DE1229289B - Process for the manufacture of plastics containing urethane groups, including foams - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08g

German class: 39 b -22/04

Number: 1229 289

File number: F 45032IV c / 39 b

Filing date: January 22, 1965

Opening day: November 24, 1966

Plastics containing urethane groups and having various physical properties are used using the isocyanate polyaddition process from compounds with several active hydrogen atoms, in particular compounds bearing hydroxyl and / or carboxyl groups, and polyisocyanates, if appropriate with the use of chain extenders, crosslinking agents, blowing agents, Activators, emulsifiers and other additives, manufactured on an industrial scale for a long time (Ang. Chemie, A 59, 1948, p. 257; pocket book "Bayer-Kunststoffe", 2nd edition, 1959, p. 25ff.). It is possible according to these procedures, with a suitable choice of components, both elastic as well as rigid foams, lacquers, impregnations, coatings or elastomers.

Polyisocyanate-based plastics are preferably made by mixing liquid, if appropriate dissolved components produced, whereby one of the starting materials to be reacted with one another either mixed together at the same time or in a multi-stage process initially from a polyhydroxyl compound using an excess of polyisocyanate to prepare a pre-adduct containing NCO groups, then in further work steps, if necessary together with crosslinking agents and / or blowing agents, is transferred into the plastic.

Essential factors in the production of polyurethane plastics are viscosity, accessibility, Hydrophobicity and reproducibility of the required polyhydroxyl compounds.

There has been no shortage of attempts to find technically easily accessible phenols as addition components, d. H. as polyhydroxyl compounds, in the isocyanate polyaddition process for the production of plastics to be used by using high molecular weight resins produced by condensation with aldehydes, phenol-formaldehyde resins, Novolaks alkoxylated on the phenolic hydroxyl group under (alkaline) catalysis and thus converted into polyhydroxyl compounds with several aliphatically bonded hydroxyl groups had been. As a result of their higher molecular structure, they have polyhydroxyl compounds of this type high viscosities which make their application technically difficult, for example as foam starting materials make, while z. B. for paint production a considerable dilution with compared to NCO groups inert solvents is required. Higher proportions of alkylene oxide residues cause a reduction the viscosity, but at the same time lead to a reduction in functionality, i. H. the number of

Method of making urethane groups
comprising plastics, including
Foams

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Rudolf Merten, Leverkusen;

Dr. Günther Braun, Cologne-Flittard

Branches per unit of measure, which is undesirable in many cases.
On the other hand, it is known by reacting phenates with z. B. formaldehyde to produce the corresponding C-hydroxymethylphenolates, which, however, condense to higher molecular weight reaction products when heated or acidified. It is difficult to isolate them in pure form, so that such polyfunctional C-hydroxymethylphenols cannot be used without further ado like the normal alcohols for the production of higher molecular weight, stable polyhydroxyl compounds.

As has now been found, surprisingly, can be used to produce polyurethane plastics usable polyhydroxyl compounds based on hydroxylalkylated phenols in a simple manner by alkoxylation of phenols with at least one condensable C-H bond in o- or p-position to the phenolic hydroxyl group and aldehydes at pH values above 7 Hydroxymethylphenols can be obtained in a known manner.

The colorless and odorless polyhydroxyl compounds produced in this way may have high functionalities at low viscosities and are also perfectly compatible with the polyisocyanates and additives commonly used.
In contrast to the known polyhydroxyl compounds based on alkoxylated phenol-formaldehyde resins or novolaks, the polyhydroxyl compounds to be used according to the invention are obtained with comparable amounts of phenol, formaldehyde and propylene oxide, due to the different structure of the polyhydroxyl compounds, not only in greater yield, which for the economy of their use in the Foam manufacturing

609 728/442

3 4

speaks, also the hydroxyl content is higher, what per alkylene oxide simply without any isolation or

Weight unit a larger branching and purification, whereby per mole of originally

Provides degree of crosslinking in the polyurethane plastic. set phenolic OH group at least 1 mol

The average smaller molecule of alkylene oxide should be used,

size · - due to the different structure of the poly- S The alkoxylation takes place at temperatures below

hydroxyl compound - finally gives the already 120 ° C in the aqueous-alkaline solution

mentioned desired viscosity reduction. men, generally in the temperature range between

