CS273343B2 - Active hydrogen containing composition - Google Patents

Abstract

Composition containing active hydrogen on a base of compounds with hydrogen atoms active towards polyisocyanates, containing at least i) one substance containing a larger number of reactive hydrogen atoms in the molecule, dispersed or dissolved in which ii) is an effective amount of an inner separation agent containing a) metal salt of carboxylic acid, amidocarboxylic acid, an acid containing phosphorus or acid containing boron, whereas 1) the acid contains at least one lipophilic group, which gives it incongruence and a substance containing several reactive atoms of hydrogen and 2) the metal is selected from a group including metals of groups IA, IB, IIA and IIB of the periodic table of elements, aluminium, chromium, molybdenum, iron, cobalt, nickel, tin, lead, stibium and bismuth and b) compatibilising an amount of tertiary amino compounds containing at least one tertiary azote, whereas one or more hydroxyterminated poly(oxyalkylene) or alkanol groups are linked to the tertiary nitrogen atom.

Description

The invention relates to active hydrogen containing compositions, for example based on polyols. or other isocyanate-reactive hydrogen-containing compounds, which compositions comprise inert release agents. Release agents or ooparators are substances or mixtures thereof which allow the molded articles to be easily separated from the mold. The invention further relates to a process for the production of molded polyurethanes and / or polyureas and similar polymers by reacting an active hydrogen-containing substance with a polyisocyanate in the presence of certain internal release agents, wherein the reaction is carried out in the form of a mold.

Molded polyurethane and / or urea products are increasingly used in the manufacture of automobiles, furniture and home constructions. Wrought polyurethanes and polyureas are particularly important because they have a low weight, are resistant to moisture, weathering, temperature extremes * aging. For example, molded polyurethane elastomers have gained particular importance in the manufacture of mechanical shock absorbers such as automotive bumpers.

The demand for molded polyurethane articles requires that they be produced in large numbers in the shortest possible time. Polyurethane molding compositions are well suited for mass production because the reactants are liquid and react rapidly. However, there is a problem associated with the molding of molded polyurethane products. Until now, the easy release of molded articles from the molds in which they have been produced has been achieved by coating the surface of the mold cavity with an agent that facilitates the release of the article from the mold cavity wall by a so-called release agent. Processes based on this are described in U.S. Patent Nos. 3,964,530, 3,640,769, 3,624,190, 3,607,397 and U.S. Pat.

Such external release agents have several disadvantages. For example, when the mold release article is released from the mold, the external release means tends to adhere to the article being removed, so that the external separator needs to be re-applied almost every time the mold is used. When applying the external separator, care must be taken to uniformly coat the entire surface of the mold to prevent the molded article from sticking to the mold. The need for repeated treatment of the mold and the care to be taken in this treatment greatly increases the cost and time required for molding the polyurethanes.

Another problem is that when the mold is reused, the remnants of an external separator accumulate in the mold. The accumulation of these residues has the effect of masking and wiping off the details of the mold cavity surface to be transferred to the molded article. Excess accumulation of these residues can even result in the loss of important dimensions of the article. The accumulated residues must therefore be periodically removed from the mold, resulting in additional time losses. Using too much external separator can lead to attack of the polymers with solvents contained in the external separators.

In addition, the use of external separators applied by spraying, especially in the case of separators containing solvents, has disadvantages with regard to environmental safety and / or hygiene.

The use of internal separators in the manufacture of molded articles of polyurethanes has been described in U.S. Patent Nos. 3,726,952, 4,024,088, 4,098,731, 4,130,698, 4,111,861,

201,847 and 4,220,727.

They have encountered various problems when using such internal separators. Many separators calculate or diffuse on the surface of the molded article and thus impair the variability of the article. Other internal separators are incompatible with the polyols used in the production of polyurethanes. Many of them seriously reduce the activity of the catalysts used in the reaction mixture, and many of them also impair the physical properties of the molded polyurethanes.

PCT International Publication No. WO 84/03296 and European Patent Application No. 119,471 disclose an internal release agent comprising a primary or secondary amine and a metal salt of certain acids. Although this internal separator precoGS 273343 B2 raises the problems encountered with earlier separators, it is often too reactive due to the presence of primary or secondary amines to be optimally useful in certain polyurethane formulations.

In view of these difficulties, it is desirable to develop an internal separator for polyurethane moldings. Such internal aeparators substantially reduce the time and cost of producing molded polyurethanes and similar polymers. The inner separator sought should facilitate the release of the polyurethane moldings from the mold cavity, should not significantly impair the activity of the catalyst, should at least change the physical properties of the molded polyurethane and / or be too reactive to be optimally used in polyurethane formulations,

The present invention provides an active hydrogen-containing composition which comprises:

(i) at least one substance containing a plurality of reactive hydrogen atoms in the molecule in which it is dispersed or dissolved; (i) an effective amount of an internal release agent comprising

(a) a metal salt of a carboxylic acid, an amidocarboxylic acid, a phosphorous acid or a boron - containing acid,

(1) the acid contains at least one lipophilic group which imparts intolerance to it with a substance containing multiple reactive hydrogen atoms; and

(2) the metal is selected from the group consisting of metals of Groups IA, IB, IIA and IIB of the Periodic Table of the Elements, aluminum, chromium, molybdenum iron, cobalt, nickel, tin, lead, antimony and bismuth;

b) a compatibilizing amount of a tertiary amine compound containing at least one tertiary nitrogen, wherein one or more hydroxylated poly (oxyalkylene) or alkanol groups are attached to the tertiary nitrogen atom. The tertiary amine compound of the internal separation agent is compatible with said metal salt, in a substance containing reactive hydrogen atoms, for example polyols, but does not compatibilize the metal salt in a reactive mixture comprising said substance containing reactive hydrogen atoms and a polyisocyanate.

