DE1769987C3 - - Google Patents

Description

R '

^20th

I-O-J- (CH ₂ L-CH-O

in which the two radicals R, which can be identical or different, are each hydrogen or alkyl having 1 to 4 carbon atoms, R 'is hydrogen or methyl, m is 1, 2 or 3 and π is an integer such that the molecular weight the compound contains at least 150

2. Thermosetting compositions according to claim 1, characterized in that this composition is used as Component B contains 1 to 20 parts by weight of oxides or hydroxides of divalent metals

3. Thermosetting composition according to claim 1, characterized in that this composition contains the alkali or alkaline earth metal salts of component C or of weak acids as component B, the vinylidene fluoride-hexafluoropropene-Mi «-inlvmeren are essential. in particular those with a content of about 30% by weight of vinylidene fluoride and about 30 to 70% by weight of hexafluoropropene (isA SaTentschrift 30 51677). Other very heavy polymers are the terpolymers of V.nyhdeniluond, sexafluoropropene and tetrafluoroethylene, especially those in which the monomer units are present in the ratio: about 3 to 35! preferably 85 to 75% by weight of vinylidene fluoride and hexafluoropropene units, the latter two being present by weight in a ratio of about 2.5: 1 to 0.5: 1 (see US Pat. No. 29 68 649). Other vinylidene fluoride polymers and their preparation are described in U.S. Patent _{Nos. 27 38 343 27 5 2} fj ,. 24 68 664, 23 93 967, 28 33 752 and 29 65 619.

The open-chain polar ethers used as accelerators have a molecular weight of at least about 50 and usually not more than 10,000, although this upper value is of particular importance. In one group of compounds, R is ethyl. Be. In a preferred group of compounds, one of the radicals R is formed from hydrogen and the other from hydrogen or methyl and R 'from hydrogen and is m gte.ch 1 Special ethers for the purposes of the invention include bis- <2- (methoxyethoxy) -äthy) -ather, where m equals 1. π equals 4, R 'equals hydrogen and R equals methyl, diethylene glycol diethyl ether, where m equals 2, R equals ethyl and R' equals hydrogen The polypropylene glycol (MoL- Gew. 400 ^ wöbe, pi equals R equals hydrogen, R 'equals methyl and equals about 7 is the polytetramethylene ether glycol, where R and R are hydrogen, m equals 3 and π has a sufficient size to give a molecular weight of about 1000, the Monomethoxypolyäthylenatherglykol with a molecular weight of about 350, the de formula

The invention relates to the vulcanization of fluorinated polymers.

The vulcanization of saturated, fluorinated, elastomeric polymers is well known and one has wide variety of amine-based vulcanization systems have been developed, however, often it is desirable to achieve the desired hardened state in less time. Beyond that, it is in this and that If you want to be able to use certain compounds as hardeners that were previously available for this purpose in Not quite in terms of time delays or the final hardening state that can be achieved with them to satisfy.

The subject of the application are those in the claim

defined masses.

The polymers used are saturated copolymers of vinylidene fluoride (VF2) with one or more other fluorine-containing, ethylene-unsaturated monomers which can be mixed with this monomers up to about 4, as in the case of perfluoro (methyl vinyl ether) and perfluoro (propyl vinyl ether), trifluorochloroethylene and pentafluoropropylene, especially inter-CH ₃ -O-ECH ₂ -CH ₂ -OJrH

has a polyethylene ether glycol with a molecular weight of about 400 that has the formula

HO-ECH ₂ -CH ₂ -OJrH

has, and 1,2-bis (2-methoxyethoxy) -ethane. The production such ether is generally known. Usually one works with up to 5 parts of accelerator Parts of polymer (parts and percentages refer to here, unless otherwise stated, throughout the weight).