The invention accordingly provides a method 60 and 9O ⁰ C. After completion of the alkoxylation

for the production of urethane groups, the alkaline catalyst is neutralized,

Plastics, including foams, based on io z. B. with hydrochloric acid, sulfuric acid or phosphoric acid,

location of polyalkoxylated reaction products removed. By concentration in a vacuum and given

Phenols and aldehydes and polyisocyanates, and if followed by filtration, the finished products are obtained

optionally crosslinking agents, blowing agents or polyhydroxyl compounds as starting material.

further additives, with shaping, which generally means the proportions

is characterized in that set as polyalkoxylated reaction 15 so that the polyhydroxyl compounds one

products made from phenols and aldehydes those with an OH content of between 0.5 and 30, especially between

or in combination with other polyhydroxyl compounds 5 and 20%.

fertilize, which are used below 12O ⁰ C in the manufacture of the polyurethane plastics

situ by addition of alkylene oxides to 'in the alkali, the poly to be used according to the invention are

Lischen aqueous medium obtained hydroxymethyl 20 hydroxyl compounds alone or in admixture with

phenols from a) monohydric and / or polyhydric phenols other polyhydroxyl compounds are used. For this

with at least one in the o- and / or p-position to come, for example, the usual linear or

OH group located condensable C-H branched polyester, ζ. B. from adipic acid, sebacic

Bond and b) aldehydes have been obtained. acid, phthalic acid, maleic acid, monomeric, dimeric

The phenols used for the production of the starting or trimeric fatty acids and ethylene glycol, poly materials mono- or polyhydric phenols with min. ethylene glycols, propylene glycol, polypropylene glycol test one condensation against an aldehyde, butanediol, hexanetriol or glycerine, linear capable C-H bond in o- and / or p-position to or branched polyethers, e.g. B. based on ethylene ends OH groups used. Examples are oxide, propylene oxide or butylene oxide, polythioether, Phenol, cresols, xylenols, pyrocatechol, resorcinol, 30 polyacetals, adducts of ethylene oxides with im Hydroquinone, 4,4'-di-hydroxydiphenylmethane, 4,4'-di-general aliphatic polyamines, polyphosphites hydroxydiphenyl, 2,4'-dihydroxydiphenylmethane, according to French patent specification 1,333,026, alkoxy-ethylphenols or called tert-butylphenols. Her- lated phosphoric acids or aminonitrile ethers z. B. to be emphasized are phenol, cresols or xylenols. according to the German patent specification 1157 387 in question.

Examples of aldehydes are formaldehyde. Polyisocyanates are aliphatic or

Its various forms of delivery, acetal aromatic polyvalent isocyanates in question, z. B.

aldehyde, butyraldehyde or isobutyraldehyde to alkylene diisocyanates, such as tetra- or hexamethylene

to name. Especially formaldehyde (aqueous solution diisocyanate, arylene diisocyanates or their alkyl

or paraformaldehyde) should be emphasized. products such as phenylene diisocyanates,

The alkylene oxides generally used are ethylene- 40 naphthylene diisocyanates, diphenylmethane diisocyanates,

oxide, propylene oxide or butylene oxide, but also tolylene diisocyanate, di- or triisopropylbenzene

Styrene oxide or epichlorohydrin are used. Ethylene isocyanate or triphenylmethane triisocyanate, p-iso-

oxide or propylene oxide are particularly suitable. cyanatophenylthiophosphoric acid trieste ^ p-isocyanato-

In the production of the polyhydroxyl compounds phenylthiophosphoric acid triesters, aralkyl diisocyanates,

the individual components (aldehydes, 45 such as! - (isocyanatophenyty-ethyl isocyanate or the

Phenols, alkylene oxides) also in the form of their mixed xylylene diisocyanates, as well as the

genes can be used. various substituents, such as alkoxy, nitro, chlorine

The preparation of the polyisocyanates substituted as starting groups according to the invention, or furthermore material to be used polyhydroxyl compounds with less than the amount of polyhydroxyl carried out such that with the addition of alkaline 50 bonds with trimethylolpropane, hexanetriol, GIy catalysts, z. B. alkali metal or alkaline earth metal or butanediol modified polyisocyanates, metal hydroxides or carbonates, further mentioned in aqueous z. B. with phenols or bisulfite Medium the phenolic components with the masked polyisocyanate, acetal-modified polyaldehyde at temperatures below 120 ° C, if possible, isocyanates and polymerized isocyanates with isocyanates 0 and 80 ° C, condensed. Here 55 cyanurate rings.

