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WO1991010698A1 - Resine d'amide-silane durcissable par humidite - Google Patents

Resine d'amide-silane durcissable par humidite Download PDF

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Publication number
WO1991010698A1
WO1991010698A1 PCT/US1991/000312 US9100312W WO9110698A1 WO 1991010698 A1 WO1991010698 A1 WO 1991010698A1 US 9100312 W US9100312 W US 9100312W WO 9110698 A1 WO9110698 A1 WO 9110698A1
Authority
WO
WIPO (PCT)
Prior art keywords
amide
silane resin
group
polycarboxylic acid
silane
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/US1991/000312
Other languages
English (en)
Inventor
Wen-Hsuan Chang
Edward Enns Mcentire
J. Alden Erikson
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.)
PPG Industries Inc
Original Assignee
PPG Industries Inc
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 PPG Industries Inc filed Critical PPG Industries Inc
Publication of WO1991010698A1 publication Critical patent/WO1991010698A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • 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
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/10—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

Definitions

  • the present invention relates to a moisture curable silane resin. More specifically, the present invention relates to a moisture curable silane resin containing an amide moiety.
  • a silane resin is generally advantaged by low viscosity and, consequently, low volatile organic content (VOC), durability and flexibility.
  • a polyamide resin is generally advantaged by good mechanical properties, such as hardness, toughness, pliability or elasticity; and chemical properties, such as solvent resistance.
  • the present invention encompasses a stable amide-silane resin which is prepared by reacting a polycarboxylic acid or a lower alkyl ester of a polycarboxylic acid and an aminoalkoxysilane.
  • the amide-silane resin of this invention is characterized as a high solids resin. It can be formulated into a stable coating composition of a low volatile organic content (VOC) which can cure (with or without a catalyst) at an ambient temperature, for example, by moisture curing to produce a film which is hard, flexible and durable and has good gloss.
  • VOC low volatile organic content
  • the curable composition and an article of matter prepared therewith are also encompassed by this invention.
  • an amide-silane resin of this invention can be prepared with a useful polycarboxylic acid or an aryl or a low alkyl ester of a polycarboxylic acid.
  • the low alkyl ester of the polycarboxylic acid contains in the alkyl group from about 1 to 3 carbon atoms.
  • the alkyl group is a methyl group.
  • the useful polycarboxylic acid or the ester thereof may contain a substituent or a moiety which can be a part of its polymer backbone linkage provided that the substituent or moiety does not adversely affect the preparation or use of the amide-silane resin.
  • the substituent can be in the form of an amide, ester, ether, urea, urethane, or a combination thereof.
  • the useful polyacid or the ester thereof can be of a number average molecular weight of about 90 to 10,000, preferably from about 90 to 4,500 and more preferably from about 90 to 2,500.
  • An illustrative but non-limiting example of the useful polycarboxylic acid or the ester thereof is preferably a dimer acid such as EMPOL 1010 (available from Emery Industries) or a carbomethoxy-terminated polyester such as the reaction product of trimethylolpropane and dimethyl cyclohexanedicarboxylate.
  • polycarboxylic acid or the ester thereof can be oxalic acid, adipic acid, sebacic acid, dimethyl adipate, dimethyl azelate, dimethyl dodecanedioic acid ester, dimethyl cyclohexanedicarboxylate; a lower alkyl ester of a polyamido polyacid such as the reaction product of dimethyl cyclohexanedicarboxylate and JEFFAMINE T-403 (a polyoxypropylene polyamine available from Texaco
  • trimer acid may be employed.
  • esters are preferred.
  • aminoalkoxysilane useful herein is of the formula: RNHR 1 Si(R 2 ) m (0R 3 ) n wherein R is hydrogen, a hydrocarbon radical group which can be substituted or unsubstituted, such as an alkyl group with no more than
  • R , R and R can broadly encompass other hydrocarbon or substituted hydrocarbon radicals provided that the nature thereof is not such as would adversely affect the preparation or use of the claimed invention.
  • An illustrative but non-limiting example of the aminoalkoxysilane can be aminoethyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, aminopropylmethyldiethoxysilane, aminoethyl-gamma-aminopropyl-trimethoxysilane, or iminobis(propyltrimethoxysilane).
  • the polycarboxylic acid or its lower alkyl ester is reacted with the aminoalkoxysilane under the following conditions.
  • the reactants can be mixed at room temperature in a properly equipped reaction vessel and heated over a range of temperature and period of time sufficient to effect reaction.
  • the temperature range is usually from about 100°C to 250°C over a period of about four hours and preferably from about 120°C to
  • a solvent and a catalyst may be used for ease of reaction.