The aromatic polyhydroxy compound enables rapid and satisfactory vulcanization of the saturated vinylidene fluoride polymers in a basic system. The aromatic polyhydroxy compound used is preferably bisphenols, which can be present as alkali metal or alkaline earth metal salts. Typical compounds include aromatic dihydroxy and ^ hydroxy compounds, such as 2 ^ -Bis- (4-hydroxyphenyl) propane (bisphenol A),
2 ^ -Bis- {4-hydroxyphenyl) -perfluoropropane (bisphenol AF),

Resorcinol, i, 3,5-trihydroxybcriZc !, 1,7-dihydroxynaphthalene,

2,7-dihydroxynaphthaIine,

1,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl,

4,4'-dihydroxystilbene, 2,6-dihydroxyanthracene,

Hydroquinone. Catechol,
X bis (4-hydroxyphenyl) butane

(Bisphenol B),

4 4-bis (4-hydroxyphenyl) pentanoic acid,

2 ^ -Bis- (4-hydroxyphenyl) -tetranuordichlorpropane,

4 4'-dihydroxydiphenyl sulfone,

44'-dihydroxydiphenyl ketone,

Tn- (4-hydroxyphenyl) methane,

3 3 '"5,5'-tetrachlorobisphenol A,

33 '55-tetrabromobisphenol A and its alkali and

Erd'aikalisab.e.

nip amount of aromatic polyhydroxy compounds

λ ä is usually 0.1 to 20 parts per 100 parts

Suorelastomeres, but depending on each

The compound used can be amounts of 0.5 to 3

τ len to be preferable. Sterically hindered aromatic

The polyhydroxy compound usually does not look like that

satisfied, and with a severely hindered connection

it can happen that one is out of practice

rründen will forego their use.

The formation of a weakly basic system should be involved in the amine; education can be based on a Can be done in a number of known ways. According to one procedure, the alkali or alkaline earth salts are used (preferably the monometal salts) of the above post-cured. Like the good values of the Properties and permanent deformation determined at 25 ° C, show, are the accruing Elastomers solid and well cured.

| _{ei | e}

_Part | _e

.

Components

Mixed polymer

soot

MgO

accelerator

Dipotassium bisphenol AF

Bisphenol AF
Test values

Module (100% elongation) *)

Tensile strength, kg / cm ²

Elongation at break,%
Shore hardness
Permanent deformation
70 hours, 25 ° C
70 hours, 204 ° C
² S ·) kg / cm * χ 0.07

Example 2

100 100 20th 20th 10 10 2 4th 2 1
0, 700 600 161 147 205 210 71 68 24 22nd 50 49

Barium, and

from Magnes.um, you get at

but can be replaced by the Hydrox.d. Usually one works with amounts from 1 to 20, preferably up to 100% elastomer.

The accelerator compounds according to the invention enable the use of provided Matena _lien as hardeners, which would not be usable for anything. S.ch has shown that the

do not cause any hardening per 100 parts of polymer.

The following examples serve to further illustrate the Invention.

B e i s ρ i e 1 1

This example illustrates the hardening of a mixture. polymers made of vinylidene fluoride, tetrafluorathyler. and Hexanuorpropyleni weight percent.MS.SO or.

25), obtained according to the method of the USA patent specification 29 68 649, with the dikahum salt from 2 * to * 4-

^ SSTS ^ S ^ S ^ afka ^ er _to J "^ _to dissolve 4 g (0.10 mol nol A ^ F one stirs _b ^ ^ ^ ^ ₀

Sispnenol AF heats the mixture for 5 min. ° ' ^S P ^h _f X _d in, then evaporated in a flask ^Db Ä Vrockne and finished 1 g ^^^, _{mm pressure} . The puWer here in emer hour, 10ü> C _{wdße becomes m | t}

Finely ground second and piJle.

ner

is on a rubber mah, example
_rf ^^ _{dje hardening of a M} ischpo-

_{en from 60} o _{/ o} vinylidene fluoride and 40% hexaJluorpropane (obtained after the ^ ^? ^ f ^ \ f "l ^.

and ^^ TSSZS ^ ÄhÄ F. ™ ^e _accelerator a polyethylene ether- ^ c ^ ^ ^ _{e {wa or}

glyKoi 1m _eingese t _z t is.

t, 2 ^ s (met y ^ _mixed polymers according to the

TaSe ° on and hardens test subjects after the work week

Si

5SS "c ^C kneads ^{the 5} ne ^m ut at 40 ° C and 5 mm pressure. This is it.

The white powder obtained in a yield of 167 g becomes a fine powder before use ground.

The potassium salt of bisphenol AF (35% basic) is prepared in a similar manner from 13.2 g of potassium hydroxide pellets (0 20 mol), 200 ml of methanol and 96 g of bisphenol AF (0286 mol) produced, with a white powder in a Yield of 108 g is obtained.

