DE1941915C - Molding compositions made from elastomeric vinylidene fluoride copolymers that can be crosslinked under the action of heat and their use for the production of crosslinked elastomeric moldings - Google Patents

Description

monoolefine ζ. B- ^a *, ^ frifluoroethylene or perfluoro-

αϊ) SSiS

in which R ', R * and R> Alkyl radicals with 1 to - ώ

W represent C-atoms, R ² an agynm _and valuable ^^ l ^ JachnugdKltermo-

with 2 to 12 carbon atoms or a phenylene _shaft arrives and «are _lowered

Sst or Phenylendialkylenrest -.m plasticity ^ moldings "crosslinked ^ .. ^ fp SaS. This Ver 8 to 12 carbon atoms and R ^euien. KfJ _A ^A * 5 to which ^P ° ^lyi be" relatively with

| j§ is stable ^below 5i £ 75 ° C, and that above tentschrift 2,951,832).

■ ψ of 125 ° C in the presence of water an _{im fo} i " _{en (} j _e n is part of the designation

fi basic, nitrogen-containing compound --—.._., ""#"»": a, _p permanent

β with at least one hydrogen atom on

! § Nitrogen atom with a molecular weight

R up to 1000 and an amine equivalent _3J

«Weight up to 500 forms, as well as

Aminoverbmdirogate tahibitor _mate rial door tone> ™ Zert "£ S £ I ^ B« ine dich-

enthalM, whereby the parts by weight are in each case to 4 ° * end ^d »rZeil ^ r _{omung er (älirli mn}

JOO Gewiditsteile viBylidennuond-Copolymerisat «" ^ '"^ SS _to general is the extent

Claim., Thereby _g e-

i ssb;

of not more than 500 and an amine equivalent form mass «^ ^ _compression deformation and marking weight of not more than 300 forms TiS The problem is solved by the invention. 3. Molding compositions according to claim 1 and 2 thereby 5 ° NEN. This Autga ^^ invention are thus identified under heat that the molding compounds as an inhibitor ^ S ^ rZS ^ oL · ^^ made of elastomeric SS di b lls

g TiS exercise

3. Molding compositions according to claim 1 and 2 thereby 5 ° NEN. This Autg ^ invention are thus identified under heat that the molding compounds as an inhibitor ^ S ^ rZS ^ oL ^^ made of elastomeric (C) hydroquinone contain ^ vSSfluoria copolymers, the given all

spää £ »" f ₅₅ SS Sa ^ eA ¹ SA

% Ä ^h Αϊ f

55 included, aie aaumui ^ au-u «,. ,

ι according to claim 4, characterized by molding compositions a mixture of Ver-Calciumhydrpxid known per se as a crosslinking agent

t is used. . , _ΛΛ -,. _{Λ / Ι}

(a) 0.05 to 0.4

gjj Quaternary Ahm «*, ... ^ -

The invention relates to crosslinkable molding compositions of the general formula (I) or (II)

P ₁ I-Nr _2n -RI] ^ [OH-L W

Twist for making verncixiciciosLuxu ^ M. ~.

body with reduced permanent compression set.

In general, linear polymers are thermo-65

plastic and soften with increasing temperature [R ⁴ - N - R |] ⁺ OH "(II)

i'iid increasing pressure until they finally called
Melts are present. This process is reversible. in which R ¹ , R ³ and R ^{5 are} alkyl groups with 1 to

18 carbon atoms, R * is an alkylene radical with 2 to 12 carbon atoms or a phenylene radical or a phenylene dialkylene radical with 8 to 12 carbon atoms and R ^{4 is} an alkyl radical with 1 to 12 carbon atoms or an aralkyl radical with 7 to 12 carbon atoms -Atoms means

(b) 0.1 to 2.5 Gewichtsleilen at least one compound that is stable in the absence of water below 75 ⁰ C and above 125 ⁰ C in the presence of V / ater a basic nitrogen-containing compound having at least one hydrogen atom on the Forms nitrogen atom with a molecular weight up to 10000 and an amine equivalent valent weight up to 500, as well as

(c) optionally 0.1 to 2 parts by weight of an oxidizable aromatic I droxy or amino compound as an inhibitor

included, whereby the weight rises to 100 parts Vinylidene fluoride copolymer are related.

The invention also relates to the use of the molding compositions according to the invention for producing crosslinked elastomeric moldings by vulcanization using customary processes. Preferably, 100 parts of the molding composition according to the invention are mixed with 0.1 to 2 parts of the oxidizable aromatic hydroxy or amino compound (c), 2 to 25 parts of an inorganic acid acceptor (d), and optionally 0.5 to 10 parts of an inorganic base (e ) mixed as a crosslinking accelerator. The mixture is then z. B. in a form, preferably for 5 minutes to 15 hours, at temperatures of 95 to 230 ° C and pressures of 7 to 210 kg / cm ² and then heated to temperatures of 150 to 315 "C for 2 to 50 hours under normal pressure .

For crosslinking vinylidene fluoride copolymers are from USA patents 3,080,336 and 2951,832 already mixtures of carbamic acid esters and tertiary amines and diamines, respectively. Furthermore is from the British patent specification 1095 836 the use of quaternary ammonium salts known for the crosslinking of vinylidene fluoride copolymers.

In contrast, the essential feature of the molding compositions according to the invention is that Combination of the quaternary ammonium hydroxide (a) and, under special conditions, a basic one Nitrogen compound-forming component (b). The simultaneous use of components (a) and (b) is for the solution of the problem, namely the production of crosslinked vinylidene fluoride copolymers with little permanent pressure deformation, mandatory requirement. This is evident from the Examples.