The inner separator according to the invention effectively reduces the adhesion of the molded polyurethane to the walls of the mold cavity in which it is molded. As a result, the molded polyurethane is more easily and / or quickly removed from the mold. The internal separator according to the invention has the additional advantages that it does not substantially affect the activity of the catalyst or catalysts used in the reaction of the polyisocyanate and the active hydrogen-containing substance, so that a large number of molded articles can be produced without the need for repeated treatment. The molded articles obtained have a surface that can be easily lacquered or otherwise coated if desired.

The inner separator comprises a metal salt of an organic acid and a tertiary amine compound as defined above which compatibilizes the metal salt in a mixture containing active hydrogen atoms, but does not overcompatate the metal salt in the reactive mixture comprising the active hydrogen and polyisocyanate containing substance. The internal separator contains a sufficient amount of a tertiary amine to compatibilize the metal salt in the active hydrogen containing material.

The ability of a particular tertiary amine to compatibilize a metal salt is readily determined by mixing the metal salt with a tertiary amine compound and then mixing the resulting mixture with an active hydrogen-containing substance. Compatibility is achieved when the mixture is dissolved or suspended in the active hydrogen-containing substance For a time sufficient to allow it to react with the polyisocyanate, the inability of a tertiary amine to compatibilize a metal salt in a reactive composition comprising an active hydrogen-containing substance results in a reduction in time and effort to remove the molded article from the mold.

As already mentioned, the tertiary amino compound contains one or more alkanolic or hydroxyterminated poly (oxyalkylene) groups attached to the tertiary nitrogen atom. The presence of such groups often tends to increase the ability of the tertiary amine to compatibilize the metal salt.

When the tertiary amine compound is a monoamine, it preferably contains at least two alkanol or hydroxyterminated poles (oxyalkylene) groups attached to a nitrogen atom. Preferably, such a monoamine is an alkylene oxide adduct to ammonia or a primary amine and can be represented by the general formula I (I) still having a value of from 1 to 5, preferably from 1 to 5

3, preferably the number 1, n represents the number 2 or 3, each of the symbols

R independently represents hydrogen, halogen or an inertly substituted lower alkyl group;

R * is an inertly substituted lower alkyl or aromatic group.

In such a monoamine, the structure of the R group may depend on the composition of the active hydrogen-containing substance in conjunction with which the internal separator is used. For example, if the active hydrogen-containing substance comprises a polyether polyol in which a substantial proportion of the repeating units are derived from propylene oxide, the substantial part of the R groups is preferably lower alkyl groups, preferably methyl groups. Similarly, when a poly (ethylene oxide) polyol is used, a substantial part of the R groups are preferably hydrogen atoms. Pre-early monoamines include, for example, tri (isopropanol) amine, methyldi (isopropanol) amine, ethyldi (iopropanol) amine, phenyldi (isopropanol) amine, triethanolamine, methyldiethanolamine, and ammonia adducts with 4-9 moles of propylene oxide.

Also suitable as monoamines are hydroxyalkyl derivatives or hydroxyterminated poly (oxyalkylene) cyclic amine derivatives such as N-hydroxypropylmorpholine, N-hydroxyethylmorpholine and cyclic amine reaction products such as morpholine with 2 to 30 moles of ethylene oxide, propylene oxide or mixtures thereof.

Preferably, the tertiary amine compound contains two or more tertiary nitrogen atoms. Suitable diamines include diamines of formulas II and III (2-m) [H (OCHHCH-) 1 -N-r ² cym | (2-m

N - [(CH.CHRO) H] m - (II) a

H (OCH ₂ CH ₂ ) _y N

N (CH ₂ CHR 0) _y H (III) wherein

R is an inertly substituted alkylene radical or a divalent dialkylene ether or polyether radical, each of y being independently from 1 to 50, preferably from 1 to 20, preferably from 1 to 5, and most preferably from 1 to 3, each of m being independently Number 1 or 2, and preferably 2, each of the symbols

R ³ is independently an inertly substituted alkylene radical and

R and R * are as defined above.

Suitable di-tertiary amines of formula II are those obtained by the reaction of an alkylenediamine, an N-hydroxyalkylalkylenediamine or an amino-terminated polyether with from 1 to 50, preferably from 1 to 20, preferably from 1 to 5 and most preferably from 1 to 3 moles of alkylene oxide. Suitable amino-terminated polyethers which may be used as starting materials include those disclosed in U.S. Patent Nos. 3,654,370 and 3,666,788, preferably those having a molecular weight of from 60 to 2000, preferably from 60 to 1000, most preferably from 60 to 1000. Alkylenediamines which are suitable starting materials include straight or branched chain alkylene groups having from 1 to 30, preferably from 2 to 5, and most preferably from 2 to 3 carbon atoms. Suitable alkylene oxide is preferably ethylene oxide, propylene oxide or butylene oxide or mixtures thereof. Most preferred is the ethylene diamine reaction product with 4-12 moles of propylene oxide or a mixture of propylene oxide and ethylene oxide and the hydroxyethylethylene diamine reaction product with 3 to 9 moles of propylene oxide or a mixture of propylene oxide and ethylene oxide.

Suitable diamines of structure III are the reaction products of piperazine having from 2 to 6, preferably about 2 moles, and alkylene oxides, which are preferably propylene oxide or mixtures containing propylene oxide.

