DE2433987B2 - Molding and coating compounds - Google Patents

Description

characterized in that it is used as co-stabilizer (E) 0.01 to 5 percent by weight - based on the sum of (A) and (B) - a compound of the general formula

H-C- (Y),

(Z) ₁ included in the

X = R-C-

Il
ο

Y = H -

Il

Z = R'-O-C- R'-N-C-

20th

25th

J5

HO

R = a phenyl radical or an alkyl radical with 1 to 8C atoms, where a (—CH ₂ - (- group is replaced by a

(A) an unsaturated polyester

(B) a vinyl monomer copolymerizable with (A)

(C) tertiary aromatic amines as accelerators

(D) usual stabilizers

(E) a costabilizer

(F) customary auxiliaries and additives.

Unsaturated polyester resins are already contained in the delivery condition for many possible applications tertiary aromatic amines as accelerators. Such pre-accelerated resins are particularly prone to especially at higher temperatures - in addition to gelling after a very short storage time. In order to they become unusable for further processing. Therefore, to extend the storage time Stabilizers too. The possible amount of stabilizer, which can be added is limited because the Otherwise the processing time increases in an undesirable manner Resins in summer temperatures! Agem, if the storage room is not particularly cooled.

From DE-PS 11 76 852 organic iron (III) compounds are known as CostabUisatoren for unsaturated polyester resins. The document is to infer that the stabilizing effect comes from the iron ions that are inevitably present Anions (carboxylate or enol groups) a certain Have an effect on the unsaturated polyester resins is not described. Connections, soft show a keto / enol tautomerism are not mentioned

The invention is based on the task of effectively stabilizing unsaturated polyester resins, without the disadvantages described occurring.

The object was achieved by using the molding and coating compositions as costabilizer (E) from 0.01 to 5 Percentage by weight - based on the sum of (A) and (B) - of a compound of the general formula

- C-O group

Il

O /

can be replaced

R '= a phenyl radical or an alkyl radical with I to

8 carbon atoms

mean and r, s, t are the values

r = 1,2 or 3

s = 0 or 1 t = 0, 1 or 2

can assume, where always applies to r + s + 1 - 3, and where the weight ratio of (E): (D) from 5: 1 to 150: 1 and of (E) :( C) from 1:50 to 100 : 1 concerned

n the O
Il (X) r
HC- (Y), Μ Il
-o — c- \
(Z), Il
O included, i X = R'-N-C Y = Z = = R - = H- = R-

The invention relates to shaping and curable with a customary radical-forming catalyst Coating compounds, consisting of

65 HO

R = a Phenylresl or an alkyl radical with I to SC atoms, where a (-CH ₂ - ^ - group by a

'■ —C —Ο — Λ group

O J

can be replaced

R '= a phenyl radical or an alkylresi with
8 carbon atoms

mean and r, s, t are the values

r = I, 2 or 3
s = 0 or!
t = 0, 1 or 2

until

Kl

20th

25th

can assume, where r + s + t = 3 always applies, and where the weight ratio of (E): (D) from 5: 1 to 150: 1 and of (E): (C) from 1:50 to 100 : 1 is

In a preferred embodiment, the costabilizer is used in amounts of 0.1 to 3 percent by weight

- based on the sum of (A) and (B) - used examples of the costabilizers according to the invention

Triacetyl methane, Diacetylmetttan (= acetylacetone), Diacetyl acetic acid ethyl acetate, Diacetyl acetic acid aDyl ester, Ethyl acetoacetate, Acetylmalonic acid diethyl ester, Butyrylacetic acid ethyester, Benzoylacetone, Ethyl benzoyl acetate, Acetondicarbonsäurediethylester or Acetoacetic anilkL

Triacetyl methane and diacetyl methane are preferably used.

In addition to the costabilizers according to the invention, customary stabilizers must: be used because the Costabilizers alone do not have a stabilizing effect. From the series of usual stabilizers becomes preferably hydroquinone used; in general, other common phenolic stabilizers also come or those with a chonoid structure, such as B. toluhydroquinone, tert-butyl hydroquinone, di-tert-butyl hydroquinone, Catechol, tert-butyl catechol, or p-benzoquinone. You will be in Amounts from 0.001 to 0.5 percent by weight, preferably in amounts of 0.005 to 0.1 percent by weight - based on the sum of 1. and 2. - used Das Weight ratio between the costabilizers according to the invention and the usual stabilizers is in the range from 5: 1 to 150: 1, preferably 5: 1 to 50: 1.