Table II of Example 1 (Experiment 1) and the comparative example show that if the Tetrabutylammonium hydroxide [component (a)] most of the physical properties of the crosslinkable Molding compound, in particular also the values for the compression set, compared to the invention crosslinked molding compositions are significantly deteriorated. Experiment 1 of Table II corresponds to Method of U.S. Patents 2951832 and 3088,938.

in Example 1 of USA. Patent 2 951 832 there is provided a compounding recipe in which a diamine adduct is used alone or in combination with a diamine carbamate for crosslinking a Viuylidenfluorid copolymer, These crosslinked polymers have after 70 hours at 12O ⁰ C only

a compression deformation of 30 to 60%. According to the values for the printing formation in Table I. (present invention) lowering the temperature from 205 to 175 ° C results in a lowering of the Compression deformation from 14 to 24% to 9 to 12%.

ίο A further decrease in temperature up to The compression set would certainly still be 120 "C further reduce. This illustrates the significant improvement in bleeding compression set in the molding compositions of the invention.

Also the values given in the USA patent specification 3,080,336 for the permanent compression set, which are determined according to the same test standard ASTM D-395, method B, as in the present invention (See column 4, line 16 of the U.S. Patent

3 080 336) are with 16 to 31% 'column 4, lines S1 / 52) significantly worse than the values for the crosslinked molding compositions according to the invention (Examples 1 and 3

through 6 of the present invention).

In the process of British Patent 1095 836, the quaternary ammonium salt is used in quantities from 2 to 8 parts by weight per 100 parts of copolymer used (page 3, table). In contrast, in According to the present invention, the proportion of ammonium hydroxide is only 0.05 to 0.4 parts by weight per 100 parts

Copolymer. The very low content of crosslinkers explains the excellent values for the permanent compression set even after accelerated aging at high temperatures (cf. Table I of the present invention with the results on pages 3 to 5 of the British patent 1095 836).

On the basis of the prior art set out above, those with the molding compositions according to the invention achieved results, namely cross-linked form

body with outstanding properties in terms of permanent compression set, as surprising be considered.

The person skilled in the art cannot infer anything from the patents mentioned as to the specific combination the subject of the invention, d. H. the joint use of a quaternary ammonium hydroxide and one under special conditions a basic, nitrogen-containing compound with at least a compound forming a hydrogen atom on the nitrogen atom.

Elastomeric vinylidene fluoride copolymers suitable for the molding compositions of the invention generally contain disordered, saturated, fluorinated _{carbon chains which contain a substantial number of CH 2} groups, generally at least 10% of all carbon atoms in the chain. The disorder in the carbon chains is generally due to the copolymerization, ie to the use of two different comonomers. If one of the monoolefins contains three or more carbon atoms, there are pendant alkyl radicals in the copolymer, e.g. B. methyl or ethyl groups, these alkyl radicals are preferably perhalogenated, in particular perfused. Through this side

groups, the symmetry of the carbon chain is disturbed, which leads to the achievement of elastomeric properties necessary is. The side groups give the chain additional degrees of freedom because they

· Change of several methylene groups £ fSStome a typical defend

as and a B.

the relevant carbon atom with which it is

is linked, becomes asymmetrical. However, it will too , - by other unsymmetrical groups, Ab. % by the CFCN group, an asymmetry in the

■ introduced a linear carbon chain. Independent there-

of whether the asymmetry is due to two different

Substituents or through a side group

is called, at least 10% of the coal .. atoms of the chain must be asymmetrical. and

The linear, saturated, fluorinated carbon- io LNCH ₂ C ₆ H ₄ CH ₂ N (CHs) ₂ ]

chains of vinylidene copolymers can also U ^^ ö

rOH-1

[(CH ₃ I ₃ NCH ₂ C ₆

) ₃ NCH ₂ CH ₂ N (C ₄ H ₉ ),]

J ₂

fluoride and monochlorotrifluoroethylene, 2-chloroperfluoropropylene, perfluoropropylene, tetrafluorethylene, 1-hydroperfluoropropylene (CFH = CFCF ₃ ), dichlorodifluoroethylene, trifluoroethylene, chlorofluoroethylene or

Vinylidene chloride. . ² pp

Copolymers of two or more comonomers can be used. You can also other olefins, e.g. B. ethylene, contained as monomer units. Copolymers are preferred Vinylidene fluoride and at least one fluoromonoolefin with a terminal ^ double bond, which has at least one fluorine atom on each double bond ^ Has carbon atoms, and fluorine or chlorine atoms or a lower fluoroalkyl radical as further substituents carries, e.g. B. a perfluoroalkyl radical, in particular perfluoro? Propylene, tetrafluoroethylene, monochlorotrifluoroethylene and 1-hydroperfluoropropylene. The copolymers of monochlorotrifluoroethylene are particularly preferred and vinylidene fluoride according to US Pat. No. 2,752,331 and the copolymers of perfluoropropylene and vinylidene fluoride according to US Pat. No. 3,051,677 and 3,318,854 and Terpolymers made from perfluoropropylene vinylidene fluoride and tetrafluoroethylene according to USA patent 2968 649. The copolymers of perfluoropropylene and vinylidene fluoride at about 15 to about 50 mole percent Perfluoropropylenes are particularly suitable and are therefore particularly preferred.

