DE1152536B - Process for the production of foams containing urethane groups - Google Patents

Description

INTERNAT. KL. C 08 g

GERMAN

PATENT OFFICE

F 36419 IVc / 39 b

REGISTRATION DATE: MARCH 30, 1962

NOTICE THE REGISTRATION ANDOUTPUTE EDITORIAL: AUGUST 8, 1963

Foams containing urethane groups and having a wide variety of physical properties are made from compounds with several mobile ones according to the isocyanate polyaddition process Hydrogen atoms, in particular compounds containing hydroxyl and / or carboxyl groups, and Polyisocyanates, optionally with the use of water, activators, emulsifiers and other additives for a long time (Angewandte Chemie, A 59 [1948], p. 257; Taschenbuch "Bayer-Kunststoffe", 2nd edition [1959], p. 25). It is possible according to this procedure, with a suitable one Choice of components, both elastic and rigid foams, or all between them Groups to produce lying variants.

Polyisocyanate-based foams are preferably made by mixing liquid components produced by mixing the starting materials to be reacted with one another either at the same time or else initially from a polyhydroxyl compound with an excess of polyisocyanate a pre-adduct containing NCO groups, which is then prepared in a second operation is transferred into the foam with water.

The invention now relates to a process for the production of urethane-containing groups Foams with very high elongation at break, tensile strength and resistance to aging based on in a certain way modified, optionally branched polyalkylene glycol ethers.

The process according to the invention relates to the production of urethane-containing groups Foams based on ethereal polyhydroxy compounds, polyisocyanates, water and / or other blowing agents as well as homopolymers or copolymers, whereby as ethereal polyhydroxyl compounds, alone or in a mixture with other known polyhydroxyl compounds, modified Polyalkylene glycol ethers are used in which polymers from polymerizable beforehand unsaturated compounds in situ with graft polymer formation with the polyalkylene glycol ether have been manufactured. It is known to separate the starting materials for the vinyl polymers Add production of foams. According to the invention, however, the polymers are in the Polyalkylene glycol ether produced in situ. It is also known that copolymers of allyl alcohol and styrene having free hydroxyl groups as raw materials for producing urethane groups to use foams containing.

Method of manufacture
Foams containing urethane groups

Applicant:

Paint factories Bayer Aktiengesellschaft,
Leverkusen

Dr. Wulf von Bonin, Leverkusen,

and Dr. Helmut Piechota, Leverkusen-Mathildenhof, have been named as the inventor

However, these are inevitably branched with respect to the hydroxyl groups and can be used for production Do not use elastic products. In general, such copolymers have the disadvantage that the degree of branching and the number and arrangement of the hydroxyl groups with the polyisocyanate react, do not allow them to vary independently of one another.

Some of the polymers produced in situ are in the polyalkylene glycol ethers as homopolymers contained dissolved or suspended. However, there are also graft polymers.

Such graft polymers of vinyl compounds on polyalkylene oxides are already known. However, it was in no way foreseeable that the polyalkylene glycol ethers modified in the manner described allow the production of foams containing urethane groups, the properties of which are significantly better than those of Foams based on the previously used polyalkylene glycol ethers.

The modified polyalkylene glycol ethers to be used as starting material according to the invention are obtained by adding polymerizable unsaturated compounds in a polyalkylene glycol ether dissolves and then polymerized with the addition of radical-forming initiators.

Suitable polymerizable unsaturated compounds here are those compounds the one or more polymerizable double

309 650/288

3 4

bindings included. Examples include: solvents for the production of the foam

Vinyl aromatics, such as styrene, olefin hydrocarbons, can be used. Sometimes it turns out to be

Vinyl esters, such as vinyl acetate or vinyl propionate, expediently, of troublesome polymer agglomerates

or vinyl halides such as vinyl chloride or vinyl to be filtered off.

