DE2556899A1 - POLYMERIC BLEND - Google Patents

Description

PCXLYiJEEB MISCHUKGi
19 ^ 12th 1974

The present invention relates to polynere Mixtures.

The mixtures mentioned are widely used in various fields of technology. So they will for example in mechanical engineering, device construction, electrical engineering, Electronic engineering, aircraft industry, in

of cosmic technology. and auto industry applied.

On the basis of such mixtures, various materials are obtained, such as films, glass fiber reinforced and carbon-reinforced plastics, molding materials.

The most important requirements of the modern state of the art of such materials are that their physical-mechanical properties (bending, compressive, tensile strength, dimensional stability, etc.) and

609827/0872

dielectric properties (specific volume and surface resistance, breakdown voltage, etc.) should be retained for a long time ^{at temperatures of 50O 0 G and higher.}

There are different polyheteroarylenes, for example « wise polyimides, polybenzimidazoles, polybenzoxazoles,

Polyoxadiazoles, known for how the process of thermo-oxidative destruction between 550 and 4 ^ 0 C with significant speed. For many of the polyheteroarylenes mentioned, for example polyimide based on pyromellitic dianhydride and ^ -, ^ - diaminodiphenyl ether or polybenzosazole based on ^ »^ '« Dioxy- ^ j ^ -diaminodiphenylmethane and isophthalyl chloride, however, the temperature of their processing is in the same range. This makes processing much more difficult these polymers and lowers the physical-mechanical characteristics of those manufactured on their basis Materials which make it necessary to combine such polyhetexo- .. arylene with stabilizing additives (stabilizers) to use. For example, phosphoric acid or its esters are used as stabilizers known for polyimides. However, the polyimide itself, even if it has a high degree of stability, has a low resistance to alkalis, which makes the use of such polymeric mixtures

609827/0872 '

.restricts. More suitable from this group of polymers are polybenzoxazoles, which are inherently high thennostabili- • fecvfa and laoiio chomisoho Boei / äjadigicoi-b voa? oinigon » It is the use of polybenzoxazoles "in the

Manufacture of fiberglass-reinforced panels known (USSE copyright Er. 4OJ577). The maximum length of time the operability of such glass fiber reinforced plastics at 300 ° 0 is limited to 500 hours, while modern technology requires a longer lifespan under such conditions.

The purpose of the present invention is to avoid the disadvantages mentioned.

·· The invention was based on the task of developing a polymer mixture that would provide a sufficient Thermostability under the conditions of their processing and their operation at a temperature of up to 450 ° C.

This object is achieved by proposing a polymer mixture which consists of polybenzoxazoles and a stabilizing additive. According to the invention, phosphoric anilides of the general formula ( ^C 5 ^H

where η = 1 to 2, m = 1 to 2, in + m = 3, anilides the phosphorous acid of the general formula

, where E is phenyl ,, θ ( -ITaphthyl or

609827/0072

- 4 - '
ß- liaphthyl or Phospha.cenderivate the general

my formula ρ R ^ P · ^ ^ * P - "" ^ E

Ί '

^ V

where E for C ₆ H ₅ O-, C ₆ H ₅ M-, 4-CH ₅ C ₆ H ₄ O-, 4- ₅₆₄ stent, 'with the following ratio of the components: 100 parts by weight of polybenzoxaz oil and 1 to 10 Gev / ichtsteile stabilizing additive.

The addition of the stabilizer in an amount of 2 to 5 parts by weight per 100 parts by weight of polybenzoxaz oil is optimal. Smaller amounts are ineffective, while larger amounts are less effective in lowering strength values the materials produced from such polymeric mixtures lead.

