DE1693218C3 - 12/26/63 USA 333729 Aminium and diimonium salts of N, N, N ', N'-tetrakis (p-aminophenyl) -phenylenediamines and benzidines American Cyanamid Co., Wayne, N.J. (V.StA.) - Google Patents

Description

where A is the group

η 1 or 2 and m 1 or A is the group

4. Bis - (p - diethylaminophenyl) - [N.N - bis- (p - diethylaminophenyl) - ρ - aminophenyl] - aminium hexafluoroarsenal.

5. Bis - (p-diethylaminophenyl) - [N.N - bis- (p - diethylaminophenyl) - 4 '- aminobiphynyl] -aminiumhe.xafluoroarsenal.

6. Bis - (p - diethylaminophenyl) - [N.N - bis- (p - diethylaminophenyl) - ρ - aminophenyl] - aminium hexafiuorantimonat.

and »ι 2, R is a straight-chain or branched alkyl radical having 1 to 12 carbon atoms, R _{1 is} hydrogen or R and X are an anion.

2. Ν, Ν, Ν ', Ν' - Tetrakis - (p - diethylaminophe- The invention relates to a new class of aminyl) - ρ - benzoquinone - bis - (imonium hexafluor- nium and diimonium salts p-amino-substituted month of month). 30 tetraphenylarylene diamines. those used as infrared absorbers

3. Ν, Ν, Ν ', Ν' - Tetrakis - (p - diethylaminophe- are beneficial.

nyl) - ρ - benzoquinone - bis - (imoniumhexafluor- The invention relates to compounds of

arsenate). formula

HlX "

wherein A is the group alkyl radical with I to 12 carbon atoms. R ₁ water

substance or R and X mean an anion.
The salts of formula 1 are p-phenylenediamine derivatives Oi = 1) or benzidine derivatives Oi = 2).

The compounds of the formula I can be prepared from readily available starting materials by reactions 50, which will be explained below. First are the appropriate nitro compounds and into the corresponding amino compounds and then into substituted amino compounds converted, as the following reaction and hi 2, R shows a straight-chain or branched 55 tion scheme:

π I or 2 and hi 1 or A denotes the group

alkali

copper

GN-

GN-

-HaI + H ₂ N (11)

-NH ₁

(111)

.v — NO,

(IVl

H ₁ N-

-N-

(V)

R,

- N ■ -

./-Nile,

R ₁

/ • - N

(VI)

R R and / ι have the meanings given above Z bcdcuiei a halide or sulfate radical. Compounds of the formulas IV, V and VI and their preparation are detailed in the patent application | 793 658.2 ~ described.

In the above formulas I and VI, the various radicals R and R _{1 can be} identical to one another or different from one another.

The reaction of a p-nitrohalogenobenzene of the formula with a p-phenylenediamine or benzidine of the formula III is carried out in a solvent, expediently dimethylformamide, in the presence of alkali. _e.g. sodium or potassium carbonate, and especially in the presence of copper powder

Compounds of the formula V. d. H. the amino compounds are obtained by reducing nitro compounds of formula IV easily accessible. The substituted amino compounds of the formula VI can by reacting these amino compounds of the formula V in a solvent and in the presence of alkali or a basic salt with a

Compound RZ are obtained, the z. B. an alkyl halide or an alkyl aryl sulfate.

The conversion of the intermediate products of the formula V! into the salts of formula 1 takes place by oxidation of the substituted amino compounds. In addition become the p-phenylenediamine or benzidine compounds of formula VI in solution in an organic Solvent reacted with a silver salt.

Dimethylformamide is a good solvent for this reaction. However, other solvents can also be used. /. B. acetone can be used. A wide variety of silver salts can be used. These include perchlorate (CK) ₄ ). Fluoborate (BF ₄ ). Trichloroacctate (CCI ₁ COO). Trilluoroacetate (CF, COO J. Picrat (NO ₂ I ₁ C ₁₁ H ₂ O. Hexafluoroarsenai (AsF ₁ ;). Hxafluoranlimonal (SbF ₁ ,). Benzene _{sulfonate (Ci 1} Il ₅ SO ₁ ). Ethanesulfonal (C, H ^ SO ₁ I. Phosphate (PO ₄ ""'), Sulphate (SO ₄ ) or Chloride (Cl).

