DE1493891A1 - Process for the production of polyols and rigid polyurethane foams from these polyols - Google Patents

Description

A 86 2U

Jefferson Chemical Company, Inc, Houston, Texas, V.St.A.

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Process for the production of polyols and rigid polyurethane foams from these polyols

The invention relates to a process for the production of nitrogen-containing polyols and the production of polyurethanes based on these polyols.

It is known to produce 1st Polyurethanhartechaumstoffe by reacting a polyisocyanate with a polyol bi a hydroxyl number ranging van about 300 s 900 has · Various polyols were used for this purpose * dl · bi · Polyurethansohäume produced today are jedooh not ▼ ollbefriedigend.

BATH ORIGINAL

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For example, polyurethane foams are needed for many applications, which are either self-extinguishing or practically non-flammable. To achieve these properties, you have to mufit previously separate fire retardants, for example organic phosphorus compounds, are added Compounds exposed to plasma equipment are usually in such amounts are required that the properties of the finished polyurethane show are adversely affected.

When producing a satisfactory rigid polyurethane foam, it is also necessary to carefully select one tee catalyst system su use «Iw generally consists of one or more tertiary amines, the catalyst or which in some cases is mixed in a known manner with organic tin compounds. Those used as catalysts tertiary amines give the finished foam in most cases Cases an unpleasant smell of amine.

In the patent application J 25 779 IVd / 39c of the same applicant, a new class of polyols was described with which "numerous disadvantages of the polyols previously used are avoided. These polyols are nitrogen-containing polyols which are obtained by adding an alkylnoxyde to a Mannich condensation product of a phenolic compound with formaldehyde and an alkanal amine.

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These polyols are sufficiently reactive that no separate Catalyst for the production of rigid polyurethane foams is required. Foams made from these polyols are characterized by higher fire resistance and in some cases, without the use of separate fire retardants, self-extinguishing or non-separable foams.

For certain applications, however, these are polyols too responsive. Beiapielaweise becomes larger when pouring SchaurastUcke developed so much heat through the exothermic reaction with the help of these polyols that charring or crack formation occurs in the center of the piece.

Ks have now been found nitrogen-containing polyols that somewhat are less reactive and can be produced more easily than the polyols described in patent application J 25 779 IVd / 39c, but which are still so reactive that no separate catalyst is required for the production of polyurethanes. The implementation of the polyols obtainable according to the invention with a polyisocyanate is less exothermic. I can therefore use for purposes for which the most reactive Polyol · are not suitable.

BATH ORIGINAL

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H93891

According to the invention, the polyols are obtained in a step process from a phenol, formaldehyde, ammonia and an alkylene oxide, all of which are readily available and inexpensive starting materials. The phenol, formaldehyde and ammonia are first reacted at a temperature below about 100 ° ^ü phenol to a Aminoraethyl. The crude aminomethyl phenol is then alkoxylated by reaction with an alkylene oxide at a temperature between about 30 and 20O ⁰ O.

Phenols can be used for the method according to the invention, which are unsubstituted in at least one of the o- and p-positions to the phenolic hydroxyl group. the other positions can be unsubstituted or substituted by groups, among those in the formation of the aminomethylphenol applied conditions are not reactive. Substituents that may be present include, for example Alkyl, cycloalkyl, aryl, halogen, nitro, haloalkyl and hydroxyalkyl groups .. Suitable phenols stud also seiche

the formula

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ο. 5 ~

In which R is hydrogen, halogen, nitro groups, or alkyl, cycloalkyl, aryl, haloalkyl or hydroxyalkyl groups each having 1 to 12 carbon atoms and is at least one that of the phenolic hydroxyl group o »and p Positions uneubstituted 1st. The reactivity of the phenol is reduced by the presence of many or space-filling substituents. For examples of suitable phenolic compounds include phenol, o-, m ~ and p-creeol, ethylphenol, o ~ bromophenol, o ~ chlorophenol, p ~ phenylphenol, o-chloromethylphenol. 2,6-dichlorophenol, 2-nltrophenol, ρ-cyclohexylphenol, 3,5-dimethylphenol, nonylphenol and 2- (2-hydroxypropyl) phenol « Phenol, chlorophenol, nonylphenol and cresols are preferred as the starting material.