Other suitable tertiary amines are, for example, alkylene oxide adducts to aminoalkylpiperazines, the structure of which can be represented by formula IV

H (OCHRCH ₂ ) _y N (CH 3 -CH 2 CHgCHRO) H ₁₂ (IV), wherein R is as defined above, and θ 2 ® 4 -alkylamino adducts to bis (aminoalkyl) piperazine, the structure of which may be represented by the general formula V [H (OCHRCH ₂ ) _y ] ₂ NCCH ₂ (CH ₂ ) _z -N [(^ CHRO) _y H] ₂ (V) where

R z

the sum of all numbers below is N, Ν ', ff is as defined above, is from 1 to 10, preferably from 1 to 3 and preferably from 2 to 3, and represents from 1 to 20} trihydroxyalkyltriazines of formula VI

TH ^ CHROH

CH '(VI)

HOCHRCH '-ff It-CH-CHROH ^d \ / 2 where

R is as defined above, and adducts of poly (alkylene amines) with 1 to 3 moles, preferably about 1 mole of C ₂ -O 4 alkylene oxide, based on the amine hydrogen.

The tertiary amines and the hydroxyl-terminated groups react with the polyisocyanate to form a polyurethane polymer. Thus, in these cases, the internal separators described above may optionally be reacted with the polyisocyanate to form a polyurethane. However, it is usually desirable to use other compounds having multiple active hydrogen atoms in the molecule that do not contain tertiary amino groups in their structure, and thus the above-described internal separator is most typically mixed with, at least one such compound.

The internal release agent according to the invention also comprises a metal salt of a carboxylic acid, amidocarboxylic acid, phosphorus-containing acid or boron-containing acid, which acid contains at least one lipophilic group which makes it incompatible with a compound with more active hydrogen in the molecule. using. The acid salt used preferably comprises at least one polysiloxane chain or a saturated or unsaturated inert substituted hydrocarbon radical containing at least 7 carbon atoms.

Carboxylic acids which can be used as metal salt components in the above-described internal separators include saturated or unsaturated aliphatic or cycloaliphatic carboxylic acids or aromatic carboxylic acids, preferably having from 7 to 30 and preferably from 10 to 18 carbon atoms.

GS 273343 B2

Suitable acids are preferably the so-called fatty acids containing 10 to 18 carbon atoms. Such fatty acids include, for example, oleic, stearic, lauric, palmitic, linoleic and ricinoleic acids, and mixtures thereof.

Suitable carboxylic acids include amidocarboxylic acids such as the reaction products of carboxylic acid halides containing 1 to 30, preferably 2 to 18, and preferably 5 to 18 carbon atoms with 2 to 4, and preferably 2 to 3, carbon atoms per molecule.

Particularly preferred of these aminocarboxylic acids are compounds of formula

O O

R ⁶ - G - N - R ⁸ . - G - OH wherein r6 represents a hydrocarbon or substituted hydrocarbon group containing 1 to 29, preferably 2 to 17 carbon atoms, »

R is hydrogen, alkyl or hydroxy substituted alkyl having 1 to 3 carbon atoms and

O

R represents a divalent hydrocarbon group containing 1 to 3, preferably 1 carbon atom.

Examples of such aminocarboxylic acids include oleoyl sarcosine, lauryl sarcosine, capryl sarcosine, oleoylglycine, octanolglycine, oleoylhydroxyethylglycine, and mixtures thereof. These amidocarboxylic acids can be prepared by acylation according to Schotten-Baumann, in which the aeyl halide is reacted with an amino acid.

Compounds of formula (I) are further suitable as carboxylic acids

About where

R represents a hydrocarbon group containing 1 to 12 carbon atoms.

Suitable substances containing at least one carboxylic acid group and siloxane chains are disclosed in U.S. Patent 4,076,695 to J. W. Keil.

Suitable organic substances containing at least one phosphorus-containing acidic group include, for example, monostearyl phosphate, cetyl dihydrogen phosphate, monolauryl phosphate, deeyldihydrogenphosphate, monobutyl monodecyl phosphate, and mixtures thereof.

Suitable organic substances containing at least one boron-containing acid group include, for example, boric acid dioctadecyleater, boric acid monododecyl mono (phenylmethyl) borate, wonododecylmonophenyl boronic acid ester, boronic acid monoheptadecyl mono (phenylmethyl) ester, boric acid monodecyl ester and theirs. eměsi.

Suitable metal salts of the above acids are those in which the metal is selected from the group consisting of zaΑ, IB, IIA. and IIB of the Periodic Table of the Elements, aluminum, magnesium, molybdenum, iron, cobalt, nickel, tin, lead, antimony and bismuth.

preferably, the metal is lithium, sodium, potassium, m 2, magnesium, calcium, barium, zinc, cadmium, aluminum, magnesium, cobalt, nickel, tin, lead, antimony or bismuth, or a combination thereof.

Even more preferably, the metal is lithium, copper, magnesium, calcium, barium, zinc, cadmium, aluminum, iron, cobalt or nickel, or combinations thereof. Most preferred metals are zinc, calcium, magnesium and nickel.

