EP0006973B1 - Composition de liant à base de résine avec organo amino silanes substitués par des alcoyles comme adjuvant d'adhésion durable - Google Patents

Composition de liant à base de résine avec organo amino silanes substitués par des alcoyles comme adjuvant d'adhésion durable Download PDF

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Publication number
EP0006973B1
EP0006973B1 EP79101054A EP79101054A EP0006973B1 EP 0006973 B1 EP0006973 B1 EP 0006973B1 EP 79101054 A EP79101054 A EP 79101054A EP 79101054 A EP79101054 A EP 79101054A EP 0006973 B1 EP0006973 B1 EP 0006973B1
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EP
European Patent Office
Prior art keywords
resin
aminosilanes
resins
mixed
silanes
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.)
Expired
Application number
EP79101054A
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German (de)
English (en)
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EP0006973A1 (fr
Inventor
Hans Dr. Jünger
Claus-Dietrich Dr. Seiler
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.)
Huels Troisdorf AG
Dynamit Nobel AG
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Huels Troisdorf AG
Dynamit Nobel AG
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Application filed by Huels Troisdorf AG, Dynamit Nobel AG filed Critical Huels Troisdorf AG
Publication of EP0006973A1 publication Critical patent/EP0006973A1/fr
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Expired legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/205—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of organic silicon or metal compounds, other organometallic compounds