can per mole of condensable o- and / or the production of urethane groups p-position C-H bond 1 mol of aldehyde used plastics from the polyhydroxyls described will; lower amounts of aldehyde lead to compounds and polyisocyanates otherwise occur incomplete hydroxymethylation, larger amounts according to the numerous processes known per se parts are also possible. The amounts of alkali 60, with or without a solvent, with or without chains, can be adjusted so that per mole of pheno-extender, crosslinking agent, propellant Lischer OH group a maximum of one equivalent or other auxiliaries, such as activators, emulga-alkali Is used, in general, rich gates, stabilizers, dyes, fillers or but smaller proportions, e.g. B. 5 to 25% of this amount, flame retardants.

completely off. After completion of the hydroxy 65 The amounts of Plyisocyanat used should

methylation, in which the water content largely generally at least the sum present

sway and z. B. varies between 5 and 80% equivalent to reactive hydrogen atoms,

can be, the further reaction takes place with the additional use of water as a driving force

A component for the production of foams is one that corresponds to the water content Use amounts of excess polyisocyanate. On the other hand, there can be more excess Fraction of isocyanate groups through polymerization or secondary addition reactions in the plastic structure to be built in. In the case of foaming, water and / or other blowing agents, such as azo compounds, low-boiling hydrocarbons, halogenated methanes or ethanes or vinylidene chloride, Find use. The reaction can be carried out in the presence of catalysts, e.g. B. amines, such as Triethylamine, dimethylbenzylamine, 1-dimethylamino-3-ethoxypropane, Tetramethylethylenediamine, N-alkylmorpholines or triethylenediamine, or metal salts, such as tin (II) acylates, dialkyltin (IV) acylates, acetylacetonates of heavy metals or Molybdenum glycolate. Emulsifiers are z. B. oxyethylated phenols or biphenylenes, higher sulfonic acids, sulfuric acid esters of castor oil or ricinoleic acid or oleic acid ammonium salts, of foam stabilizers are z. B. those with siloxane and alkylene oxide units or basic To name silicone oils. Coatings or impregnations can be made using inert solvents, such as esters, hydrocarbons, halogenated hydrocarbons or aromatics can be obtained.

Manufacture of the raw materials

General working regulation

After dissolving the phenol used in the specified amount of water and sodium hydroxide solution, at

ίο Temperatures between 20 and 40 ° C formaldehyde added as a 40% aqueous solution or paraformaldehyde and 8 to 10 hours at room temperature stirred.

Alkylene oxide is then added dropwise to the aqueous solution at the stated temperature in accordance with the reaction. After the addition, the added sodium hydroxide is neutralized with the calculated amount of aqueous hydrochloric acid or sulfuric acid, concentrated in vacuo at 8O ⁰ C and freed optionally substituted by filtration of solid fractions.

(The data in the table are parts by weight, unless otherwise stated, as phenol is found in A 8 and A 9 m-cresol, in A12 4-chlorophenol is used.)

No. phenol NaOH H ₂ O Formaldehyde
(40% aqueous
Solution) Ethylene
oxide Propylene
oxide temperature
with addition
⁰ C Raw-
yield 7.OH viscosity
cP / 25 ° A 1 188 80 200 255 500 90 to 100 750 19.8 1180 A 2 188 20th 200 255 - 500 90 to 100 754 18.2 15680 A 3 188 5 200 255 - 120 90 to 100 390 17.5 > 100,000 A 4 376 20th 20th 490 - 500 90 to 100 1023 16.9 > 100,000 A 5 376 20th 20th 490 - 1000 90 to 100 1510 16.9 17700 A 6 376 20th 20th 250 90 100 70 to 80 1534 15.2 6280 A 7 376 30th 30th 720 - 1500 70 to 80 2127 16.3 4740 A 8 216 15th 30th 540 - 550 80 932 20.0 71500 A 9 216 15th 30th 370 - 400 80 732 18.3 > 100,000 AlO 188 40 100 540 - 400 *) 70 840 5110 Alles 188 40 100 540 - 600 *) 75 950 192 12260 A 12 256 40 100 360 - 450 80 785 8940

*) A 10 contains ethylene oxide, A11 contains 1,2-butylene oxide.

example 1

50 parts of A 1 are permethylated with 50 parts of a propoxylated ethylene diamine (hydroxyl number 450), 1 part Aminoethylpiperazine, 0.5 part of polysiloxane-polyalkylene glycol ester and 2 parts sodium ricinus oil sulfate (50% water) mixed thoroughly.