The elastomeric vinyl fluoride copolymers contain reactive substituents, such as hydrogen, fluorine or chlorine atoms, and are at least half halogenated. The term "halogenated to adhere" means that at least half of the hydrogen atoms bonded to carbon in the analogous, non-halogenated polymers have been replaced by halogen. It is important, however, that the polymer chain also contain unsubstituted methylene groups. Homopolymers of tetrafluoroethylene and other perfluorinated olefins and their copolymers with other perfluorinated comonomers require very high temperatures to be crosslinked and are therefore not used. Be _one very high temperatures is beautiful Wieng to control · Vernfzungsdichte, and you erhah easily unrestricted

^^^ ⁶⁵

w weight results
kuiargewicBτ

cherishes

_η1ε (bj is preferably a Verrhalb 125 C in the presence of water _ n _{d res Amili) em H} ydraz »n

briefly below beer as a nurse _P K value of Aoune cherishes preferential ^ 14 amines having _bad high Molekularn "." _while Vulkamsations- «« _by Vinylidenfluond-Coje ^ ^ ^ ia _unequal moderate encryption

^ _{Is o} f the physical properties _of f tei! Ig impact. Generally ™ _ei ^ _it A _n Ua However, an amine ^^ 2 ^ 1, not the üegt 500 _{is 5 mkn} with a MOIE-1000 Ver satisfactory, with an optimal Motekgug "physical preferred. Go to troa ^ g ^^^. ^^ ^ _Me _

^El S ^en ™ „ _H 7_ _{speed and} solvent resistance, • SSSewicbt should not exceed 500;

about 300.

mc ^ " _d " _{the K.}

hereinafter referred to as amine

ZnnbMn _e T from C ^ rbonyl _{hin kufZ & h Carbo} .

although the used ^^ 4 that certain presence able to form in the absence of z _'in the presence of water, for example carb carbodiimides and thiourethanes. arD saturated co-

_{rfd and z} . _{B. Perfluoro} . known. Presumably agreement with sl ^ d «ba« «k« lal ^ hydrogen with formation of ^^ eSTR ₀ Ue. This Doppelbindunounge ^ _{h, yon} Vemetzungs-

^ ^el « ^{e D} £ ™ _{ebung suffice} at first, place ^ ^to r ^ WD g _bUden

While rend de '«J ^ Smesaturated structures, the itself ^ pus ^ «c ^ unge g ^ ^^ ^^

b ^ zokrtige ^ ζ ^ ξ hypothesis coincides with

a range of amines

designer nyleddukte
Arninbilcteer

amate of

set; don't do it yourself

Represent amine formers, as well as hydrazine and ammonia are not suitable as crosslinking agents. Your ÄÄi ehe ^zu " *

The excellent results with regard to the compression set, which is, for example, less than 20% and generally less than 10% after 24 hours at 205 ^° C., can only be achieved with the vulcanization system described above. The results can neither be assigned to the individual components, nor can a similar result be obtained if one component is omitted.

The aforementioned carbonyl adducts can be produced either from the carbonyl compound and the amine or by an appropriate chemical process. Carbonyl adducts which form the same amine thermally or by reaction with water are considered to be equivalent in this regard. For example, hexyl isocyanate, hexanecarbodiimide, hexyl carbamate and hexylacetamide are chemically equivalent carbonyl adducts of hexylamine and carbon dioxide and acetic acid, respectively, since they give the same amine, as shown in the following reaction equations.

[C ₆ H ₁₃ NHCO ₂ ] - [C ₆ H ₁₃ NH ₃ I ⁺
* 2C ₆ H ₁₃ NH ₂ + CO ₂

CHN = C = NC H + 2HO
* 2C ₆ H ₁₃ NH ₂ + CU ₂

C ₆ H ₁₃ NCO + H ₂ O

> QH Njj + CO,

^{6 13}
(C ₆ H ₁₃ NCO) ₂ + 2H ₂ O

► 2C ₆ H ₁₃ NH ₂ + 2CO ₂

¹ ",,» "'*, rinn u

(C ₆ H ₁₃ NH) ₃ P = O is not an equivalent carbonyl adduct of hexylamine, since it does not liberate a carbonyl compound; however, it is a suitable amine former.

The carbonyl radical of the carbonyl adduct is generally comprised of carbon dioxide, including carboxylic acids Polycarboxylic acids, aldehydes or ketones. Preferred aldehydes, ketenes or carboxylic acids have the general formula III or IV

Examples of carbonyl adducts are the adducts from

'· ^A "" w + ^Α ™ * - ^B ·

6CH ₂ O + 4NH ₃

> Hexamethylenetetramine + 6H ₂ O

² · aldehyde + primary amine, e.g. B.
R ⁶ CH = O + H ₂ NR ⁷

3. aldehyde + secondary amine, e.g. B.

R ⁶ CHCH = O + HNR ⁷ R ⁸

² 06C-CWKm ¹ R ³ 4- HO

* ^{2 L} " ^{K +} " ²

4. ketone + primary amine, e.g. B.

R ⁷ r = O4-HNR ^{7 2} ₇ ^{+ 2} ^
* RzC = NR + H ₂ O

5 ketone + secondary amine, e.g. B.

_η
R ₂ CHCORO + HNR R

► R ⁶ C = CR ⁷ NR ⁷ R ⁸ + H ₂ O

2S ^{c 2 + ζ}

R ⁶ C = O
R ⁶ CCOOH) ₁ -4

(III)
(IV)

in which R ^{6 is} a hydrogen atom *, an alkyl or cycloalkyl radical with 1 to 25, preferably 1 to 12 carbon atoms, an arylalkyl radical with 7 to 25 carbon atoms or an aryl or alkaryl radical with 6 to 25 carbon atoms - two A% ^ branches can be linked together to form an alicyclic IV, as is the case with cyclohexanone.