idene chloride. Also (meth) acrylic acid or its 5 The modified polyalkylene glycol ethers can Derivatives such as methyl methacrylate, ethyl acrylate or either pure or in a mixture with other poly-acrylonitrile, are suitable for this. The use of hydroxyl compounds can be used. As a polyvon Polyvinyl compounds, such as triallyl cyanurate hydroxyl compounds for the aforementioned mixtures or glycol dimethacrylate, is also possible. The genes for the purpose of foam production are Unsaturated compounds can be pure or in the io numerous types suitable. An example mixture may be mentioned are used together. from mono- or polyfunctional alcohols Polyalkylene glycol ethers and carboxylic acids or oxycarboxylic acids are mentioned in particular by polymerization of alkylene oxides, possibly with the use of amino alcohols, such as ethylene oxide, propylene oxide, 1,2-, 1,3-butylene diamines, oxyamines or aminocarboxylic acids, oxide, styrene oxide, epichlorohydrin or tetrahydro- 15 linear or produced by known processes furan, obtained linear polyalkylene glycol ethers, branched polyesters or polyester amides, which also different molecular weight, preferably such heteroatoms, double or triple bonds thus a hydroxyl group content of 0.5 to 15%. like modified residues of saturated or un-also Copolymers can be used. contain saturated fatty acids or fatty alcohols

Mention should also be made of the addition of the 20 can.

mentioned alkylene oxides on z. B. polyfunctional also unmodified polyalkylene glycol ethers,

Alcohols, amino alcohols or ¹ amines obtained as described above for the preparation of the invention

linear or branched addition products. Listed as the starting material to be used

polyfunctional components for the addition of were, are here as blending components too

Alkylene oxides are ethylene glycol and 1,2-propylene 25 to be mentioned.

glycol, trimethylolpropane, butanetriol-1,2,4, Glyce- As polyisocyanates are preferred diisocyanate rin, castor oil, ethanolamine, diethanolamine, tri- such. B. n-butylene diisocyanate, hexaethanolamine, aniline, alkylenediamines of the methylene diisocyanate type, m-xylylene diisocyanate, p-xylyethylene diamine, tetra- or hexamethylene diamine diisocyanate, 4,4'-dimethyl-1,3-xylylene diisocyanate, called. Of course, mixtures of cyclohexylene-4,4'-diisocyanate, m-phenylene diisocyanate or branched polyalkylene glycol ether anate, p-phenylene diisocyanate, l-alkylphenylene-2,4-various types can also be used. Isocyanates, 3- (α-isocyanatoethyl) -phenyl isocyanate, also include hydroxyl-containing polyethers, 1-alkylphenylene ^ ö-diisocyanates, 2,6-diethylphenyl which contain urethane groups or ester groups, len-1,4-diisocyanate, diphenylmethane-4, 4'-diisocyz. B. the reaction product of a diisocyanate with 35 anat, diphenyldimethylmethane-4,4'-diisocyanate or an excess of a low molecular weight poly-naphthylene-1,5-diisocyanate, also tri- or polypropylene oxide or the reaction product of a functional isocyanate can also be used, dicarboxylic acid, like adipic acid, with an over- z. B. 2,4,6-triisocyanatotoluene.
shot of a low molecular weight polypropylene oxide. For the modification of the polyalkylene glycol ethers according to the known method by simple, 1 to 60 percent by weight, preferably rapid and thorough mixing of the 1 to 30 percent by weight, of vinyl compounds components in the presence of water and / or dissolved and after the addition of the polymerization initiator, blowing agents such. B. haloalkanes.
optionally with the exclusion of atmospheric oxygen, used in the production of the foams, brought to polymerization with stirring. _The usual activators such as dimethyl-AIs polymerization initiators are benzylamine, N-methyl-N '- (N-dimethylaminoethyl) radical formers commonly used, such as bei- piperazine, triethylenediamine, permethylated peroxides of the lauroyl peroxide type, or ethylenetriamine Organotin compounds, benzoyl peroxide or dicumyl peroxide, or nitrogen, for example dibutyltin dilaurate, or substances containing tin (II), such as azodiisobutyronitrile. ₅₀ octoat. In addition, there are stabilizers such. B. Redox systems, such as benzoyl peroxide-dimesulfonated castor oils or their sodium salts, thyltoluidine, can also be used. Same use.