Examples of particularly suitable metal salts are zinc atate, zinc oleate, zinc palmitate, zinc laurate, calcium stearate, calcium oleate, calcium palmitate, calcium laurate, magnesium stearate, magnesium oleate, magnesium laurate, magnesium palmitate, nickel stearate, nickel oleate palmitate, nickel laurate, nickel stearate, copper oleate copper laurate, copper palmitate, copper, zinc Btearoylsarkosinát, oleoylearkooinát zinc -palmitoylsarkosinát zinc lauroylsarkoainát zinc Btearoylsarkosinát, calcium oleoyl sarcosinate, calcium palmitoyl sarcosinate, calcium lauroyl sarcosinate, calcium stearoyl stearate, magnesium oleoyl sarcosinate, magnesium palmitoyl sarcosinate, magnesium lauroyl sarcosinate, nickel stearoyl sarcosinate, nickel oleoyl sarcosinate, nickel palmitoyl sarcosinate, nickel lauroyl sarcosinate, copper stearoyl sarcosinate, copper oleoyl sarcosinate, palmitoyl sarcosarkate copper osinate, copper lauroyl sarcosinate or mixtures thereof.

The acid metal salts described above may be prepared by reacting the corresponding acid with a suitable amount of a metal containing compound such as a hydroxide. If the metal in the Beketov series is in front of hydrogen, it can be reacted directly with the acid or acid amide. Mixtures of the above metal salts with acids, which are commercially available, may also be used.

The amount of metal salt used must be sufficient to reduce the adhesion of the molded polyurethane, polyurea and similar polymers prepared in the presence of an internal separator to the walls of the mold cavity in which they are formed. Such an amount is referred to herein as an effective amount of a metal salt or internal separator. The metal salt is preferably used in a relatively small amount, i.e. in an amount of from 0.25 to 20, preferably from 0.25 to 10, and preferably from 0.5 to 5% by weight, based on the weight of the active hydrogen-containing substance, in conjunction with which it is used. However, some metal salts are more effective at reducing polymer adhesives to form than others. As a result, particular metal salts may also be used in amounts slightly higher or lower than the above.

To facilitate the mixing of the internal separator with a substance containing a plurality of active hydrogen atoms in the molecule and / or polyisocyanate in the preparation of polyurethane, polyurea and similar polymers, it is often desirable to prepare a concentrate. In this case, the internal separator dissolves or disperses in the active hydrogen-containing part of the substance at a slightly higher concentration than mentioned above. Such a concentrate preferably contains 5 to 40, preferably 10 to 40, and most preferably 10 to 25% by weight of the metal salt and a compatibilizing amount of the tertiary amine compound dissolved or dispersed in a suitable active hydrogen-containing material. the active hydrogen to be reacted with the polyisocyanate. The concentrate may optionally contain still further additives and ingredients as described below. The active hydrogen-containing substance and optional additives and components should not essentially contain primary or secondary amines or should be more than the amount ensuring the compatibility of the metal salt and the active hydrogen-containing substance.

The ratio of the amount of the metal salt to the tertiary amine compound is chosen such that when mixed into the active hydrogen-containing composition, the acid metal salt is compatible with the active hydrogen-containing agent by the action of the tertiary amine compound. The tertiary amino compound is preferably present in an amount corresponding to 0.5 to 20, preferably 1 to 10, preferably 1 to 5 times by weight of the metal salt, although this ratio is somewhat dependent on the molecular weight of the particular substances.

Usually, the smallest amount of tertiary amine compound is preferred, since the tertiary amine is a catalyst for urethane and urea reactions, as well as certain blowing reactions (gas releasing foaming reactions), and its excess causes the reaction to accelerate.

The internal release agent used according to the invention is prepared by mixing the tertiary amine compound, the metal salt and any other components at a temperature above the melting point of most of the components. ie, up to 150 ° C. Of course, the internal release agent of the invention can be prepared by mixing a tertiary amine and a metal salt in the presence of an active hydrogen-containing substance, a polyisocyanate or a reaction mixture comprising the active hydrogen-containing substance and a polyisocyanate.

In addition to the metal acid salt and the tertiary amino compound, the internal release agent of the invention may contain any optional carboxylic acid, amidocarboxylic acid, phosphorous acid or boron-containing acid as described above, but this time in free form and not in the metal salt form. Mixing such acids is often useful to further improve the release properties of the polyurethane in which they are used. The optional carboxylic acid, amidocarboxylic acid, phosphorus-containing acid or boron-containing acid is preferably present in an amount by weight corresponding to 0.1 to 2, preferably 0.1 to 1 times by weight of the metal salt.

The active hydrogen-containing composition of the invention comprises, in addition to the internal release agent described above, a compound or mixture of compounds containing a greater number of active hydrogen atoms per molecule. Typically, such a compound is a compound with which the metal salt is intolerant. The active hydrogen atoms are preferably amino, amidiocyanate, hydroxyl or thiol hydrogen atoms, preferably they are amino or hydroxyl hydrogen atoms, and most preferably es give hydroxyl hydrogen atoms, active hydrogen is most preferred for polyol blends that are substantially free of primary or secondary amines or contain less than the amount of compatibilizing active hydrogen and metal salts,

AND

Suitable active hydrogen-containing substances include polyether polyols, polyether polyols, phosphorus-containing polyhydroxy compounds, hydroxyterminated acetal resins, hydroxyterminated amines and polyamines, corresponding amino-terminal polyether- and / or polyester polyols, the so-called polymer or copolymer polyols, which consist of a dispersion of addition polymer or copolymer in continuous and other active hydrogen-containing compounds known to be useful in the preparation of polyurethanes and similar polymers. Examples of these and other suitable materials of this type are set forth in greater detail in U.S. Patent No. 4,394,491, in particular paragraphs 5 to 5. Suitable copolymer polyols are disclosed, for example, in U.S. Patent Nos. Re 28,118 and 4,324,491. In general, active hydrogen-containing substances with which the metal salt is non-sensitive are suitable.

In addition, low molecular weight active hydrogen-containing substances can be used as chain extenders for the preparation of hard segment polymers. The use of low equivalent weight polyols and polyamines as chain extenders is described, for example, in U.S. Patent Nos. 4,269,945 and 4,444,910.

