DE1149163B - Process for the production of polyurethane foams - Google Patents

Description

INTERNAT.KL. C 08 g

GERMAN

PATENT OFFICE

H 44712 IVc / 39 b

REGISTRATION DATE: JANUARY 25, 1962

NOTICE
THE REGISTRATION
AND ISSUE OF
EDITORIAL: MAY 22, 1963

The invention relates to a process for the production of polyurethane foams from organic polyisocyanates and polyesters of polymeric and monomeric fatty acids having 14 to 88 carbon atoms as well as other auxiliaries, depending on the selection 5 and proportions of the constituents primarily the for known polyester production used carboxylic acids, elastic, semi-rigid or rigid products can be obtained.

The production of foams from polyisocyanates, polyesters and polyester amides is known Crosslinking agents in the presence of tertiary amines and / or tin compounds, with very predominantly Polyester of adipic acid come to use. It's also no longer new, in place of adipic acid or similar low molecular weight dicarboxylic acids with an unsaturated aliphatic dicarboxylic acid Use 36 carbon atoms by dimerizing higher unsaturated fatty acids has been received. Those generated on this basis with the necessary aid of crosslinking agents Polyurethane foams are characterized by a significantly improved resistance to the effects of moisture during use and storage. Since there are fundamental structural differences between these long-chain and the commonly used, low molecular weight dicarboxylic acids do not exist, this effect was solely due to the reduction in the proportion of ester groups in the process products expected.

However, working with this long-chain dicarboxylic acid also has significant disadvantages, which consist in the fact that crosslinking agents must be used in the production of foam had to and that the production of the designated dicarboxylic acid in sufficient technical purity was associated with a lot of effort.

Surprisingly, it has now been found that it does not matter at all to maintain the degree of purity of the long-chain dicarboxylic acid required up to now, that it is also not even necessary to use exclusively dicarboxylic acids, but rather that polyurethane foams with very different functionality can be used with polyesters made from mixtures of mono- and polycarboxylic acids can produce with excellent and largely variable properties, provided that the average molecular weight of the polyester is between 750 and 6000 and suitable mixing ratios of the carboxylic acids with 14 to 88 carbon atoms have been observed. This is all the more surprising as, according to the previous view, the use of monocarboxylic acids due to processes for production
of polyurethane foams

Applicant:

Harburger Fettchemie
Brinkmann & Mergeil GmbH,
Hamburg-Harburg, Seehafenstr. 2

Dr. Josef Baltes, Hamburg,

and Dr. Friedrich Weghorst, Hamburg-Harburg,

have been named as inventors

Prevention of foaming appeared impossible. Furthermore, there is no need for the one according to the invention Process the use of crosslinking agents, so that the production is foamed Polyester urethanes considerably simplified.

The invention accordingly provides a process for the production of polyurethane foams Conversion of polyesters, which are condensation products of glycols and carboxylic acids, and in part can be replaced by polyethers, with polyisocyanates in the presence of wetting agents, water and optionally other blowing agents and a tertiary amine and optionally fillers with the characteristic that as polyester polycondensation products with an average molecular weight between 750 and 6000 and a hydroxyl number between 25 and 150 and an acid number below 4, made from glycols and a mixture of monocarboxylic acids and polycarboxylic acids with 14 to 88 carbon atoms of the following composition;

Monocarboxylic acids with 14
up to 20 carbon atoms .. up to 50 parts by weight

Dicarboxylic acids with 36

to 44 carbon atoms

(dimer fatty acids) 10 to 70 parts by weight

Tricarboxylic acids with 54

up to 60 carbon atoms

(trimeric fatty acids) 10 to 70 parts by weight

Tetracarboxylic acids
and higher with more than
60 carbon atoms to 30 parts by weight

be used. The carboxylic acid mixtures used to produce the polyester are created by

309 597/351

weight are the proportions of carboxylic acid mixture and glycol have to be adjusted so that the The hydroxyl number of the polyester is between 25 and 150, preferably between 40 and 90.

