MXPA00003044A - Improved internalrelease agents for producing polyurethane moulded bodies - Google Patents

Abstract

The invention relates to improved internal release agents with a base consisting of special ammonium or metal salts of phosphoric acid esters, ammonium salts of carboxylic acids and/or ammonium or metal salts of sulphonic acids for producing cellular or compact polyurethane moulded bodies. Said moulded bodies are optionally reinforced with glass fibres and/or natural fibres. The polyurethane moulded bodies produced according to the inventive method can be laminated or coated with other materials.

Description

Improved internal mold release agents For the production of polyurethane molding bodies Background of the invention: The present invention relates to improved internal mold release agents for the manufacture of polyurethane, cellular or compact molding bodies, especially those that are Laminated or coated with other materials. Internal mold release agents for the production of polyurethane moldings, in particular polyurethane foams, have been known for a long time. Thus, for example, DE-A 21 21 670, 19 53 637 and 23 07 589 describe demolding agents for the manufacture of foams consisting of salts of aliphatic carboxylic acids with preferably primary amines or amines containing amide or amide groups. ester, whose total number of carbon atoms is at least 25. In US Pat. No. 4,024,088, internal organometallic release agents are mentioned, inter alia, organophosphorus compounds containing at least 8 carbon atoms in the molecule. In addition, internal release agents based on metal salts of a carboxylic acid, amidocarboxylic acid, phosphoric acid or boric acid in combination with certain tertiary amines are known from US Pat. No. 4,098,731. US 4,098,731 also describes internal mold release agents in the manufacture of polyurethane molding bodies based on salts of carboxylic acids with at least 8 atoms REF .: 33001 carbon and tertiary amines. Furthermore, according to US 4,220,727, internal demolding agents are known, which, among other components, are constituted by metal salts of fatty acids and certain quaternary aralkylammonium salts. Zinc carboxylates with long chain carboxyl residues (8 to 24 carbon atoms) as internal mold release agents are known, for example, from US 4,519,965, US 4,581,386 and US 4,161,861. In addition to this, the use of higher fatty acid esters as internal mold release agents is known from US 4,130,698. The internal demolding agents known hitherto have the most diverse disadvantages in the manufacture of polyurethane, cellular or compact molding bodies. Thus, the metal salts of higher carboxylic acids tend after some time to crystallization and to the formation of gels if they are added to the starting components for the manufacture of polyurethane molding bodies, whereby the viscosity and the flow behavior of the polyurethane masses are modified inconveniently. With other release agents, especially those with apolar or polar components, a two-phase system is formed due to the often insufficient solubility of the components in the starting materials of the polyurethane, which leads to difficulties in processing the molding compositions. of polyurethane.