In particular, the active hydrogen-containing substance or mixture thereof used depends on the properties required of the polymer being prepared using it. It is well known that the equivalent weight, number and type of functional groups are parameters affecting the properties of the polymers obtained. The relationship between the structure of the active hydrogen-containing substance (s) and the properties of the resulting polymer is not substantially affected by the presence of an internal separator. As a result, active hydrogen-containing substances are used in the production of the polymers of the invention in a substantially conventional manner.

The active hydrogen-containing composition of the invention can be prepared by adding an internal separation composition of the invention to a suitable active hydrogen-containing composition. The components of the active hydrogen-containing composition may be premixed together or added individually to the active hydrogen-containing substance. The concentrates described above may also be used.

When the active hydrogen-containing composition of the invention is prepared from an internal separation agent and a suitable active hydrogen-containing substance, the amounts by weight of the metal salt, tertiary amino compound and optionally free acid present are such as to form an active hydrogen-containing composition containing an effective amount of internal separation. means.

The active hydrogen-containing composition is expediently reacted in the mold with a polyisocyanate to form a molded polymer.

Suitable polyisocyanates are organic aromatic polyisocyanates, aliphatic polyisocyanates or mixtures thereof.

Suitable organic aromatic polyisocyanates which may be used include, for example, any polyisocyanates containing 2 or more NCO groups per molecule, such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, p, p'-diphenylmethane diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenylisocyanates, or mixtures thereof.

Also suitable as organic aromatic and / or aliphatic polyisocyanates are prepolymers containing isocyanate groups prepared from such polyisocyanates and compounds containing 2 or more active hydrogen atoms, and also polyisocyanates and / or prepolymers thereof modified to contain urethonimine or carbodiimide bonds.

Suitable organic aliphatic polyisocyanates include, in addition to the hydrogenated derivatives of the above-mentioned organic aromatic polyisocyanates, 1,6-hexamethylenediisocyanate, isophorone diisocyanate, 1,4-cyclohexyldiocyanate, 1,4-bis-isocyanatomethylcyclohexane or mixtures thereof.

Corresponding polyisothiocyanates are also suitable,

Polymers can be prepared either in the presence or absence of a catalyst. Polymers prepared from less preferred amine-containing active hydrogen compounds do not always require a catalyst, although catalysts may be used if desired. In contrast, polymers prepared from polyols that do not contain nitrogen atoms are usually prepared in the presence of a catalyst. The tertiary amine compound itself may be a sufficient catalyst for the polymerization reaction.

Suitable catalysts that can be used to prepare polymers include, for example, organometallic compounds, tertiary amines, alkali metal alkoxides, or mixtures thereof.

Suitable organometallic catalysts are, for example, organometallic compounds of tin, zinc, lead, mercury, cadmium, bismuth, antimony, iron, manganese, cobalt, copper or vanadium such as metal salts of carboxylic acids containing 2 to 20 carbon atoms such as stannous octoate , dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, ferric acetylacetonate, lead octoate, lead oleate, phenylmercuripropionate, lead naphthenate, manganese naphthenate, copper naphthenate, vanadylnaphthenate, cobalt (II) octoate, cobalt acetate, or their cobalt acetate.

Suitable amine catalysts are, for example, triethylenediamine, triethylamine, tetramethylbutanediamine, Ν, Ν-dimethylethanolamine, N-ethylmorpholine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine, N-ethylpiperidine, 1,3-bis- (dimethylamino) -2 propanol, NNN, N, tetramethylethylenediamine, or mixtures thereof.

Suitable alkali metal alkoxides which can be used as urethane catalysts are, for example, sodium ethoxide, potassium ethoxide, sodium propoxide, potassium propoxide, sodium butoxide, potassium butoxide, lithium ethoxide, lithium propoxide, lithium butoxide, alkali metal salts with polyols such as those disclosed in U.S. Patent No. 3,728,308 or mixtures thereof.

The urethane-forming catalysts are preferably in liquid form, but if they are solid at the application temperature, they can be dissolved in a suitable liquid, such as dipropylene glycol, or they can be dissolved or dispersed in one of the components.

The optional catalysts may be used in amounts of from 0.001 to 2, preferably from 0.01 to 1 part by weight per 100 parts by weight of the substance containing more active hydrogen atoms per molecule, depending on the activity of the catalyst. Very weak catalysts could perhaps be used in amounts above 6 parts per 100 parts of the substance containing more active hydrogen atoms.

If desired, the polyurethanes may be modified to contain isocyanurate or isothiocyanurate groups. Relatively high values of the ratio of NCO or NOS groups to active hydrogen atoms are used, for example above 1.5: 1 preferably above 2: 1 and / or a trimerization catalyst is used. Suitable trimerization catalysts which may be used include the zwitterionic compounds described by Kresta and Shen in U.S. Pat. No. 4,111,914 and tertiary amines, alkali metal salts of lower alkanoic acids, or mixtures thereof disclosed in U.S. Pat. U.S. Patent No. 4,126,741 to Carleton et al.

The zwitterions can also act as catalysts for the condensation poles which form urethane bonds.

The density of the polymers produced can optionally be reduced by introducing a blowing agent into the mixture. Suitable blowing agents are described in detail in U.S. Patent No. 8,125,487 to U.S. Patent No. 753,933. Particularly suitable blowing agents are, for example, water, azo-type blowing agents and low-boiling halogenated hydrocarbons such as methylene chloride and trichloronofluoromethane.