In the preferred embodiment, the stabilizer used is hydroquinone and the costabilizer Triacetyl methane or diacetyl methane used; in this case the weight ratio of co-stabilizer is to hydroquinone in the range of 5: 1 to 25: 1.

The tertiary aromatic amines known for this purpose are preferably used as accelerators Bia- (hydroxyethyl) -p-toluidine is used. Other known tertiary aromatic amines are also 'if into consideration, such as. B. dimethylaniline, dimethyltoluidine, Bis (hydroxyethyl) aniline, diisopropylaniline or other alkyl or hydroxyalkylaniline derivatives. You to are in amounts of 0.01 to 5 percent by weight, preferably in amounts of 0.1 to 3 percent by weight

- based on the sum of (A) and (B) - used The weight ratio between the costabilizers according to the invention to the aromatic 1,5 see amine accelerator ranges from 1:50 to 100: 1. It has been shown to be beneficial when that Weight ratio of costabilizers according to the invention to bis (hydroxyethyl) p-toluidine 1: 5 to 5; t, is preferably 1: 1

To produce the unsaturated polyester, fumaric acid is usually used for the acid component, Maleic acid or maleic anhydride, also itaconic acid, mesaconic acid or citraconic acid are used Up to 75 mole percent of the «^ -unsaturated, copolymerizable dicarboxylic acids can by saturated di- or polycarboxylic acids, such as, above all, o-phthalic acid or o-phthalic anhydride Tetrahydrophthalic acid, isophthalic acid, trimellitic acid, Succinic and adipic acid, tetrachloric or tetrabromophthalic acid or hexachloroendomethylenetetrahydrophthalic acid or their anhydrides be replaced.

Furthermore, monobasic acids such as benzoic acid, oleic acid, linseed oil fatty acid or Ricin fatty acid can be used in minor amounts.

Ethylene glycol (l ^), propanediol (1,3), butanediol (1,4) are suitable as diols for polyester production or Hexandio! - {1,6) as unbranched, free from ether groups Dioie; Propanediol- (1,2), butanediol- (1,2) or Butanediol- (1,3), also e.g. neopentylglycol as branched, ether group-free diol; unbranched chain diols containing ether groups are suitable all diethylene, also triethylene or tetraethylene glycol; as branched / straight-chain containing ether groups, especially dipropylene glycol or tripropylene glycol

The unsaturated polyesters are produced at temperatures from 150 to about 250 ^° C. by customary azeotrope or melt condensation of the components. In general, the diols are used in an approximately 2 to 10% molar excess over the dicarboxylic acids. However, the molar ratio of diols to dicarboxylic acids is not critical.

The acid numbers of the unsaturated polyesters are generally between 10 and 70, preferably 20 up to 50, in particular 25 to 40. The molecular weight is accordingly not critical for the invention is, between 5500 and 800, preferably between 3000 and 1000, in particular 2500 to 1500.

As unsaturated, copolymerizable vinyl monomers the usual ones, such as styrene, substituted styrenes, such as tert-butylstyrene, «-methylstyrene are suitable or divinylbenzene; also mixtures of the latter with styrene. Other ethylenically unsaturated Monomers that are used in combination with styrene in amounts of less than 50 percent by weight, based on the Monomer mixture that can be used are lower (Ci- G ») - alkyl esters of acrylic acid or Methacrylic acid and halogenated styrenes such as chlorostyrene, dichlorostyrene, and also diallyl phthalate, triallyl phosphate, Triallyl cyanurate, acrylonitrile or vinyl acetate

Acyl peroxides such as acyl peroxides are used as catalysts which form free radicals in order to fully cure the polyester resin compositions Berizoyl peroxide or lauroyl peroxide, also isopropyl peroxydicarbonate or mixtures of acyl peroxides or isopropyl peroxydicarbonate with methyl ethyl ketone penoxide, Cyclohexanone peroxide, acetylacetone peroxide, Cumene hydroperoxide or dicumyl peroxide in amounts up to 5 percent by weight - based on the Sum of 1st and 2nd - used

Likewise, the addition of other curing accelerators, such. B. of cobalt salts, possible. Furthermore, the compositions according to the invention can be cured with the aid of γ, UV or IR rays.

The dissolved in the polymerizable vinyl monomers Polyesters can also contain auxiliaries and additives, such as mineral fillers, pigments, paraffin, thixotropic agents, Contains color brighteners, light stabilizers, etc.

The costabilizers according to the invention belong to the class of the keto-enol-tautomeric or C-H-acidic Links. Their effect as an additional accelerator in the curing of unsaturated polyester resins in Presence of z. B. Ketone peroxides and cobalt salts as an activator system is known. It is also known that they are used in non-pre-accelerated resins or those containing certain metal salts as activators (e.g. cobalt or vanadium) drastically reduce the storage stability of polyester resins (silks: glass fiber reinforced Kunststoffe, page 132 [1967]).