Another major disadvantage of the internal demolding agents known up to now is the so-called mold structuring which, in long cycles, involves the progressive aggregation of mold contours. The fine contours of the mold adhered and added with the polyurethane masses in the molds used can only be restored to their original state by a subsequent costly cleaning, which naturally leads to the interruption of production. It is therefore the object of the present invention to provide internal mold release agents which avoid the above-described drawbacks of current internal mold release agents and thus have an improved properties picture. Accordingly, it is an object of the invention to provide improved internal mold release agents for the production of polyurethane molding bodies composed of a) Ammonium or metal salts of phosphoric acid esters of formula (I) wherein R represents d-C10 alkyl, preferably C4-C8, X means OR1, where R1 is equal to R or 0"Y + and Y represents NH4 and N (R2, R3, R4, R5), wherein R2 to R5 are identical or different and they mean hydrogen or Cx-C10 alkyl, the C10 alkyl radical being mono or polysubstituted with OR6 or NR6R7 having Re and R7 the meaning of hydrogen or alkyl d-do, or meaning R2 to R5 wherein R8 and R9 are the same or different and represent d-C10 alkyl or hydrogen, m means an integer from 2 to 4 and n an integer from 1 to 5, Y represents metals of the first major group of the periodic system of elements (Mendeleev), Ammonium salts of carboxylic acids of formula (II) R10COO "Z + (II) wherein R10 represents hydrogen, dC ^ alkyl or C6-C10 aryl, which can optionally be substituted with d-C3 alkyl groups, and Z has the meaning of Y with the exception of the indicated metals of the first main group of the periodic system of the elements, and / or O Ammonium or metal salts of sulfonic acids of formula (III) where R11 has the meaning of R10 and Y has the meaning indicated in formula (I). As the d-C19 alkyl radicals of the formulas mentioned above, mention may be made in particular of n-butyl, iso-butyl, n- and iso-pentyl, 2-ethylhexyl, octyl, n-propyl, iso-propyl, ethyl, methyl, nonyl , decyl, especially n- and iso-butyl, n- and iso-pentyl, 2-ethylhexyl, octyl. The remainder Y of the formulas indicated above preferably represents NH4® N (CH3) 3H®, N (C2H5) 3H®N (C2H5) 4®, HO-CH2CH2-N (CH3) 2H® NH2 (CH2) 3N (CH3) 2H®, (CH3) 2N- (CH2 ) 3-N (CH3) 2) H®, HC II-NH- (CHi) -N (CH3) 2H-CH3O- (CH2) 2-N (CH3) 2H® HO-CH2-CH2-NH3®, (HO-CH2-CH2) 2NCH3H®, (HO-CH2-CH2) 2NH2® Preferably m represents an integer from 2 to 3 and n from 1 to 3. As metals of the first major group of the periodic system of the elements are to be cited especially: lithium, sodium, potassium. As release agent for the production of polyurethane molding bodies, the following salts are suitable: or HC NH- (CH 2) 3-N (CH 3) 2 H + (C 4 H 90) 2 P (0) 0" O NH2C -NH- (CH2) 3-N (CH3) 2H (C4H90) 2P (0) O HOCH2-CH2NH3 + (C4H9O) 2P (O) O " NH 2 - (CH 2) 3 N (CH 3) 2 H + (C 4 H 9 O) 2 P (O) O " ®NH3- (CH2) 3-N (CH3) 2H + 2 (C4H9O) 2P (O) O ' HO-CH2-CH2-NH3 + (C8H170) 2 P (O) O " HO-CH2-CH2-N (CH3) 2H + (C8H17O) 2P (O) O " NH 2 - (CH 2) 3 N (CH 3) 2 H + (C 8 H 17 O) 2 P (O) O 2 HC-NH- (CH 2) 3-N (CH 3) 2 H + 2 (C 4 H 80) 2 P (0) 0 HÓ-CH2-CH2-N (CH3) 2H + C7HI5-COO- HO-CH2-CH2-N (CH3) 2H + C6H13-COO- HO-CH2-CH2-N (CH3) 2H + CH3SO3- HO- • CH- CH¿- -N (CH.j) 2H * Na + (C4H9O) 2P (0) O- H-C-NH- (CH2) 5-N (CH3) 2H + (C4H90) 2 P (0) 0" O H C-NH- (CH2) rN (CH3) 2H + CH3- "S03" The following salts are very especially preferred: O H- C- NH- (CH 2) 5-N (CH 3) 2 H + (C 4 H 90) 2 P (0) 0" OR II H-C-NH- < CH2) -N (CH3) 2H + C7H15- COO 'H As mentioned, the demolding agents according to the invention are suitable for the manufacture of polyurethane, cellular or compact molding bodies. The polyurethane molding bodies can be produced in a customary manner by reacting a) polyisocyanates or polyisocyanate prepolymers with b) at least one compound having at least two groups reactive towards isocyanates, with a molecular weight of 400 to 10,000, given the case in the presence of chain extenders of molecular weight from 32 to 399, it being possible to carry out the reaction of components a) and b) if necessary in the presence of water and / or organic expansion agents, stabilizers, activators, as well as other adjuvants and additives known by themselves. In addition to the aforementioned additives to the polyurethane compositions obtained, both organic and inorganic fillers can be added to the processing to reinforce the molding bodies. For example, glass fibers, wollastonite, sisal, flax, jute, hemp and / or wood chips are to be mentioned. Stabilizers are primarily polyethersiloxanes. These compounds are structured in such a way that a copolymerization of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane moiety. Such foam stabilizers are described, for example, in US Pat. Nos. 2 834 748, 2 917 480 and 3 629 308 and in US Pat. No. 2,917,480. Catalysts include, for example, tertiary amines. , such as triethylamine, tributylamine, N-methylmorpholine, N-ethyl-morpholine, N, N, N ', N '-tetramethyl-ethylenediamine, pentamethyl-diethylenetriamine and higher homologs (DE-A 2 624 527 and 2 624 528), 1,4-diazabicyclo- (2, 2, 2) -octane, N-methyl-N' - dimethylaminoethylpiperazine, bis- (dimethylaminoalkyl) -piperazines, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylbenzylamine, bis- (N, N-diethylaminoethyl) -adipate, N, N, N ', N' - tetramethyl-1,3-butanedimine,, N, N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole, monocyclic and bicyclic amidines as well as bis- (dialkylamino) -alkyl ethers such as 2,2-bis- (dimethylaminoethyl) ether, but also metal carboxylates such as potassium acetate or potassium octoate. As catalysts, organometallic compounds, in particular organic tin compounds, can also be used. Organic tin compounds are also considered to be sulfur-containing compounds, such as di-n-octyl tin ercaptide, preferably tin (II) salts of carboxylic acids, such as tin (II) acetate, tin octoate (II) ), tin (II) ethylhexate and tin (II) laurate, and tin compounds (IV), eg dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or diacetate of dioctyltin. To obtain for example cellular polyurethane molding bodies, the reaction of component a) with component b) can be carried out as mentioned with water and / or organic blowing agents. Suitable organic blowing agents are all known blowing agents, in particular hydrocarbons, such as n-pentane, c-pentane and iso-pentane, and also fluorinated hydrocarbons, such as tetrafluoroethane and monofluorodichloroethane. Polyisocyanates or polyisocyanate prepolymers (component a)) include known aliphatic, cycloaliphatic, araliphatic polyvalent isocyanates, preferably aromatics, such as those described, for example, in EP-A 364 858. Toluene diisocyanates and diphenylmethane diisocyanates are particularly suitable. , their modification products or their corresponding prepolymers, which may be modified with urethane, urea, biuret, allophanate, cabodiimide or uretdione groups. In particular, mention may be made, as aromatic polyisocyanates, of 4,4'-diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate or types of crude methyldiisocyanate. As reaction component b), polyols or mixtures of polyols having an OH number of 20 to 1800 are particularly suitable, with an average OH value of a total of 300 to 900 being adjusted. The individual components b) have an average molecular weight of 400 to 10,000. In particular, polyols of the group of polyether polyols and polyester polyols such as those obtained by the addition of alkylene oxide, such as ethylene oxide or propylene oxide, to polyfunctional initiators, such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, sorbitol, have proved successful. ethylenediamine or by condensation of dicarboxylic acids, such as adipic acid, succinic acid, glutaric acid, suberic acid, sebacic acid, maleic acid, phthalic acid, with hydroxyl components, especially bifunctional, such as ethylene glycol, propylene glycol and diethylene glycol. Chain extenders which can be used in the reaction together with component b) are especially suitable compounds with molecular weights of 32 to 399. They are to be mentioned: ethylene glycol, 1,4-butanediol, glycerin, trimethylolpropane adducts, glycerin, sorbitol with propylene oxide and / or ethylene oxide. The release agents according to the invention are usually used in amounts of 0.5 to 20, preferably 1 to 15 parts by weight, based on 100 parts by weight of reactive component b). Using the internal mold release agents according to the invention, for example, polyurethane molding bodies can be produced by the foaming process by working in closed molds in which a polyisocyanate reaction mixture foams., compounds with reactive hydrogen atoms, water and / or organic blowing agents and, where appropriate, other coadjuvants and additives using the above-mentioned internal mold release agents at mold temperatures of preferably approx. 60-75 ° C. The manufacture of polyurethane mold bodies is described, for example, in Kunststoffhandbuch (Manual de Plastics), vol. 7, Polyurethane, 3rd updated edition, Cari Hanser Verlag, Munich / Vienna, 1993. The manufacture of PUR molding bodies correspondingly reinforced with natural fiber mats or glass fiber mats from PUR reaction mixtures free of agents of expansion or almost free of expansion agents is carried out according to the process of compression molding at mold temperatures of approx. 95-135 ° C. As already mentioned above, the demolding agents according to the invention provide an optimum demolding performance and a good creep and impregnation behavior when using the components a) and b) for the preparation of the molding compositions and have no tendency to the structuring in the mold, that is to say a soiling of the mold is prevented by depositions of the polyurethane masses.