Oxidation of an amino group of compounds of the formula VI gives aminium compounds of the following formula VIl:

R,

(VIl)

Ί ί

N N

RR ₁ RR ₁

The oxidation of two amino groups of compounds of the formula VI, in which / 1 is 1, gives rise to diimonium compounds of the following formula VIII:

—-N—- ■ '

R,

2X

(Vl

In these formulas, R., R ₁ and X have the meanings given above. Various amini to compounds, z. B. (Tris- (p-dialkylamino phenyl K> minium salts

are already squirming

for use in various substances / for reduction the transmittance in the infrared region of the spectrum is proposed. Absorb such salts strong in the near infrared range of the spectrum. However, the most effective protection is found nearby of 960 mu .. Compounds that are capable of absorption in a wider range at larger wavelengths are capable of near infrared, however, were not yet known.

The new compounds of the formula 1 given above absorb in a wide range of the near infrared of the spectrum at longer wavelengths than the previously known compounds. So will an improved absorption in the range of longer wavelengths between about KM) O and 18 (K) Γημ is achieved. Many of the new compounds also show desirable absorption at shorter wavelengths in the near infrared. However, they allow high proportions of visible light to pass through.

There are many organic plastics with generally good permeability properties visible area.

Examples of such plastics include, but are not limited to

30th

Cellulose derivatives such as cellulose nitrate, cellulose acetate, regenerated cellulose and cellulose ether, such as ethyl and methyl cellulose; Polystyrene plastics such as polystyrene itself and Polymers and copolymers of various ring-substituted styrenes, e.g. B. o-, m- and p-methylstyrene, as well as styrenes substituted in the side chain, e.g. B. alpha-methyl and -Ethylstyrene and various other polymerizable and copolymerizable vinylidene compounds;

various vinyl polymers and copolymers, such as polyvinyl butyral and other acetals, polyvinyl chloride, Polyvinyl acetate and its hydrolysis products. Polyvinyl chloride acelate copolymers;

various acrylic resins, such as polymers and copolymers of methyl acrylate, methyl methacrylate, Acrylamide, methylolacrylamide, acrylonitrile; Polyolefins such as polyethylene and polypropylene; Polyester and unsaturated modified polyester resins such as those obtained by condensation of Polycarboxylic acids obtained with polyhydric phenols or with unsaturated carboxylic acids modified and further by reacting the alkyd resin with another monomer modified polyester resins;

45 Polymers of allyl diglycol carbonal and various copolymers in the manufacture of which an allyl ester of an acid was used as a crosslinking monomer *.

Cellulose acetate, methyl methacrylate, polystyrenes, and polymers of allyl diglycol carbonates are im In the context of the invention of particular interest and preferred as substrates.

The substrates mentioned above are in most cases with regard to their permeability for Radiation energy of different wavelengths is very different from one another. But what they have in common that an additive is necessary for them. to lower the infrared transmission without reducing the transmission to adversely affect in the visible range.

The heat resistance of the invention Salts can be applied to dispersions of the aminium salts in plastics or to their solutions in suitable Solvents can be detected. They are sufficient at temperatures up to about 200 ° C Heat resistant dimensions. Temperatures of around 200 C often occur when processing the ones enumerated above Plastics on. The compounds according to the invention can therefore also be used in such cases.

After being introduced into organic plastics, the products according to the invention have good light and heat resistance. A satisfactory absorption of radiant energy in the range of 1000 to 2000 mix as they come from the sun or other light sources is emitted through transparent or translucent plastics was previously not achievable. This part of the infrared radiation is a considerable part of the total infrared radiation the sun as well as incandescent and other lamps.

When used, the salts according to the invention can be incorporated into or added to any plastics transparent or translucent substrates made of plastic or glass are applied. This can take place according to any known working methods, for example by pouring solutions or with Dip solutions, hot rolling, polishing or coloring. Organic plastics that contain the salts can be deformed to moldings, for example films and sheets.