Another suitable method for reducing density is foaming, which is accomplished by introducing an inert gas into a mixture of urethane or other polymeric components. Suitable inert gases are, for example, nitrogen, oxygen, air, carbon dioxide, xenon, helium or mixtures thereof.

If desired, cell size control agents may be used, particularly when foams or microcellular products are prepared and with reduced density. The use of such agents to regulate cell structure also increases the variability of polyurethane. Non-limiting examples of cell structure regulators that can be used include surfactants such as DC-193, DC-195, DC-197, DCP1-1630, DC-5043, and DC-198 commercially available from Dow Corning Corp., SP-1034, PFA-1635, PPA-1700, and PFA-1660 commercially available from General Electric Co., 1-520,

1-5320, 1-5309 »1-5307 and 1-5340 commercially available from Union Carbide Corp., and B-1048, B-8610, B-8612, B-8404 and B-8407 commercially available from TH Goldschmidt , AG., Or mixtures thereof.

The polyurethanes and other polymer products may optionally further contain coloring agents, flame retardants, fillers or modifiers.

The components which interact with each other to form polymeric products can be formed into useful articles by bringing the reactive mixture into molds capable of withstanding the exothermic polymeric masses and which are non-reactive and insoluble in contact with the liquid reactive mixture. Particularly suitable molds are molds made of metal, for example aluminum, copper, brass or steel. In some cases, non-metallic forms, such as those made of polyethylene, polypropylene, polyethylene terephthalate or silicone elastomers or epoxy composites, may be used. The present invention is useful in any method by which molded polyurethane, polyurea or the like polymer is prepared.

Although it is possible to use molds with an untreated metal surface, it is often advisable to treat the mold with an external separator such as soap or wax at the beginning of the production of the molded articles according to the invention. The outer separator is usually applied to the mold before the first molding and sometimes also after the first or first two moldings have been produced. After making the first molded article or the first pair of molded articles, it may be necessary to apply the outer separator periodically after about 10 to 100 mold cycles. However, in many cases, a satisfactory release is achieved with the composition of the invention even when no external separator is used. In contrast, when the internal separator according to the invention is not used, treatment with the external separator must be carried out after each molding cycle.

The internal separators according to the invention are suitable for all polyurethane forming processes, but are particularly suitable for reaction injection molding (RIM).

Particularly suitable reaction injection methods are those disclosed in THE BAYFLEX 110 SERIES - THE NEW GENERATION OE RIM MATERIALS, WA Ludwico and RP Taylor, presented at the Society of Automotive Engineers Passenger CAR Meeting, Detroit, Michigan, September 26-30, 1966 ; in the paper THE PROPERTIES OP HIGH MODULUS RIM URETHANES, RM Gerkln and PE Critchfield, delivered at the same conference, in British Patent No. 1,534,258 entitled PROCESS POR THE PRODUCTION OF POLYURETHANE-POLYUREA MOLDED PRODUCTS HAVING A COMPACT SURPACE Melvin Sweeney's title INTRODUCTION TO REACTION INJECTION MOLDING, Technomics Ing., 1979.

When injecting relatively fast curing compositions into massive metal molds, it is necessary to preheat to a certain temperature in order to obtain good surface characteristics of the mold spray to prevent dissipation of polymerization heat from the reaction mass and thus to avoid improperly delaying the time during which the formulation expects solidification. On the other hand, thin-walled molds will exhibit minimal heat sink for relatively wide cross-sections, in which case they will not need to be preheated.

After sufficient curing of the polymer to ensure dimensional stability of the article, the article is removed from the mold. The force and / or time required to remove the article from the mold is less than if no internal separator is used. In addition, the mold usually does not require any treatment before the next molding cycle. As already mentioned, in some cases, it may be necessary to treat the mold with an external release agent prior to the first or first several molding cycles when starting the molding.

The invention is illustrated in more detail in the following examples; The examples are illustrative only and do not limit the scope of the invention in any way. All parts and percentages are by weight unless otherwise indicated.

Example I

Active Hydrogen-containing compositions I and II are prepared by mixing the ingredients listed in Table I.

Polyol A ^ ·

Diethylene glycol

Triethylene glycol

Dibromneopentylglycol

Ul-24 ²

UI-28 ³

Tertiary amine A ⁴ Tertiary amine B ^ Zinc stearate

Table I

Composition I of parts by weight.

w n li n

0.03 • 0.03

6.5

Composition II parts by mass.

(j tl II

II II

0.03

0.03

6,5 ” ¹ Triol prepared by reacting glycerol as a starter with 92/8 propylene oxide (PO) / ethylene oxide (EO) to give a polymer with a molecular weight of 3000,

Mercaptocin catalyst, manufactured by Witco Chemical Corp.

Dimethyltin dilaurate, a catalyst available from Witco Chemical Corp.

⁴ Aminoethylethanolamine-initiated poles (propylene oxide), molecular weight 278.

Polyol prepared by condensation of ethylenediamine with 5,5 mol of propylene oxide to give a polymer with an equivalent mass of 89.

In both Composition I and Composition II, zinc stearate is dissolved in the presence, but not in the absence, of a tertiary amine.

Compositions I and II are reacted at number 103 with a polymeric polyisocyanate commercially available under the designation Rubinate M from Rubicon Chemicals Inc. in the Aocuratio VR HT-60 reaction injection molding unit to form 254 x 254 x 3 mm wrought plates. A base wax coating (Chemtrend KOT 200L) is applied to the injection mold. The number of successive forming cycles in which the article is released from the mold walls when it is removed is shown in Table II below. In addition, Table II lists the density, flexural strength, flexural modulus, tensile strength, and hot shape stability (at 455 kPa and 1.82 MPa) of the resulting compacts.