Definitions

  • the present invention relates to synthetic resin-silane mixtures with particularly good storage stability for the production of moldings, in particular foundry molds. They consist of thermosetting resins, in particular phenolic resins, to which aminoalkylsilanes are mixed in to improve the adhesion to inorganic oxide material.
  • aminoalkyl trialkoxysilanes e.g. y-Aminopropyl-trimethoxysilane
  • adhesion of thermosetting resins to inorganic oxide material is improved.
  • these aminosilanes can be mixed with cold-curable and thermosetting phenolic resins, in order to then mix these resins directly with sands or other inorganic oxidic material and then to bond them firmly under shaping (cf. DE-AS 1 252 853 and DE -PS 1494381).
  • N- (aminoalkyl) -aminoalkylsilanes as an adhesion improver between thermosetting resins and inorganic oxidic material is also known. These compounds are used in the same way as those of the aminosilanes which are unsubstituted on the nitrogen atom (cf. US Pat. No. 3,234,159).
  • aminosilanes all of the substituted aminoalkylsilanes mentioned in these property rights, which are referred to below as aminosilanes, improve the adhesion of cold-curable and thermosetting phenolic resins to inorganic oxide substances to a practically equal extent when they are mixed in with the resins.
  • this improvement in adhesion diminishes over time if these aminosilane-containing resins are stored for a long time at room temperature.
  • the adhesion-improving effect of aminosilanes has decreased by about 40% and after a month the effect of y-aminopropyltriethoxysilane in phenolic resin has dropped to half of the original value.
  • thermosetting resins the hardening capacity of which is improved by aminosilanes, has now been found, which is characterized in that it contains those aminosilanes mixed in which contain the nitrogen and / or silicon atom additionally contain an unsubstituted alkyl group.
  • thermosetting resins e.g. B. phenol formaldehyde resins containing the claimed substituted aminosilanes mixed, little or no decrease in their adhesiveness to inorganic oxide materials, the absolute adhesiveness of these binders being equal or even greater than that of unsubstituted aminosilanes.
  • thermosets The stability of aminosilanes in thermosets is already greatly improved if only one hydrogen atom of the amino or imino group of the aminosilanes is replaced by an alkyl group. It is also sufficient if there is only one additional alkyl group on the Si atom.
  • the stability is further increased if one of the hydrogen atoms in the amino group is substituted by an alkyl group and another alkyl group is located either on the Si atom or on the second nitrogen atom.
  • aminosilanes that can be used are therefore: N-methyl-y-aminopropyltriethoxysilane, N-ethyl-y-aminopropyltrimethoxysilane, N-methyl-ß-aminoethyltrimethoxysilane, y-aminopropyl-methyldimethoxysilane, N-methyl-y-aminopropylmethyldim ß-N-methylamino-ethyl) -y-aminopropyltriethoxysilane, N- (y-aminopropyl) -y-aminopropylmethyldimethoxysilane, N- (y -aminopropyl) -N-methyl-y-aminopropylmethyldimethoxysilane and y-aminopropylethyldiethoxysilane.
  • silanes to be used are known compounds. Their production can be done in several ways known per se, such as, for. B. in German patents 1023462, 1 138 773 or DE-AS 1 152 695 are described.
  • thermosetting resins whose adhesion to inorganic oxidic materials are improved by the substituted aminosilanes, are also known compounds.
  • the term “thermosetting resins” is to be understood primarily to mean phenol-formaldehyde resins and resins based on fur uranium alcohol and mixtures of furfury alcohol with urea / formaldehyde precondensates, which are also referred to as furan resins.
  • the phenol-formaldehyde resins are generally obtained by alkaline condensation of phenols and formaldehyde in a ratio of 1:> __ 1 and then distilling off the water contained in the condensation mixture to the desired solid resin content. They can also be modified with urea and / or furfury alcohol.
  • the pH of the resins is generally above 7. They are generally in liquid form, but can also be used as solutions in suitable solvents.
  • the silanes are also mixed into the resin in a manner known per se.
  • the amount of silanes contained in the resin is of the same order of magnitude as that of the previously known phenolic resin-based binders which contain aminosilanes mixed in. Amounts of 0.1% by weight, based on the weight of the resin, are sufficient to obtain a clear effect.
  • the resin generally contains between 0.2 and 2% by weight of the silanes; however, it is also possible to mix in up to 5% of silanes based on the weight of the resin.
  • the storage stability is obtained with both cold and thermosetting phenolic resins if they contain the alkyl-substituted aminosilanes mixed in.
  • the improving effect is particularly evident in the case of cold-curing phenolic resins.
  • the new binders are mainly suitable for the production of composite bodies with sand as an inorganic oxidic filler.
  • Such composite bodies are, for. B. used in the foundry industry.
  • the best way to test the adhesion-promoting effect and the shelf life of the new binder is to measure the flexural strength of test specimens made of sand, which has been consolidated with the aid of the new binder. After the sand has been mixed with the binding agent and hardener, the test specimens are allowed to harden and the bending strength is tested after various hardening times using the + GF + bending tester. Since the curing or the strengths depend on many factors, the flexural strength of three samples was always determined after 1-, 2-, 4-, 6-, or 24-hour curing in all the following examples; the mean values of the individual determinations were again averaged with the results of the measurements after the other curing times. With the mean values obtained in this way, the influence of the external conditions on the curing is largely compensated for; they can be compared well with the correspondingly determined average values from test specimens which were obtained with the same binder after a shorter or longer storage time.
  • the silanes listed in Table 1 below were mixed into the resin in amounts of 0.2% by weight, based on the total resin. The mixture was stored in the laboratory at temperatures between 20 and 26 ° C.
  • test specimens were produced as follows from each mixture: 100 parts by weight of Halterner Sand H 32 were mixed with 0.48 parts by volume, based on resin, of a 65% strength aqueous p-toluenesulfonic acid solution. After the sand had been moistened uniformly, 1.2 parts by weight, based on sand, of the resin were mixed in.
  • the earth-moist, free-flowing mixture obtained was placed in a + GF + test rod shape and compacted by ramming three times with a + GF + piling device.
  • the test specimens were then removed from the mold on a glass plate. They then hardened there.
  • test specimens were produced from the resin / silane mixtures after a storage period of 14 or 30 days in the same way as after the storage period of one day, and their flexural strength was determined after curing.
  • the mean values obtained are entered in the table as M A14 and M A30 .
  • a measure of the shelf life is the decrease in strength (in%) of the test specimens, based on the storage time of the binder.
  • Another measure of the shelf life is the increase in strength in%, which is obtained compared to a resin that does not contain silane, only a comparison of the values after a storage time of 30 days is of interest here.
  • the mixtures were stored at temperatures between 20 and 26 ° C.
  • Examples 7 and 8 are comparative examples.
  • Halterner Sand H 32 100 parts by weight of Halterner Sand H 32 were placed in a mixer and 16 parts by volume, based on resin, of a commercially available aqueous hardener solution based on NH 4 NO 3 / urea / sulfite waste liquor were added. After the hardener solution had been mixed in, 1.2 parts by weight, based on sand, of the above-mentioned resin were mixed into the sand. After a mixing time of about 4 minutes, the mixture was homogeneous. This resin / sand mixture was shot on a core shooter at a temperature of 220 ° C and a pressure of 7 bar to test bars.
  • test specimens obtained were removed from the mold and their bending strength (hot) was measured directly (heat bending strength).
  • test bars of the various curing times were stored for 3 hours without draft and their bending strength (cold) was then measured.
  • Example A The values after the different curing times were again averaged and are given in Table 4 (sample A).
  • thermosetting resins alkyl-substituted aminosilanes have a better shelf life than unsubstituted aminosilanes.
  • the improvement can be seen in the fact that, after a storage time of about 6 weeks, composite bodies can be produced with the resins according to the invention, the flexural strength of which is about 15% better than that of composite bodies which were obtained with a known resin after its storage for 6 weeks.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Mold Materials And Core Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Silicon Polymers (AREA)