The polyesters required can also be obtained from the esters of the carboxylic acid mixtures, preferably the Methyl esters, made by alcoholysis with glycols, have become more notable Result in advantages. Not only can the reaction

Polymerization of unsaturated fatty acids with
16 to 24 carbon atoms or their esters
during known polymerization processes. Highly unsaturated fatty acids such as linoleic acid are excellent,
Linolenic acid, eleostearic acid, licanic acid, the higher
unsaturated fatty acids of the marine animal oils as well as those from
isolated-unsaturated fatty acids by isomerization
available conjugated unsaturated fatty acids of the
Polymerization accessible, in which monounsaturated fatty acids, such as oleic acid and palmitoleic acid, can participate to varying degrees under considerably gentler conditions than the acid. As the usual esterification, they serve as the starting material, which also allows partial conversion of these fatty acids, so that a retaining fat or the fat part of the ester groups obtained therefrom is retained. These occur acids or esters, so that, as is well known, the resulting polymers, when reacted with polyisocyanates, are always mixtures of monocarbons that do not react, and the molecular parts concerned

the polyester thus act as an internal plasticizer. In addition, this method of preparation has enabled the functionality of the polyesters to be adjusted in a targeted manner, so that from this point of view, too, other dimeric, trimeric, tetrameric, etc. fatty acids are known 20 possible variations with regard to the carboxylic acid and unsaturated nature. The proportions of or ester mixtures are given, the individual carboxylic acids of such mixtures are each
subject to considerable fluctuations depending on the type of starting material and the polymerization process. Usually contents of 25 positions each are observed
30 to 70% monocarboxylic acids and polycarboxylic acids. will.
In the latter, in turn, dimers, trimers,
tetrameric etc. fatty acids occur and the individual
polymeric fatty acids differ from case to case

30th

represent acids and polycarboxylic acids or their esters. The polycarboxylic acids consist of dicarboxylic acids, Tricarboxylic acids, tetracarboxylic acids and higher acids, also under the designation

The other components used in the process according to the invention correspond those commonly used to make polyurethane foams

The following organic polyisocyanates can be used:

2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, Ethylene diisocyanate, propylene diisocyanate, propylene 1,2-diisocyanate, Butylene diisocyanate,

Ethylidene diisocyanate or mixtures of these diisocyanates.

Small amounts of triisocyanates, tolylene triisocyanate or diphenyl ether triisocyanate can also be used.

make up the majority.

To dimer fatty acids in the so far for the foam production Both the polymerisation products have to achieve the required technical purity practically completely freed from the monocarboxylic acids as well as the starting material and type 35 of the polymerization process or the remaining polycarboxylic acid mixtures in are processed in a technically cumbersome way. All of this requires expensive technical measures and also means that only a fraction of the starting material used is the intended use can be found, while the remainder is difficult and only for low-value Products can be exploited. how

Depending on the properties required, the foam cyanate 45 may be present.

substances is a changeable composition of the To catalytically accelerate the conversion

Fatty acid or ester mixture used, which is between isocyanate groups and the reactive still significantly facilitated by the fact that for the groups of polyester and the reaction between the same purpose always several of the possible, within isocyanate groups and water are tert. Amines The combinations 50 resulting from the above limits are used, primarily trialkylamines, N-alkylmorpho usable are. It is also possible to use polyester line or tert. Alkylarylamines.

Batches of different carboxylic acid compositions To ensure the water distribution in the foam

To be used in a mixture to achieve the desired mixture and thus also the pore size of the foam-foam properties to reach. To regulate the substance, wetting agents are used, such as

The polyesters required are usually made up of lecithin, alkylphenol polyglycol ethers, or silicone oils. Esterification of the carboxylic acid mixtures with glycols The propellant usually functions through the

has been manufactured. Suitable glycols are e.g. B. Reaction between isocyanate groups and water Ethylene glycol, diethylene glycol, triethylene glycol - released carbon dioxide. In addition, you can also Ethylene glycol, diethylene glycol, triethylene glycol or low-boiling substances are used in the higher polyethylene glycols, propylene glycol, poly- 60 reaction temperature of foam production, propylene glycol, Vapor trimethylene glycol, butylene glycol, primarily fluorinated hydrocarbons, or neopentyl glycol and mixtures of these It is also possible to use some of the

Glycols. The average molecular weight of the polyester coming from higher polyglycols such as polyester should be between 750 and 6000 and preferably between polyethylene glycols and polypropylene glycols, too 1500 and 4000 lie. Their acid number must replace itself and in this way polyester / polyether understandable keep within low limits and should preserve the urethane.