the initiation with the help of high-energy comes into consideration. The radical formers are in accordance with the invention the use of this so-Modin amounts of 0.01 to 15 weight percent, ₅₅ ed preferential polyalkylenglycol ether is present in an bemerweise 0.1 to 5 weight percent, based on the improvement of the mechanical kenswerten Eigenpolymerisierbare vinyl compound. shafts of the foams produced therewith. The most expedient is the polymerisation improvements in tensile strength, elongation at break, initiator dissolved in the vinyl compound and this compression hardness, impact elasticity and compression deformation solution combined with the polyalkylene glycol ether on the modification addition polymerized. However, it can easily be traced back. As an example, those in Table 1 can be used to vary the method of operation and to name the compiled values to match the foam requirements of the individual case. substances based on an unmodified, the modified in this way polyalkylene glycol 65 linear polyalkylene glycol ether ozw. its Modicol ether can be measured either directly or after removal of the fication products. Any unreacted residues of the vinyl compound in the products were scooped up in each case using the same mixture or the optionally used Lö recipe.

Table 1

Modifying agents
(Polymers)

salary space train fracture Push Weight weight strength strain elasticity percent kg / m ³ kp / cm ² % % 0 32 0.2 60 28 7th 31 1.1 415 32 7th 33 1.1 330 34 7th 34 1.1 330 35 7th 31 0.9 250 34 7th 33 1.2 365 —_

Compression hardness

p / cm ²

20 <y ₀ [40% [60%
Compression

Compression set

Vinyl chloride

Vinyl acetate

Acrylonitrile

Methyl methacrylate
Styrene

Another advantage of using polyalkylene glycol ethers, which have been modified in the sense described, for the production of soft polyurethane foams is that these foams have increased resistance to organic solvents. Such foams Polyethers modified in this way are suitable for textile lamination because, in addition to their known good hydrolysis resistance due to the modification are now also resistant to the organic solvents used in the dry cleaning process. So far for this Purpose only polyester foams are used, which although good solvent resistance, however have only low resistance to hydrolysis. Exemplary for the influence of the modification on the behavior against solvents is Table 2, the values of which are from foams based on non-modified materials or partially branched polypropylene glycol ether modified in this way were obtained.

Table 2

13th 14th 21 24 26th 31 17th 27 18th 23 23 28

Modification
middle
(Polymer) salary
Weight 24h
Trichloro
ethylene ge storage
Perchloric
ethylene gin
petrol 25.0 11.0 Tabel 1 benzene percent Change in length in% 17.0 8.2 a) - 0 42.0 35.0 b) acrylonitrile 15th 29.0 25.0 Test specimen 13.4 x 4.5 x 0.7 cm. to

200 parts by weight (possibly modified) Po-

lyalkylene glycol ether,
0.5 part by weight of endoethylene piperazine,
0.2 part by weight of dibutyltin dilaurate,
2.0 parts by weight of polysiloxane polyalkylene glycol ester,

6.0 parts by weight of water,
77.0 parts by weight of tolylene diisocyanate.

To table 2

a) As above.

b) 200 parts by weight of modified polyalkylene glycol

Kolether,

0.5 part by weight of endoethylene piperazine,
0.2 part by weight of dibutyltin dilaurate,
4.0 parts by weight of polysiloxane polyalkylene

glycol ester,

6.0 parts by weight of water,
85.0 parts by weight of tolylene diisocyanate.

21 84

38 23

43 13

42 41

34 29
41

Manufacture of the raw materials

a) 2000 parts by weight of a linear polypropylene glycol ether are introduced into a stirred autoclave (Molecular weight about 2000; OH number 61.2), 1000 parts by weight of vinyl chloride and 2.0 parts by weight Benzoyl peroxide. The mixture is stirred for 6 hours at 75 °, then evacuated to remove residual monomer Completely remove vinyl chloride. The reaction product is then a milky substance with the following values: OH number 56.6; Cl content 3.8%.

b) 1000 parts by weight of a linear polypropylene glycol ether (molecular weight about 2000; OH number 61.2) and 3.0 parts by weight of benzoyl peroxide, which are dissolved in 100 parts by weight of vinyl acetate, are introduced into a stirred pipe under a nitrogen atmosphere. The mixture is stirred for 21 hours at 75 ^° C. and then nitrogen is blown through the clear solution for 1 hour in order to remove unreacted vinyl acetate. The reaction product has an OH number of 56.6.