Table II

Composition I Composition II density kg / m ³ 1 180 1 190 flexural strength ^3- (MPa) 71.4 78.9 flexural modulus ^3- (GPa) 2,034 2,072 p tensile strength (MPa) 40.0 44.8 3 hot shape stability (455 kPa) 115 ° C 104 ° C 1,82 MPa 90 ° 68 ° C number of subsequent releases ² * ^- > 15 > 15

* ASTM D-790 ² ASTM D-638 ³ D-648 ASTM

Teat ended after 15 consecutive releases.

As can be seen from the data in Table II, the introduction of an internal separator according to the invention into an active hydrogen containing composition imparts excellent mold release properties and good physical properties to molded polyurethane products made therefrom.

Example 2

Active hydrogen-containing compositions III to 7 are prepared by mixing the ingredients listed in Table IH.

Table III

Composition III Composition IV Composition V Polyol A ¹ 45 45 45 Ethoxylated glycerol ² 50 - Polyol B ³ - 50 - Trimethylolpropane - - 50 Diethylene glycol 10 10 10 Dibromneopentylglycol 35 35 35 Flame retardant ^ 10 10 10

Table III - continued

Zinc stearate 5 5 Tertiary amine 5 5 UL-24 ⁵ 0.03 0.03 UL-28 ⁶ 0.03 0.03

0.03

0.03 ¹ Triol prepared by reaction of a glycerol initiator with a 92/8 mixture of propylene oxide (PO) / ethylene oxide (EO) to give a polymer having a molecular weight of 3000.

p

Triol with a molecular weight of 345.

³ Glycerol-initiated polypropylene oxide of molecular weight 255.

⁴ Pryol PCP, chlorinated phosphoric acid ester, manufactured by Staufier Chemical.

⁵ Mercaptocin catalyst, manufactured by ffitco Chemical Oorp, g

Dimethyltin dilaurate, a catalyst available from Witco Chemical Gorp.

Each of Formulas II-V is reacted with a polymeric polyisocyanate and molded under the conditions described in Example 1. The number of successive molding cycles and the different physical properties of the moldings are shown in Table IV below.

Table IV

Composition III Composition IV Composition V

Density (kg / m ³ ) 1 200 1 150 1 150 Flexural strength (MPa) not determined 84.1 120.7 Flexural modulus ^ (GPa) 1,379 1,965 3,310 O Tensile strength (MPa) not determined not determined 64.1 Hot shape stability ³ (1,82 MPa) 93 ° C not determined 104 ° C Impact toughness ⁴ (m.kg) 0.35 0.29 0.46 Number of subsequent releases from mold ³ > 10 > 10 50

ASTM D-790

ASTM D-638

ASTM D-648

ASTM D-2794

The> symbol indicates that the test was completed after the specified number of releases in which all parts of the moldings were released from the mold ·

From each of the compositions III to V, a polyurethane article with excellent physical properties is obtained which is well released from the mold.

Example 3

Various active hydrogen-containing compositions are prepared having a composition similar to that of Composition I of Example 1 except that the zinc stearate is replaced with the other fatty acid salts listed in Table V. In all cases, the fatty acid salt was dissolved in a tertiary-containing polyol with the exception of a composition containing lithium stearate, in which case a stable dispersion of the salt in the polyol is formed.

To determine the effect of the release agent on the reactivity of the active hydrogen-containing composition, each composition is mixed with the polymeric polyisocyanate described in Example 1 at number 103 and poured manually into an aluminum mold having dimensions of 305 x 305 x 6 mm. The following table V shows the time it takes to gelatinize the mixture. All molded polymers are easily released from the mold and can be repeated.

Table V

Composition number Metal Eel gelatinization time (s)

AND Zinc stearate 14.5 VI Zinc dilaurate 13.0 VII Calcium stearate 15.0 VIII Cadmium stearate 15.0 IX Lithium stearate 26

The above results show that unacceptably high reaction rates can be avoided by using the internal release agents described above.

Example 4

An active hydrogen-containing composition X is prepared from the following components:

Component

Polyol C ¹ Ethylene glycol Diethylene glycol Triiaopropanolamine Zinc Laurate parts by weight

Glycerol-initiated primary poly (propylene oxide) triol with protected hydroxy groups, molecular weight 6000,

Active hydrogen containing compositions are prepared by mixing the amine and zinc laurate at a temperature of 80 to 110 ° C and then mixing the mixture with the remaining ingredients at room temperature. A homogeneous mixture is formed, «

Example 5

To 93 parts of polyol D (glycerol-initiated primary polypropylene oxide with 4900 protected hydroxy groups) was added 7 parts of tertiary amine A, the mixture was heated to 80-100 ° C with stirring and 3 parts of zinc dilaurate were added. The mixture is stirred until homogeneous and then cooled. 5 parts of a 15% dispersion of carbon black in polyol D, 4 parts of ethanenglycol, 2 parts of polyethylene glycol of molecular weight 2000, 0.65 parts of a 33% triethylenediamine catalyst solution in a glycol carrier and 15 parts of a blowing agent freon 11 (trichlorofluoromethane) ).

To 100 parts of the above mixture was added 35.2 parts of Mondur E-448 polyisocyanate, available from Mobay Chemical Corporation. The mixture was vigorously stirred for 2-3 seconds and spread into an untreated aluminum mold having dimensions of 305 x 305 x 13 mm, which is preheated to 43 to 49 ° C. The reaction mixture was heated to 51.7 ° C for 3 minutes and then removed from the mold. The polymer formed is quickly and easily removed from the mold. The object has a microcellular structure with an integral surface layer of 4.8 mm thickness.