2S ²
> [R ⁷ NHCO ₂ -3 [R ⁷ NH ₃ ⁺ ]

In the above formulas, R ^{6 has} the aforementioned meaning; R ⁷ and R ^s are the same or different

* ^unt bed ^Suten an aromatic radical having 6 to 25, preferably 6 to 12 carbon atoms, an alkyl or cycloalkyl radical having 1 to 25, preferably 1 to 18 and particularly preferably 1 to 6 carbon atoms or an aralkyl or arylcycloalkyl radical with 7 to 25, preferably with 7 to 12 carbon atoms.

In addition to the monoamines, diamines and polyamines can just as well be used; in some cases ^{they are} preferred- ^For example, ammonia and hexyiamine can be replaced by hydrofoil and hyoxane diamine, respectively; The compound can just as easily be found on the stiffness of C ₆ H ₅ NHQ ₈ H ₃₇

C ₆ H ₅ NHC ₃₆ H ₇ NHC H
^{72 6 s}
use. In the formation of the carbonyl adduct

one, several or all of the amino groups of the amine can be involved. On the grounds of the easy Symmetrical connections are preferred; however, it can just as easily be asymmetrical Compounds such as 6-methylaminohexyl-

amine, can be used.

In the production of carbonyl adducts from Aldehydes or ketones and secondary amines must have at least the aldehydes and ketones one of the carbons adjacent to the keto group

substance atoms have at least one hydrogen atom. Hydroxyl groups od _; he halogen atoms, such as chlorine or fluorine atoms, have no effect either on the production of the carbonyl adduct or on their functional capacity with regard to crosslinking.

teÜig from.

Particularly preferred amine formers are adducts of dialdehydes and aliphatic diamines general formula V

R ⁷ - CH = (CH - CH =) "N (CÄ ,,) N (= CH - CH) _1n = CHR ⁷ (V)

where R 'has the aforementioned meaning, m is O or 1 and η is a number from 2 to 36, preferably from

209 684/365

2 to 6, as well as carbamates of the general formula VI

YHN-C _n H _2n -X

(VI)

'- ■ in the Y is a hydrogen atom, an alkyl radical with 1 'bi ", 6 carbon atoms or an aryl radical from 6 to / Represents 12 carbon atoms (where Y is preferably a hydrogen atom), X is a carbamyl radical and η is a number Wipe 2 and 36, preferably between 2 and 6. , _ The amine former can be of the mold to be hardened ■ mass to be incorporated directly; in the case of using carbonyl adducts, the corresponding Components or their precursors of the molding compound to be crosslinked, for. B. during the mixing process are added, the desired amine adduct being formed in situ.

A particularly suitable amine former is the i ^ .iffsche base from cinnamaldehyde and trimethylenediamine, hereinafter referred to as cinnamaldehyde-trimethylenediamine-azomethine. Particularly preferred Amine formers are made from an aliphatic or cycloaliphatic diamine in a known manner an aldehyde or with carbon dioxide

Carbonyl adducts of diamines with carbon dioxide,

d. H. Carbamates in U.S. Patent 3,096,314 in connection with the networking of high level Elastomer described.

The following overview shows the formulas of the Alde-

hyde and amines and the adducts produced therewith, which in practice for the molding compositions of the invention be used.

aldehyde

Amine Adduct

15th

C ₅ H ₁₁

- O

H ₂ NCH ₂ CH ₂ NH ₂

20th

H
C = O

^S 0CH ₃

C = O

^S 0H

H ₂ N (CH ₂ J ₃ NH ₂

H ₂ N (CH ₂ J ₃ NH ₂

C = N-CH ₂ ,
/

OCH ₃

CN CH ₂

/ 2

25th

H
CH ₃ C-O

0 ·

CH ₂ CH ₂ -C = O

H ₂ NCH (CH ₃ ) CH ₂ NHj H ₂ N (CH ₂ ) ₂ NH ₂ CH ₃ C = NCH (CH ₃ ) CH ₂ N = CCH ₃

H \
/ V- CHjCH ₂ C = NCH ₂

H
C ₅ H ₁₁ C = O

HHH

H ₂ N (CHj) ₃ NH ₂

H ₂ N (CH ₂ J ₂ NH ₂ C ₃ H _n C = N-CH ₂

CH ₂

HHH
/ VC = C- C = N- CH ₂ -

The oxidizable aromatic hydroxy or amino compound component (c) used as an inhibitor can be characterized by its reduction potential. A platinum electrode is used and a concentration of about 10 ^-3 mol / l is used in anhydrous dimethylformamide, which contains 0.2 mol / l of a strong electrolyte, e.g. Sodium perchlorate contains _s. The oxidizable compounds must oxidize at voltages below 1.5 volts, preferably below 1 volt, based on a saturated standard calomel electrode. Among the compounds that oxidize between J and 1.5 volts are e.g. B. phenol, m-cresol, resorcinol, pyrocatechol, bisphenol A and p-bromophenol. Below 1 volt, z. B. p- and o-hydroquinone and pyrogallol. Preferred aromatic hydroxy or amino compounds have the general formula VII

ArZ _n

(VII)

- in which Z is an OH or an NH ₂ substituent on an aromatic ring, η is the number 1 or 2 and Ar is an n-valent aromatic ring system, e.g. B. represents a phenyl or naphthyl group. The aromatic ring system is preferably not substituted; however, it can also be substituted. If substituted compounds are used, electron donors, such as alkyl, alkoxy, aryl, aryloxy and aralkyl radicals, are preferred, since electron acceptors, such as halogen atoms, nitro or carboxyl groups, give rise to aromatic compounds which, when the molding compositions are crosslinked Invention result in molded bodies with high compression deformation. p-Hydroquinone is particularly preferred.

