DE1595649A1 - Aminoaryl phosphites as hardeners for polyepoxide compounds - Google Patents

Description

159S549 FARBENFABRIKEN BAYER AG

LEVERKUS1N-B «yeiwetk June 23, 1966 Pitcnt Abbey

Aminoaryl phosphites as hardeners for polyepoxy compounds

The invention relates to a method for curing polyepoxide compounds with the help of aminoaryl phosphites.

It is known to use polyepoxide compounds, i. H. links with more than one epoxy group per molecule with aliphatic To convert polyamines into the crosslinked state at room temperature.

It is also known to use aromatic polyamines, for example phenylenediamines, 4,4 ^I- diaminodiphenylmethane. or aniline-formaldehyde resins at room temperature with polyepoxide compounds by using an acidic accelerator, for example organic acids such as acetic acid, acrylic acid, β-chloropropionic acid, oxalic acid, maleic acid, phthalic acid and their half-esters. A solvent is also required to dissolve the amine, which at the same time reduces the viscosity of the batches and ensures greater reactivity due to the better distribution of the individual components.

Known solvents are, for example, dimethyl sulfoxide,

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• 'Formamide, dimethylformamide, N-methylpyrrolidone, lactones from Type of iT-butyrolactone, ester, such as ethyl acetate, Methyl glycol acetate and ethyl glycol acetate. However, such systems have several disadvantages. The amines are solid and tend easy to crystallize even in solution, especially when stored in a cool place. In addition, these amines are physiological Relationship, especially with regard to their carcinogenic effectiveness, not harmless.

It is also known that polyepoxide compounds derived from monohydric or polyhydric phenols can be reacted with triaryl, tricycloalkyl or trialkyl phosphites at a reactive atmospheric humidity of more than 25 ° to form insoluble and crosslinked products. The phosphites used do not contain any reactive groups as substituents, such as carboxyl, carboxylic acid anhydride, phenolic or alcoholic hydroxyl groups or primary or secondary amino groups which can react with epoxy groups.

"A disadvantage of the hardening products produced by this process is their inadequate resistance to saponification (see German publication 1.210.116).

Finally, it is also known to use Arylphösphate at least contain a primary amino group bonded to an aryl nucleus, to use for the hardening of polyepoxides (see Belgian patent specification 656,982).

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A disadvantage of this class of hardeners - especially when curing at room temperature - is the extraordinary tendency of the aminoaryl phosphates to crystallize

making their use extremely difficult. Another disadvantage is the additional use of a solvent which, because of the poor solubility of the aminoaryl phosphates, has to be used in relatively large quantities.

The present invention now provides a process for the production of moldings, coatings and coatings by curing polyepoxides at room temperature with aromatic polyamines, optionally in combination with organic solvents and in the presence of acidic accelerators., Characterized in that as aromatic Polyamines those of the general formula

wherein R is a phenyl or naphthyl radical optionally substituted by alkyl, alkoxy, carbalkoxy groups or halogen atoms, R ^{1 is} a phenyl and / or naphthyl radical optionally substituted by lower alkyl groups with 1-6 C atoms in the alkyl radical or halogen atoms and η means 0 or 1 can be used.

The substituents of R are preferably: alkyl groups with 1-12 carbon atoms, alkoxy groups with 1-6 carbon atoms and carbalkoxy groups with 2-7 carbon atoms.

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BATH ORIGINAL

Examples of aminoaryl phosphites that may be mentioned are:

3 '

O -

NILE

NH,

- NH

^H 2 ^N

0 -

NH,

- O - VZ

O -

O - P ³

- NH,

H ₂ N

-0-P =

NH,

The aminoaryl phosphites can be prepared by the process of German patent application F 28 607 IVb / 12qu.

For example, phosphorous acid trihalides or

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Phosphorigaäuremonoaryleeterdihalogenide, preferably dichloride, with the corresponding aminophenols !! at temperatures from 70 - 160 ° C in a solvent such as toluene or chlorobenzene or dichlorobenzene converted in equivalent amounts to the corresponding aminoarylphosphite hydrochlorides. Afterward is made from the resulting hydrochloride by adding a base, for example ammonia gas at temperatures of 60 - 100 ° C, the free aminoaryl phosphite set in freedom and after filtration of the resulting salt and evaporation of the Solvent isolates the aminoaryl phosphite.