Components

Copolymer of Example 3

Copolymer of Example 1

soot

MgO

Polyethylene ether glyco!

(Mol.wt. 400)

Potassium salt of bisphenol AF

6594 basic

35% basic 1,2-bis (2-methoxyethoxy) ethane

Test values (at 25 ° C) Module (100% elongation) Tensile strength, kg / cm ² elongation at break,% Shore hardness Permanent deformation 70 hours, 25 ° C 70 hours, 121 ° C 70 hours, 204 ° C

3-A 3-B Parts Parts 100 100 30th 30th 4th 4th 2 1.5 2.5 1 2 520 400 94.5 136.5 220 285 70 70 17th 25th 10 26th 41 49

Example 4

This example explains the effect of different fillers and shows the usefulness of Magnesium hydroxide instead of magnesium oxide. It further explains that with different curing recipes according to the invention, good vulcanizate properties

-, ο ten are also available without post-curing.

The mixed polymer from Example 3 is mixed on a cold rubber grinder according to the table. The table also gives the properties after press hardening (without post-hardening) as well as after

usual 24-hour post-curing at 204 ⁰ C.

Components

Mixed polymer

soot

MgO

Magnesium hydroxide

Accelerator of example 1

Monopotassium bisphenol AF

zinc oxide

Calcium oxide

Barium carbonate

Magnesium fluoride
Scorch at 121 ° C according to Mooney minimum

Increase 10 points, min.

After press hardening, 30 min. At 165 ° C, and without post-hardening

Shore hardness

Compression Set, 70 hrs., 204 C ⁰ After Press-Cure, 30 min. At 165 ° C, and post-curing oven, 24 hrs. At 204 ⁰ C (test at 25 ° C) modulus (100% elongation)

Tensile strength wedge, kg / cm ²

Elongation at break,%

Shore hardness

Permanent deformation
70 hours, 25 ° C
70 hours, 121 ° C
70 hours. 204 ⁰ C

4-A
Parts 4-B
Parts 4-C
Parts 4-D
Parts 4-E
Parts 4-F
Parts 100 100 100 100 100 100 30th 30th 30th 30th 30th 30th 4th 4th 4th 4th 4th 4th
2 2 2 2 2 2 2.5 2.5 2.5 2.5 2.5 2.5 5

24
> 45 28
30th 31
32 32
23 27
30th 28
36 66
84 64
63 63
100 63
too + 64
100 + 69
65 510
129.5
240
69 400
112
280
66 400
122.5
310
64 800
119
180
"7 Λ
I * Τ 680
119
180
71 810
133
180
72 11th
10
33 U) -
NJ CJl NJ 18th
10
59 10
10
52 8th
8th
37 10
8th
32

7 8

Example 5

This example illustrates the satisfactory press hardening (without post-hardening) as well as after dei

Curing of the elastomer in a press without the usual 24-hour post-curing at 204 ^° C. The one without

Post-curing using the monopotassium salt 5 Post-curing using the monopotassium salt;

properties obtained from bisphenol AF and the accelerator from bisphenol AF are wi <

Example 1. the table shows almost as well as that of the mi

The copolymer of Example 1 is cured on a cinnamylidene hexamethylenediamine and de

cold rubber grinder mixed up. The table of copolymers subjected to postcuring gives

names the properties both for the state according to ions.

5-A 5-B 5-C *) Parts Parts Parts Components Mixed polymer 100 100 100 soot 20th 30th 20th MgO 10 4th accelerator 2 2 Monopotassium bisphenol AF 2.5 2.5 MgF ₂ 5 MgO 15th Cinnamylidene hexamethylenediamine 3 Vulcanization at 121 ° C according to M ο ο η e y minimum 86 56 Increase 10 points, min. 3 21 After press hardening, 30 min. At 165 ° C Shore hardness 67 71 Module (100% elongation) 420 550 Tensile strength, kg / cm ² 105 105 Elongation at break,% 315 310 Permanent deformation 70 hours, 25 ° C 15th 16 70 hours, 121 ° C 45 48 70 hours, 204 ⁰ C 66 60 After press curing, 30 min. At 165 ° C, and oven after hardening, 4 hrs. to 204 ° C, 24 hrs. at 204 ⁰ C Module (100% elongation) 630 950 550 Tensile strength, kg / cm ² 175 171.5 175 Elongation at break,% 260 210 • 270 Swelling (acetone, 1 day), vol .-% 294 230 302 Shore hardness 72 74 71 Permanent deformation 70 hours, 20 ° C 12th 12th 22nd 70 hours, 121 ° C - - - 70 hours, 204 ⁰ C 32 26th 66

*) Not required. just for comparison.

