DE2358761A1 - POLYMERIZABLE O, N-ACETALS - Google Patents

Description

CH ₂ = C-CO-J- (CH ₂ -CH-O) _n -CH ₂ -H

X stands for hydrogen or an alkyl radical with 1 to 6 carbon atoms,

Y stands for -NH-, -ffC _m H _{2m + 1} - (m = 1 - 6) or -0-,

Z represents hydrogen or an alkyl radical with 1 to 4 carbon atoms,

R and E 'represent the same or different radicals and isweils an alkyl radical with 1 to 18 carbon atoms / a cycloalkyl radical with 5 to 7 carbon atoms, where R and R ^r together with the nitrogen atom can also form a heterocyclic heterocyclic ring, optionally containing further heteroatoms and where

η stands for an integer from 1 to 1o.

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The present invention also provides a process for the preparation of these compounds, characterized in that that one compounds of the formula

CH ₂ = C-CO-Y- (CH ₂ -CH-O) _n H

with formaldehyde and secondary amines of the formula

R '
HN

brings to reaction, where X, Y, Z, R, R ¹ and η have the meanings given above.

Saturated Ο, Ν-acetals are known from the literature (Hellmann, Opitz, oC-aminoalkylation, page 13, Verlag Chemie, Weinheim, i960). They are produced by converting carbonyl compounds, such as aldehydes with alcohols and secondary amines.

Surprisingly, it has now been found that, according to this principle, unsaturated O, IT acetals are also accessible without any The secondary amine is added to the polymerizable double bond.

This is because it is known (Angewandte Chemie, 6J [, page 234 (1949)) that secondary amines were activated very easily Add double bonds. However, this addition is unexpectedly prevented by the presence of formaldehyde, because the Ο, Ν-acetal formation takes place preferentially. Surprised is furthermore that the use of an excess of the hydroxy compound is unnecessary. Already by implementing equi-

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Molar amounts of hydroxyl compound, formaldehyde and secondary metal form the claimed compounds in good yield without the formation of ΐΓ, Ν-acetals. Only when using one Excess formaldehyde and secondary amine was the formation of ΐί, ϊΤ-acetals, which are easily different from the desired Allow the reaction product to be separated off by distillation, observed. Based on a publication by H. He Umarm and G-. Opitz, Reports, 89_, page 81, (1956) would have been expected dais when using an equimolar amount of hydroxy compound, a reaction product is obtained which is strongly linked to IT, IT— Acetals is contaminated.

The process according to the invention is carried out in such a way that the formaldehyde, which is expediently used as paraformaldehyde, is initially taken in the hydroxy compound and the secondary amine is added dropwise with stirring. The reaction, which is advantageously carried out in the presence of dehydrating agents such as anhydrous potassium carbonate, is exothermic at temperatures of, for example, 20 to 100 ° C. The resulting 0, Έ acetals according to the invention can be purified by distillation .

As starting materials for the present process, ' For example, the following acrylic or methacrylic acid derivatives containing hydroxyl groups can be used:

CH ₃
CH ₂ = C-COO-GH ₂ -CH-OH ■■ ■ ■

₂ = C-COO-GH ₂ -C

CH ₂ = C-COO-CH ₂ -CH-OH

CH, '

CH ₂ = C-COO- (CH ₂ -CH ₂ -O) _n H (n = 1 to 1o)

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ΓΗ
CH ₂ = C-CO-KH-Ch ₂ -CE ₂ -OH

♦ 7 *

CH ₂ = C-CO-K-CH ₂ -CH ₂ -OH

₅
CH ₂ = C-CO-IIH-CH ₂ -CH (CH,) -OH

As secondary amines in the process according to the invention both aliphatic amines, such as. B. Diethylainin, Dibutylamine, N-Kethylstearylamine, cycloaliphatic amines, such as N-methyl cyclohexylamine, or saturated heterocyclic amines such as piperazine and morpholine can be used.

The process products according to the invention are partly water-soluble, distillable liquids that are stable in aqueous solution or emulsion at room temperature and only at Temperature above 70 ° C hydrolytically back into the starting components be split.

The unsaturated O, IT acetals polymerize on addition of Badikalbiidnern, such as peroxides or azoisobutyronitrile, and are therefore outstandingly suitable for the production of copolymers. The copolymerization is expediently carried out in an anhydrous medium. Acrylic acid esters, styrene, acrylamide, vinyl acetate, diene hydrocarbons and other copolymerization components are suitable as copolymerization components. However, it is also possible to use saturated, higher molecular weight components containing hydroxyl groups as starting materials, for example polypropylene ether and graft the unsaturated O, N-acetals according to the invention onto this component in the presence of radical formers such as azodiisobutyronitrile. Such graft polymers are valuable starting materials for the production of polyurethane foams.