Do not exceed the range between approximately 0.1 and 3. For the production of the polyurethane foams

In accordance with the desired average molecular weight, the components described are

5 6

The proportions used are derived from the following dimeric fatty acid, 29.0% trimeric fatty acid and

Statement. 23.0% tetrameric and higher polymeric fatty acids,

Parts by weight and 496 g of ethylene glycol were, if necessary, after

Polyester 100 addition of 5 g esterification catalyst (concentrated

Polyisocyanate 15 to 100 ⁵ sulfuric acid, toluenesulfonic acid or the like), [under nitrogen

,. substance or carbon dioxide] with stirring and reflux

tert. Amine U, 5-4 _{erMtzt It was dk temperature of the} R _ea ktions-

Wetting agent 0.5 to 2 mixtures slowly increased. Once they are around 120 ° C

Water reached 0.2-10, water began to distill over. the

ίο temperature of the reaction mixture was now further

To produce a foamable mass, it is increased up to 200 ° C and at this temperature all components with the exception of the can be held until no more water passed over. The Ver-

Polyisocyanate are mixed together. Such permanent product was a viscous liquid with

Mixtures are then made with the polyisocyanate having a hydroxyl number of 53.4 and an acid number of 1.8.

intimately mixed and poured onto it or with the help of 15

a spray gun or in some other way distributed polyester B or applied. But you can also use part of the _,,. ,, _,,,,, reacting the amount of polyisocyanate used with the reaction product of diethylene glycol and the polyester component to form a prepolymer, adding the various auxiliaries to this mixture of fatty acid methyl esters and then polymerizing 20 3685 g of a fatty acid methyl ester mixture with the remaining polyiso product, consisting of 19, Convert 4% of the amount of monomeric fatty cyanate. The reverse route is also feasible for methyl acid esters, 32.3% dimeric fatty acid methyls, by converting part of the amount of polyester used for the ester, 31.6% trimeric fatty acid methyl ester and application with the 16.7% tetrameric and more highly polymeric fatty acid polyisocyanate into this reaction product 25 methyl esters and 954 g of diethylene glycol were mixed in with the auxiliaries except water and then 3 g of sodium methylate as a transesterification catalyst, the mixture with the remaining polyester portion and heated (under nitrogen) with stirring and reflux, the intended amount of water to react. The reflux condenser was doing with 70 to 90 ⁰ C. Additional blowing agents charged with the help of spray warm water. As soon as the temperature guns of suitable construction are introduced. 30 of the reaction mixture reached about 100 ⁰ C, then began taking place at atmospheric pressure with or methanol distill over which the foam rising condenser was precipitated in a abohne application of external heat. Deformation. The resulting foam can be tempered in accordance with the escape of the released, but usually the exothermic reac- methanol, if the temperature of the retention heat is increased enough to allow a sufficiently crosslinked action mixture up to 200 ° C and keep the product for a long time . at this temperature until all of it has become free

A particular advantage that according to the invention was removed from methanol. The thickened foam left behind is that when the reaction product was liquid, it had a hydroxyl number ordinary temperature, d. H. at room temperature, of 84.9 and an acid number of 0.2. and directly on the spot, for example with a 40

Spray gun and, if necessary, with the aid of polyester C

shaping elements, can be produced. _,. ,, _... ,,. . ,,

In this manner, producible foams can _c reaction product of diethylene glycol and also with fillers and dyes, such as chalk, heavy Sojaolfettsauremethylesterpolymerisationsprodukt late, kieselguhr, carbon black or colored pigments, equipped 45 4912 g turned gestures one of Sojaölfettsäuremethylester which are expediently of the polyester wonnenen polymerization, Consists of containing component mixed with 27.3% monomeric fatty acid methyl esters, 42.6% polyisocyanate before the reaction. dimeric fatty acid methyl ester, 22.1% trimeric fatty

The foam acid methyl esters and 8.0% tetrameric and higher which can be produced by this process Substances show good and variable physical 50 polymeric fatty acid methyl esters, have been turned into counter properties insofar as elastic, semi-rigid and waited by 4 g of sodium methylate as transesterification rigidity Foams in any gradation obtained in the same catalyst with 1060 g of diethylene glycol can be. They also have a special way of producing polyester B. Shelf life in a humid atmosphere. led, implemented. The polyester obtained had the