It is known that the phosphorus compounds are effective stabilizers of thermo-oxidative destruction different types of polymers at temperatures up to li? 0-200 ° C. It is also known that one and the same Compound shows different effectiveness as a stabilizer with polymers of different constructions. So show For example, phosphoric acid and its esters have a stabilizing effect on polyimides. The use of the said phosphorus-containing compounds as a stabilizer for polybenzoxazoles did not provide any significant " Effect. We carried out laboratory tests

60 98 2 7 / 08.72

carried out. The test results showed that "when adding to the polybenzoxazole, for example on the basis of 5.3 ^f -dioxy-4.4 ^l -diaminodiphenylEiethan and isophthalyl chloride, of 3 wt such a mixture prepared JO / um thick film for 30 minutes at a temperature of 35O ⁰ G and an oxygen "- pressure of 400 Torr recorded oxygen 6.7» 6.9 and 7.1 mmol per 1 mole of polymer weight, while the non-stabilized Pclybenzoxazol of the named structure 7, 'A mmoles of oxygen takes up. This shows the low effectiveness of these compounds as stabilizers of the thermo-oxy dative destruction of the polybenzoxazoles. Although the polyimides and polybenzoxazoles belong to the group of highly thermo-

a
belong to more stable aromatic polyheterorylenes, phosphoric acid and its esters, which are used as stabilizers of polyimides, have proven to be ineffective as stabilizers of polybenzoxazoles acid and the phosphazene HIGHSP / ffective stabilizers, - "th'ermöbxydativen destruction of polybenzoxazoles in a range of temperatures are of 300 to 450 ⁰ C.

The effectiveness of the added to the polybenzoxazole stabilizing additives was rated according to the Gewicirbs-

609827/0872

loss of the sample, for example a film of the glass fiber reinforced or carbon reinforced plastic, obtained on the basis of the polymer mixture at (temperatures of 400, 450 ⁰ C and an oxygen pressure of 200 Torr, according to the amount of oxygen absorbed by the samples 55O ⁰ C and an initial oxygen pressure of 400 Torr and after the weight loss of the sample and the change in its physical-mechanical properties under the conditions of prolonged aging in air at a temperature of 300 "to 25O ° P ·

The results obtained show a significant stabilizing effect on all polybenzoxazoles Exercise anilides of phosphoric acid and phosphorous acid and the phosphazene derivatives.

For example, the addition of 3 parts by weight of 1 ^ 3 »5-hexaanilicfc'yQlotriphosphacen to 100 parts by weight of polybenzoxazole on the basis of 3» 3 ¹ -Dio2cy-4,4 ^I -diaminodii / henylmethane and isophthalyl chloride reduces the weight loss of the polymer itself (in form of a film) in two hours at a temperature of 4 ^ 0 ⁰ C more than um. twice. The addition of 3 parts by weight of dianilide of h -napthylphosphorous acid reduces the weight losses of the polymer mentioned under the same conditions by more than three times.

As pointed out above, on the basis of polymeric mixtures, which are used as stabilizing additives, anilides

. - S09827 / 0872

of phosphoric acid and phosphorous acid and phosphazene derivatives contain various materials, "for example films, glass fiber-reinforced and carbon-reinforced plastics, molding materials, adhesives, which are obtained through increased stability of the physical-mechanical properties at temperatures from 300 to q- 50 ° G. during for a longer period of time compared to materials based on non-stabilized polybenzoxazoles.

The compounds selected have high decomposition temperatures on, are soluble in many organic solvents, not colored and mit.den Polybenzooxalen well tolerated. - "

Loving the compounds mentioned can Inilide of phosphoric acid and phosphorous acid and phosphase derivatives a different composition can be used; however, they are either less effective or less effective accessible.

The technology for making mixtures based on. the basis of the polybenzoxazoles and the stabilizing additives according to the invention is not complicated. The stabilizer can be added to a solution of the finished polybenzoxazole or of the polyosgramide, which is a prepolymer of the polybenzoxazole; is. It leads zv / ecklaäßigerweise said addition of the stabilizing additive at a temperature of 20 to 8O ⁰ C.

■ '609827/0672 \

• - 8th -

When the stabilizer is added to the polyoxyamide, the polybenzoxazole structure is formed in the process of manufacturing the material by heat treatment to 400 ⁰ C converts to a Polybenzoxazolfilm. the solutions containing the stabilizer of the polymer can be used for the manufacture according to known methods, for example, of films, glass fiber-reinforced and carbon-reinforced plastics, coatings are used. the stabilizer can the polybenzoxazole by mixing with the polymer in dry form or in the presence of small amounts of solvent, for example water, acetone, chloroform, benzene. The pulverulent mixtures obtained can be used for the production by known methods, for example of molding materials and coatings.