When crosslinking by customary methods, an inorganic acid acceptor [component (d)] the task of reacting with hydrogen fluoride and forming water.

Suitable acid acceptors are bases such as magnesium, zinc and lead (II) oxide and dibasic ones Lead phosphite. Magnesium oxide is preferred. The acid acceptor is used in an amount of 2 to 25 parts, based on 100 parts of polymer used.

As a crosslinking accelerator (c), a base, e.g. B. an inorganic oxide or hydroxide, such as calcium or strontium hydroxide or barium carbonate can be used. The base is preferred in a Amount of 0.5 to 10 parts per 100 parts of copolymer used.

The amine binder (b) and the quaternary ammonium hydroxide (a) are preferably premixed and incorporated into the vinylidene fluoride copolymer. This matrix of the invention can be used at room temperature, e.g. B. at 27 ⁰ C, longer time, z. B. be stored for at least 6 months. Before crosslinking, the acid acceptor (d), the oxidizable aromatic hydroxy or amino compound (c) and, if appropriate, the crosslinking accelerator (c) are incorporated into this matrix.

After the addition of the acid acceptor (d) and the aromatic hydroxy or amino compound (c) is the storage time of the mixture at room temperature limited; it is advisable to use the mixture within 2 or 3 weeks. Everyone can do it too Components of the molding compound with the exception of the vinylidene fluoride copolymer prior to addition to the Copolymer are mixed. Although the use of hydroquinone is generally satisfactory Providing results according to the method of the invention, it may in some cases be desirable be to use conventional inhibitors. In addition, the molding compound can also have additional Auxiliaries, e.g. B. fillers, plasticizers, pigments, inhibitors, processing aids and the like., Incorporated will.

Table I gives an overview of the proportions of the components in the preparation of the components according to the invention Molding compounds. Parts data mean parts by weight, based on 100 parts of vinylidene fluoride copolymer. The proportions of the individual components vary depending on the cross-linking

. system and the physical networking conditions within the limits given in Table I.

Table ί

²⁰ component. Parts by weight Vinylidene fluoride copolymer 100 Amine former (b) 0.1 to 2.5 ² 5 Quaternary ammonium hydroxide (a) 0.05 to 0.4 Acid acceptor (d) 2 to 25 Networking accelerator (s) .... 0.0 to 10 ₃ p Oxidizable hydroxy or Amino compound (c) 0.1 to 2

Moldings with low compression set are obtained within the limits given in Table I with values of no more than 10%. Preferably the quaternary ammonium hydroxide (a) or a equivalent compound in solution, ζ. B. in Methanoi added.

For 100 parts of elastomeric copolymer, at least 0.1 part of amine binder (b) must be present «. A higher proportion of amine former leads to higher crosslinking rates and results in firmer ones Moldings. Too large an excess of amine

However, formers leads to post-curing of the molded body on aging and results in z. B. higher values for compression deformation and lower elongation values. Generally one chooses the amount Amine former not higher than for the desired crosslinking density and the desired compression set is required. More than 2.5 parts of amine former per 100 parts of copolymer are disadvantageous.

Quaternary ammonium hydroxides in an amount of 0.05 parts per 100 parts of copoly-

merisat a significant acceleration of the networking at the given concentration of the amine former. The proportion of quaternary ammonium hydroxide increases over 0.4 parts, an over-crosslinked vulcanizate is obtained. In general, however, one can use the Use quaternary ammonium hydroxides of higher molecular weight in larger amounts than those with lower molecular weight. The optimal amount of quaternary ammonium hydroxide is in general, the higher the lower the amount

of amine former used. The preferred proportions in a system with tetrabutylammonium hydroxide and cinnamaldehyde-trimethylenediaminazomethine are indicated by the hatched portion of the

Fig. 1 shown. This hatched area becomes by the equation

χ ± 0.1 = 0.3 (l ~ y / 2)

in which χ the parts of quaternary ammonium hydroxide and y the parts of amine formers, • each based on 100 parts of vinylidene fluoride copolymer, where χ is always 5 0.05 and y is always 5 0.25.

Magnesium oxide is preferred as the acid receptor (d). At least 2 parts of magnesium oxide are required to achieve sufficient crosslinking densities and crosslinking speeds. An excess beyond the maximum amount given in Table I is not critical, but from 50 to 60 parts of acid acceptor, α ?? · * has a hard base mass. In general, it requires no more than '25 parts of the acid acceptor for a satisfactory cure. Instead of magnesium oxide, zinc and lead (II) oxide or dibasic lead phosphite and occasionally calcium oxide can be used in approximately the same amounts.

If, in addition to the acid acceptor (d), a base is used as a crosslinking agent (e), so this is generally used in an amount of 0.5 to 10.0 parts. It is preferred as a crosslinking accelerator (e) an inorganic base used which is more basic than the quaternary ammonium hydroxide (a) is. In addition to the preferred calcium hydroxide, the weaker Ba Use rium carbonate, occasionally in somewhat larger quantities.

To modify <in properties are often Fillers, e.g. B. carbon black, clay or barite, in an amount up to 100 parts, preferably between 15 and 50 parts added. Furthermore, plasticizers and processing aids can preferably be added to the molding compositions Esters and ketones.

In practice, the molding compound of the invention is • produced in such a way that the individual components mixes intensively with each other, e.g. B. in conventional Kautschükmischerri, such as Banbury mixers or Roller mills. It has been shown that a two-roller mill with rollers that can be cooled is particularly good is suitable because the heat generated by the high shear forces during the mixing process is better can be discharged, so that good temperature control is possible.