Claims (3)

1. Agents liants pour matériaux minéraux oxydés, à base de résines phénoliques ou furanni- ques et d'aminosilanes comme promoteurs d'adhérence, caractérisés en ce qu'ils contiennent des aminosilanes qui contiennent supplémentairement sur l'atome d'azote et/ou de silicium un groupe alcoyle non substitué.
2. Agents liants selon la revendication 1, caractérisés en ce qu'ils contiennent comme aminosilanes ceux de formule
Figure imgb0009
dans laquelle n = 2 ou 3, q = 0 ou 1, R et R' représentent le radical méthyle ou éthyle et R' peut aussi représenter H lorsque q = 1.
3. Agents liants selon la revendication 1, caractérisés en ce qu'ils contiennent comme aminosilanes ceux de formule
Figure imgb0010
où m = 2 ou 3, o = 1 à 3, q et R ont la signification indiquée plus haut et R" représente H ou le radical méthyle.
EP79101054A 1978-07-06 1979-04-06 Composition de liant à base de résine avec organo amino silanes substitués par des alcoyles comme adjuvant d'adhésion durable Expired EP0006973B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2829669A DE2829669C3 (de) 1978-07-06 1978-07-06 Harzbindemittel mit lagerstabilen Haftvermittlern
DE2829669 1978-07-06

Publications (2)

Publication Number Publication Date
EP0006973A1 EP0006973A1 (fr) 1980-01-23
EP0006973B1 true EP0006973B1 (fr) 1984-08-01

Family

ID=6043676

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79101054A Expired EP0006973B1 (fr) 1978-07-06 1979-04-06 Composition de liant à base de résine avec organo amino silanes substitués par des alcoyles comme adjuvant d'adhésion durable

Country Status (7)