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self

The Ο, Ν-acetals according to the invention are also / as structural components suitable for the production of polyurethane foams. she are in this case by polymerization and, if appropriate, by inserting the isocyanate group into the O, IT-acetal group (See. Angewandte Makromolekulare Chemie, 34, 2Tr- 5o7 (1973)) built into the polyurethane framework. In order to they take on the role of lengthening or crosslinking compounds without z- 3. primary or secondary Amino or hydroxyl groups need to be present. The way of working is that you get the unsaturated compounds the foamable mixture is added and after further Addition of catalytic amounts of radical formers, such as Peroxides or aliphatic azo compounds, such as azodiisobutyric acid dinitrile, make the foaming.

Here, the polymerization catalysts cause the formation of higher-functionality parts in situ, i.e. H. several O,] J-acetal groupings containing polymers, which in turn have the effect of crosslinkers; Polyurethane foams, which were prepared using such crosslinkers formed in situ, in particular, have the surprising Advantage of a significantly increased adhesive strength between foam and plastic films, such as. B. ABS / PVC foils on.

example 1

CH ₀ = C-COO-CH ₀ -Ch-O-CH ₀ -IT

CH ₅ CH ₃ X) H ₂ -CH

X NoI 22Q

₅ CH ₃ X) H ₂ -CH ₃ ^U0 ^

In 144 g 2-hydroxypropyl methacrylate (1 mole) and o, 1 g of 2,6-di-tert-butylphenol-4- (methoxy-methyl) ether and 3o Paraforraaldehyd g is g at 25 to 40 ⁰ C 80 Diethylamine (1 mol) was added dropwise. Then 60 g of anhydrous potassium carbonate

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added and then stirred for 8 hours at 7o C. Man sucks off and distilled the piltrate under high vacuum. Bp-: 73 ° C / 0.05 mm; Yield 187 g = 81.6 $ of theory.

calculated: C 62.9 H 10, o 5, N 6.1 0 21, o found: C 62.2 H 1o, oo N 6, ο Ο 21.5

Example 2

CH ₉ = G-COO-CH ₉ -CH-O-CHp-N

/ 4-9 C _1fi H,., NO η ^{Mo1 285}

In 144 g of 2-hydroxypropyl methacrylate (1 mol), 1 g of 2,6-di-tert-butylphenol-4- (methoxymethyl) ether and 3o g of paraformaldehyde, 129 g of dibutylamine (1 Mole) was added dropwise. Then 60 g of anhydrous potassium carbonate are added and the mixture is then stirred at 70 ° C. for 8 hours. It is suctioned off and distilled under high vacuum Piltrat, "p .: 1o2 ° C / o, o1 .mm; yield 2o5 g ^ · 72 fo of theory

calculated: C 67.3 H o.9 H 4.9 0 16.85 found: C 67.4 H 10, 9 .H 4.9 0 16.8

0.01 moles spent 1o, 1 ml η HCl (calc. 1o, o ml η HCl) Example 3

Under the conditions given in Example 1, using 0.1 g of phenothiazine as a stabilizer, 78o g 2-hydroxypropyl acrylate "(6 mol), 180 g paraformaldehyde (6 mol) and reacted 438 g of diethylamine (6 moles).

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.y

Yield: 122ο g (undistilled) ·; Kp.: 69 G / o, b 1 mn

calculated: C 61, 5 H 9 ,8th N 6, 5 0 22nd , 4 found: C 61, 3 \. H 9 ^ 7-: ff ■ "■: £, 3 0 22nd , 5 "... Example 4 - CH ₂ J = C-CO-
CH, N-CH ₂
CH ₃ -CH 2 -0-CH ₂ -N
X ₂ H ₅ C ₁₂ H ₂₄ N
Mol .228

In a solution of 75 g of N-methyl-ethenolamine (T mol), 138 g of anhydrous potassium carbonate (1 mol) and o.1 g of 2,6-di-tert-butylphenol-4- (methoxymethyl) ether in 2oo ml V / ater is added dropwise at 25 to 40 C to 4.5 g of methacrylic acid chloride (TMoI). Thereafter, heating is continued for 6 hours at 70 ° C., the water is distilled off under reduced pressure and then 75 g of diethylamine and Jo g of para.

formaldehyde ". Now it is again 6 hours at 7o C ■ -.

reheated, suctioned off and-the Piltrat distilled.

B.p .: 11-2 to 115 ° C / 0.05 mm; Yield 9o g = 39.5 f of theory

calcd: C 63.2 H 10.5 N 12.3 0 T4, o found: G 62.5 "'H 10, 1 N 11.2 0 15.2

Example 5 CH

/ ^ tTT ^ _ / * 1 Yl f \ f \ OTT / ** ΪΤΤ / ~ \ i ^ *! TT T ^ '

V _- / Xl ο ^ ~ ν ^ vV / \ J ^ ^m OXi ο ^ "ν XI ™ \ J " * νΧΐΛ ^ X * ""

kr ta ^: \ π ^: π mol 257 Uu ₃ .- UIi ₃ ^U 3 ^Ü 7

In "144 g of 2-hydroxypropyl-methacr: ylate (T mol), 0.1 ^ 2,6-di- ¹ tert-butylphenor ^ 4 - ('methoxymethyl) -ether and Jo g paraformaldehyde become at 25 to 40 C. To 1 g of dipropylamine (T mol) are added dropwise, then 60 g of anhydrous potassium carbonate are added and the mixture is then stirred for 8 hours at 7 ° C. Man.