After adding a solution of 40 parts of trichlorofluoromethane 148 parts of 4,4'-diphenylmethane diisocyanate (90%) give a hard foam with the following physical properties:

Volume weight 24 kg / m ³

Compressive strength 1.7 kp / cm ²

Impact strength 0.2 cmkp / cm ^a

Thermal flexural strength 152 ⁰ C _6q

Example 2

50 parts of A 2 are mixed with 50 parts of a propoxylated trimethylolpropane (hydroxyl number 550), 3 parts Ethyl morpholine, 0.5 part of polysiloxane polyalkylene glycol ester and 2 parts of sodium ricinus oil sulfate (50% water) stirred thoroughly. After adding a solution of 30 parts of trichlorofluoromethane in 152 parts 4,4'-Diphenylmethane diisocyanate (90%) gives a hard foam with the following mechanical properties Characteristics:

Volume weight 29 kg / m ³

Compressive strength 2.2 kp / cm ²

Impact strength 0.2 cmkp / cm ²

Heat bending strength 16O ⁰ C

Example 3

30 parts of A 3 are mixed with 70 parts of a propoxylated trimethylolpropane (hydroxyl number 380), 3 parts Dimethylbenzylamine, 0.5 part polysiloxane-polyalkylene glycol ester and 2 parts sodium ricinus oil sulfate (50% water) mixed thoroughly. After adding a A solution of 30 parts of trichlorofluoromethane in 121 parts of 4,4'-diphenylmethane diisocyanate (90%) is obtained a fine-pored rigid foam with the following physical properties:

Volume weight 28 kg / m ³

Compressive strength 1.6 kp / cm ^a

Impact strength 0.2 cmkp / cm ²

Thermal flexural strength 125 ⁰ C

Claims (1)