The formaldehyde is preferably in the form of paraforraaldehyde used". Water-containing formaldehyde, for example as Formalin solution can be used but is preferably avoided. Introduced with the respondents In the first alkoxylation stage, water increases the likelihood that some alkylene oxide will mix with water Implementation of polyglycols. Because of this, too anhydrous ammonia preferred to aqueous ammonia inclusions.

The aminomethylphenols are made by adding dao Phenol and formaldehyde at a temperature of about 20 to

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10O ⁰ Cj ₁ preferably 40 to 60 ⁰ G mixed and then anhydrous ammonia is added to the mixture at such a rate that the reaction temperature is maintained. The ratio of phenol to formaldehyde is 1: 1, while an excess of ammonia of about 1: 1 to about 2 moles is used to ensure complete conversion. "The use of excess formaldehyde generally leads to the formation of a resinous polymer"

As a product from the conversion of phenol, formaldehyde and Ammonia is obtained a complex mixture, of which exact composition is unknown. The main component of this mixture is an aminomethylphenol. The mixture is therefore referred to herein as an aminomethylphenol and by the formula

2 0 9 812/1617

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U93891

- 7 reproduced, in which R has the meaning given above.

Attempts to remove the unreacted ammonia and the water formed during the reaction from the crude reaction product in vacuo led to decomposition. The product is therefore preferably alkoxylated in a 2-step process. First, a portion of the alkylene oxide is added to the crude reaction product under non-catalytic conditions. In this first λ Teilalkoxylierung about 1 mole of alkylene oxide is added per mol aminomethylphenol. Although more alkylene oxide can be added in this first stage, it is no longer necessary. This addition is to 'performed 200 ⁰ C at a temperature of about 30 microns. Water and other volatiles are removed at a temperature of up to about 125 ⁰ C under a partial vacuum. Spell it sets the treated product under non-catalytic conditions at a temperature of about 30 to 200 ⁰ C further alkylene oxide to, se "that a product with a Hydrozylzahl in the desired range of about 300 is formed through '675, surprisingly it was found that practically no reaction of the alkylene oxide with the free ammonia or water occurs in the first alkoxylation stage. If all of the oxide, which does not react in too long a time, is added in the second alkoxylation stage, a product with the desired hydroxyl number is generally obtained. All of the oxide can be done in one stage before removing the ammonia

209812/1617

and water can be added, but this procedure increases the likelihood that some oxide will be with it Ammonia or water reacts «.

Examples of alkylene oxides which can be used according to the invention are ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and Bpichlorohydrin and hetero mixtures and blocked mixtures thereof. One can also use glycidol because of the presence of the Hydroxyl groups, however, complex mixtures are obtained.

Ba the aminomethylphenol as used herein from consists of a mixture, the alkylene oxide adduct of aminomethylphenol is also a mixture Purposes this polyol can be regarded as a triol with the exception of cases in which the phenol has one or more hydroxyalkyl substituents contains or in which glycidol is used. The polyol can therefore be expressed by the formula

O (CH ₂ CHO) _x -H

i ·

H- (OCHCH ₉ ) -S- (CH ₀ -CHO) -H 1 c * · [^

E ^f R '

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H93891

cn Q η. ■ '

represent, wherein χ, y and ε each mean at least 1 and the sum of χ + y + ζ is 3-8, R each hydrogen, halogen, a nitro group or alkyl, cycloalkyl, aryl or haloalkyl group having 1 to 12 carbon atoms and R 'denotes hydrogen, methyl, ethyl, chlorine thy 1 or phenyl groups or mixed groups of this type.

The following examples illustrate the invention without restricting it.

example 1

A 11 l stirred autoclave was charged with 1880 g (20 mol) of anhydrous phenol and 600 g (20 mol) of paraforaaldehyde. The autoclave was evacuated, rinsed with nitrogen and heated to 40 ⁰ C · and the agitator was put in motion. Anhydrous ammonia was fed at a rate such that the reaction temperature is between 40 and 60 ⁰ C was maintained until a total of 544 g (32 mol) of trains "were set. The product was stirred for 1 hour and then propoxylated at 50 to 60 ⁰ C and 1,160 g (20 mol) of propylene oxide. This Reaktionsmiechung was digested for 45 minutes and then stripped under vacuum at 110 ⁰ C and pressure of 8 mm volatiles. The product was dried at 110-120 ⁰ C propoxylated further 3.22 kg of propylene oxide so that a total of 34 # 38 kg of

BATH ORIGINAL

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- ίο -

Were oxide reacted · The mixture was digested to completion Oxydzugabe 4 hours at 120 ⁰ O and then dried in vacuo at 110 ° E and 6 mm pressure of volatile components is freed The product had a Hydroxylaahl of 483 egAöH / f _f a viscosity at 25 ⁰ C of 98 400 cF. and a total ton of 2.30 milliequivalents per gram.