Another possibility is the transesterification of triaryl phosphite, in particular triphenyl phosphite and the aminophenol in an equivalent ratio in the presence of a catalytic. Amount of a .basic catalyst, such as JKTatriuraraethylat Temperatures of 130 - 170 ° C, with the split off phenol being distilled off in vacuo »

The aminoaryl phosphites stand out from the previously known aromatic amines are characterized by their extremely easy solubility in epoxy resins and in organic solutions. They have a very low tendency to crystallize and are completely harmless from a physiological point of view. It is It is easily possible to use the aminoaryl phosphites obtained as raw products during production directly for hardening

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turn around. In this case they are often at room temperature liquid and can therefore be processed as such without the addition of solvents.

Practically all compounds compatible with the systems are suitable as solvents. Examples include: esters, such as ethyl, butyl, methyl acetate, ethyl glycol acetate, acid amides, such as formamide and dimethylformamide, ketones such as acetone and methyl ethyl ketone. Lactones such as i * "- butyrolactone, acetals such as Glycerin formal, sulfoxides, such as dimethyl and diethyl sulfoxide, Pyrrolidones, such as N-methylpyrrolidone. The additives can make up between 5-30 wt. # of the total batch.

As polyepoxide compounds for the process according to the invention practically all polyepoxide compounds are suitable, the contain more than one epoxy group in the molecule. However, it is also possible to use mixtures of polyepoxide compounds

and monoepoxide compounds such as phenyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ethers or butyl glycidyl ethers substituted by alkyl groups having 1 to 4 carbon atoms or cyclohexyl groups etc. to use.

The polyepoxide compounds to be used can be polyglycidyl ethers polyhydric phenols, for example 4,4'-dioxydiphe » nylmethane, 4,4'-dioxydiphenyldimethylmethane, 4,4'-dihydroxy

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diphenyl sulfone, trie (4-hydroxyphenyl) methane, from the Chlorination and bromination products of the aforementioned diphenols, from hydroquinone, reorcinol and lovolaks (i.e. reaction products of monohydric and polyhydric phenols and aldehydes, especially formaldehyde in the presence of acidic catalysts), from diphenols obtained by esterification of 2 Get the latriumsalees of an aromatic oxycarboxylic acid with one mole of unte dihaloalkanes or dihalo dialkyl ethers were obtained (see British patent specification 1.017.612), from polyphenols obtained by condensation of phenols and long-chain haloparaffins containing at least 2 halogen atoms (see British patent 1,024,288).

Also mentioned are polyepoxide compounds based on aromatic amines and epichiorhydrin z. B. N-di-2,3-epoxypropylanilin, H, N ^{1-dimethyl-Ν,} Ν'-diepoxypropyl-4,4'-diamino-diphenylmethane, N, N ^l -Tetraepoxypropyl-4,4 ^{'l-diaminodiphenylmethane,} N-diepoxypropyl-4-aminophenyl glycidyl ether (see British patents 772,830 and 816,923).

Glycidyl esters of polybasic carboxylic acids, for example phthalic acid diglycide ethers, adipic acid, are also suitable diglycidester, hexahydrophthalic acid diglycideater, glycidyl ethers of polyhydric alcohols, for example from 1,4-butanediol, Glycerine, trimethylolpropane, pentaerythritol.

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BATH

Of further interest are cyanuric acid ^{triglycides, dili, N 1} -diepoxypropyloxamide, polyglycidyl thioethers from polyvalent thiols, such as from bismercaptooethylbenzene.

After all, epoxidation products of unsaturated ones are said to be Compounds mentioned, for example epoxidized cycloolefins such as diepoxide from limonene, dicyclopentadienes, vinyl

eyelohexen, the diepoxide from the esterification product of Tetrahydro- or methyltetrahydrobenzoic alcohol and tetrahydro- or ethyltetrahydrobenzoic acid, the diepoxide from the acetalization product from 1 mole of dimethyl oil tetrahydrobenzaldehyde and 1 part of tetrahydrobenzaldehyde.

The polyglycidyl ethers are preferably polyvalent Phenols, especially the 4-, 4 '-dioxy diphenyl dimethyethane used.

) Pur the implementation of the polyepoxide compounds with the aminoaryl phosphites. Aminoaryl phosphites are mixed directly or dissolved in one of the specified solvents with the polyepoxide compounds at room temperature. The amount of aminoaryl phosphite is chosen so that there are 1 aolnow hydrogen atom of the aminoaryl phosphites for one epoxide group. Ss but can also be used up to 70 f> excess and up to 50 # deficiency of aminoaryl * phosphite.

