WO1988008868A1 - Colle a fusion ulterieurement reticulable par oxydation - Google Patents

Colle a fusion ulterieurement reticulable par oxydation Download PDF

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Publication number
WO1988008868A1
WO1988008868A1 PCT/EP1988/000357 EP8800357W WO8808868A1 WO 1988008868 A1 WO1988008868 A1 WO 1988008868A1 EP 8800357 W EP8800357 W EP 8800357W WO 8808868 A1 WO8808868 A1 WO 8808868A1
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WO
WIPO (PCT)
Prior art keywords
acid
copolymers
weight
parts
hot melt
Prior art date
Application number
PCT/EP1988/000357
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German (de)
English (en)
Inventor
Heinz-Günther SCHULTE
Herbert Fischer
Klaus Marten
Onusseit Hermann
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1988008868A1 publication Critical patent/WO1988008868A1/fr

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    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/025—Copolymer of an unspecified olefine with a monomer other than an olefine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification

Definitions

  • the invention relates to oxidatively postcrosslinking hot melt adhesives containing
  • Post - crosslinking hot melt adhesives which crosslink or, after application, via terminal isocyanate groups due to moisture. harden, are already known (cf. DE-PS 24 01 320 and DE-AS 32 36 313).
  • Another possibility as a hot melt adhesive to give suitable systems the ability to obtain moisture-curing properties are conceivable by incorporating alkoxysilane functions and have already been described in the literature (cf. DE-OS 35 1 8 357).
  • a certain insensitivity to incorrect operation is required.
  • Polyurethane systems with free NCO groups in particular are very sensitive to temperature and crosslink quickly to insoluble and infusible polymers when the permissible temperature is exceeded.
  • the invention is directed to oxidatively postcrosslinking hotmelt adhesives of the type mentioned at the outset, whose heat resistance after crosslinking exceeds 200.degree.
  • R 2 is hydrogen, methyl or ethyl and R 3 is hydrogen and C 1 -C 4 alkyl, and optionally formed in the ⁇ -position alkyl-substituted maleic anhydride, and
  • the acid or ester functions of the copolymers are at least partially esterified or transesterified with unsaturated fatty alcohols having an average of 12 to 20 carbon atoms and iodine numbers of an average of 50 to 200 and / or tricyclodecenols,
  • the copolymers have melt indices of 500 g / 10 min at 150 ° C. to 10 g / 10 min at 190 ° C. (according to DIN 53 735) before the esterification or transesterification.
  • the proportion of the compounds of the formula (II) or of the maleic anhydride which is optionally substituted in the ⁇ -position and the terpolymer component is preferably such that the copolymers have a total of 15 to 350 acid and saponification numbers before the esterification or transesterification , in particular 30 to 350, have.
  • olefins of the general formula (I) for example ethylene and ⁇ -olefins having up to 20 carbon atoms, such as propylene, isobutylene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-octadecene starts and these with carboxyl group-containing olefins of the general formula (II) such as acrylic acid, methacrylic acid and ethacrylic acid and esters thereof with C 1 -C 4 -alkanols, in particular the methyl esters, or maleic anhydride, which may be in the ⁇ -position is alkyl-substituted.
  • carboxyl group-containing olefins of the general formula (II) such as acrylic acid, methacrylic acid and ethacrylic acid and esters thereof with C 1 -C 4 -alkanols, in particular the methyl esters, or maleic anhydride
  • Maleic anhydride optionally substituted in the ⁇ -position can also be present as a terpolymer component if it has not already been used as a copolymer component.
  • Maleic anhydride as such is preferred in both cases; however, it is also possible to use derivatives of maleic anhydride substituted with C 1 -C 20 -alkyl or polyalkenyl radicals in the ⁇ -position.
  • copolymers containing acid or ester groups are copolymers of ethylene with vinyl acetate and terpolymer components which have acid or ester functions, and of ethylene with acrylic, methacrylic or ethacrylic acids or esters thereof with C 1 -C 4 -alkanols, the optionally with maleic anhydride as
  • Terpolymer component are modified; further copolymers of C 2 -C 20 - ⁇ -olefins with maleic anhydride.
  • copolymers containing acid or ester groups are those of olefins of the formula (I), in particular ethylene with 10 to 50 mol% of compounds formed from that of acrylic acid, methacrylic acid and ethacrylic acid and esters thereof with alkanols having 1 to 4 carbon atoms group.
  • copolymers containing acid or ester groups are not used as such in the hotmelt adhesives of the invention, but only after esterification or transesterification of at least some of their free acid or ester functions with unsaturated fatty alcohols with an average of 12 to 20 carbon atoms and iodine numbers of 50 to 200 and / or tricyclodecenols used on average.
  • the unsaturated fatty alcohols used are e.g. obtained in the industrially customary hydrogenation of unsaturated fatty acid esters or mixtures of unsaturated fatty acid esters obtained from natural fats and oils of animal, marine or vegetable origin. Unsaturated fatty alcohols with an average of 16 to 18 carbon atoms and iodine numbers between 80 and 170 are preferred.
  • the esterification or transesterification is preferably carried out in such a way that 40 to 90 mol% of the carboxylic acid or ester functions of the copolymers are esterified with the fatty alcohols or are transesterified.
  • tricyclodecenols can be used, which are obtainable industrially by dimerization of cyclopentadiene and subsequent hydration of a double bond.
  • transesterification or esterification takes place in the presence of customary acidic catalysts, such as those e.g. in Ulimann, Encyclopedia of Industrial Chemistry, 4th Edition, Volume 11, page 89 (1976), the disclosure of which is incorporated herein by reference.