The invention is illustrated in more detail by the following examples. Parts and percentages are related on weight, unless otherwise stated.

The preparation of the starting materials is described in the above-mentioned patent application P 17 93 658.2.

Example I.
Bis-ip-diethylaminophynylJ-fN.N-bis-tp-diethylaminophenyU-p-aminopheny ^ -aminium-hexafiuorarsenat

(C ₂ H ₅ I ₂ N -

N (C ₂ H ₅ I ₂

AsF ,,

N (C ₂ H ₅ I ₂ N (C ₂ H ₅ I ₂

To a solution of 149 parts (0.005 mol) of N.N.N'N'-tetrakis-lp-diälhylamiiiophen.vlj-p-phenylenediamine 1.49 parts (0.005 Moll of silver oxafluoroarsenate in 25 parts) are added to 25 parts of warm dimethylformamide

elliylformamide. After stirring for a minute, the mixture is filtered off and the filtrate with 350 parts of ether ünnt. When cooling in dry ice acelon, the product separates out. You get about .15 parts of a .cn solid substance from F. = 184 to 185 C.

Example 2
is-lp-diäthylaminophcnyll-fN.N-bis-lp-diethvlaminophcnylH'-aminobipheny ^ -aniinium-hexafluoroarsenate

N (C ₂ H ₅ ),

AsF, /

N (C ₂ H ₅ ),

u of a solution of 0.77 parts (0.001 mol) of N, N.N ', N'-Tctrakis- (p-diethylaminophenyl) benzidine in 40 parts Ton is added dropwise with stirring a solution of 0.30 parts (0.001 mol) of silver hexafiuorarsenate in serve acetone. After about 5 minutes of stirring, the mixture is filtered and the filtrate with 200 parts of ethyl ; r diluted. Upon cooling in dry ice acelon, a green solid substance separates in an amount of Share out. Melting point 195 C with prior softening.

Example 3
NNN'.N'-Telrakis-fp-dialhylaminophenylJ-p-bcnzoquinone-bis-iirnonium-hexafluoroantimonate)

(C ₂ H ₅ I ₂ N

N (C ₂ H ₅ ),

2SbF ₁ ,

V /

N (C ₂ H ₅ I ₂ N (C ₂ H ₅ ),

'.u a mixture of 1.39 parts (0.002 mol) of N, N.N'.N'-tetrakis- (p-diethylaminophenyl) -p-phenylenediarnine ! 0 parts of acetone are added while stirring 1.38 parts (0.004 mol) of silver hexafluoroantimonate. After '/ j hour The dark blue solution is filtered off and the filtrate is diluted with 100 parts of ether. The mixture d cooled, and the solid substance which separates out is collected, washed with ether and petroleum ether j dried. 2.1 parts of product with a melting point of 216 ° C. (decomp.) Are obtained.

Example 4
NN ^ '. N'-Telrakis-fp-diethylaminophenyll-p-benzoquinone-bis-iimonium-hexafluoroarsenate)

The procedure described in Example 3 is carried out using an equivalent amount of silver hexaoroarsenate repeated in place of the silver hexafluoroantimonate. The product obtained melts at 170 "C tcr decomposition.

Example 5

A number of aminium compounds of the formula given above were carried out according to the method described in Example 1 Procedure from the corresponding N, N, N ', N'-tetrakis- (p-dialkylaminophenyl) -p-phenylcnimine and silver salts.

CH,
CH ₁
C ₂ H ₅
C ₂ H ₅

nC, H ₇ '>
HC ₁ II- ¹ I.
nC ₄ H _q

AsF ₁₁

SbF ₁ ,

SbF ₁ ,

BF ₄

AsF ₁₁

SbF ₁₁

AsF ₁ ,

SbF ₁₁

SbF ₁ ,

SbF ₁₁

ι · '., c ¹

ISO

IS4

IS6

170

214

215

I7O ² )

175 ² I.