c) Process as b), except that a solution of 3.0 parts by weight of azodiisobutyronitrile in 100 parts by weight is used Vinyl acetate used. The product has an OH number of 56.6.

d) Procedure as in b), but instead of vinyl acetate Acrylonitrile used. The product has an OH number of 48.7.

e) The method as d), but is used in place of benzoyl peroxide lauroyl peroxide, and polymerization was conducted at 6O ⁰ C. The product has an OH number of 48.6.

T) Procedure as in b), except that methyl methacrylate is used instead of vinyl acetate. The product has an OH number of 56.3.

g) Procedure as in b), but instead of vinyl acetate Styrene used. After the end of the polymerization, any precipitated products are filtered off Polymer agglomerates from. The product has an OH number of 52.7.

h) Procedure as in T), except that 200 parts by weight of methyl methacrylate and, in addition to 3.0 parts by weight of benzoyl peroxide, 0.2 parts by weight of N, N'-dimethyl-p-toluidine were used. The product has an OH number of 55.0.

i) Procedure as in a), except that a branched polypropylene glycol ether is used (Molecular weight about 2500 to 3000; OH number 56.8) used as the starting product. The end product has an OH number of 49.1.

k) Process like d), except that the starting product is a branched polypropylene glycol ether (molecular weight about 4000; OH number 47.3) was used. The product has an OH number of 37.7.

1) Procedure as in b), but instead of the vinyl acetate one is used Mixture of 60 parts by weight of vinyl

acetate and 40 parts by weight of acrylonitrile are used. The product has an OH number of 52.6.

Examples 1 to 11

200 parts by weight of modified polyalkylene glycol ethers a) to 1) are added with rapid stirring 0.5 part by weight of endoethylene piperazine, 0.2 part by weight of dibutyltin dilaurate, 2.0 parts by weight Polysiloxane polyalkylene glycol ester, 6.0 parts by weight of water and with that given in Table 3 Amount of toluylene diisocyanate added. After thorough mixing of the components, the Response a. It is poured into a mold, a foam with the ones given in Table 3 Properties arises.

Table 3

lot
Toluene
diisocyanate Starting
material space
weight train
strength fracture
strain Compression hardness p / cm ²
40 ° / o 600/0 24 38 Push
elasticity Print ver
forming residue Ver
foaming
example kg / m ³ kp / cm ² % 20% Compression 31 43 % ° / o 78 a 31 1.1 415 21 30th 41 32 23 1 78 b 33 1.1 330 26th 27 42 34 13th 2 78 C. 32 1.1 325 27 28 41 38 10 3 75 d 34 1.1 330 17th 24 35 35 41 4th 75 e 31 1.2 330 25th 28 41 37 10 5 78 f 31 1.1 370 20th 29 43 34 19th 6th 76 G 33 1.2 365 23 36 48 36 12th 7th 77 H 33 1.0 265 24 42 61 34 41 8th 75 i 33 0.8 165 33 29 41 36 8th 9 72 k 34 1.0 140 29 41 15th 10 76 1 31 1.2 330 26th 38 14th 11

Claims (2)

PATENT CLAIMS: 1. A process for the production of foams containing urethane groups on the basis of ethereal polyhydroxyl compounds, polyisocyanates, water and / or other blowing agents and homopolymers or copolymers, characterized in that modified polyalkylene glycol ethers are used as ethereal polyhydroxy compounds, alone or in a mixture with other known polyhydroxyl compounds be, in which previously polymers of polymerizable unsaturated compounds in situ under graft polymer education with the polyalkylene glycol ether have been made. 2. The method according to claim 1, characterized in that the modified polyalkylene glycol ether one is used in which previously copolymers of polymerizable unsaturated Compounds in situ with graft polymer formation with the polyalkylene glycol ether have been manufactured. Considered publications:
Belgian patent specification No. 601 128;
British Patent No. 851 668. © 309 650/288 7.63