The following examples explain the hydroxyl number according to the invention is 40.8 and the acid number is 0.4. proper procedures. All specified proportions

are, unless otherwise stated, parts by weight. Polyester D

Production of the poly-reaction product of ethylene glycol and used as starting materials

"",. "",. c fatty acid polymerisation product

esters, for the production of which there is no ^Do

Protection is sought after 3600 g of a fatty acid polymerisation product

consisting of 8.2% monomeric fatty acids, 61.8%

Polyester A dimeric fatty acid, 21.3% trimeric fatty acid and

",. ,, γ,,,,, 8.7% tetrameric and higher polymeric fatty acids,

Reaction product of ethylene glycol _{6 were mk 620g} ethylene glycol in the same way,

and carboxylic acid _{mixture as described in the preparation of} polyester A,

3600 g of a fatty acid polymerization product, implemented. The polyester obtained had the hydroxyl

Consists of 35.5% monomeric fatty acids, 12.5% number 111.8 and the acid number 2.1.

Polyester E.

Reaction product from diethylene glycol uno. Fatty acid methyl ester polymerization product

2718 g of a fatty acid methyl ester polymerization product, consisting of 4.3% monomeric fatty acid methyl esters, 11.9% dimeric fatty acid methyl ester, 55.8% trimeric fatty acid methyl esters and 28.0% tetrameric and higher polymeric fatty acid methyl esters, were with 424 g of diethylene glycol in the same way as described for polyester B, implemented. The proportions of diethylene glycol and fatty acid methyl ester polymerization product were chosen so that only some of the methyl ester groups of the polycondensation product reacted; while the remainder was preserved. The polyester thus produced had a hydroxyl number of 51.8 and an acid number of 0.5.

Polyester F

Reaction product of polypropylene glycol and fatty acid polymerisation product

900 g of a fatty acid polymerization product, consisting of 9.2% monomeric fatty acids, 44.6% dimeric Fatty acid, 26.9% trimeric fatty acid and 19.3% tetrameric and higher polymeric fatty acids, were reacted with 4200 g of polypropylene glycol (average molecular weight 1200), as in the Production of the polyester A described. The reaction product obtained was a mixture of Polypropylene glycol ester and excess polypropylene glycol and showed the hydroxyl number 71.2 and the acid number 1.2.

Polyester G

Reaction product of ethylene glycol and fatty acid methyl ester polymerization product

184 kg of a polymerization product of fatty acid methyl esters, consisting of 14.1% monomers Fatty acid methyl esters, 59.6% dimeric fatty acid methyl ester, 16.3% trimeric fatty acid methyl ester and 10.0% tetrameric and higher polymeric fatty acid methyl esters were mixed with 28 kg of ethylene glycol in Presence of 100 g of sodium methylate as a catalyst in the same way as in the preparation of the Polyester B described, implemented. The polyester obtained had a hydroxyl number of 74.3 and an acid number 0.6.

The analytical characteristics of the polyesters are summarized below.

Hydroxyl number
Acid number ...

53.4
1.8

84.9
0.2

Polyester C DIE

40.8
0.4

111.8 2.1

51.8 0.5

71.2 74.3 1.2 0.6

Production of the foams

In the production of the foamable compositions, the polyester, the tert. Amine, water and Wetting agent (lecithin or alkylphenol polyglycol ether), if necessary fillers (chalk) and pig-

ments (soot), intimately mixed. Then the diisocyanate was added, at a high shear rate mixed within 15 to 30 seconds and poured into a mold of the desired shape. The latter mixing process was also done in a

Appropriate spray gun made from which the mixture was injected into the mold. Within Complete puffing occurred in 2 to 6 minutes and the foam was free after 10 to 40 minutes can be removed from the mold. The final

However, crosslinking was only possible after storage for several days at normal temperature, i.e. H. at room temperature, achieved.

The composition and properties of the various polyurethane foams are in the

Listed below, in which the quantities are parts by weight.

Polyester A, parts

Alkylphenol polyglycol ethers, parts.

Lecithin, parts

Water, parts

Triethylamine, parts

Filler (chalk), parts

Pigment (carbon black), parts

4,4'-diphenylmethane diisocyanate,
Parts

Foam properties

Foam weight, kg / m ³

Polyester B, parts

Alkylphenol polyglycol ethers, parts.