Examples Description of the raw materials 1) Release components (CD) according to the invention O 1 * H2N-C- H- (CH ^ CHCHa ^ H * (C <H90) 2P02" From 210 g (1 mol) of dibutyl phosphate by dropwise addition of 145 g (1 mol) of 3-dimethyl-aminopropylurea at 30 ° C: acid number: 158 mg KOH / g P.f .: 105 ° C 2. HC-NH- (CH3) 3-N (CH3) jH * (C, H9?) 2PO, From 210 g (1 mol) of dibutyl phosphate by dropwise addition of 130 g (1 mol) of 3-dimethyl-aminopropylformamide at 30 ° C: acid number: 165 mg KOH / g P.f .: 35 ° C HOC2H4-N (CH3) 2H + (C4H90) 2P02- From 210 g (1 mol) of dibutyl phosphate by dropwise addition of 89 g (1 mol) of N, N-dimethyl-ethanolamine. acid number: 187 mg KOH / g 4. H? C2H4-N (CH3) 2H + (C8H, 70) 2P02- From 322 g (1 mol) of bis-2-ethylhexyl phosphate by dropwise addition of 89 g (1 mol) of N, N- dimethyl-ethanolamine. acid number: 135 mg KOH / g . H? CH2CH2N (CH3) 2H + C7H15-COO- From 144 g (1 mol) of 2-ethylhexanoic acid and 89 g (1 mol) of N, N-dimethylethanolamine. acid number: 240 mg KOH / g 6. HOCH2CH2N < CH3) 2H-t- CH3C6H4-S03- From 172 g (1 mol) of 4-methylbenzenesulfonic acid and 89 g (1 mol) of N, N-dimethylethanolamine. acid number: 213 mg KOH / g II) Polyols Polyol 1 Polyethylene of OH 470 value, prepared by the addition of propylene oxide to a starter mixture of 80 parts by weight of sugar, 15 parts by weight of propylene glycol and 5 parts by weight water weight. Polyol 2 Polyolether of OH number 380, prepared by the addition of propylene oxide to a starter mixture of 45 parts by weight of sugar, 50 parts by weight of diethylene glycol, 5 parts by weight of water. Polyol 3 Polyethylether of OH 865, prepared by the addition of propylene oxide to trimethylolpropane. Polyol 4 Polyol ether of OH 515 index, prepared by the addition of propylene oxide to propylene glycol. Polyol 5 OH 475 polyol ether, prepared by the addition of propylene oxide to a starter mixture of 80% sugar and 20% propylene glycol. Polyol 6 Polyethylether of OH 1000, prepared by the addition of propylene oxide to trimethylolpropane. Polyol 7 OH 640 polyol ether, prepared by the addition of propylene oxide to ethylene diamine as initiator. Polyol 8 OH OH 480 index polyol, prepared by the addition of propylene oxide to ethylene diamine as initiator. Polyol 9 OH-index polyol ether 42 prepared by addition of 86% propylene oxide and 14% ethylene oxide to propylene glycol as initiator.