Example 2

Sin with a mechanical stirrer, a thermometer and a Trockeneisklihler equipped three-necked flask was charged with 376 g (4 mol) of phenol and 120 g (4 moles paraformaldehyde. They mixture was heated to 4O ⁰ C and ammonia was fed at such a rate that the temperature between 40 and 60 ° C. The solution became clear and the ammonia supply was continued for a further 30 minutes. The weight increase of the reaction mixture shows that 92 g of ammonia were converted or absorbed. Part (372 g) of the crude reaction product was transferred into a 1 1 flask and 166 g of propylene oxide were added at 40 to 100 ° 0 · After had reacted βion the propylene oxide, water and other volatiles at a temperature of 100 ⁰ C in a water jet vacuum were removed "

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A portion dee partially propoxylated, volatiles liberated product (362 g) was transferred to a HUhrautoklaven and further 230 g Propylenpxyd were added at 100 to 120 ⁰ C. After completion of the reaction, the product at 11O ⁰ C and 2 mm pressure of volatiles was released. The product was a yellow viscous liquid with a hydroxyl number of 525 mg / KOH / g, an osmometrically determined molecular weight of 321 and a total amine content of '2.92 equivalents per gram. The functionality of the product, calculated from the hydroxyl number and the molecular weight, was 3 «

Example 3

A polyoil with a hydroxyl amount of 445 mg / KOH / g was made from phenol , paraformyldehyde, ammonia and 1 _# 2 ~ butylene oxide

manufactured. ' *

Example 4 : From o-chlorophenol, paraformaldehyde, aaawniak and

ozyd was obtained a polyol with hydroxyl steel 482 **

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- 12 - Example 5

Made from nonylphenol, paraforaaldehyde, ammonia and propylene oxide A polyol bit of a hydroxyl grade of 344 was obtained. The nonylphenol used was a commercially available one Product that mainly consisted of the p-isora, however also contained something o-isomer.

The polyols obtainable according to the invention can be used as einsige polyol component in the production of polyurethane foam or a conventional polyol used up to 70 $> with. Numerous representatives of these customary polyols are known, including, for example, polyols which are prepared by reacting an alkylene oxide with a polyhydroxy compound, which can be a carbohydrate or an aliphatic or aromatic compound with about 3 to 8 hydroxyl groups, for example hexanetriol, pentaerythritol , Sorbitol, methyl glucosite, sucrose and 1,3,3-trie (hydroxypropoxyphenyl) propane. It is also possible to use alkylene oxide adducts of certain amines, for example of ethylenediaoin, aminoethylpiperasine or triethanolamine. Polyesters with hydroxyl end groups are also used in cases for the production of rigid polyurethane materials.Such polyesters are usually made from dibasic acids, e.g. phthalic or adipic acid and diols or triols, e.g. diethylene glycol, glycerine or tri

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"he-

methylolpropane produced.

For the production of foams from the polyols obtainable according to the invention, customary processes are used for Foam production used with the exception that no separate catalyst is required. The production of

Polyurethane foams suitable polyisocyanates fuels M medium, foam stabilizers and fire retardant fabrics are committed. Both single-stage and quasi-prepolymer processes can be used.

When used to manufacture rigid urethane foams in the frame the invention the quasi ~ prepolymer process is used the quasl prepolymer preferably prepared by a conventional polyol of the type described above reacts with such an amount of polyleocyanate that, based on the total amount about 20 to 40 free weight of polyisocyanate used Ieocyanate groups are present in the quasi-prepolymer obtained as the reaction product. Then a polyol obtainable according to the invention is added to the quasi-prepolymer in the presence of a foam stabilizer, a propellant and, if necessary, a flame-retardant, in such an amount that about one Hydroxyl group on a free isoyanate group in the quasi-prepolymer comes.