7 8 Example4 examples 50 parts of A4 are with 50 parts of a propoxy- 50 parts of A 8 are with 30 parts of a propoxylated Trimethylolpropane (hydroxyl number 380), 2 parts trimethylolpropane (hydroxyl number 550), 20 parts permethylated aminoethylpiperazine, 0.3 parts of len permethylated ethylenediamine (hydroxyl number Polysiloxane-polyalkylene glycol ester and 6 parts of Na-5,450), 2 parts of dimethylbenzylamine, 0.3 part of polytrium ricinus oil sulfate (50% water) thoroughly stir siloxane polyalkylene glycol ester and 6 parts sodium, Ricinus oil sulfate (50% water) stirred thoroughly. After adding 159 parts of 4,4'-diphenylmethane. After adding 186 parts of 4,4'-diphenylmethane diisocyanate (90%) a tough hard diisocyanate is obtained (90%) a tough hard foam is obtained With the following physical properties: Foam with the following physical properties: stocks: Volume weight 50 kg / m ³ Volume weight 45 kg / m ³ Compressive strength 3.9 kp / cm ² Compressive strength 3.2 kp / cm ² Impact strength 0.3 cmkp / cm ^2, impact strength 0.3 cmkp / cm ² Thermal flexural strength 151 ° C ⁵ Thermal flexural strength 181 ° C Example5 example9 50 parts of A 5 are mixed with 30 parts of a propoxy 30 parts of A 9 are mixed with 70 parts of an adipine trimethylolpropane (hydroxyl number 550), 20 partic acid, phthalic anhydride, oleic acid and trimethylol len of a propoxylated ethylenediamine (hydroxyl number propane-made polyester (hydroxyl number 380), 450), 2 parts of tetramethylethylenediamine, 0.5 parts of 2 parts of permethylated aminoethylpiperazine, 0.5 parts Polysiloxane-polyalkylene glycol ester and 2 parts of Nalen polysiloxane-polyalkylene glycol ester and 2 parts triumricinus oil (50% water) mixed thoroughly. Sodium ricinus oil sulfate (50% water) thoroughly After stirring in a solution of 30 parts of Tri-25 mixes. chlorofluoromethane in 143 parts of 4,4'-diphenylmethane After adding a solution of 30 parts of trichloro diisocyanate (90%) gives a rigid foam fluoromethane in 123 parts of 4,4'-diphenylmethanediiso- with the following mechanical properties: cyanate (90%) produces a fine-pored hard Volume weight 30 kg / m ³ , foam with the following mechanical properties Compressive strength 2.2 kp / cm ^{2 3} ° ^scüaIten · Impact strength 0.2 cmkp / cm ² density 30 kg / m ³ Heat bending strength 154 ° C compressive strength 1.0 kp / cm ² Impact strength 0.2 cmkp / cm ² B is ρ ie 1 6 ₃₅ Thermal flexural strength 142 ° C 70 parts of A 6 are mixed with 30 parts of a propoxylated ethylenediamine (hydroxyl number 450), 3 parts of B e 1 s ρ 1 e 1 10
Methylmorpholine, 0.5 parts of polysiloxane-polyalkylene- 100 parts by weight of an adduct of tolylene-2,6-glycol ester and 2 parts of sodium ricinus oil sulfate (50% and -2,4-diisocyanates of trimethylolpropane with water) were stirred thoroughly. 40 17.65% NCO in 100 parts by weight of glycol Dissolved after the addition of a solution of 30 parts of trichloro monomethyl ether acetate. 50 parts by weight of each fluoromethane in 131 parts of 4,4'-Diphenylmethandiiso- so obtained solution are then with a) 8.9 Ge cyanate (90%) gives a tough rigid foam parts by weight A11, b) 10 parts by weight A 5, c) 10 parts by weight with the following physical properties: parts by weight A 6 mixed and the solutions up τ,. ,. „ _Λ1,, 45 paper, textile or metal applied. When drying _Volume weight 30 kg / m ³ _b / _{room temperature} ^& _{you get after 24 hoursL} c ^ · ΐ · 1 · ϊ υ ι ™, 2 solvent-resistant coatings, by baking at Impact strength 0 3 cmkp / cm ² _m ^ _22QaQ ^ ^ _{dry temperature} Heat bending strength 140 C ₂ g ^^ _or _ _{15 minutes reduced we} 4 _Q _ Example 7 ⁵ °. . Example 11 70 parts of A 7 are mixed with 30 parts of a polyester prepared from adipic acid, phthalic anhydride, oleic acid and trimethylol- 100 parts by weight of A 5 with stirring with propane (hydroxyl number 380), 125 parts by weight of 4,4'-diisocyanatodiphenylmethane, 3 parts of permethylated diethylenetriamine, 0.5 Parts 55 offset and placed in a mold. In the exothermic polysiloxane-polyalkylene glycol ester and 2 parts Na reaction, a solid and insoluble formtrium ricinus oil sulfate (50% water) is thoroughly embodied,
mixes. After adding a solution of 30 parts Tri-claim:
chlorofluoromethane in 133 parts of 4,4'-diphenylmethane 60 diisocyanate (90%) gives a fine-pored process for the production of urethane groups Rigid foam with the following mechanical plastics, including foam shafts: substances based on polyalkoxylated Reaction products from phenols and aldehydes Volume weight 29 kg / m ³ _{65 and} polyisocyanates and, if necessary, compressive strength 1.9 kp / cm ² wetting agents, blowing agents or other impact strength 0.2 cm kp / cm ² additives, with shaping, thereby Thermal flexural strength 142 ° C indicates that as polyalkoxylated 9 10 Reaction products from phenols and aldehydes one in o- and / or p-position to the OH group those, alone or in conjunction with other condensable C-H bonds located Polyhydroxy compounds are used, which and b) aldehydes have been obtained. below 12O ⁰ C in situ by addition of Alkylene oxides in an alkaline aqueous medium 5 Hydroxymethylphenols obtained from a) a. and / or polyhydric phenols with at least German Auslegeschriften No. 1121 801, 1156 227. 609 728/442 11.66 © Bundesdruckerei Berlin