182 IS5 IS7 172 216 216 of a tungsten element is used. From the curve obtained, the wavelength of the maximum absorption was determined (A ₁₁₁₁₁ J. The absorption capacity at the wavelength of maximum absorption, since: _{is denoted by ί /, 11ι1Λ} , is an arid pressure for the degree of absorption. Fs is given by the following Be / iehun; calculated:

1 . V ₁ , "" hc ^l0p 7 ■

I lierih means

C ₈ H ₁ -C ₁₂ H ₂₅

') The l-'iltial wildly diluted with an equal volume of ethanol.

-) Aniienahert.
') Not determined.

Example (i

Bis- (p-ethylaminophenyl) - (N.N-bis- (p-älhvlaminophenyD-p-aminophenyli-aminium-hexaluoroarsenate

C ₂ H ₅ NH

a = absorption capacity.

/ '= the strength of the cell (Spectrophoiometeri in cm c the concentration in grams I Her. • T = light passed through the solution T ₁₁ - light passed through the solution alone in the same cell.

The molar absorption at the wavelength of maximum absorption (.-, _miv | is also an expression of the degree of absorption. It can be calculated using the following relationship:

■ y

nc

= Ma.

AsF ,,)

The procedure described in Example I is followed using an equivalent amount of is N.N.N'.N '- Tetrakis - (p - äthylaminophenv 1) - ρ - phenylenediamine instead of N.N.N'.N '- tetrakis- (p-diethylaminophenyD-pphcnvlenediamine repeated.

Herein means:

· ■ = the molar absorption capacity. A / = molecular weight of the solute.

■ ·, ""., Is thus the absorption capacity, be / ogei to a molar concentration of 1 g-mole of compound per liter of solution, or as a MaH the Absorp tion of one g-mole of the compound. The larger the value for · ■ “,,, is. the great

Example p Example 7

(C ₂ H ₅ I ₂ N-

^Λ \.

> - Ν—,

45

N (C ₂ H ₅ ),

(X Γ

According to the procedure described in Example 2 using equivalent Meneen the corresponding silver salts instead of silver hexafluoroarsenate the two ammonium compounds given below manufactured.

The absorption curves of solutions of the Ami niumsal / e according to Examples I. 2. 5 and 7 in Aeetor were determined in the visible range and in the near infrared from 0.35 to 2.00 microns as described above. The results are listed below. It can be seen from this that in the case of the phenylenediamine derivatives according to Examples 1 and ^; two absorption peaks occur in the near infrared region.

Product after
example

55

Connection

CIO ₄
SbF ₁ ,

Melting point

lunter previous softening.

194 C
181 C

5a)

6o

Absorption curves of the normal salts in organic solvents in the "visible and 6s near infrared region from 0.35 to 2.00 microns were determined" ^5c) . For this purpose, a registration spectrophotometer with an additional device for the near infrared and 1450
930
414

1325
930
410

1310
970
410

1450
930
414

Absorption iinavl IS 500
20800
19 700 Il 14900
14600
15 100 20.9
23.5 12 SOO
13 100
13 500 19.2
1p.9
19.5 17400
19 900
ISOOO 15.6
16.0
16.4 1p.7
21.3
19.3

11th

To continue »

Product after
Example

1440
950
415

1460
950
415

1460
950
415

1460
9SO
410

1420
980
415

1050
610 '|
400

1050
610
365

1055
600
365

AriMirplion (mavl a

20.7
24.1
21.7

18.4
20.5
18.6

17.1
19.4

17.7

14.1
26.0
16.4

13.8
23.1
16.4

31.9

3.3
24.8

21.0

2.6

35.0

24.1

2.6

31.6

¹ I don't

Example 9

16 200 18 900 I 7 000

IO

18 400 20 500 18 600

1 7 900 ι s 20 300 18 500

1 5 700 28 900

18 200

16 000 26 700

19 0 (X)

30 700 3 200

23 800

18 300 2 300

30 500

24,300 vs 2,600

31 900

4 °

solvent 1470 nw 940 nw 414m acetone 21.5 23.9 22.7 'Max <'"," X 1450 nw 950 nw 414m Methanol 20.9 23.5 22 2 '; m, x « Χ I550rrw 910m _{; J} i 420 m Methyl salicylate 26.8 21.5 '- .., "*

iles /.usat/sloffes is checked by examining an atlas-fade-ometcr measured. Curves determined before the test and after certain test periods. the The percentage of additive still present is calculated from the following formula:

Remainder in "'» ■ - ■ - A _1. -1 ,, ■ 100.

where I _{11 is} the absorbency at 950 nv /. before the test and A ₁ the absorption capacity at ίο 950 nii. means after 7 hours.