OftenJGfNAL

209812/1817

The most commonly used foam stabilizers are organic silanes or siloxanes, usually silicone-glycol copolymers. A compound of the formula

R · Si / 0- (R ₂ SiO) _n "(oxyalkylene) _m R"

in which R, R ³ and R "are alkyl groups with 1 to 4 carbon atoms, η is 4-8 and m is 20-40 and the oxyalkylene groups are derived from ethylene or propylene oxide.

Blowing agents used in the manufacture of urethane foams are described, for example, in US Patent Specification 3,072,582 « Propellants are generally volatile liquids, for example fluorocarbon compounds. Sometimes the puffing of foams is done by using a small one Reached amount of water and an excess of polyisocyanate. The water will sit with the Ieocyanat with the release of Carbon dioxide, which acts as a propellant.

Fire-retardant substances that can be incorporated into the foamable mixture can be divided into 2 types. the the first type includes substances that are produced by mere mechanical

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»Laugh to be incorporated. These include, for example, trie (chloroethyl) phosphate -pho e, trie (2,3 Dibrompropy 1) phosphate Diamaoniumphosphat _t, various halogenated compounds and antimony oxide. The second type of fire retardant substance falls over substances that are chemically incorporated into the polymer chain. Examples of this type include derivatives of hexachlorendo ethylene tetrahydrophthalic acid (chlorodioic acid) and various phosphorus-containing polyols.

To produce a polyurethane foam, an amine catalyst, for example triethylenediamine, TrI. ethylamine, Dlmethylpiperazln, H-methylmorpholine, N-XthylMorpholin or N, N, N ³ , N'-tetraethylbutanediarain are used. However, such a catalyst is unnecessary when using the polyols obtainable according to the invention. If a faster rise time or tack-free time is desired, one of the amine catalysts described above and / or an organic metal catalyst can be added. Organometallic catalysts suitable for this purpose are generally known. The most frequently used catalysts of this type are organic tin compounds, for example stannous octoate, 3tannolaurate, di-butylsilnidilaurate and dibutyltin oxide. · ·.

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The polyisocyanates which can be used to produce polyurethane foams are also known. Such Polyieocyanat sweokmäßigerweise is an organic aromatic or aliphatic polyisocyanate, for example diphenyl-4,6,4 ^f ~ triieocyanat, 3 '3'-Diohlor ~ 4,4'-hiphenyl-diisooyanat, diphenyl diisocyanate, Ä'thylen-diisooyanat , Propylene-1,2-diisooyanate, octa-

methylene-diieooyanat, 1,4-tetramethylene diisocyanate, m-and p-Phenvlen diieocyanat, xylylene-1,4-diisocyanate ~ _f xylylene-1, 3 = diisocyanate, naphthylene-1,4-diisocyanate, 2,4-and 2,6-toluene diisocyanate, o ^ o ¹ -, o, p 'and p, p ^e -diphenylmethane-' diisocyanate, p-isooyanatobenzyl isocyanate, polymethylene ^ polyphenyl isocyanate and Geraische thereof.

The following examples illustrate the production of polyurethane foams using those obtainable according to the invention Polyols in a one-step process. All foams were made as follows: All ingredients with Except for the polyisocyanates were mixed together. then the polyisocyanate was added, the mixture θ seconds at

/ stirred at 4200 rpm with a 2 HiLift stirrer and then ⁷ poured an open mold into which it was allowed to expand «. The formulations, the processing values and the foam properties are given in the following table. "A polymethylene polyphenyl isocyanate was used as the polyisocyanate"

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bath

Table I.
important parts a

Poiyol, example 1 148 - » 200 170 180 ,. .162 RS ». 200 234 Poiyol, example 2 ··· 2
55 ... 1
3
55 200 Polyoi, example 3 - 1
3
56 Polyoi, example 4 45 200 35 Poiyol, example 5 240 200 1
3.
58 150 67 Polyisocyanate 240 3
57 ■ 80 230 ^ Triethylenediamine
- * Sehauia ata facilitator
K>
^ Propellant 35 200 °! processing 75 165 Rahmzeit, see.
■ M 300 135 CB
σ rise time, see. 240 3 Freedom from tack aside, see. 5. Physical properties