The best results are obtained when the temperature of the molding material does not rise above 120 ⁰ C and does not fall below ⁰ C O. The crosslinking agent must be distributed evenly in the * -rmmasse by the mixing process. In addition, premature crosslinking during the mixing process must be prevented, since above a certain degree of crosslinking the molding compounds can no longer be pressed or extruded.

For crosslinking by conventional methods, the molding compound is pressed, for. B. in a form and then heated it. The pressure curing takes place between 95 and 230 ° C, preferably between 150 and 205 ° C, and the curing time is 1 minute to about 15 hours, generally 5 to 30 minutes. It is carried out with a pressure between 7 and 210, preferably between 35 and 70 kg / cm ^z . The mold can be pretreated beforehand with a mold release agent, for example with a silicone oil, and preheated postcured 205 ⁰ C, between about 2 and hours depending on the dimensions of the molding. During the post-cure temperature generally is gradually increased from the lowest value to the maximum value which preferably is at 260 ⁰ C and at least hours is maintained.

The ¹ examples explain the invention; The test results were determined according to the following test methods:

Mocney Vulcanization Test:
ASTM D 1646-63, small rotor.

Permanent compression deformation:

ASTM D 395-61 method B, test cylinder 25 mm in diameter and 12.5 mm in thickness; squeezed out 9 5 mm for the specified time and the specified / er / ipers · \ '/..:£·. ^J -m releasing the pressure was ¹ I Sfunde for the purpose of equilibration pew '*** the term meant in the examples * "compression" the compression set.

Tensile strength; Elongation at break; Modulus of elasticity at 100% elongation:

ASTM D 412-62 T, sample panels (A, L, C) from a plate of 1.8 mm thickness cut with a punch of the following dimensions:

A: 3.5mm
L: 19 mm
C: 51 mm

Accelerated aging:
ASTM D 573-53, 16 hours at 315 ⁰ C.

Pressure curing:

Unless otherwise noted, test specimens with dimensions of 75 × 150 × 1.8 mm are exposed to a pressure of 70 kg / cm ^{2 at 160 ° C. for 20 minutes.} The test cylinders for determining the compression deformation, which is carried out for 30 minutes at 160 ° C and a pressure of 140 kg / cm ² , have a diameter of 25 mm and a thickness of 12.5 mm. '

Post-curing:

The test specimens are removed from the mold and placed in a convection oven. The temperature is controlled as follows: 2 hours at 150 ⁰ C, 2 hours at 175 ° C, 20 hours at 205 ⁰ C and 24 hours at 260 ⁰ C.
Two different vinylidene fluoride copolymers are used, namely: Copolymerisatl, consisting of vinylidene fluoride and perfluoropropylene in a molar ratio of 76:24 (Examples 1 Ws 6, and copolymer II, consisting of vinylidene fluoride and 1-hydroperfluoropropylene in a molar ratio of 80:20 (Example 7).

16

example 1

The interrelationships between the composition the molding compounds with regard to the amounts of amine adduct, quaternary ammonium hydroxide, hy-

Table II

drochinone and the citrus accelerator on the one hand and the crosslinking rate and the physical properties of the molding compositions on the other hand can be seen from Table II.

Copolymer I

MgO

soot

Cinnamon acid aldchyd-trimethylenediarninazomethine

Tetrabutylammonium hydroxide,

Hydroquinone,

Ca (OH) ₂

CaS

Mooney test, increase of 10 points in

120 ⁰ C

165 ⁰ C

Pressure deformation

ITAG at 205 ⁰ C

7 days at 2O5 ° C

7Tagebei 175 ⁰ C

3 days at 25 ° C

Tensile strength (kg / cm ² )

A *)

Elongation at break (%)

A.

B.

Shore hardness, A ₂ .

A.

B.

100% module ***) (kg / cm ² )

A.

B.

100 10 20

1 1 0.5

> 25 min. 3.0

10 32 18

148

45

220 80

71 78

15 torn

Weight tslcile
attempt 4th 5 2 3 100
10
20th 100
10
20th 100
10
20th 100
10
20th 0.5
0.2
2
1
0.5 0.5
0.2
1
1
0.5 0.7
0.1
0.5
3 0.3
0.3
2
1 > 25 min.
6.5 > 25 min.
6.0 > 25 min.
2.5 - 6th
18th
7th
3 6th
14th
9
6th 7th
24
12th
5 4.5 145
36 140
29 132
38 • - 270
160 330
220 260
180 - 70
71 68
68 . 69
69 - 33
26th · - NJ
OO N) 32
29

*) A: Values of the hardened probes. ♦ *) B: Values of the post-cured sample after accelerated aging (16 hours at 316 "C). ***) Modulus of elasticity at 100% elongation.

Table I clearly shows that, for good comparison, Example 2

wetting both the presence of the diamine adduct _Dej . _{Influence of} hydroquinone on crosslinking

was investigated with the following mixture recipe:

as well as that of the quaternary ammonium hydroxide is necessary. In experiment 1, the quaternary Ammonium hydroxide was omitted and in runs 2 to 5 the amount of quaternary ammonium hydroxide was varied. Experiment 1 is the compression deformation much higher than in tests 2

to 5. In addition, the 60 Copolymensa!

higher content of diamine adduct borrowed poorer MgO

Values relating to the aging resistance of carbon black

Consequence, what from the greatly reduced values for the elongation at break, from the greater hardness and from the low elongation values of the post-cured sample can be seen. This aging behavior is an indication on how the hardened molding compound will behave in practice.

component

Ca (OH ₂ )