In order to better understand the present invention, the following specific examples are given below. . .

For example . 99 parts by weight of aromatic polyoxyamide based on isophthalyl dichloride and 5f5 ^l -dioxy-4.4 ^l -diaminodiphenyliaethane is dissolved in 1000 parts by weight of dimethyl at a temperature of 20 ^{0 O}

609827/08 7 2

acetamide. 1 part by weight of phenylphosphoric dianilide is added to the solution to. From the solution obtained, a film is poured, which is initially carried out in vacuo 50 minutes at a (temperature of 140 C and then during Holds at a temperature of 320 ° C. for 2 hours. You get thereby a sample of JO / µm thick polybenzoxazole Im. The test results of the film in the process of heat aging are listed in Table 1.

Example 2-27 . With the aid of the methodology described in Example 1, samples of polybenzoxaz oil films were obtained which contain 1 to 10% by weight of various phosphorus-containing compounds.

The composition of the polymeric mixtures and the results of their examination in the process of heat aging are listed in table 1.

For comparison, the table shows the test results for a film made from pure polybenzoxazole. the The conditions for the examination of the films are · in all cases ..... "identical." ~~

EXAMPLES 28-31 A solution of polyamide in dimethylacetamide with additions of phosphorus-containing compounds, prepared according to the methodology described in Example 1, is used to impregnate a glass vial. The soaked tissue is first kept in air for 50 minutes at a temperature of 120 ° C. and then below

609827/0 8.7

Vacuum for 2 hours at a temperature of 30O ⁰ C. The thermally treated glass fabric is cut to ■

Scroll äie maxi to a Palco-b susoauaejales-ü and: bei

a temperature of 400 ⁰ O and a pressure of 20 _; kp / cm presses · · '-.

The composition of the polymeric mixtures and the Results of the testing of the glass fiber reinforced plastics obtained are given in Table 2 »For comparison in Table 2 are the test results of the glass fiber reinforced obtained using the pure polybenzoxazole Plastic. The examination conditions are identical. \ ·

A solution of polyoxyamide in dimethyl ac et amide with the addition of dianilide of $ -liaphthylphosphoric acid was also used in the preparation of samples to determine the extent of the adhesion of the polymeric binder to glass fibers. ■

; The composition of the polymeric mixture and the Test results of the samples in the process of heat aging are also listed in Table 2. For comparison

are, in the table the test results of the pure Polybenzoxazole samples obtained. The test results are identical. .

609827/0 8 72

Example 52 . 98 parts by weight of polybenzoxazole based on ^, ^ '- Diphenyloxydicai-bonsäuredichlorids. In addition to the 5.5 ^{% t} -Dio2y-4,4 ^t -aiaiainodiphenylmethaxla one dissolves "at a temperature of 80 ⁰ C in 1000 parts by weight • Dimethvlacetamid. The solution is added, 2 parts by weight of hienylphosphorsäuredianilid. From the solution obtained according to the method described in Example 1, a film sample of 30 ram. Dicice. The test results of the film are given in Table 5 *

Example 3? “On the basis of the polybenzoxazole described in Example JO, samples of a film are prepared which contain 2% by weight of diphenylphosphoric anilide; The test results are given in Table 3,

For comparison, the results are shown in the table ρ the examination of an IT film obtained from the same poly- "bezoxazole. without stabilizing additive. The examination conditions are identical in all cases.

Example 5 ^ . Parts by weight polybene oxazole based on isophthalic acid and 5> 3 ^l -diamino-4,4 ^t -dioxydiphenyiaethane are intimately mixed with 3 parts by weight of diandylid of β-naphthylphosphorous acid. The mixture obtained is compressed into tablets (diameter 10 mm, height 10 mm) at room temperature under a pressure of 1000 kgf / cm. The results of the testing of the tablet are given in labeile 4.