Example 6

This example illustrates the hardening of the elasto- phenolic hydroxyl group on the double bond

rcn using the dipotassium salt of tetrade inhibits copolymers. Even with the 1st

Brom-bisphenol A in connection with hydroquinone or do brom-bisphenol A as hardener is used

Trabromo-bisphonol A. useful, slightly crimped gum obtained.

The mixed polymer of Example 1 is used for the production of dipotassium sal / .cs from Tciral

cold rubber grinder mixed up; The proper bisphenol A is 13.2 g of potassium hydroxide (0.20

shafts are listed in the table. Using 200 ml of methanol and 54.4 g (0.10 mol) of tetrabroi

Hydroquinone as hardener will give better results ds phenol A cingcsct / .i. Evaporation in the flask

than obtained with the tetrabromo-bisphenol A, what Fcrligbchandeln at 40 "C and 5 mm pressure licfci

probably based on the fact that in the name of a white powder, which one before use

th case the severe hindrance the accumulation of the finely ground.

6-Α parts

6-B
Parts

6-C parts

6-D parts

6-E parts

Components

Mixed polymer

MgO

Accelerator of example 1

Dipotassium salt of tetrabromo-bisphenol A

Hydroquinone

Tetrabromo bisphenol A.
Vulcanization at 121 ⁰ C according to M ο ο η ey

minimum

Increase 10 points, min.

After Press-Cure, 30 min. At 165 ° C and post-curing oven hrs. At 204 ⁰ C

Shore hardness

Module (100% elongation)

Tensile strength, kg / cm ²

Elongation at break,%

Permanent deformation
70 hours, 25 ° C
70 hours, 204 ° C

Swelling (acetone, 1 week),% by volume 100

0.5

58 18

70 520 154 260

18th

339

100

20th

10

54 31

71 550 140 260

12th

40

364

100

20th

10

0.5 0.5

60 13

72 650 119 190

16

50

287

100

20th

10

55 24

73 650 126 200

11th

41 267

100 30

73 300

98 450

798

Example 7

This example illustrates the curing of the elastomer using the accelerator of Example 1, the monopotassium salt of bisphenol A and hydroquinone. The mixed polymer from Example 1 is mixed on a rubber grinder; the vulcanizate properties are given in the table. For runs 7-A, 7-B and 7-C, in which the ratio of potassium to phenolic hydroxyl groups is 0.5 to 0.27, the samples are well cured, but for run 7-D, in which this The ratio is only O ₁ Ii, no curing of the elastomer is obtained.

The monopotassium salt of bisphenol A is obtained from 52.8 g (0.80 mol Potassium hydroxide, 660 ml of methanol, and 176 g of bispheno A (0.77 mol) were prepared, with a light tan

free flowing powder is obtained in a yield of 172 j.

Components
Mixed polymer
soot
MgO

accelerator

Potassium salt of bisphenol A
Hydroxhinone

Vulcanization at 121 ° C according to M ο ο η ey minimum
Increase 10 points, min.

After Press-Cure, 30 min. At 165 ° C and post-curing oven, 24 hrs. At 204 ⁰ C
Shore hardness
Module (100% elongation)
Tensile strength, kg / cm ²
Elongation at break,%
Permanent deformation
70 hours, 25 ° C
70 hours, 204 ⁰ C

7-A 7-B 7-C 7-D Parts Parts Parts Parts 100 100 100 100 20th 20th 20th 20th 10 10 10 10 2 2 2 2 2 2 2 1 0.5 0.75 0.75 53 84 45 33 4th 4th 7th 45 71 72 72 360 700 830 112 140 133 310 200 170 32 12th 8th 65 36 30th

Example 8

This example illustrates the curing of the elastomer using the dipotassium salt of tetrachlorobisphenol A in connection with hydroquinone or with bisphenol A. The mixed polymer is on a cold rubber grinder mixed up; the vulcanizate properties are given in the table. All Samples are hardened well.