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It has also proven advantageous to add the reaction mixture. au · polyepoxy compound, aminoaryl phosphite and optionally a solvent for the aminoaryl phosphite to add accelerators for salt hardening. As an accelerator Practically all soluble or compatible hydrogen donates, preferably compounds containing carboxyl groups, such as aliphatic and aromatic, for example Poly- and monocarboxylic acids, which can optionally be substituted by HO, NOg groups or halogen atoms, preferably chlorine, are used »Examples include: acetic acid, propionic acid, acrylic acid, ß-chloropropionic acid, Lactic acid, oxalic acid, maleic acid, phthalic acid,, oxalic acid half esters, maleic acid half esters, phthalic acid half esters with each 1 - 4 carbon atoms in ssteralkyl, half-esters from maleic acid and monomethylethylene glycol.

The additions of accelerator are depending on. Acioity between 0.3-15% by weight, based on polyepoxide plus hardener, preferably between 1-6% by weight .

The hardening itself takes place with a thin layer Room temperature or when hardening in a greater layer thickness as a result of the exothermic reaction with elevated sea temperatures.

In this application, under hardening or crosslinking, the

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BAD ORiGlNAU

Formation of an insoluble polyaddition product two-i- or three-dimensional structure understood.

In the resin-hardener approaches can be inorganic or organic Filling materials such as chalk, slate, barite, talc, cork flour and dye pigments, metal powder, metal shavings and metal fibers, especially in larger quantities from $ 20 to $ 500, ^ based on the resin-hardener mixture. In addition, a combination with fibers such as glass, asbestos, jute, sisal, synthetic fibers, in forts of strands, mats and fabrics is possible to reinforce the plastics. The proportion of these reinforcing inserts is in the range from 25 to 400 #, based on the resin-hardener combination.

The present process allows the production of moldings, tools, models, gauges and foundry mold boxes, coatings and coverings, the latter on a wide variety of W documents, such as. B. on metal, wood or ceramic masses.

The products obtained by the process of the invention are crystal clear, have a tack-free surface of high hardness and are characterized by good mechanical properties »which can be increased by further heat treatment. In particular The cured compositions surprisingly have a low sensitivity to alkali.

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Veiter · Details can be found in the following examples. # The parts given are in weight.

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Example 1 .

100 parts of a diglycidyl ether from 4,4'-dioxydiphenylditBethylmβthan (Bpoxidaquivalent 200) with 1.) 29.5 2 ") 35.5 3.) 41) 5 files trie (n-aBinophenyl) phosphite and each 3 (a), 5 (b) and 10 (o) parts of the maleic acid half and monoethylglycol at room temperature. Setting - behavior and mechanical properties can be found in the following list:

Approach binding max · reac- impact-strength · victories. peek-a-boo

since in tionetemp, keit firm- hard 100 g-pot- (^ C) (oekp / ca ^z ) keit « (kp / approach (min) (kp / oe ^z ) 1O«

H5 2.9

176 3.4

^ 250 5.0

> 250 4.1

> 25O 3.7

I 2 + c 8> 25O 3.1

^ 25O 3.7

> 250 3.3

> 25O 2.7

1 + a * 32 2 1 + b AtSOlel 20th 1 + c 8th 2 + a 28 P + b 16 2 + c 8th 3 + a 21 3 + b 12th 3 + c 6th

588 1710 1640 567 1760 1680 505 1645 1585 528 1655 1585 513 1695 1635 492 1725 1665 553 1720 1655 485 1670 1605 515 1695 1675

70 parts of a diglycidyl ether au x 4.4 ^I -Dioxydipheuyldimethjlmethan (Spoxidäquivalent 200) and 30 T _e ile of a monoglycidyl

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ethers made from 3-tert butylphenol (epoxy equivalent 250) are mixed with "1.) 2.7.5 2.) 33 3.) 38.5 parts of tris (m-aminophenyl) -phos- • "is missing and 3 Ca), 5 (b) and 10 (c)! parts of the half-ester 'Mixed from maleic acid and monomethylglycol at room temperature. Setting behavior and mechanical properties are can be found in the following list:

Approach setting max. Reaction impact bending ball pressure time in the temp. Toughness strength hardness «100 g-pot TC) (cmkp / cnr) (kp / cm ^z ) (kp / cnr) approach 10 ^M 60 ^w

(min)

1 + a 67 92 2.8 538 1715 1645 Ub 26th 174 3.3 524 1680 1610 1 + c 13th 205 3.8 503 1770 1695 2 + a 45 143 2.9 488 1745 1675 2 + b 25th 184 3.2 509 1770 1680 2 + c 12th > 25O 4.2 517 1665 1600 3 + a 28 ^ 25O 3.3 547 1700 1635 3 + b 25th ^ 250 2.9 468 1790 1710 3 + c 11 i> 250 2.4 512 1690 1615