609827/0072

. Example e 35- ^ 3 · According to the methodology described in Example 54 "one prepares samples of polybenzoxazole / tablets which contain additions of phosphorus compounds".

th.

The composition of the polymer mixtures and the results of their testing "in the process of thermal aging" are listed in Table 4.

For comparison, the table shows the results of testing the tablets made from pure polybenzo: sc & 2olenän ^:. The conditions of the test are identical in all cases.

609827/0872

Table No. 1

No. of the example

Polybenz oxaz ol stabilizer
additive

Stabilizer
Lisa

ver

Concentrations · Conditions of the Ge _M

tration waro-aging weight f®? fL ™

door,
⁰ C

tors in & f the mi-

recorded -> .._ +. "nen Sauerer of the PO substance, St. lyneren""· * ^ν ^ ·

Mi- '1 mole of po-

schung,
Weight%

schung, wt. 56

lymer

2 5

, 0.

dd

Dianilid the ti 1 - 200 Enn 45Ο O 2 68 phenylphospho- η tt ti 42 acid dd Dianilid the ß-naphthyl- 1 dd, dd dd 7? phosphorous 2 dd dd dd . 42 acid

(JR CJI CD OO CD CO

Table Kr. 1 (continued)

• 7 8

OT O CO

»T.

It

ti

Dianilid the 3 • It tt ß-naplrfchylpho- It ti spherical acid 3 200 mm 4-50 It tt 7th ° 2 10 I » » tt ii Diardlid the rL -naphthyl- 3. phosphorous It I acid 1 »315-He2: aa- 3 nilidcyclo- triphosphazene

It

11

dd

Il

dd

OO CO CO

00 CN

UN νθ

as

ITV

ο

νΟ

lf \

O O

0 CVl '

01 O

UN KN

4 ·

-P O

CVJ

KN

4 "

•H

O H O i>. 'Q

OT

rf

pi

rf a

O I O UN

KN

■ Η

HO

CD

M H

cJ IA ft KN

CVl

UN H

νΟ

r-i

609827/0072

ORIGINAL INSPECTED

Table No. 1 (continued)

7th

cn

CD

OO

17th

18th

19th

20th

cyclotriphosphacene

Dianilide of the Phenylphosphiior acid

<l

Anilide of the "" Dipiienylpho

phosphoric acid, "

Diardlid of Ca -naphthylpho s -

phosphoric acid "

Dianilid the

ß-napht & yl-

400 mm 550 0.5 -

It

dd

Il

It

It

5.7

5.1

5.0

CJl

• Ρ α> οι -P

H-

CO

OJ

IA

O O

IA

O CVi C

^ s- ο

CJ LA CO «Η
H η CTv
H ο O
CJ O
ΓΑ 3 ο
IA O
O- ο °
O
IA
ΓΑ ε O
O
O
LA
ΓΑ ··
·· air air «* * ·

KN S

approx

1 O) a z • f4 Ph rf H ϋΟ ι * ι a> iH : aJ ti Ä • Η -
U y ^r d approx & • Ρ O id -P a Ή λ4 x \ approx •H <y r-1 Ph pi r-l Ph fco • Η egg 01 ^! * Ή •H fj <Α O c3 O ■ Η approx Pa •H CQ Pl Ph

CM

6 0 9 8 2 7/0 β 7 2

^ - LA »-O CJ CJ CJ

CM

OO

CN
CM U.N. O
H 'JN
iH CO
H CM CM U.N. OOT O
r-i O
CM O
KN O U ^ ο
CN 00t ο
ο
O
U.N. ε · *
W * * »

I I

I. "λ
ο M. ö> 'd • Η -P • Η Pt S. • Η I. ft cc »

φ W)

■ α

CM

609827/0872

Table 2

cn example.