The preparation of the dipotassium salt of Tctrachlo bisphenol A takes place according to the working method of Beispi < from 79.2 g (1.2 mol) of potassium hydroxide, 50 ml of methane and 221 g of tetrachloro-bisphenol A (0.60 mol). Tuesday Product, which is obtained in a yield of 264 g, is ground to a fine powder before use.

Components 17 69 987 After press hardening, 30 min. At 165 ° C, and oven post-hardening, 73 \ - 12th 8-D 8-E 11th Copolymer of Example 1 24 hours at 204 ° C 680 8-C Parts Parts soot 8-A Shore hardness 133 8-B Parts MgO Parts Module (100% elongation) 215 Parts 100 100 Accelerator of example 1 Tensile strength, kg / cm ² 100 30th 30th Dipotassium salt of tetrachloro-bisphenol A 100 Elongation at break,% 11th 100 30th 4th 4th Hydroquinone 30th Permanent deformation 11th 30th 4th 2 2 Bisphenol A. 4th 70 hours, 25 ° C 34 4th 2 3 3 Magnesium fluoride 2 70 hours, 121 ° C 2 2 0.75 2 70 hours, 204 ° C 3 0.75 1.5 0.75 0.75 5 5 5 76 76 77 1000 630 73 850 126 87.5 750 126 180 230 122.5 190 210 12th 30th 12th 12th 30th 12th 11th 35 55 12th 32 40

Example 9

This example illustrates the curing of the elastomer using the potassium salt of 2, 4, 6-trichlorophenol in connection with hydroquinone. The interpolymer is mixed as above Vulcanizate properties are given in the table.

The potassium salt of 2, 4, 6-trichlorophenol is nacl the procedure of Example 3, but using 13.2 g (0.20 mol) of potassium hydroxide, 39.6 g (0.2 ( Mol) 2, 4, 6-trichlorophenol and 150 ml of methano produced, leaving a white powder in a yield of 43 g accrues.

9-A Parts Components Copolymer of Example 1 100 soot 30th MgO 4th Accelerator of example 1 2 Potassium 2,4-6-trichlorophenoxide 3.5 Hydroquinone 0.75 After press curing, 30 min., At 165 ° C and oven post-curing, 24 hours at 204 ° C Shore hardness 78 Module (100% elongation) 1100 Tensile strength, kg / cm ² 140 Elongation at break,% 165 Permanent deformation 70 hours, 25 ° C 25th 70 hours, 121 ° C 18th 70 hours, 204 ⁰ C 71 Swelling (acetone, 12 days),% by volume 227

Example 10

This example illustrates the hardening of the Hlastomcren using potassium benzoate and hydroquinone with or without the accelerator (s) from example 1.

Approaches 10-A, 10-B and 10-D, all 2 to 4 parts Contain accelerators, have been shown to be qualitative on the basis of manual tensile tests, after 30 minutes 165 ° C cured in a press to be quite good. After a

do oven post-cure at 204 "C is a good look of these three samples and, as the values of the permanent deformation and the volumetric swelling show, a good hardening. However, the IOC approach, which does not contain an accelerator, shows

there is a substantial underhardening. Post-curing after oven at 204 ° C the 10-C block has many bubbles, and its hardening state is like the strong swelling In Acetone shows low.

10-A
Parts

ΙΟ-B
Parts

10-C)
Parts

10-D
Parts

Components

Copolymer of Example 1
soot
MgO

Accelerator of example 1
Magnesium fluoride
Hydroquinone
Potassium benzoate

After press curing, 30 minutes at 165 ° C and Oven post-curing, 24 hours at 204 ° C

Shore hardness
Module (100% elongation)
Tensile strength, kg / cm ²
Elongation at break,%
Permanent deformation

70 hours, 25 ° C

70 hours, 121 ° C

70 hours, 204 ° C
Swelling (acetone, 8 days),% by volume

*) not according to the invention, only for comparison.