III Polyisocyanates Polyisocyanate prepared by reaction of fatty acid polyester C of DE-OS 2 307 589 to form the prepolymer according to DE-OS 2 307 589 with an NCO content of 28.4%. Examples of Reaction Components were used for the fabrication of thin-plate coating parts and prototypes. The manufacturing was carried out under the PUR processing conditions. The temperatures of the raw materials in the processing were between 25 and 30 ° C. Formulation 1 Polyol 1 40 parts by weight Polyol 2 50 Polyol 3 40 Comp. CD 1 10 Dibutyltin dilaurate (DBTL) 0.15 K 0.5 acetate (25% in SDR) Polyisocyanate 1 129 Approximately 250 g of formulation 1 were applied on both sides of a mat of natural sisal / flax fibers (1: 1) of a surface weight of 1,000 g / m2 and then compressed in a steel mold with a surface area of approx. 1 m2 at a temperature of 125-135 ° C for 60-80 sec. up to a wall thickness of 1.8-2 mm. After the opening of the mold the molded part was removed from the mold without mold release adjuvants. More than 250 desmóldeos were made without visible structure in the mold, separation occurred in the first release. Formulation 2 Analogous to formulation 1, but instead of CD 1, 10 parts by weight of CD 2 were used and processed accordingly. The molded part left the mold in the first demoulding without problems, no structuring of matter was observed in the mold after a long period of production. Formulation 3 Analogous to formulation 1, but instead of CD 1, 8 parts by weight of dissolved CD 3 component were used and processed accordingly. The piece of coating left the mold without problems, no structuring of matter in the mold was observed either after a long period of operation. Formulation 4 Analogous to formulation 1, but instead of CD 1, 8 parts by weight of component CD 4 were used. The molding part separated somewhat more unfavorably from the mold than with formulation 3, no structuring was observed in the mold after a long period of production. Formulation 5 Analogous to formulation 1, but instead of CD 1, 10 parts by weight of the CD 5 component were used. The door covering left the mold from the beginning without problems, no structuring was observed in the mold after a long period of time. manufacturing. Formulation 6 Analogous to formulation 1, but instead of CD 1, 10 parts by weight of component CD 6 were used. The door coating left the mold without problems, no structuring was observed in the mold after a long period of operation. The good processing properties of the aforementioned formulation variants were accentuated in such a way that in molds with partial structuring due to the use of formulations based on conventional internal mold release compositions, a good demoulding effect was immediately provided and the structuring disappeared. in the course of subsequent manufacturing. Furthermore, the problem-free gluing of fasteners and plastic inserts was advantageous. These were inserted into the mold and during the compression of the molding they were joined with the PUR matrix. The takeoff tests showed good adhesion properties with cohesive breaking behavior.