Country Link
US (1) US4256623A (fr)
EP (1) EP0006973B1 (fr)
JP (1) JPS5512190A (fr)
CA (1) CA1157184A (fr)
DE (2) DE2829669C3 (fr)
DK (1) DK160262C (fr)
NO (1) NO151709C (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4626560A (en) * 1981-10-08 1986-12-02 Union Carbide Corporation Novel binding agent compositions, foundry sand compositions and ureido functional organosilicon compounds
US4374237A (en) * 1981-12-21 1983-02-15 Union Carbide Corporation Silane-containing isocyanate-terminated polyurethane polymers
USRE32812E (en) * 1982-01-21 1988-12-27 Borden (Uk) Limited Foundry moulds and cores
US4474904A (en) * 1982-01-21 1984-10-02 Lemon Peter H R B Foundry moulds and cores
US4782102A (en) * 1982-12-27 1988-11-01 Union Carbide Corporation Novel organofunctional silanes containing hindered group
GB8609909D0 (en) * 1986-04-23 1986-05-29 Borden Uk Ltd Manufacture of frictional elements
US5190993A (en) * 1988-04-08 1993-03-02 Borden, Inc. Process to enhance the tensile strength of reclaimed sand bonded with ester cured alkaline phenolic resin using an aminosilane solution
US5234973A (en) * 1988-04-08 1993-08-10 Acme Resin Corporation Compositions for foundry molding processes utilizing reclaimed sand
BR8806482A (pt) * 1988-04-08 1990-07-31 Acme Resin Corp Processo para producao de artigo modelado com areia aglutinada com resina; processo para producao de agregados de areia; solucao aglutinante; e composicao de mistura mestra
US5238976A (en) * 1990-06-15 1993-08-24 Borden, Inc. Process to enhance the tensile strength of reclaimed sand bonded with ester cured alkaline phenolic resin
DE4324384A1 (de) * 1993-07-21 1995-01-26 Huels Chemische Werke Ag Haftvermittler für Ester-härtende Harzbindemittel für die Gießereiindustrie
US20070039703A1 (en) * 2005-08-19 2007-02-22 Lee Jerry H Wet formed mat having improved hot wet tensile strengths
DE102005056792B4 (de) * 2005-11-28 2008-06-19 Saint-Gobain Isover G+H Ag Zusammensetzung für formaldehydfreies Phenolharzbindemittel und deren Verwendung
CN104690214A (zh) * 2015-02-04 2015-06-10 繁昌县金科机电科技有限公司 一种添加多种树脂的热法用覆膜砂及其制备方法
CN104690215A (zh) * 2015-02-04 2015-06-10 繁昌县金科机电科技有限公司 一种添加增效剂的铸造用覆膜砂及其制备方法
US11160733B2 (en) 2017-05-15 2021-11-02 3M Innovative Properties Company Dental adhesive composition, preparation and use thereof

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2832754A (en) * 1955-01-21 1958-04-29 Union Carbide Corp Alkoxysilylpropylamines
GB1008462A (en) 1960-08-18 1965-10-27 Union Carbide Corp Improvements in and relating to organosilicon compounds
US3234159A (en) * 1961-05-15 1966-02-08 Dow Chemical Co Phenolic resins containing amino-functional silanes for use in cements and binder compositions
US3259518A (en) * 1962-03-15 1966-07-05 Union Carbide Corp Inorganic oxide materials coated with monoepoxide-aminoalkylsilicon compound adducts
DE1252853B (de) * 1965-06-26 1967-10-26 Dr Arno Mueller Bindemittel fuer Giessereisande
US3403721A (en) * 1966-06-13 1968-10-01 Ashland Oil Inc Tensile strengths of certain sand cores
US3847860A (en) * 1969-10-29 1974-11-12 Dynamit Nobel Ag Adhesive agents comprising phenolic resins and a mixture of silanes
US3646999A (en) * 1970-05-20 1972-03-07 Shell Oil Co Epoxy resin sand consolidation rejuvenation
US3734936A (en) * 1971-02-03 1973-05-22 Quaker Oats Co Process of producing a foundry core composition
US3745139A (en) * 1971-05-03 1973-07-10 Ashland Oil Inc Foundry processes and products
US4111253A (en) * 1972-08-21 1978-09-05 The White Sea & Baltic Company Limited Foundry processes and compositions
DE2254117C2 (de) * 1972-11-04 1984-08-02 Dynamit Nobel Ag, 5210 Troisdorf N-substituierte β-Aminoethylsilane und deren Verwendung
GB1462366A (en) * 1973-06-28 1977-01-26 Dow Corning Ltd Process for manufacture of moulds and cores
US4083817A (en) * 1977-06-15 1978-04-11 The Quaker Oats Company Blends of furan-aldehyde resins with phenolic resins and molded articles produced therefrom

Also Published As

Publication number Publication date
DE2829669C3 (de) 1981-04-16
US4256623A (en) 1981-03-17
DE2829669A1 (de) 1980-01-17
JPS6315312B2 (fr) 1988-04-04
CA1157184A (fr) 1983-11-15
JPS5512190A (en) 1980-01-28
EP0006973A1 (fr) 1980-01-23
DE2829669B2 (de) 1980-08-21
DK284479A (da) 1980-01-07
DE2967148D1 (en) 1984-09-06
NO792245L (no) 1980-01-08
NO151709B (no) 1985-02-11
NO151709C (no) 1985-05-22
DK160262C (da) 1991-07-22
DK160262B (da) 1991-02-18

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