  • a typical catalyst is e.g. the one commercially available under the name Swedcat 5.
  • the hot melt adhesives of the invention may further be 0 to 60 Parts by weight of natural or synthetic resins contain, for example, rosin and terpene resins, aliphatic hydrocarbon resins, alkylaromatic hydrocarbon resins and hydrogenated or non-hydrogenated dicyclopentadiene resins, phenolic resins and terpene-phenolic resins.
  • natural or synthetic resins contain, for example, rosin and terpene resins, aliphatic hydrocarbon resins, alkylaromatic hydrocarbon resins and hydrogenated or non-hydrogenated dicyclopentadiene resins, phenolic resins and terpene-phenolic resins.
  • the use of these resins is common in the adhesive industry, cf.
  • the total iodine number of the esterified or transesterified copolymers, even after the optional mixing with resins and / or waxes, is preferably not less than 10.
  • the hot melt adhesives of the invention may contain natural and / or synthetic waxes, e.g. Paraffin waxes (melting range 32 to 72 ° C), microcrystalline waxes (melting range 60 to 96 ° C), Fischer-Tropschwachs.se (melting range 100 to 115 ° C) and polyethylene waxes (melting range 86 to 140 ° C).
  • natural and / or synthetic waxes e.g. Paraffin waxes (melting range 32 to 72 ° C), microcrystalline waxes (melting range 60 to 96 ° C), Fischer-Tropschwachs.se (melting range 100 to 115 ° C) and polyethylene waxes (melting range 86 to 140 ° C).
  • Siccatives are also added to the hotmelt adhesives of the invention, for example heavy metal salts of carboxylic acids such as cobalt octoate or lead naphthenate, and furthermore manganese salts such as manganese linoleate or calcium, cerium, zinc and zirconium salts.
  • heavy metal salts of carboxylic acids such as cobalt octoate or lead naphthenate
  • manganese salts such as manganese linoleate or calcium, cerium, zinc and zirconium salts.
  • the use of these heavy metal salts is known from alkyd resin technology, cf. also Ullmann, Encyclopedia of Technical Chemistry, 4th edition, volume 23, page 428, the disclosure of which is referred to here.
  • the invention is explained in more detail below on the basis of preferred exemplary embodiments.
  • the stated viscosity data were determined according to ASTM D 3236-72 at 200 ° C.
  • Example 2 Under the conditions of Example 1, 327 parts by weight of the copolymer used there and 0.4 part by weight of the catalyst were reacted with 47 parts by weight of a C 16 -C 18 fatty alcohol with an iodine number of 80 to 85.
  • the viscosity of the end product was 22000 mPa.s.
  • Example 2 Under the conditions of Example 1, 327 parts by weight of the copolymer used there and 0.4 part by weight of the catalyst were mixed with 26 parts by weight of tricyclodecenol (iodine number: 169) set. The viscosity of the end product was 100,000 mPa.s.
  • Example 2 Under the conditions of Example 1, 40 parts by weight of an ethylene-acrylic acid copolymer with an acrylic acid content of 17.8 mol%, an acid number of 140 and. a melt index of 325 g / 10 min / 160 ° C (DIN 53 735), 0.5 part by weight of the commercial esterification catalyst mentioned and 13.4 parts by weight of an unsaturated C 16 -C 18 fatty alcohol with an iodine number implemented by 85.
  • the product obtained had a Brookfield viscosity of 21,000 mPa.s at 25 ° C.
  • Example 2 Under the conditions of Example 1, 251 parts by weight of a maleic anhydride-octadecene-1 copolymer with a maleic anhydride content of 50 mol%, a molecular weight of 50,000, a melt index were in a heated stirred reactor 500 g / 10 min at 150 ° C (DIN 53 735) and an acid number of 270 to 310 and 0.4 part by weight of the catalyst with 95 parts by weight of an unsaturated C 16 -C 18 fatty alcohol mixed with an iodine number of 80 to 85 and heated under protective gas at 140 ° C for 2 hours.
  • the end product had a viscosity of 5000 mPa.s (200 ° C).
  • the esterified or transesterified copolymers obtained according to Examples 1 to 6 above were each mixed with 0.1% by weight of a commercially available siccative mixture (containing Co and Zr) and tested for their heat resistance and adhesive performance on wood after 24 hours.
  • the results obtained are summarized in the table below;
  • the corresponding values for the copolymers containing carboxyl groups were also included in the table without addition of desiccant before they were esterified or transesterified with the unsaturated fatty alcohols.
  • the copolymers esterified or transesterified with unsaturated fatty alcohols show improved tensile shear strengths with a significantly increased heat resistance compared to the starting copolymers.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Des colles à fusion ultérieurement réticulables par oxydation contiennent entre 30 et 100 parties en poids de polymères ayant des liaisons doubles oléfiniques réticulables, entre 0 et 60 parties en poids de résines naturelles et/ou synthétiques, entre 0 et 40 parties en poids de cires naturelles et/ou synthétiques, entre 0,01 et 1,0 partie en poids de siccatifs et éventuellement des agents protecteurs usuels contre la lumière et le vieillissement, des charges et des pigments. Ces colles présentent une adhérence et une résistance à la chaleur améliorées si elles contiennent comme polymères des copolymères renfermant des groupes acide ou ester formés d'une part d'alpha-olefines et d'autre part d'oléfines contenant des groupes carboxyle, dont les fonctions acide ou ester sont estérifiées ou transestérifiées au moins en partie avec des alcools gras insaturés ayant en moyenne, entre 12 et 20 atomes de carbone et, en moyenne des indices d'iode compris entre 50 et 200, et/ou avec des tricyclodécénols.
PCT/EP1988/000357 1987-05-06 1988-04-28 Colle a fusion ulterieurement reticulable par oxydation WO1988008868A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873715027 DE3715027A1 (de) 1987-05-06 1987-05-06 Oxidativ nachvernetzende schmelzkleber
DEP3715027.8 1987-05-06