Example 6

To 95 parts by weight of polyol E (glycerol-initiated primary polypropylene oxide and blocked hydroxyl groups of 4850 molecular weight) was added 6 parts of tertiary amine C (reaction product of aminoethylpiperazine with 6 moles of propylene oxide). The mixture is heated to 80 DEG C. and 3 parts of zinc laurate are mixed into it. After obtaining a homogeneous dispersion, the mixture is cooled and 20 parts of a styrene / acrylonitrile polymer dispersion in polyether polyol, 2.5 parts of water and 0.5 parts of triethylenediamine solution (amine catalyst) are added.

By reacting aliquots of the resulting composition containing active hydrogen with polyisocyanate PAPI 901 (polymethylene polyphenylene isocyanate available from Upjohn Polymer Chemical Division) at number 98, several molded articles having dimensions of 305 x 305 x 25 mm are produced. The reactions were carried out in aluminum form with an untreated surface at 43 ° C for 4 minutes. All products are easily detached and have good physical properties.

Example 7

Active hydrogen containing compositions are prepared from the following components:

Ingredient parts by weight

Polyol D 100

Tertiary amine C 8

Zinc Laurate 4

Ethylene glycol 4

Freon 11 (trichlorofluoromethane) 15

Triethylenediamine catalytic solution 0.15

The polyol D and the tertiary amine C are mixed, the mixture is heated to 80 [deg.] C., mixed with zinc laurate and mixed until a homogeneous dispersion is obtained. Then mix the remaining ingredients. The respective parts of the active hydrogen-containing composition are successively reacted with Mondur E-448 polyisocyanate at number 100 in aluminum form with an untreated surface for 4 minutes at 43 ° C. Wrought objects are easily detached.

Example 8

The active hydrogen-containing composition is prepared by mixing 30 parts of tertiary amine A, 35 parts of dibromneopentyl glycol and 2 parts of zinc dilaurate at about 95 ° C with nitrogen atmosphere until a solution is formed. The solution is cooled to 65 ° C and 45 parts of polyol E, 10 parts of diethylene glycol and 20 parts of neutral phosphorus polyol are added. A stable blend is formed, 1 part of a surfactant and 4 parts of an amine terminated polyol having a molecular weight of about 400 are added to give the molded article a green strength.

The resulting active hydrogen-containing composition is formed by reaction injection molding using an Accuratio VR HT-60 injection molding machine at 1.03 using Rubinate M as a polyisocyanate. The mold temperature ranges from 57 to 66 ° C. The forming time is 2 minutes. Molds of dimensions 3 x 254 x 254 mm are used. After 13 consecutive moldings have been easily demolded, the test is interrupted. All moldings have good physical properties.

Claims (7)

(1) the acid contains at least one lipophilic group which imparts intolerance to a substance containing multiple reactive hydrogen atoms; and 1. An active hydrogen-containing composition comprising i) at least one substance containing a plurality of reactive hydrogen atoms in a molecule in which it is dispersed or dissolved ii) an effective amount of an internal release agent comprising (a) a metal salt of a carboxylic acid, an amidocarboxylic acid, a phosphorous acid or a acid containing mountains, wherein: 2. The composition of claim 1, wherein the tertiary amine compound comprises a monoamine of the formula * (3-n) < ^(CH 2 ^CHRO ) A where XX represents a number from 1 to 5 n is 2 or 3, each of of symbols R independently represents hydrogen, halogen or an inertly substituted lower group; and R ' is an inertly substituted lower alkyl or aromatic pin. 2) the metal is selected from the group consisting of kovyΑ, IB, IIA and IIB metals of the Periodic Table of the Elements, aluminum, chromium, molybdenum, iron, cobalt, nickel, tin, lead, antimony and bismuth; b) a compatibilizing amount of a tertiary amine compound containing at least one tertiary nitrogen, wherein one or more hydroxyterminated poly (oxyalkylene) or alkanol groups are attached to the tertiary nitrogen atom. 3. The composition of claim 2, wherein the tertiary amino compound is triethanolamine, alkyldiethanolarain, alkyldi (isopropanol) amine or tri (isopropanol) amine, 4. Composition according to claim 1, characterized in that the tertiary amine compound comprises a diamine of general formula II,? 2-m) [H (OCHRCH ₂₎ - HR ^{2 R} (2-m) H - [(CH ₂ CHR0) _y H] _ffi (II ) where each of the symbols R * independently represents an inertly substituted lower alkyl or aromatic group, each of y being independently from 1 to 50, R is an inertly substituted alkylene radical or a divalent dialkylene ether or polyether radical and each of m is independently 1 or 2. 5. The composition of claim 4, wherein the tertiary amino compound is the reaction product of an alkylenediamine, a N-hydroxyalkylalkylenediamine or an amine-terminated polyether of from 1 to 50 alkylene oxide relative to the amine hydrogen. and CS 27334-3 B2 6. 5. The composition of claim 5 wherein the tertiary amine compound is the reaction product of ethylenediamine or hydroxyethylethylenediamine with from about 1 to about 3 moles of propylene oxide or a mixture of propylene oxide and ethylene oxide, calculated on the equivalent of the amine hydrogen. 7. Composition according to claim 1, characterized in that the tertiary amine comprises the reaction product aminoalkylplperazinu or bis (aminoalkyl) piperazine with 1 to 20 moles of C ₂ ^{"G Al} 4" alkylene oxides per mole aminoalkylplperazinu or bis (aminoalkyl) piperazine.