It was therefore surprising and unforeseeable that selected keto-enol-tautomeric or C-H-acidic compounds of the general according to the invention Formula combined with tertiary aromatic. Amines in pre-accelerated unsaturated Polyester resins, the storage stability "; on polyester resins improve significantly. Triacetylmethane and acetylacetone are particularly effective.

Keto-enol-tautomeric or C-H-acidic compounds that do not meet the general formulas have an effect not within the meaning of the invention. So are z. B.

Malonic acid diethyl ester (r = 0), MaIodinitrile (r = 0, Z = CN-),

2-chloroacetoacetic acid ethyl ester
(Y = Cl-) or

2-oxo-cyclopentanecarboxylic acid ethyl ester,

Dihydroresorcinol, Dimedon (cycloaliphatically bound S3 CH group) and Acetylglutaric acid diethyl ester

(Y-CH ₂ CH ₂ CCX) R)

no costabilizers for amine pre-accelerated polyester resins.

The compounds according to the invention can be processed into fillers, joint compounds and casting compounds. Even the production of various GRP articles is possible. For this purpose, glass fiber mats, fabrics or -rovings used In addition, they can also be used to produce polyester varnish.

The molding and coating compositions according to the invention have various advantages. Thus, the storage stability at 50 ⁰ C of a resin which contains 0.02 percent by weight hydroquinone and 0.5 percent by weight bis (hydroxy- in ethyl) p-toluidine, after adding 0.5 percent by weight of triacetyl methane or acetylacetone to the three- up to four times, in some cases even ten times. Additions of 1 percent by weight of triacetyl methane or acetylacetone increase the shelf life at 50 ° C by a factor of twenty to thirty. The mechanism of action is not known. The costabilizers according to the invention do not affect the reactivity of the resins. Since the costabilizers are colorless liquids, on the one hand they can be handled and metered very easily and, on the other hand, they do not in any way impair the color quality of the resins, which are already yellow in color due to the amine accelerator.

Examples

To carry out the tests and comparative tests, four unsaturated polyester resins!, It, III and IV used

Resins 1 and I! were aws 2 mo! Fumaric acid, 1 mol of phthalic anhydride and 3.1 mol of propanedioI- (U) condensed up to an acid number of 30-35, 65 parts by weight dissolved in 35 parts by weight styrene, according to Table 1 with 0.02 (I) and 0.04 (II ) Weight percent hydroquinone stabilized and accelerated with 0.5 or 1.0 weight percent (each based on the styrenic solution) bis (hydroxyethyl) p-toluidine

Resins III and IV were made from 1 mol fumaric acid, 3 mol tetrahydrophthalic anhydride and 4.1 mol Diglycol condensed to an acid number of 30-35, 65 parts by weight dissolved in 35 parts by weight styrene, stabilized according to Table 1 with 0.02 (III) or 0.04 (IV) percent by weight hydroquinone and with 0.5 or 1.0 Percentage by weight (based on the styrenic solution) of bis (hydroxyethyl) p-toluidine pre-accelerated

In table 1, column a shows the storage time at 50 ° C. in days. Serve as a storage vessel 140 ml tinplate jars with lids, each 100 g Resin included. The storage stability ends when gelation begins.

Under column b, the hardening data are given in the order named, processing time, hardening time and maximum temperature. The “processing time [min]” is the time in which a 100 g sample undergoes a temperature increase to 21.5 ° C. ^{at 20 ° C. after adding 1 g of benzoyl peroxide powder (50%).} During the curing time [min], the temperature then rises further from 21.5 ° C to the maximum temperature [° C].

Table 2 contains comparative examples. Table 1 Bet games of the invention

Trial weight · / » Costabilizer Resin I Resin II Resin HI Resin IV Nf. [% By weight]
0.02 Hydroquinone
0.04 0.02 0.04 [% By weight I.
0.5 Bts- (hydro:; yethyl) -p-toluidine
0.5 0.5 0, * away off off away