  • the useful solvent can be xylene, n-butanol, and the like.
  • the useful catalyst can be an acid, a tin compound or the like.
  • the ratio of reactants can be from about 0.25 to 1.8:1-and preferably from about 0.33 to 1.2:1 based on the equivalent of acid or ester to the equivalent of aminosilane (based on the amine content).
  • the reaction product comprising the amide-silane is an ungelled liquid which is preferably clear in appearance. By the term “ungelled” used herein is meant that the reaction product would flow and dissolve in a solvent such as methanol.
  • the reaction product is of a high solids content of about 50 to 100 percent and 2 more preferably from about 60 to 80 percent by weight based on the total weight of the reaction product, measurable by ASTM Method No. 4 23690.
  • the viscosity of the reaction product can range from about 50 to 5000 and preferably from about 500 to 4000 centipoise ⁇ , measured at 6 25°C with a Brookfield viscometer.
  • the weight average molecular weight of the amide-silane resin can be from about 300 to 10,000 and 8 preferably from about 500 to 5000 based on polystyrene standard as measured by gel permeation chromatography.
  • the respective amide or 0 silane equivalent weight can be less than 1000 and preferably less than 500.
  • the reaction product is "stable" in that it is storage 2 stable for a period of at least one month at ambient temperatures in the absence of moisture.
  • a curable composition of the amide-silane resin can be prepared with the resin by itself or in combination with another resin and utilized with or without a catalyst.
  • the curable composition can be employed as a coating for various substrates such as metal, paper, wood, hardboard, plastics or the like.
  • the curable composition may be pigmented or unpigmented.
  • An additive such as a flow control agent, surfactant, leveling agent, anti-mar agent, fungicide, mildewcide, or a mixture thereof can be employed herein.
  • pigments include any of the generally known pigments including extender pigments used in the coatings and resins industry such as titanium dioxide,- magnesium carbonate, dolomite, talc, zinc oxide, magnesium oxide, iron oxides red and black, barium yellow, carbon black, strontium chromate, lead chromate, molybdate red, chromoxide green, cobalt blue, an organic pigment of the azo series, etc.
  • extender pigments used in the coatings and resins industry
  • extender pigments used in the coatings and resins industry such as titanium dioxide,- magnesium carbonate, dolomite, talc, zinc oxide, magnesium oxide, iron oxides red and black, barium yellow, carbon black, strontium chromate, lead chromate, molybdate red, chromoxide green, cobalt blue, an organic pigment of the azo series, etc.
  • extender pigments used in the coatings and resins industry
  • such as titanium dioxide,- magnesium carbonate, dolomite, talc zinc oxide, magnesium oxide
  • Coating compositions utilizing the amide-silane resins of the invention may be applied to substrates using any suitable technique such as brushing, spraying, roll coating, doctor blade coating, etc.
  • Coating compositions utilizing the reaction products may be cured at room temperature over a period of about 5 hours to 3 days or at elevated temperatures of about 80°F to 350°F and preferably about 120°F to 250°F over a period of about 5 to 60 minutes and preferably 10 to 30 minutes.
  • catalysts which may be utilized to promote curing of the compositions include tetraisopropyl titanate, triethylamine, gamma-aminopropyltriethoxsilane, trifluoromethanesulfonic acid, dibutyltin dilaurate, stannous octoate, aluminum tris( ⁇ ec-butoxide), and a mixture thereof.
  • the catalyst typically may be present in an amount ranging from about 0.1 to 5 percent by weight based on the weight of the reaction product of the invention.
  • the amide-silane resin of the invention also may be utilized as an additive to modify the property of a generally known coating composition.
  • the amide-silane resin may be incorporated in additive amounts to modify a property such as rheology, by way of viscosity, surface tension, flow, leveling, etc.
  • An "additive amount” is understood herein to mean an amount of up to about 50 percent by weight based on the weight of resin solids in the coating composition (i.e., excluding pigments and solid fillers).
  • the curable compositions of this invention are of a VOC of about 0.1 to 6 pounds per gallon and preferably about 0.2 to 4 pounds per gallon.
  • VOC is herein defined as weight per volume of organic compound that evaporates from the curable composition under the conditions of determining the non-volatile content of the curable composition. VOC can be determined by ASTM Method No. D3690.
  • Films of the cured composition can be hard and flexible.
  • hard or “hardness” is meant that films derived from a coating composition of the invention (at a solids content of 60 percent) would have a pencil hardness of B to 6H.
  • flexible used herein is meant that a dry film thickness of 1 mil obtained from a curable composition of the invention (at a solids content of about 60 percent) on a BONDERITE® 1000 pretreated steel substrate can withstand 20 inch-pound ball drop.