100 100 100 100 30th 30th 30th 30th 2 4th 4th 4th 2 4th 0 2 5 5 5 0.75 0.75 0.75 0.75 3 3 3 2.5 74 75 75 600 850 370 900 115.5 98 40 122.5 240 160 450 175 42 37 33 37 31 26th 82 96 74 283 246 586 249

Examples 11-15

These examples illustrate the curing of the elastomers using hydroquinone, the accelerator of Example 1 and various salts. In example 11 potassium stearate, in example 12 Lithium benzoate, in example 13 potassium hydrogen phthalate, in example 14 potassium acetate and in example 15 Cesium benzoate used. The mixed polymer is mixed on a cold rubber grinder; the Vulcanizate parameters are given in the table.

Potassium stearate-containing batch 11 proves itself, determined by manual tensile testing, after 30 minutes. Press hardening at 165 ° C as well hardened. After oven post-curing, the elastomer is like the low one volumetric swelling in Acton and the values of tensile strength and permanent set show tight networked.

The lithium benzoate-containing batch 12 shows substantial undercuring after 30 minutes of press hardening at 165.degree. After 24 hours of post-curing at 204 ° C, that's it

Elastomers, such as the volumetric swell values in acton and the tensile strength show well cured.

The batch 13 containing potassium phthalate is uncured after 30 minutes of press curing at 165 ° C, which leads to is to be expected because the potassium phthalate is too weak

Represents base in order to remove hydrogen fluoride from the copolymer. For o-phthalic acid, the "Handbook for Chemistry and Physics", 48th Ed., S. D-91, 1967/68, Chemical Rubber Co., Cleveland, Ohio, V. St. A., names K \ as ionization constants = 1.3 χ IQ- ³ and K ₂ = 3.9 χ 10-6.

The potassium acetate-containing batch 14 is solidly hardened after 30 minutes of press hardening at 165.degree. After 24 hours post-cure at 204 ⁰ C, the elastomers such as low volumetric swelling in Acton shows diehl crosslinked.

11th 12th 13th 14th 15th Parts Parts Parts Parts Parts Components Copolymer of Example 1 100 100 100 100 100 soot 30th 30th 30th 30th 30th MgO 4th 4th 4th 4th 4th Accelerator of example 1 2 2 2 2 2 Magnesium fluoride 5 5 5 5 5 Hydroquinone 0.75 0.75 0.75 0.75 0.75 Kaüumstcarnt 6th Lithium benzoate 2.5 Potassium Hydrogen Phthalal 4th Potassium acetate 2 Cesium benzoate 4th After press hardening, 30 min. At lb5 "C, and Oven curing, 24 hours at 204 "C Shore Hilrtc 7b not 78 77 Module (100% elongation) 780 400 her 950 U) OO ' Tensile strength, kg / cm ² 105 133 tet 105 91

15th

continuation

By Press-Cure, 30 min. At 165 ⁰ C and
Oven post-curing, 24 hours at 204 ° C

Elongation at break,% permanent deformation 70 hours, 25 ° C 70 hours, 121 ° C

70 hours, 204 ⁰ C swelling (acetone, 8 days),% by volume

In Examples 10 to 15, the amount of potassium salt 15 is that ^de / ^a , ^rt J ^ r ⁱⁿ ^ "is probably somewhat above the appropriate value.""""- The equivalents of potassium per equivalent of phenolic groups in the hardener, Hydroquinone, range from 1.1 to 1.5, as has now been shown.

U parts

180

22nd

21

66

222

12th Parts

440

365

13th Parts

14 TeU

145

26th

28

69

251

15 parts

125

36

42

94

182

uou um:. · ..... c _o "like 0.17 to 0.80

Potassium equivalents / phenolic group equivalent can work, the range from 0.2 to 0.5 too should be preferred.

Claims (1)

Patent claims: 1. Thermosetting composition aas A: vinyl fluoride copolymers and B: a compound from the alkali or alkali group causing a weakly basic system Alkaline earth salts of an aromatic polyhydroxy compound or of weak acids, or of oxides or hydroxides of divalent metals, characterized in that that the mass in addition C: 0.1 to 20 parts by weight, based on 100 parts by weight of A, of an optionally halogen-substituted one aromatic polyhydroxy compound or alkali or alkaline earth salts thereof as crosslinking agents and D: as accelerator 0.1 to 20 parts by weight, based on 100 parts by weight of A, open-chain aliphatic polyether of the general formula