0 Triacetyl methane 5 13/13/184 0.1 the same 11 13/12/186 0.3 the same 12th 13/10/190 0.5 the same 16 13/12/187

16 21/26. '.89

29 21/24/187

61 21/23/182

41 21/24/189

10/11/113
10/12/113
10/12/110
10/13/110

5 15/15/112

11 15/15/110

12 15/15/108

13 15/15/112

• 0
0.3
0.6
1.0 7th 24 33 987 Ha" .11 8th b a b a b Resin IV b 0
0.1
0.3
0.5 Costabilizer [Ow%] hydroquinone
0.02 0.04 Resin III 7/7/194
7 / 7/191
11 6/190
11 7/186 32
60
60
66 11/15/181
11/14/186
11/13/186
11/16/184 1
23
32
49 9/10/110
9/10/110
9/10/110
9/10/107 0.04 14/19/108
14/19/106
14/20/108
14/20/104 continuation 0 Har 0.02 12/11/186
12/11/187
12/11/182
12/13/179 20th
37
40
42 22/27/182
22/23/188
22/22/182
22/23/156 2
2
9
18th 8/10/116
8/11/116
8/11/116
8/11/114 0.5 15/15/112
15/15/110
15/16/108
15/16/107 Test ow .-% 0.6
1.0 [% By weight] bis (hydroxyethyl) p-toluidine
0.5 0.5 0.5 25/20/179 32 13/18/187 1 9 / 9/110 a 15/17/104 No. 0
0.5 H L Jl I ft * IO +
25/19/184
26/20/184 OU
60
60 IJ / IJ / 1OJ
13/17/178
13/17/188 JU
48
55 • fl IU / IUV
9/11/111
9/10/108 26th
45
54
54 IJ / ΙΟ / IUJ
15/18/102
15/17/100 0
0.1
0.3
0.5 Triacetyl methane
the same
the same
the same 15th
16
19th 14/13/186
14/14/184 17th
26th 22/27/190
22/25/193 1
3 8 / 9/114
8 / 9/114 5
12th
18th
20th 15/15/111
15/16/112 0
0.1
0.3
0.5 Acetylacetone
the same
the same
the same 4th
17th
17th
15th 19th
22nd
22nd
23 22/35/186
22/34/188
2 ^ / 30/186
22/33/186 1
2
5
7th 8/10/116
8/10/116
8/10/116
8/11/118 26th 14/15/112
14/15/112
14/17/112
14/17/104 2 0
1.0
2.0
3.0 Acetylacetone 8th 14/12/190
14/14/19)
14/12/188
14/14/18? 22nd
25th
23
25th 23/29/190
23/30/188
23/25/186
23/30/188 62
66 13/18/112
13/18/113
13/18/112
13/18/111 3 0
0.5
1.0 UCSgI.
the same
the same 19th
23 11 7/188
11 7/184
11 7/184
11 7/184 16
24
24
26th 12/13/192
12/12/182
12/15/187
12/14/178 2
2
8th 9 / 9/108
9 / 9/106
9 / 9/104
9 / 9/102 5
8th 15/17/105
15/17/101
15/17/101
15/17/98 4th 0
1.0
2.0
3.0 Diacetylacetic acid
ethyl ester
the same 4th
6th 2
3
4th 9/10/110
9 / 9/109
9/10/111 5
6th
8th
12th 0
0.3
0.6
1.0
2.0 Diacetylacetic acid
allyl ester
the same
the same
the same 11 8/185
11 7/187
11 7/188
11 7/183 1
2
3
3 9 / 9/110
9 / 9/109
9/10/110
9/10/108 5
6th
8th
7th 5 0
O ^
0.6
1.0 Ethyl acetoacetate
the same
the same
the same 4th
8th
10
9 19th
24
20th
23
24 11 / 15.5 / 181
11 / 13.5 / 186
11 / 13.5 / 186
13/15 / 180
13/17 / 180 2
19th
24
25th 13 / 17.5 / 106
13 / 17.5 / 106
13 / 17.5 / 106
14/16 / rs
14 / 17.5 / 103 6th 0
0.3
0.6
1.0
2.0 Ethyl acetoacetate
the same
the same
the same 2
16
16 74 / 6.5 / 186
74/7 / 182 16
33
25th
24 11/13 / 181
11/14/176
Η / 15.5 / Π4
11/16 / 179 6th
18th
27 13.5 / 9/110
13.5 / 10/107
I34 / IO / 107
9 / 94/105 7th 0
0.3
0.6
1.0
2.0 Acetylmalonic acid diethyl
ester
the same
the same 16
17th
22nd 10/15/184
10/13/182
10/15/173 13 / 17.5 / 108
13 / 16.5 / 105
13/164/104
13.5 / 16.5 / 102
13.5 / 16.5 / 100 8th Acetylmalonic acid diethyl
ester
the same
the same
the same 0.5
1.0
1.5
2 13th
20th
22nd
22nd
21 11/12 / 180
U / 14/155
ί 1 / 13.5 / 176
11/154/175
11/14 / 177 16
16
16
21
23 14/17/108
14/16/107
14/16/107
16/16/106
16/16/106 9 Ethyl butyrylacetate
the same
the same
the same
the same 10 Benzoylacetone
the same
the same
the same 8th 2
4th
4th
4th
12th 11 Benzoyiacetic acid ethyl
ester
the same
the same
the same
the same 2
4th
3
3
8th 12th Acetone dicarboxylic acid
ethyl ester
the same
the same
the same
the same 13th