  • the amide-silane resin of the invention also may be utilized either as a major or minor ingredient of a sealant composition and an adhesive composition.
  • a sealant composition and an adhesive composition.
  • This example illustrates the amide-silane resin of this invention and a method of preparing the same.
  • This example illustrates the amide-silane resin of this 26 invention and a method of preparing the same.
  • Example 1 In a properly equipped reaction vessel as described in 28 Example 1 were charged 2600 g (4 moles) of TERETHANE 650 (a dihydroxy-functional polyether, available from DuPont Chemical Co.); 30 and 1600 (8 moles) of dimethyl cyclohexanedicarboxylate; dibutyltin oxide (8.4 g) and triphenyl phosphite (4.3 g). The charge was heated 32 to up to 210°C over 12 hours with the removal of 235 milliliters of methanol to yield a product having X- viscosity (Gardner-Holdt at 34 25°C).
  • the resultant product comprising the amide-silane resin was thinned 38 with 100 g methanol and 100 g of xylene.
  • Example 3 This example further illustrates the amide-silane resin of this invention and a method of preparing the same. To a properly equipped reaction vessel, as described in
  • Example 1 was charged 80.4 g of a polyester (made from 2 moles of Ester Diol 204 from Union Carbide Co. and 3 moles of dimethyl cyclohexanedicarboxylate (DMCD)) and 35.8 g of 3-aminopropyltrimethoxysilane and heated to 200°C over two hours. Five and one-half (5.5) grams of distillate was removed. An additional five grams of DMCD was added and the mixture was further heated from at 200°C for 20 minutes with 6.5 g of distillate removed. The resultant product was a liquid containing an amide-silane resin
  • This example also illustrates the amide-silane resin of the invention and a method of preparing the same.
  • Example 2 To a properly equipped reaction vessel, as described in Example 1, was charged 364 g of a polyester (derived from 1 mole of neopentyl glycol, 1 mole of hexahydrophthalic anhydride and 1 mole of hexanediol), trimethylolpropane (268 g, 2 moles) and dimethyl cyclohexanedicarboxylate (1600 g, 8 moles). The charge was heated over a period of 16 hours from about 178°C to 218°C, during which time there was added 4.5 g of dibutyltin dilaurate. Two hundred twenty (220) grams of methanol was removed as distillate. The product yield was 1994 g.
  • a polyester derived from 1 mole of neopentyl glycol, 1 mole of hexahydrophthalic anhydride and 1 mole of hexanediol
  • trimethylolpropane (268 g, 2 moles)
  • a draw down of the above product was made with a 0.003 Bird applicator and air cured for 22 hours.
  • the cured film had the following properties: Pencil hardness was B; mar resistance was excellent; appearance was excellent; gloss was excellent.
  • the coating was lint free after one hour of drying when touched with a cotton ball.
  • Example 5 This example also illustrates the amide-silane resin of the invention and a method of preparing the same.
  • a suitable reaction vessel as described in Example 1, was added 231 g (1.58 moles) of diethyl oxylate and then 446 g (1.58 equivalents) of VERSAMINE® 551 (available from Henkel Corp.) was added portionwise with stirring. An exothermic reaction occurred, and the temperature reached 80°C. After three hours of stirring, the amine content was 0.0186 milliequivalent per gram.
  • To 216 g of the above reaction mixture was added with stirring 90.2 g gamma-aminopropyltrimethoxysilane (1.58 moles). The resulting exothermic reaction reached 45°C. The mixture was heated to 80°C for two hours. After cooling, the amine content was 0.0165 milliequivalent per gram.
  • a film was drawn down with a 6 mil Bird applicator from a mixture of 38.2 g of the above product, 0.37 g of dimethyldodecylamine, and 0.37 g dibutyltin dilaurate. The film cured to a hard, clear coating with good distinctness of image.
  • This example also illustrates the amide-silane resin of the invention and a method of preparing the same.
  • Example 1 To a properly equipped reaction vessel as described, in Example 1 was charged dimethyl azelate (3.91 g, 1.8 mole), dimethyl sebacate (414 g, 1.8 moles), and isophoronediamine (306 g, 1.8 moles). The charge was heated to 200 C C over 3.2 hours while 104 g distillate was collected. The reaction mixture was cooled to 80°C. To the vessel was added 709 g of gamma-aminopropyltrimethoxy- 2 silane (A-1110) and heating was continued for 3.5 hours from 72°C to
  • the coating was clear and tack free within one 12 hour, and had excellent water spot resistance after one hour.
  • the forward impact resistance was 60 inch-pounds, and the pencil hardness 14 was H to HB.
  • This example also illustrates the amide-silane resin of the 18 invention and a method of preparing the same.
  • Triphenyl phosphite 14 24 (1) A polyoxypropylamine available from Texaco Co.
  • Example 2 A product similar to that of Example 1 was made, except that gamma-aminopropyltriethoxysilane was substituted for gamma-aminopropyltrimethoxysilane.
  • the reactor charge was as follows:
  • Pencil hardness was 3H. Direct impact passed at 40 inch-pounds.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyamides (AREA)