Example 3

50 parts of a diglycidyl ether from 4,4'-dioxydiphenyldimethyl methane (epoxide equivalent 200) and 50 parts of a tri-glycidyl ether from trimethylolpropane (epoxy equivalent 165) 1.) 32, 2.) 38.5 and 3.) 45 parts of tris (m-arainophenyl) phosphite and 3 (a), 5 (b) and 10 (c) parts of the half-field

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from maleic acid and butanol mixed at room temperature. Setting behavior and mechanical properties are as follows The list can be found in:

Approach setting time max.

at 100 g temp. Toughness hardness ₂

Pot base (C) (cmkp / cm) speed _o (kp / cm) (min) (kp / cnT) 10 *

1 + a 29 4th 1 + b 23 1 + c 11 2 + a 26th 2 + b 15th 2 + c 9 3 + a 22nd 3 + b 12th 3 + c 6th example

233

> 25O

6.8 925 1690 1 * 590 7.4 902 1720 1580 7.7 937 1815 1710 10.3 853 1915 1785 9.8 875 1975 1805 9.0 927 1910 1790 11.2 924 1690 1605 10.0 980 1730 1610 9.2 888 1795 1680

100 parts of a diglycidyl ether from 4,4'-dioxydiphenyldimethylmethane (Epoxy equivalent 200) were 1.) 29.5, 2.) 35.5 and 3.) 41.5 parts of tris (m-aminophenyl) phosphite and mixed in all 3 cases with 20 parts of ^ -butyrolactone at * room temperature. The accelerator was a) 2 parts of fl-chloropropionic acid and b) 5 parts of the half ester of maleic acid and monomethyl glyc oil added. Setting behavior and mechanical Properties can be found in the following list:

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Sowings Ligation
since la
100 g-
Xopfan-
sats
(a) max. Eeak
tionsteep. Impact
Kähigk. r
(cakp / cB Bending
, strengthening
) speed ₉
(kp / co ^) Ball pressure
hardness ₀
(kp / cB ² ).
10 "60" 1160 Among other things 41 103 28.7 933 1210 1035 1 + b 59 76 30.0 857 1180 1165 2 + a 35 153 32.3. 965 1225 990 2 + b 53 136 28.0 1005 1140 1100 3 + a 31 165 29.9 .983 1175 1210 3 + b 40 151 26.5
* 970 1340 example 5

100 parts of a diglyeid hydrate aua 4,4′-ioxydiphenyldimethylaethane (Spoxidttequivalent 200) are with 35.5 parts Tris-Ce-aainophenyD-phoiphit, 10 parts Xthylglykolacetat and 1.) 4 »2.) 6, 3.) 8 and 4.) 10 parts of half a bed % ml € ineKure and Honoeethylglykol at room temperature. The setting behavior and “echaalache” properties are as follows See list below:

Ansftts binding- oax. Reaction- impact- bending- Xugeldruck-

ztit ie temperature viscous. hardness ₀

. 100 «- ( ⁰ C) (cfkp / keit ₂ (kp / ce ^z )

Topfaneat "cb ^z ) (kp / cw *) 10 * 60"

1 49 98 6.6 953 1680 1580 2 42 127 6.4 940 1655 1525 3 36 188 8.6 1005 1635 1505 4th
If A 31
10 ip8 225 7.1
- 15 - * 1625
/ 1638 ■ · BAO ( 3RiQINAt.

Claims (2)

Claims: λ * 1.) Process for the production of moldings, coatings and Coatings by curing polyepoxides at room temperature with aromatic polyamines, optionally in Combination with organic solvents and in the presence of acidic accelerators, characterized in that that as aromatic polyamines those of the general formula (RO) _n - P (OR'NH ₂ ) ₃ " _n where R is a phenyl or naphthyl radical optionally substituted by alkyl, alkoxy, 3arbalkoxy groups or halogen atoms, R ^{1 is} a phenyl and / or naphthyl radical optionally substituted by lower alkyl groups having 1 to 6 carbon atoms or substituted by halogen atoms and η 0 or 1 mean can be used. 2.) Polyadducts of polyepoxides and aminoaryl phosphites the "formula (RO) _n - P. (0R'NH ₂ ), _ _n wherein R is a phenyl optionally substituted by alkyl, alkoxy, carbalkoxy groups or halogen atoms Le A 10 108 - 16 - 0098 12/1638 or Napirthylreet, R ^{1 is} a phenyl and / or naphthyl radical optionally substituted by lower alkyl groups of 1 to 6 carbon atoms in the alkyl radical or by halogen atoms, and η is 0 or 1. Le A 10 108 - 17 -