. Dense, g / om ³ (lfc./?t. ⁵ ) 0.0314 (1.96) 0.0311 (1.94) 0.0333 (2.08) 0.02560.60) 0.0417 ( 2.60)

Compressive strength, kg / om

(Ib./®) 2.24 (32.0) 2.35 (33.6) 2.46 (35.5?) I, V2 (16.0) 2.95 (42.2)

2 ^ω

inefficiency ke / om * 3.08 (44.0) 3.89 (55.5) 3.23 (46.1) 3.28 (46.8) 1.76 (25.1) - »

Table I (portrayal)

166 0.127 EJ 175 to σ 160 0.170 d 169 0.160 ■ ' heat deformation temp. C. 0.66 (0.26) (S .: 10.4 (4.1) S.E. + IT B .. K-factor 91 0.124 90.8 80.0 Burn rate
cm / min * (in- / min. ♦) S.E. fi closed cells week
-1.00 - -1.50 -2.00 Dimensional stability -1.96 -1 -2.23 -3.30 S -18 ⁰ O (O ⁰ P.) dry, 1
CO
- * ¥> change
IO
*** linear 0.0 -3 .49 . +0.23 -5.36 _ Volume K) , 57 weight +1.49
+1.99
-0.49 , 24 +3.00
+4.06
-1.34 -H, 49
+2.70
«4.13 32 ⁰ C (180 ⁰ P), dry,
1 week . + O
+2
-O cd £ pre-change
^σ linear
3 volumes
O
ζ weight , 99
, 16
, 48

8.4 (3.3) 90.1

Table I continued)

70 ⁰ C (-.58 ⁰ P), rel. Humidity 1> Lino & rs change 12 hours 24 hours 1 V / oche

12 hours 24 hours 1 toilet ^;

ic ^v te change

12 hours 24 hours

+ 1.00 +1 "00 + 1.99

■ ii, 00 '«• 1.00 -f-3.01

-0.24 ~ 0 _t 48 -0 * 49 -0.95 -0.73 -1.67

+1.01
+2.01
+3.02

+0.50
41.76
+3.04

-0.70
-1.64

+1.01 +1.51 +2.01

+2.02 +2.19 +3.20

ί 1 week

> »ASTM 1692-59T. S.S. means self-extinguishing and N.B. non-burning.

-3.11 4.66

+0.5C +1.49 +2.49

+1.00 +2.51 +4.39

-1.89

As can be seen from the table, the polyols obtainable according to the invention are also used without the use of special ones catalysts excellent polyurethane hard foam obtain. Bas burning behavior and dimensional stability These rigid polyurethane foams are particularly noteworthy. It should also be emphasized · that the foam is made of the polyol based on o-chlorophenol without adding any special Fire retardant is not burning «.

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Claims (1)

•1. Process for the production of nitrogen-containing poly oils, characterized in that there is an external ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin and heterogemic and blocked mixtures thereof beetehendea alkylene oxide with an aminomethylphenol of formula in which R in each case denotes hydrogen atoms, halogen atoms, nitro groups or alkyl, cycloalkyl, aryl, haloalkyl or hydroxyalkyl groups each having 1 to 12 carbon atoms, where at least one of the positions o- or p-position to the hydroxyl group is unsubstituted, at a temperature in the range from about 30 to about 200 ⁰ C. 2 · Process according to Claim 1, characterized in that an aminoethylphenol is used which is obtained by reaction ORIGINAL 209812/1617 of ammonia, formaldehyde and a phenol of the formula wherein R is as defined above and at least the sine has been obtained at a temperature below about 11O ⁰ C o to the hydroxyl group or ρ-Ρtändigen is unsubstituted positions. 3 »Method according to claim 1, characterized in that the alkylene oxide is propylene oxide and an aminomethylphenol of the formula given in claim 1, wherein each R is hydrogen. 4 «Process according to claim 1, characterized in that the alkylene oxide is a mixture of propylene oxide and Ethylene oxide used 5. The method according to claim 1, characterized in that BATH ORIGINAL 209812/1617 U93891 ■ to produce the nitrogen-containing polyol in two stages, with part of the alkylene oxide being added in each stage. 6. Process for the preparation of a polyurethane, characterized in that one uses an organic polyisocyanate converting a nitrogen-containing polyol which has been produced by the process according to any one of claims 1 to 5. f 209812/1617 bad original