Abstract

On produit des résines à fonction alcoxysilane contenant de l'amide, durcissables par humidité, en faisant réagir un acide polycarboxylique ou un ester d'alkyle inférieur de l'acide polycarboxylique avec un aminoalcoxysilane.
PCT/US1991/000312 1990-01-18 1991-01-15 Resine d'amide-silane durcissable par humidite Ceased WO1991010698A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US46689190A 1990-01-18 1990-01-18
US466,891 1990-01-18

Publications (1)

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WO1991010698A1 true WO1991010698A1 (fr) 1991-07-25

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242978A (en) * 1990-10-27 1993-09-07 Bayer Aktiengesellschaft Alkoxysilylamines as curing agents for plastics precursors containing acetoacetate or acetoacetamide groups
EP0714953A3 (fr) * 1994-12-01 1996-12-27 Dow Corning Sa Compositions de polymères à groupes silyle durcissables en fonction de l'humidité
EP0714925A3 (fr) * 1994-12-01 1996-12-27 Dow Corning Sa Polyétheresters contenant des groupes silyle
CN118667146A (zh) * 2024-05-23 2024-09-20 浙江皇马科技股份有限公司 一种低粘无毒的硅烷封端聚醚树脂及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5135992A (en) * 1990-01-18 1992-08-04 Ppg Industries, Inc. Amide-amine silane resin

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4789710A (en) * 1986-12-22 1988-12-06 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for preparation of a room-temperature curable resin
US4810759A (en) * 1986-12-16 1989-03-07 E. I. Du Pont De Nemours And Company Polyester graft copolymers, flexible coating compositions comprising same and branched polyester macromers for preparing same II

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4810759A (en) * 1986-12-16 1989-03-07 E. I. Du Pont De Nemours And Company Polyester graft copolymers, flexible coating compositions comprising same and branched polyester macromers for preparing same II
US4789710A (en) * 1986-12-22 1988-12-06 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for preparation of a room-temperature curable resin

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242978A (en) * 1990-10-27 1993-09-07 Bayer Aktiengesellschaft Alkoxysilylamines as curing agents for plastics precursors containing acetoacetate or acetoacetamide groups
EP0714953A3 (fr) * 1994-12-01 1996-12-27 Dow Corning Sa Compositions de polymères à groupes silyle durcissables en fonction de l'humidité
EP0714925A3 (fr) * 1994-12-01 1996-12-27 Dow Corning Sa Polyétheresters contenant des groupes silyle
CN118667146A (zh) * 2024-05-23 2024-09-20 浙江皇马科技股份有限公司 一种低粘无毒的硅烷封端聚醚树脂及其制备方法

Also Published As

Publication number Publication date
AU7254991A (en) 1991-08-05

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