The absorption curves of solutions of the compound prepared according to Example 1 in three different Solvents were determined. The results are summarized below.

Example 10

The product obtained according to Example 1 is introduced into a cellulose acetal film by pouring a solution of the plastic and the additive in acetone onto sheet glass. The thin films obtained in this way show strong absorption in the near infrared with maxima at 1450 and 950 ma. The light resistance Hiile-Omelcr-l'riifLMii! Resi in
!Hours)

> at 99 K) 1 example 1 93 20th 86 30th 79 40 73 50 69 game 11 received

The product obtained according to Example 1 is described in Example 10 for cellulose acetate In a way, it was introduced into a poly (methyl methacrylate) film. The films / own an intense absorption in the near infrared with maxima at 1450 and 950 nw. The light resistance of the additive is checked and results in the following values:

I.iile-Omck'i-l'riifuni; ReM in ".,
iSuimicnl

15th
20th

95
33
20th

example

mil there!

The product obtained according to Example I is
a concentration of 0.10%. related to
Weight of the plastic, introduced into Pohmethylmcthacrxlatpreßpulver by processing on steam-heated mixing rollers. Leaflets 1.88 mm (74 mils) thick are resealed by compression in a mold. A permeable wedge curve of these leaflets shows that the additive acts as a highly effective barrier in the near infrared, but lets through a small amount of visible light.

60

wavelength % Permeability (nwl 2000 20th 1700 0 1000 0 825 0 800 I. 700 21 530 57 445 0 400 0

Example 13

The stability of the product obtained according to Example I for a prolonged period at high temperatures is measured using methyl salicylate as a high-boiling solvent. Dilute solutions of the additive are heated to different temperatures in an oil bath. The percentage the remaining additive is determined spectrally.

temperature 2 (HI C Temperature 210 C " Erhit / ui ^ s- Additive lirhiizunps- To s; i l / stofT permanently daiicr (Min.) (in% | (Min.) (in "oil 5 96 S. Sl 8th 94 S. 59

Dissolve the polymer and additive in acetone on glass plates and dry at 70 (prepared for a few hours to remove the solvent. Then the permeability wedge curve of the cast film is determined. It is assumed that no decomposition occurs during this mild heat treatment. Sections of the cast film are deformed by pressing / wiping electrically heated plates at different temperatures.The curves of the pressed strips are compared with those of the cast film to determine the loss of additive due to heating / ti

men. Yei rormunusieinpeiatur

20th

14th

example

The heat resistance of the product obtained according to Example I in a Polymethylmetliacrvlal is determined as follows: Films with an additive content of 0.32% based on weight of the plastic are made by pouring a

C C

160 C 170 ΟΙΚΟ 190 200 C 210 C 220 C 230 C loss; iii / usal / slofl minute (",,. Middle ball

negligible
5

10
15th
20th
25th
2S

example

(Alkyl) ₂ N

Following the procedure described in Example 3, a number of p-benzoehinone diimonium salts of the formula given above using the corresponding N.N.N '- Tetrakis - (p - dialkylaminophenyi) -p-phenylenediamines and silver salts. The substituents are in the following list listed.

NiAlkyl),

2X '

Vcr-
binduni! Alkyl AsF " Melting point
(O al CH., SbF ₁ , > 300 b) CH ₃ BF ₄ 300 (existing exp
chen) O nC, H ₇ SbF, 213-215
(Salt with AsF _h as
Anion) d) nC ₃ H ₇ AsF " 213 214 e) nC ₄ H, SbF ,, 186 187 D. C ₈ H ₁ - AsF " G" C ^ H ^ example 16

product
after
example The absorption
/ im-jl B. (ma \. |
Il 49.cS
55.0 3
4th 1050
1050 according to example game 17 e i received 14th

5S 200
59 100

Product wild in a cellulose acetate film is introduced by mixing a solution of the plastic and the additive in Pouring acetone onto glass plates. The thin film shows strong near infrared absorption with a Maximum at 1075 rrw. The light resistance of the additive is as described in Example 10 by Test measured in an Allas-Fade-Ometer.