Lecithin, parts:

Water, parts

Triethylamine, parts

Filler (chalk), parts

Pigment (carbon black), parts

4,4'-diphenylmethane diisocyanate,

Parts

2,4-tolylene diisocyanate, parts

Foam properties

Foam weight, kg / m ³

300 3

10

40

170

elastic 65 to 70 300
6th

6th
80

180

elastic
75 to 80

300

100
2

160

rigid
70 to 80

300

15th

16

200 2

200

rigid 65 to 70

300 300 300 300 300 4th 6th - - - - 10 18th 20th 6th 8th 8th 10 12th 6th 8th 6th 12th 8th 60 120 120 240 120 1 2 2 2 - 180 200 160 120 180 - - 40 80 - elastic elastic semi-rigid semi-rigid rigid 80 to 85 55 to 60 50 to 55 60 to 65 70 to 75

300

20th

20th

10

200

260

rigid 60 to 65

ίο

Polyester C, parts

Polypropylene glycol

(Molecular weight 1200), parts. Alkylphenol polyglycol ethers, parts.

Lecithin, parts

Water, parts

Triethylamine, parts

Filler (chalk), parts

Pigment (carbon black), parts

4,4'-diphenylmethane diisocyanate,

Parts

Foam properties

Foam weight, kg / m ³

300

5
60

150

elastic
70 to 75

300

12 6

200

elastic 50 to 55

250
50

10
6th

7th
160

220

semi-rigid
up to 60

250 50

12th

12th

200

240

semi-rigid to

Polyester D, parts

Alkylphenol polyglycol ethers, parts.

Lecithin, parts

Water, parts

Triethylamine, parts

Filler (chalk), parts

4,4'-diphenylmethane diisocyanate,
Parts

Foam properties

Foam weight, kg / m ³

300
6th

185

highly elastic
60 to 65

300 6

120

210

highly elastic 80 to 90

300

16

100

150

rigid
up to 80

300

180

240

rigid up

Polyester E, parts

Alkylphenol polyglycol ethers, parts.

Water, parts

Triethylamine, parts

Filler (chalk), parts

Pigment (carbon black), parts

4,4'-diphenylmethane diisocyanate,
Parts

Foam properties

Foam weight, kg / m ³

300

8th
12th

8th
100

210

elastic
65 to 70

300 4 7 6

40 1

150

elastic 60 to 65

300
4th
8th
5

120

200

semi-rigid
up to 75

300 6

12 6

180

220

semi-rigid to

Polyester F, parts

Alkylphenol polyglycol ethers, parts

Lecithin, parts

Water, parts

Triethylamine, parts

Filler (chalk), parts

4,4'-diphenylmethane diisocyanate, parts

Foam properties.
Foam weight, kg / m ³

300

8 10

100 200

semi-rigid 60 to 65

300

16

10
160
240

semi-rigid
up to 75

Polyester G, parts

Polypropylene glycol

(Molecular weight 1200), parts. Alkylphenol polyglycol ethers, parts.

Lecithin, parts

Water, parts

Triethylamine, parts

Filler (chalk), parts

Pigment (carbon black), parts

4,4'-diphenylmethane diisocyanate,

Parts

Foam properties

Fabric weight, kg / m ³

200

100

50
1

160

highly elastic
60 to 65

200

100

60 2

200

highly elastic 55 to 60

240
60

20th

16

120
2

200

rigid
up to 70

240 60

20 20

8 180

200

rigid up

309 597/351

Claims (1)

PATENT CLAIM: A process for the production of polyurethane foams by reacting polyesters which are condensation products of glycols and carboxylic acids and may be partially replaced by polyether, with polyisocyanates in the presence of surfactants, water and optionally other blowing agents as well as a tertiary amine and, if appropriate, fillers, characterized in that as polyester polycondensation products with an average molecular weight between 750 and 6000 and a hydroxyl number between 25 and 150 and an acid number below 4, made from glycols and a mixture of monocarboxylic acids and polycarbonate 12 acids with 14 to 88 carbon atoms of the following composition: Monocarboxylic acids with 14 to 20 carbon atoms Dicarboxylic acids with 36 to 44 carbon atoms (dinate fatty acids) Tricarboxylic acids with 54 to 60 carbon atoms (trimeric fatty acids) Tetracarboxylic acids and higher with more than 60 carbon atoms .. be used. up to 50 parts by weight 10 to 70 parts by weight 10 to 70 parts by weight up to 30 parts by weight © 309 597/351 5.63