Publications (1)

Publication Number Publication Date
WO1988008868A1 true WO1988008868A1 (fr) 1988-11-17

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Family Applications (1)

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PCT/EP1988/000357 WO1988008868A1 (fr) 1987-05-06 1988-04-28 Colle a fusion ulterieurement reticulable par oxydation

Country Status (4)

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EP (1) EP0314772A1 (fr)
JP (1) JPH01503547A (fr)
DE (1) DE3715027A1 (fr)
WO (1) WO1988008868A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996023036A1 (fr) * 1995-01-24 1996-08-01 Henkel Kommanditgesellschaft Auf Aktien Adhesif a durcissement aerobie
GB2334258B (en) * 1996-11-14 2001-05-16 Bp Exploration Operating Inhibitors and their uses in oils

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5656692A (en) * 1995-10-16 1997-08-12 E. I. Du Pont De Nemours And Company Process for transesterification of olefin/acrylic-ester copolymers
US6803424B2 (en) 2000-03-30 2004-10-12 E. I. Du Pont De Nemours And Company Process for crosslinking of ethylene/acrylic ester copolymers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2182213A1 (fr) * 1972-04-28 1973-12-07 Sumitomo Chemical Co
FR2213974A1 (fr) * 1973-01-11 1974-08-09 Mitsubishi Petrochemical Co
EP0064893A1 (fr) * 1981-04-30 1982-11-17 Société Chimique des Charbonnages Compositions applicables à la fabrication de colles thermofusibles et leur procédé de préparation
EP0195218A2 (fr) * 1985-02-13 1986-09-24 Henkel Kommanditgesellschaft auf Aktien Adhésif applicable à chaud

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2182213A1 (fr) * 1972-04-28 1973-12-07 Sumitomo Chemical Co
FR2213974A1 (fr) * 1973-01-11 1974-08-09 Mitsubishi Petrochemical Co
EP0064893A1 (fr) * 1981-04-30 1982-11-17 Société Chimique des Charbonnages Compositions applicables à la fabrication de colles thermofusibles et leur procédé de préparation
EP0195218A2 (fr) * 1985-02-13 1986-09-24 Henkel Kommanditgesellschaft auf Aktien Adhésif applicable à chaud

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996023036A1 (fr) * 1995-01-24 1996-08-01 Henkel Kommanditgesellschaft Auf Aktien Adhesif a durcissement aerobie
US6096842A (en) * 1995-01-24 2000-08-01 Henkel Kommanditgesellschaft Auf Aktien Aerobically curable adhesive
GB2334258B (en) * 1996-11-14 2001-05-16 Bp Exploration Operating Inhibitors and their uses in oils

Also Published As

Publication number Publication date
EP0314772A1 (fr) 1989-05-10
JPH01503547A (ja) 1989-11-30
DE3715027A1 (de) 1988-11-17

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