Folybenz oxaz ol

Stabilizing additive

des n the
Heat aging

Flexural strength of the glass
_ fiber reinforced

"th plastic

In the

_TT - right

Ml-

Schung:., wt.% St.

at at
20 ⁰ O 500 ⁰ O

Adhesion to the glass fiber se! reinforced plastic ρ

res
kp / cin *

Dianilide of the ß-naphthylphosphate

phosphoric acid air 300 '

Il

ti

1 »3» 5-hexaani-

lidcy'clotriphos-

phazen Tt

5500- 2300-

-3700 -2500

'2000-1200-

-2500 -1500

5200- 2200-

-3 ^ 00 -2400

cn cn

cn

OO (JO CD

O O O KN

0-

CJN

CO

ο ι

O Q

KN

CVl CvJ

CVl I CVl

O O O

O O

CvJ

KN

CVJ Q

CVJ O »Η

ι ο. ι

ε <

° 8 ο

H O KN

air

(Q

O • rl, Cj

ίο · Η

ίί ^h

M -P <U O

KN

Pl

d · Η H α>

Pi pi ei ta

P ₁

ι ε <ε

CVJ

r-l KN

s <ε c

609827/00 7

O
H

OO H

O O KN

O <\ J

co

OQO O O

η (Λ m

U \

O OO

Fl

t (D I. H Λ α CQ ο θ ¹ ft. a co
O ι

I.

60982 7/087

Talbelle 3

Mr. of

o play co

Polybenz oxaz ol

Stabilizing additive

Stabilizer
in the

Mixture,
Weight%

re

Face

losses

the polymer mixture,

Dianilid the

phenylphosphorous acid Anilide of diphenylphosphoric acid

it

dd

»T

Air 350 ° 100 32

34

cn oo co

Table 4

Mr.
of
Example

Polybenz oxaz ol

Stabilizing additive

Concentration

Stabilizer
in the
Mixture,
Weight%

Conditions of normal aging

Atmo- Teiape- Dasphärature, outer,

re

St.

Loss of weight of the polymer mixture,% by weight

VO

It

Dianilide of the ß-naphthylphosphorus acid

Anilide of diphenylphosphoric acid "

Air 550 ° 100

It

dd

36

cn

CD

oo.

CO CO

Table 4 (continued)

36 ·

1!

Dianilide of ß-naphthylphosphorous acid. 1 anilide of
Diphenyl phosphoric acid 1

mm wm

1, * 3 »5-hexaanilide cyclotriphosphacene 5

Dianilide of phenylphospho- '. rig en acid '2

Air 350 ° 100

ti

dd

ti

dd

Il

ti

21

13th

19th

CD OO OO

oo

co

r-i

O O r-i

π ■ s ■ <

K \

pi

Pt

• Η U O

ca ο

pi

t ο OJ U S-I O : cS ο pi CQ H <ό ί? ■ Η -P 10 H • ri H pi O % CD
α

• Η ν I Λ

ft V ^ft

OJ

= £ O

509027 / ϋϋ / 2

Table 4 (continued)

(4-anisyloxy) -

phaeen

lylosycyclo-

trlphosphacene

Air 35CT 100 16

tt π η , 20th

ti

21

ti

dd

Dianilide of phenylphosphoric acid 1

Anilides of diphenylphosphoric acid 1

Air 350 °. 100

26th

CO

"Α

CM

■ 6 0 9 Γ-2 7 /i.u /

Claims (2)

·· (l / .. Polybenzoxazole with a stabilizing additive containing -. Polymeric mixture, characterized in that it contains phosphoric anilides of the general formula as a stabilizing additive where η = 1 to 2; m = 1 to 2 and ^ PC OGr-EcL Hi! OP JXi
H- η + ms J is anilides of phosphorous acid of the general formula (C Al ₁ ^ E) ₂ POR, in which E is phenyl, (A -eaphthyl or β-kaphthyl, or phosphacene derivatives of the general formula ^: E "-. '■' E Ü 1 E E wherein _{E- is C 6} H 1 O-, Cg H 4, ₅₆₄ , ₅₆₄ contains, with the following ratio of components: , Polybenzoxaz oil 100 parts by weight, stabilizing, Addition 1 to 10 parts by weight *. 2. Polymeric mixture according to claim 1, characterized characterized in that they contain 2 to 3 parts by weight of stabilizing additive per 100 parts by weight Contains polybenzoxazole. 0 9 8 2 7/0872