Cinnamon aldehyde-trimethylenediamine-

azomeihin

Trabutylammonium hydroxide CaS

Parts by weight

100

10

20th

0.5 0.2 0.5 209 684/365

,"The sample Result of the investigation Table ill C. »Shows Table III. ί C. Hydro
chinone, Hardening
conditions C. 1 Parts by weight
to 100 parts C. Result 2 Copoly- C. 3 merisat I 20 min. / 160 ° C. 4th 0 5 min. / 200 ° C. blistered 5 0 20 min / 160 ^c no hardening 6th 0.25 20 min. / 160 ° Well 7th 0.5 5 min / 200 ^c Well 0.5 5 min / 200 ^c Well 1.0 5 min / 200 ^c Well 2.0 Well

IO samples were 0.5, 1.0 and 1.5 GewichtsMen Eamethylendiamincarbamat prepared. De product "s wu then the 1 to 30 minutes under pressure at 165 ° C heated. In case kcnem Iral e.ne ^H dSVersuche show that enSenden in a hydroquinone system Door satisfactory ÜR H _u Tdh, for the production of a shaped body "with good physical properties. S of the low compression set, the property healing a quaternary ammonium hydroxide included notwend _lg.

Example 3

The influence of various diamine adducts on the following Standard formulation was examined:

If only 0.1 part of hydroquinone is used, so. slightly increased amounts of diamine-zo are required adduct, tetrabutylammonium hydroxide and / or calcium hydroxide to ensure satisfactory cure to reach. Comparative example According to the following mixture recipe; component

Copolymer I
soot

component

Copolymer I

MgO

soot

Ca (OH ₂ )

CaS

Hydroquinone ..

Parts by weight

100

10

20th

0.5 2

MgO

Ca (OH) ₂

Tetrabutylammonium hydroxide

Hydroquinone

Weight tstcile

100

20th

10

0.2 1.

The amine adducts were approximately equimolar

Quantities added to the molding compound and then this

kneaded on a roller mill. The pressure hardening

and post-curing took place as in Example 1.

Table IV shows the results.

Table IV

Cinnamaldehyde-ethylenediamine-azomethine cinnamaldehyde-trimethylenediamine-

azomethine,. ,,,,.

Cinnamaldehyde hexamethylenediamine

azomethine,

Trimethylene jamine carbamate

Hexamethylenediamine carbamate .. ,,.,.

Mooney test, increase of 10 points in

167 ° C (min.)

Pressure strain (%) 205 ⁰ C, 1 day ... tensile strength, kg / cm ²

B **)
100% module (kg / cm ² )

B.
Elongation at break (%)

Shore hardness A ₂
A.
B.

Parts by weight to 100 parts
Copolymer I

0.5

4.7 6

142 41

31 41

240 100

70

75 0.5

4.5
6th

165
39

36

200
90

70

71

0.6 - - 0.25 3.4 4.2 5 7th 140 146 50 44 50 27 - 32 220 260 90 160 70 71 73 70

0.25

3.5 6

147 38

39

210 95

70

74

*) A: Values of the post-cured sample. **) B: Values of the post-cured sample after accelerated aging.

"K

"* wV

i 1

Example 4

^h - ^d Ji'ASK * ^U ^ W ?, ^{8 2 zuzUglicl1} '' ^ ⁰ "hydroquinone molding compounds produced - ^depending λ nS Wnüi« «L ü ^{labellc.?" V} listed dialdehyde trimethylene adducts incorporated ^ ere, The molding compositions were pressed and post-cured, Table V shows the result.

Adduct \
/ -CH ₂
2 ί C ₆ H ₁₃ CH = NC ₁₂ -4-CH ₂
\ / ² OCH ₃ OTT 2 2 Pressure deformation (%) 7 days, (75 ⁰ C / N-CH = NCH ₂ - CH ₂ \
- - CH ₂ I day, 205 ° C 7th 6th 6th Table V 5 CH ₂ / \
fill TyTfIl 4th 4th x ^ ri - INCH, -
/ \ / (X broken 6th OC \ / \
OH
\ / 5 5

Example 5

According to the following mixture recipe

component Parts by weight Copolymer I
soot 100
20th
10
1
0.2
0.5 MgO
Ca (OH) ₂
Tetrabutylammonium hydroxide ..
Zirataldehyde trimethylenediamine
azomethine

Molding compositions were prepared in which 1 part by weight of each of the aromatic compounds listed in Table VI was incorporated. The mixture was kneaded on a roller mill to form a homogeneous dispersion. The sample plates and test cylinders were cured under pressure for 20 minutes at 165 ° C and 30 minutes at 160 ⁰ C, post cured and debugged. V ^s '. Table VI shows the corresponding test results.

Table VI Aromatic compound Compression deformation *)
(%) Tensile strength
(kg / cm ² ) 100% module
(kg / cm ² ) Elongation at break **)
(%) phenol 15th 132 29 270 o-droquinone 10 140 24 270 * *) 24 hours at 2O5 ° C.
**) The recipe contains 3 parts of Ca (OH) ₂ .

continuation

Aromatic compound Compression deformation *)

Tear strength wedge (kfe / cm ') .

m-Hydroquinone 12 144 31 230

p-hydroquinone 6 165 36 M)

m-cresol 13 179 52 260

P-cresol 13 182 43 230

m-aminophenol 10 177 112 W

m-phenylenediamine 14 152 66 TO

p-phenylenediamine 12 175 90 ¹ ^

2,2-bis (p-hydroxyphenyl) propane 11 157 32 250

p-bromophenol **) .'.- .. 19 175 26 320

*) 24 hours at 205 ° C. ■ **) Recipe contains 3 parts Ca (OH) ₂ .