Ow .-% Wt% 9 24 33 987 0.04 ill resin 0.5 b 0.5 1.0 κ 1.0 1 10 0.04 resin Resin IV 2 0.5 16 0.5 b 1 a 10/14/183 a 7/10/182 S. 22nd 13th 16 50 C 15/16/109 Costabilizer 0.02 14th 10/14/178 <1 7/10/188 32 III 0.02 0.04 14th Storage stability in days at 15th 1 15/15/106 I. Resin I Har [% By weight] bis (hydroxyethyl) p-toluidine 20th 10/16/149 30th 7/10/180 49 Il 3 13th 1 15/15/106 I. continuation [% By weight] hydroquinone 0.5 18th 11/16/167 34 7/10/186 1 0.5 3 16 1 15/15/103 1 Experimental 0.02 away 16 34 7/10/184 28 a 1.0 3 10 1 I. No. 0 0 [% By weight | Bis (hydroxyethyl) p-toluidine 1 7/10/184 49 <1 7th 2 1 0.3 0.1 1.0 30th 7/11/181 54 b 12th 3 3 <1 0.6 0.3 Acetoacetic anilide away 30th 7/11/183 28 <1 18th <1 9/11/92 1.0 04 the same <1 4/6/186 17th 46 <1 <1 <1 9/11/94 0 the same I 4/5/190 resin <1 <1 <1 9/12/94 15th 0.1 the same 2 4/7/177 Resin I 19th <1 <1 <1 0.3 6 4/6/183 43 <1 27 <1 10/10/93 - 0 04 <1 5/6/186 54 <1 9 <1 10/10/91 0.3 0 2 5/6/188 54 <1 <] 1 10/10/90 0.6 0.1 Triacetyl methane 2 5/6/186 5/7/98 <1 <I. <1 10/10/88 1.0 0.3 the same 2 5/6/185 5/7/98 <1 20th <1 0 04 the same 5/8/100 III <1 19th <1 16 0.3 0 the same 5/9/98 <1 16 1 Resin IV 0.6 0.1 Acetylacetone 5/7/99 <1 20th 1 1.0 0.3 the same 5/9/98 [% By weight of 1 bis (hydroxyethyl) p-toluidir 1 21 1 0.04 04 the same 5/8/95 0.5 <1 18th 3 17th Comparative examples 0 the same 7/7/91 3 15th <1 0.5 Experimental 0.1 <1 13th <1 No. 0.3 3 33 <1 5 04 additive Ethyl 2-oxo-cyclopentanecarboxylate II <1 33 <1 6th Table 2 0 the same [% By weight] hydroquinone <1 34 2 5 0.1 the same 0.02 <1 33 2 7th 0.3 the same 1 2 5 A. 04 1 3 <1 0 1 <1 1.0 <1 2.0 2. Ch! Or-acetic acid methyl ester 3 R. 3.0 the same <I. the same <1 the same <1 Dihydroresorcinol 5 C. the same <1 the same <1 the same <1 3 D. 3 i 3 i 3 B. 3 S.
% E. 3 1 1 -S 54-dimethyl-1,3-cyclohexanedione 1 the same 34 I. F. desgL 27 1 the same 23 -j Malonic acid diethyl ester 26th I. the same I. G the same I. the same j Malononitrile ! the same I. the same the same Malonic acid diethyl ester the same the same the same

continuation

Il

12th

Trial no.

% By weight additive

Resin I Resin II Resin III Resin IV

[Ow%] hydroquinone

0.02 0.04 0.02 0.04

[% By weight of 1 bis (hydroxyethyl) p-toluidine

0.5 0.5 0.5 0.5

Storage stability in days at 50 ° C

0 Acetylglutaric acid diethyl ester 0.3 the same 0.6 de3gl. 1.0 the same 2.0 the same

20 18 18 18 16

Claims (1)

Claim: Molding or coating compositions, consisting of curable with customary radical-forming catalysts the end (A) an unsaturated polyester (B) a vinyl monomer copolymerizable with (A) (C) tertiary aromatic amines as activators (D) usual stabilizers (E) a costabilizer (F) customary auxiliaries and additives