All the formulations were stable for at least 6 months and without loss of reactivity. When using in formulations 1 to 6 according to US Pat. No. 4,585,803, Example 3, as a demolding agent 5 parts of zinc stearate dissolved in 5 parts of amine 5 as a solubilizer, a clear solution was first obtained, however, in the course of a week became cloudy, gelified and experienced a strong increase in viscosity. It was left to process and apply on the natural fiber mats used substantially worse. Also the creep behavior and the impregnation of natural fiber mats were adversely affected in the compression process.

Formulation 7 Polyol 3 30 parts by weight Polyol 6 20 Polyol 9 33, 5 Polyurax SR 242 (Fa.OSi) 2, 3 Thancat AN 10 (Fa.Air Products) 1, 3 Acetic acid 0.3 Water 1, 4 Baydur Schwarzpaste DN 3, 3 (Fa Bayer AG) Component CD 4 8 Polyisocyanate 1 154 The formulation was introduced under the usual conditions for the processing of polyurethane starting materials in a steel mold of dimensions 600 x 1000 x 3 mm containing I insert a glass mat with a surface weight of 600 g / m2. The temperature of the mold reached approx. 75 ° C. It resulted in a total apparent density of 950 kg / m3. The demolding time amounted to 120 sec. The molding pieces could be removed without problems with the first part of the mold open without producing a product structuring in the mold after numerous demolitions. Formulation 8 Formulation analogous to 7, in which the CD 4 component was replaced by 8 parts by weight of CD 1 component dissolved by heating. The plate fell from the mold when opened. No structuring was observed in the mold by progressive deposition of the raw material even after the production of numerous pieces.

The further processing of the manufactured molding parts, such as foaming of semi-hard PUR foam systems, laminating of foils and embellishments, eg based on ABS, PVC, TPO and blocked textile materials and gluing with PUR glues 2C was performed without problems without laborious post-treatments. According to the procedure can be manufactured interior and exterior parts of cars such as door coverings, seat covers and trays, linings of columns A, B, C, hangers, coverings of luggage compartments, sliding roof boxes, instrument dashboards and insulation of spaces for engines.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (3)

1. The iiwap áán has been described. Prior to this, it is claimed that it is necessary to carry out the month: 1. Internal mold release agents for the production of polyurethane molding bodies, co-mingled with a) Ammonium or metallic salts of esters of phosphoric acid. formula (I) characterized because; R represents alkyl d-do, preferably C4-C8, X signifies OR1, where R1 is equal to R or 0"Y + and Y represents NH4 and N (R2, R3, R4, R5), where R2 to R5 are the same or different and they mean hydrogen or C 1 -C 10 alkyl / wherein the d-C 10 alkyl moiety may be mono or polysubstituted with OR 6 or NR 6 R 7 having R 6 and R 7 the meaning of hydrogen or C 1 -C 10 alkyl, or meaning R 2 to R 5 wherein R8 and R9 are the same or different and represent alkyl d-do or hydrogen, m means an integer from 2 to 4 and n an integer from 1 to 5, or Y represents metals from the first major group of the periodic system of the Elements (Mendeleev), Ammonium salts of carboxylic acids of formula (II) R10CC - Z + (II) wherein R10 represents hydrogen, C-C19 alkyl or C6-C10 aryl, which can optionally be substituted with CX-C3 alkyl groups, and Z has the meaning of Y except for the indicated metals of the first major group of the system periodic of the elements, and / or ammonium or metal salts of sulphonic acids of formula (III) where R11 has the meaning of R10 and Y has the meaning indicated in formula (I).
2. 2. Internal mold release agents for the production of polyurethane molding bodies according to claim 1, characterized in that the internal release agents are used in amounts of 0.5 to 20 parts by weight, based on 100 parts by weight of the reactive component b ).
3. 3. Use of internal mold release agents according to claims 1 and 2 for the manufacture of polyurethane molding bodies reinforced with glass fibers and / or natural fibers. Improved internal mold release agents for the manufacture of polyurethane molding bodies Summary of the invention The present invention relates to improved internal demolding agents based on ammonium or metal salts of esters of phosphoric acid, ammonium salts of carboxylic acids and / or ammonium or metal salts of sulfonic acids, special, for the manufacture of bodies of molding of cellular or compact polyurethane, if necessary reinforced with glass fibers and / or natural fibers. The polyurethane molding bodies produced by the process according to the invention can be laminated or coated with other materials.