55

60

Spectral absorption curves of solutions of the products of Examples 3 and 4 in acetone in the near Infrared were determined as described above. The results are shown below.

Fadc-Omctcr exam Rest in% (Hours) 5 80 10 72 20th 65 40 54 60 47 80 41 100 33 125 26th 150 21 175 IS

16 93 21 δ

Notification of search

There were some connections in accordance with the invention with representative compounds known from USA.-Palcntschrift 28 13 802 with regard to the Width of the wavelength range of absorbed infrared radiation compared, with a 50% absorption an effective filtering capacity was established as the lower limit of the door the substances mentioned were compared with regard to their lightfastness with the help of the fadeometer test. The number of hours after which half of the absorbent was still present was determined was (half-life).

Of the compounds according to the said USA patent, the compounds according to

Example 2

1,1,5,5 - Tetrakis - [4 - | N.N - dimcth \ lamino) -phenylj-divinyl-carbonium-perchlorate.

Example 3

1,1.7,7 - Tetrakis - [4 - (N.N - dimelhjlamino) -phenyl] -lrivinyl-carbonium-perchlonu.

Example 5

1,5 - bis - [4 - (NN - dimethylamine.)) - phenyl] -IS-bis-1-phenyD-divinyl carbonium perchlorate. * ⁵

Example 6

1,7 - bis - [4 - (N, N - dimethylamine)) - phcnyl] -1.7-bis (phen > l) -trivinyl carbonium perchlorate

with compounds according to the invention according to Example 5c) and 50 (aminium compounds with 1 oxidation center) as well as 3 and 15d) (diimonium bonds with 2 oxidation centers).

I. Width of the wavelength range with filter effect

The absorption was measured spectrophotometrically in Acetone solution measured at a concentration of 20 mg 1. The following results were obtained:

connection Wave lunycn mn min- 860 ureii Area 50% 985 Bcre at least Absorption (nni) 1010 in 111 13 802 900 GcmiUi of US-PS 28 1 7 (K) Example 2 700 1600 160 Example 3 700 1575 285 Example 5 700 1260 310 Example 6 1260 200 According to the invention S25 - Example 5 c) 890- 775 Example 50 SOO 685 Example 3 825 460 Example 15d) 435

IL comparison of light stability

The infrared absorbers were wrapped in a cellulose acetate film exposed to ultraviolet radiation from a fadeometer. From the mimes Spectra were recorded before and after exposure. The percentage of after irradiation The 1R absorber still present in the film was then calculated from the following formula:

. _. A exposed - A. 100
Remainder in % = --- - - _c -.- _c -— * ■ - -,
A uncleared - A _p

where A is the absorption at the wavelength of maximum absorption and A _{s is} the scattered absorption caused by the cellulose acetate.

The cellulose acetate films containing the absorbers were poured onto microscope slides from a solution. The films were made by immersing the slide in a 30% solution of cellulose acetate, containing 0.1% infrared absorber in acetone dipped in and allowed the acetone to evaporate. The following results were obtained:

35

connection Half-life <20 Measurement
took place at (Hours) <20 I now 40
According to US-PS 28 I. 3 S02 <35 Example 2 <35 800 Example 3 900 ₄₅ Example 5 > 100 825 Example 6 > 100 900 According to the invention > 50 Example 5 c) > 50 1480 50 Example 50 1520 Example 3 1075 Example 15d) 1090

The other compounds falling under the general formula show a corresponding effect.

Claims (1)

Palent claims: 1. Aminium and diimonium salts of N.N.N'.N'-tetrakis- (p-aminophenyl) -p-phenylenediamines and -benzidines of the general formula R ₁ N— ■ / - N HlX