DE1795840A1 - NEW POLYMER COMPOUNDS - Google Patents

Description

Bayer Aktiengesellschaft

Eliminated from our patent application P 17 70 144.9 of April 6, 1968

Central area of patents, trademarks and licenses

New polymer compounds

509 Leverkusen. Bayerwerk Jan. 27, 1976

The invention relates to new polymeric compounds that statistically the formula I.

609831/0771

Le A 17 073

where R ₁ , R ₂ .... R _x , identical or different ^ " * ^

can be and hydrogen or halogen or a lower alkyl or aryl radical, an ester group a monohydric alcohol, an amide, a nitrile, a carboxylic acid ester or an alkyl ether group, R '= hydrogen or the methyl group, A = hydrogen or the ^ ethyl group, B = halogen or the methyl group,

= a divalent, optionally ring-substituted one aromatic residue,

= a monovalent, optionally ring-substituted one

aromatic radical or the radical Ar ₁ s of about 5 and are a hydroxyl group with 1 = a number to about 2oo, I _1, l _o .... 1 β identical or different numbers

m β 0 or 1,

η β 0 or 1,

o = 0, 1 or 2,

ρ = an integer from about 5 to about loo, q = * 1 or 2 and

r = an integer from about 5 to about 1,000.

These new connections can be made by Implementation in a manner known per se of copolymers with free or blocked hydroxyphenyl side chains Formula TT,

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609831/0771

where D = hydrogen or the chlorocarbonic acid ester, the Monophenylkohlensaureester- or the Trimethylsilyl- ■ group and r 'means an integer from about 5 to about looo, with dihydric, optionally ring-substituted phenols and

a polycarbonate-forming derivative of carbonic acid and optionally a monohydric phenol.

The copolymers of the formula II can be mixed

merize

monohydric or dihydric phenols of the formula III

with an ethylenically unsaturated substituent

C = CH ι c

CH ₀ ι c-

(O)

(III)

so z. B. of o-, m- or p-isopropenylphenol, p-isopro-

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6098 3 1/0771

penyl-o-cresol, 2,6-dichloro-p-isopropeny! phenol,

m- and p-vinylphenol, p-viny.l-0-cresol, p-allylpnenox, ^y

m-AUyloxyphenol, 3,4-dihydroxyallylbenzene and 2,4-dihydroxyallylbenzene or their chlorocarbonic acid or mono-

phenyl carbonate or the corresponding trimethyl

silane derivatives,

with copolymerizable monomers

of the formulas

R ¹ HR * HR ¹ H

R ₁ HR ₂ HR _x H

in the Molvex ^ ratio lsClj + lg + .. · I ₂ ) can be obtained by methods known per se, e.g. B. by ionic Mlschpolymerisierung (compare z. B. German Patent No. 1,155,527) or preferably by radical copolymerization, preferably using the blocked phenols, in particular the trimethylsilane derivatives. The latter are easily obtainable by reacting the corresponding phenols with z. B. hexamethyldisilazane or with trimethylchlorosilane in the presence of acid acceptors.

To produce the copolymers can be used as reactants to the unsaturated phenols z. B. used: ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, Acrylic and methacrylic acid alkyl esters and amides, acrylic and methacrylonitrile, vinyl acetate, vinyl propionate and benzoate, vinyl methyl, ethyl and isobutyl ether, styrene,

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609831/0771

O-methylstyrene, vinyltoluene, p-3thylstyrene, 2,4-dim'ethylstyrene, Orthochlorostyrene and 2,5-dichlorostyrene, namely ■. individually as well as mixtures thereof.

As dihydric phenols, which are mixed with the copolymers of the formula II, all those known per se for the production of polycarbonate chains can be used, e.g. B. hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis- (4-hydroxyphenyl) -alkanes, such as -methane, -1,1-Ä.thane, -1,1, - and -2,2-propane _> -l, l- and -2,2-butane etc.,. 1, l-bis- (hydroxyphenyl) -cycloalkanes, -methers, -sulfides, dm

-ketones and sulfones and bisphenols, which are halogenated in the nucleus, undöi, ö6 ^f - Bls- (p-hydroxyphenyl) -p-diisopropylbenzene.

This implementation can, as far as it is copolymers. ^. with free hydroxyphenyl side chains or with phenyl carbonic acid ester or trimethylphenoxysilane side chains, with diesters of carbonic acid, preferably Diaryl carbonates, such as diphenyl carbonate, the cresyl car-

carbonates, dichlorophynyl carbonates and the bisphenyl carbonate

■■ - ■ '■■ ·' fl

natural divalent phenols, after the transesterification process

take place at temperatures between about 150 and about 35o ° C, it being possible, if necessary, to add basic or acidic esterification catalysts in the usual ways. If the silane copolymers are used, these react practically in the same way as the copolymers, the side chains of which have free hydroxyphenyl radicals as terminal groups, since the trimothylnilane radicals as a result of re-silylation; are easily split off.

- ^L ° ^{A 17} - ^ 6 0 9 8 3? / T) 7 7 1 ■■■ ""'. · '· Bad A

The folycarbonate side chains can also through. Use of phosgene or bishopric carbonic acid esters Dihydric phenols in horror solution: or in one A phase solution mixture based on the so-called phase interface method using acid acceptors, v; ie tertiary anines or alkali or alkaline earth metal hydroxides, preferably with addition? of catalysts, in particular tertiary amines, also in a manner known per se, getting produced. With these procedures are the Reaction temperatures generally between about 0 and φ etv; a 5o ° C. The solvents to be selected are those in which the copolymer and preferably also that End product are soluble. For this purpose, z. B. methylene chloride, Chloroform and chlorobenzene or mixtures thereof. To carry out this lottery procedure can in addition to the phenol and trimethylphenoxysilane copolymers mixed polymers are also used in which the end groups of the side chains are composed of phonylchlorocarbonic acid esters exist.

