture, the heating is stopped.
  • the mixture is deposited on a flat substrate (glass or aluminum) and crosslinked for 15 minutes at 85 ° C. and then 12 hours at 115 ° C.
  • the co-polyester obtained in step a) has a number-average molecular weight (Mn) equal to 3200 g / mole, a polydispersity index equal to 2.1, and an iodine number equal to 66 g / 100 g. and a glass transition Tg of -20 ° C.
  • Adhesive compositions 1-1-3 and 2.1 are used to make adhesive papers.
  • the adhesive compositions have a life of at least 24 hours (stable viscosity during this period).
  • a first layer of the adhesive composition (thickness: 150 ⁇ ) is applied and abrasive grains are then distributed homogeneously over said layer. The whole is heated at 85 ° C for 15 minutes. Good adhesion of the adhesive layer to the paper and good anchoring of the abrasive grains are observed (these do not come off when subjected to the test of passing the hand on the grain surface).
  • a second layer of the adhesive composition is applied to cover the abrasive grains and treated at 60 ° C for 50 minutes.
  • the abrasive paper obtained with each of the adhesive compositions tested is devoid of tackiness.
  • the abrasive paper obtained then undergoes an additional heat treatment (post-baking) at 120 ° C. for 2 hours.
  • the second layer of adhesive adheres well to the first layer, covers the abrasive grains satisfactorily and maintains them effectively.
  • the manual peel test of the abrasive paper shows a cohesive break in the paper with all the adhesive compositions tested, which indicates a very good adhesion of the adhesive composition to the support.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP11726913.4A 2010-05-28 2011-05-27 Haftzusammensetzung mit einem wasserlöslichen oder in wasser dispergierbaren ungesättigten polyester und einem ethylengesättigten monomer und verwendungen davon Withdrawn EP2576140A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1054156A FR2960546B1 (fr) 2010-05-28 2010-05-28 Composition adhesive renfermant un polyester insature hydrosoluble ou dispersable dans l'eau et un monomere ethyleniquement insature, et utilisations.
PCT/FR2011/051213 WO2011148111A1 (fr) 2010-05-28 2011-05-27 Composition adhesive renfermant un polyester insature hydrosoluble ou dispersable dans l'eau et un monomere ethyleniquement insature, et utilisations.

Publications (1)

Publication Number Publication Date
EP2576140A1 true EP2576140A1 (de) 2013-04-10

Family

ID=43414042

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11726913.4A Withdrawn EP2576140A1 (de) 2010-05-28 2011-05-27 Haftzusammensetzung mit einem wasserlöslichen oder in wasser dispergierbaren ungesättigten polyester und einem ethylengesättigten monomer und verwendungen davon

Country Status (3)

Country Link
EP (1) EP2576140A1 (de)
FR (1) FR2960546B1 (de)
WO (1) WO2011148111A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013036907A1 (en) 2011-09-09 2013-03-14 Nanobio Corporation Nanoemulsion respiratory syncytial virus (rsv) subunit vaccine
ES3026558T3 (en) 2021-03-17 2025-06-11 Akzo Nobel Coatings Int Bv Alkyd resin, coating composition, and substrate coated with such coating compositon

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5118977B1 (de) * 1971-01-28 1976-06-14
JPS5218956B2 (de) * 1973-02-20 1977-05-25
JPS52108488A (en) * 1976-03-08 1977-09-10 Kao Corp Preparation of liquid resin dispersions
CH641490A5 (de) * 1978-02-13 1984-02-29 Asahi Chemical Ind Heissschmelzklebstoff.
JPH0747267B2 (ja) * 1986-06-26 1995-05-24 東亜製砥工業株式会社 発泡研摩体の製造方法
FI990195L (fi) * 1998-09-29 2000-03-30 Neste Oyj Tyydyttymätön polyesterihartsi ja sen käyttö

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2011148111A1 *

Also Published As

Publication number Publication date
FR2960546B1 (fr) 2012-07-13
WO2011148111A1 (fr) 2011-12-01
FR2960546A1 (fr) 2011-12-02

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