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1 "Λ rt η ^ *"> / Λ Λ Λ rt

2353761

sucks off and distills the piltrate.

Bp .: 95 "to 1o5 ° C / 0.1 mm; yield 175 g ^ 68 <fo the theory

calculated: C. 65 , 4 H 1 N 5 , 45 0 18 7th found: C. 65 , 3 H 1 5 , 5 0 18 4th Example 6 lo, 5 lo, 5

In 1933 g of a higher molecular weight linear polypropylene ether, CHZ 56, after the addition of 1.35 g of azodiisobutyric acid dinitrile 67 g of the compound described in Example 1 were stirred in. Heated while passing nitrogen over it and stirring

ser

T. O,

the mixture is gradually increased to 120 ° C. The mixture is stirred for 2 hours at this point Temperature continued and treated after 1/2 hour at 13o C / 14 mm.

The slightly cloudy graft polymer has an OH number of 48.

Example 7

90 g of a polyether with a molecular weight of 48oo, which was obtained by adding propylene oxide (87 % by weight) and ethylene oxide (13% by weight) to trimethylolpropane, 5 g of the compound according to Example 1, 0.5 g of in-methyl -IT (N ^! -ß-dimethylaminoethyl) piperazine, 2.5 g of water and 0.1 g of dicumyl peroxide are mixed. 100 g of this mixture are mixed well with 47 g of a polyphenyl-polymethylene-polyisocyanate which has been obtained by phosgenation of an aniline / formaldehyde condensate and has an iTCO content of 31 ° .

The foamable mixture is placed in an aluminum mold, into a vacuum-formed ABS / PVC-Poly (acrylonitrile-butadiene-styrene copolymer with polyvinyl chloride and plasticizer) has been inserted.

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The foam reaction starts immediately after the application. The degree of compression is about 1 : \ - 2 .. A foam is removed from the mold which has the following properties: · Whispered weight - '- . "." ■ "'■■ ■.

DBT 53 42o (kg / m ^) 117 ': ■. ".- ■

Elongation at break. .

DI2T 53571, (^) 9o

Adhesion Strength (p). 137o --15oo - -

between foam '"

: and AEBS / PVC film: _....:.

Example 8 (comparative example 1)

For comparison, a "wird- the foam of Example 7 under analogous foam -Use / ^a: classical higher-functional crosslinker prepared (triethanolamine):

90 g of polyether example 7 of molecular weight 48oo.5 g of diethanolamine, 2.5 g of water, 0.5 g of IT-methyl-IT (IT'-ßöiTiiethylaninoäthyl) -pip.erazin "and 60 g of the polyisocyanate mentioned in Example 7 (the ITGO code in both examples is 1 oo) are mixed well. -. "■,

The foamable mixture is entered in an aluminum mold, into which a vacuum-formed ABS / PVC film (acrylonitrile-butadiene-styrene copolymer with .polyvinyl chloride and plasticizer) ■ - "has been inserted, - _-. ..- ,. / r.: .." - /

The foam reaction starts immediately after the. Register a. -. The degree of compression is about 1: 2. A foam is removed from the mold, which "has the following properties?. _: .

Volume weight. . .- .. '_' ■ "-. -. ■ = -. .--... DIN 5342ο '(kg / m ^) ' 15ο

Elongation at break

DET 53571. ", ■ - (#) ■. 35

Adhesion strength (ρ): 3oo - 5oo

ζ v / i see foam and

ABS / PVC foil

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Claims (2)

Claims 1. Compounds of the formula X R CH ₂ = C-CO-Y- (CH ₂ -CH-O) _n -CH ₂ -Ii ^ Z ^X R in which X stands for hydrogen or an alkyl radical with one to six carbon atoms, Y is -2ΓΗ-, -NC _m H _{2m + 1} - (m = 1-6) or -0-, Z is hydrogen or an alkyl radical with one to stands for four carbon atoms,
R and R 'represent the same or different radicals and in each case an alkyl radical with one to ■ or eighteen carbon atoms / - ^ inen cycloalkyl rest with five to seven carbon atoms. mean, where R and R 'together with the Nitrogen atom also a heterocyclic, optionally containing further heteroatoms can form heterocyclic ring and where η is an integer from 1 to 1o. 2. "Process for the preparation of compounds according to claim 1, characterized in that compounds of the formula CH ₂ = C-CO-Y- (CH ₂ -CH-O) _n H with formaldehyde and secondary amines of the formula R ^{! X} E
Le A 15 413 -1ο- S09823 / 0999 brings to reaction, where X, -Y, 'Z, R, R ¹ and η have the meaning given in claim 1. "- Le A 15 413. - It- 509 823/09 99