A'oipstische hydroxy and amino compounds that contain an electron withdrawing group, (e.g. ip-bromophenol), generally require larger amounts of the crosslinking accelerator (1), a longer one Time or higher temperatures to cure.

Example 6

This example describes the influence of various amine-carbonyl adducts. The following base material was produced: '

(kg / cm ⁸ )

Elongation at break *

component Weighted parts Copolymer I,
MgO
soot 100
10
20th Ca (OH) ₂
Tetrabutylammonium hydroxide. .
Hydroquinone 1
0.2
1

This basic mass was in each case made up together with the amount of amine former shown in Table VII kneaded in a roller mill to form a homogeneous dispersion. The samples were produced according to Example 1. The results of the test 7dgt Table VII. Those belonging to the corresponding amines of the amine formers Molecular weights and amine equivalent weights are listed in Table VIII.

Amine formers Table VII Compression deformation *)
(%) Tear
strength
(kg / cm ² ) 100% module
(kg / cm ² ) fracture
strain
(%) attempt Cyclohexylamine
2-Hydroxyäthylamii?
Cinnamaldehyde cyclohexylamine
azomethine
Cinnamaldehyde-aniline-azomethine ..
Zirataldehyd-o-Nitroanilirt-
azomethine
CH ₃ CH = N - CH (CH ₂ ^ CH ₂ .. Parts by weight no hardening
no hardening
11th
8th
8th
8th
8th
7th
7th
7th 175
161
183
192
202
200
173
202 31
68
76
46 ·
30th
62
44
36 260
150
170
230th 1
2
3
4th
5
^r 6 C ₆ H ₁₃ CH = NCH (CH ₂ ^ CH ₂ ... 0.25
0.25
0.5
0.5
0.5
0.5
0.5
0.75
0.25
0.25 300 7th (C ₆ H ₅ J ₂ C = N - CH (CHACH ₂ 190 8th HOCONCHjiCH ^ CH / *) 220 9 HOCONHCHiCHACHa ***) ... 300 10

*) After 24 hours at 205 ° C. **) As a piperidine salt. ***) As cyclohexylamine salt.

23

continuation

ti

attempt Amine formers Weight is rush ! .....
Compression deformation *)
(%) Tear
strength
(kg / cm ² ) 100% module
(kg / cm ² ) fracture
strain
(%) 11th Cinnamaldehyde methylamine
azomethjn 0.25
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.2
1.0
0.5 30th
7th
6th
7th
6th
6th
8th
8th
12th
9
11th 175
159
151
157
134
154
189
160
166
168
175 46
29
32
98
89
80
76
55
'66
100
114 240
250
200
140
170 - 12
13th
14th Cinnamaldehyde-2-hydroxyethyl
amine-azomethine:
Cinnamaldehyde-2-methoxyethyl
amine-azomethine
Cinnamaldehyde trimethylenediamine
azornethin 170
160
190
170
140
140 15th
16 C ₆ H ₅ (CH ₃₎ C = N (CH ₂₎ - |
L _n = QCH ₃ ) QH ₅
[(CH ₃ ^ C (OH) CH ₂ -, 17th
18th
19th
20th
21 L- C (CH ₃ ) = NCHJ ₂ CH ₂ ....
C ₂ H ₅ C (CH ₃ ) = N-NHC ₆ H ₅ ..
Isophthalyl hydrazide
Dimethyl glyoxime
OCNC ₃₆ H ₆₈ NCO
C ₁₈ H ₃₇ NCO

*) After 24 hours at 2O5 ° C.

Table VIII

attempt 4th Amine Molecular
Weight Arnin
Equi-
vafent-
weighted 1, 3, 6, 7,
8, 10 5 Cyclohexylamine 99 99 2, 12 9 2-hydroxyethyl
amine 61. 61 11th aniline 93 93 13th o-nilroaniline 138 138 14, 15, 16 Piperidine 85 85 17th Methylamine 31 31 18th 2-methoxyethyl
amine 75 75 19th Trimethylene
diamine "74 37 20th C ₆ H ₅ NHNH ₂ 108 54 21 Hydrazine - 32 16 Hydroxylamine 33 33 H ₂ NC ₃₆ H ₆₈ NH ₂ 532 266 Q ₈ H ₃₇ NH ₂ 269 269

Example 7

In this example, a commercially available copolymer with a molar ratio of

CFH = CFCF ₃ to CH ₂ = CF ₂

like 20; o0 πίίί a specific Gedicht of 1.8 Γ6 at 25 ° C and a Mooney viscosity (ML 1 + 4, 100 ⁰ C) of 90 used (copolymer II). The mix recipe is as follows:

component

Copolymer II

soot

MgO ..

Ca (OH) ₂

Tetrabutylammonium hydroxide Zimialdehyde trimethylenediamine

azömeihin.

Hydroquinone .................

Parts by weight

100 20 10

0.2

0.5

The molding compound was on a roller mill mixed and as in the example. 5 hardened. The following properties were achieved: 6o

Deformation,

(24 hours, 205 ° C) 18%

Tensile strength,; 2.5 kg / cm ²

100% module 75 kg / cm ²

Elongation at break 190%

Shnre hardness A ...... * _,. ,, itJ. _iJ _30

2W 484/365

Claims (1)

■ **. cind in general in certain Die Polymerisate nd im aMg _nd ^^ Tongues made of thermoplastic ζ «> ^ver " ⁿ gten. The networking (a) 0.05 to 0.4 _{parts by weight of at least one and} higher product ^^ generally than Vulcani- r i _e ammonium hydroxide quartäien _asto mer polymers & Wiru of the general formula (I) or (II) sation. _vulcanizable thermo-