As suitable monovalent, optionally ring-substituted aromatic compounds that can lead to the Arp end groups are mentioned z. B. the phenol, the cresols, the dio fTono- and dichlorophenols and p-tort.-butylphonol.

The quantities of dihydric phenols and carbonic acid derivatives to be used per mole of liquid polymer can be widely

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BATH ORIGINAL

Limits vary, depending on whether "one is shorter or." wishes to obtain longer polycarbonate side chains. For every phenolic hydroxyl group in the copolymer should, however, at least 1 mole of dihydric phenol and Carbonic acid derivative is omitted, so that on every phenol group of the copolymer at least one carbonate or PälycarbonatkC'tte is grafted. The preferred result from the · numerical values for ρ of the formula

The new polymeric compounds are distinguished from the known linear polycarbonates by improved flow behavior of the melt and increased stability of the solids against thermal and hydrolytic cleavage. Since they can be used as plastics to be processed thermoplastically, they are particularly suitable for the production of objects that are to have a particularly high resistance to hot water, steam and hydrolyzing liquids in the heat, e.g. B. of everyday objects such as dishes, surgical instruments, m containers and the like. The new polymeric compounds can also be used as paint raw materials.

I> Λ 17 073 - - 7 -

609831/0771 BATH ORIGINAL

In the following examples, the following polymers used:

M. = a product made by interpolymerizing 475 g of methyl methacrylate and 25 g of trimethyl- (p-isopropenyl phenoxy) silane in £ 00 g of methyl glycol acetate in the presence from 5 p; Azodiisobutyronitrile under nitrogen at 80 ° C during 11 hours and precipitation of the product with petroleum ether is obtained as a colorless product (flow viscosity the one containing 37 * 5 weight percent solids Ethyl glycol acetate solution at 20 ° C in Mr. 6 DTH beaker 257 seconds).

This product corresponds to the formula II, where Rj is the carboxymethyl group,

R ^f the methyl group, ^

I ₁ = l = 4o, ■ '· ■ ·

A = methyl

η = 0,

o = 0, ·

D β trimethylsilyl,

q = 1,

r '= about 5 ^ o,. -. _; ,,> ·

mean. ,

Γ4 ₂ = a product that is produced by copolymers of

3960 p. Styrene, 790 R acrylonitrile and 25o f, Trlm »methyl- (p-iso-

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propenylphenoxy) silane in 5oo g of chlorobenzene is obtained in the presence of 1 735 840 25 g of azobisisobutyronitrile under nitrogen at Sun ⁰ C for 3 hours. A solution of this product in chlorobenzene containing ^ o percent by weight of solids has an outlet viscosity at 20 ° C. in a DIN cup of 200 seconds.

This product corresponds to formula II, where R, or R ^ = the phenyl group, ■ _ ', R. or R ₂ = the nitrile group, ■

R '= hydrogen,

■. ■■■■■ '... · - .. · ■

I ₁ «1-31 or - 12.3 -

1 «r 1-12.3 or -31

i, -0-45.3

A = methyl ■
η = 0> - ^; ·
ο β Ο,
D = trimethylsilyl,

r '= 56o.
mean.

f /, ■ β. a product obtained by copolymerizing 11 ^ 7.5 ζ methyl methacrylate, 1187.5 iS styrene and trimethyl- (p-isopropenylphenoxy) -silane in 25oo g chlorobenzene in the presence of 12.5 8 azodiisobutyronitrile under nitrogen at'Ro- ⁰ C. after Io hours

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609831/07 7 1

BATH ORIGINAL

is obtained. A solution of this product in chlorobenzene containing 50% by weight solids has an outflow viscous at? O ° C ir. DI?: - Beaker Vv. 6 of 32 seconds.

This product corresponds to dor ^ ornel II, where R ₁ or R ₂ = the carboxymethyl group,

R. or R ~ = the Phrnyl -π'ppe,

R ¹ = hydrogen or the riethyl "group,

1 ₁ = 1-19.5 or -13.75

1 ₂ = 1-18.75 or -I9.5. '"

i _z - 0-58.25
1 "38.25

Λ = methyl. ·

o = 0,.

D = trinethylsilyl,

r '= 445

mean.

M ^ β a product obtained by interpolymerizing ^Vi

57o £ butyl acrylate, 3R0 g styrene and 5o ζ trimothyl- (p-iso-

propenylphenoxy) silane in looo ζ xylene in presence

of 10 g of azodiisobutyronitrile and 2 g of tert-dodecyl mercaptan

is obtained under nitrogen at 80 ⁰ C after 32 hours and the solution containing 49 percent by weight ^ ststoff

an outlet viscosity at 20 ° C in DTN cup # 4 of Seconds.

Le Λ 17 07g 609831/0771

• ORIGINAL BATHROOM

This product corresponds to the ^ orr: «! TI,

R ₁ or H ₂ = the carboxybutyl group _s 1795840

R. or Rp = the phenyl group, R '= ". Hydrogen

1 ₁ = 1-18.5 or -I5

1 ₂ = 1-15 or -18.3 I ₂ = 0-33..3

1 = 33.3 · '■

Λ = methyl ■

η = O,

D = trimethylilyl, σ «1,

ι «= 25o -

mean.

M_ = a product, which by mixed polynes «riEier« n 'of 1 $ ο η; MM «thoxynethylmsthacrylanid, 225 P, butylacrylatj ϊοο ζ styrene and 25 % trimethyl- (p-isopropenylph» * no3cy} -silan in 500 5 xylene and'100 <x. N-butanol in Geg «m -. 'Kind of 5 f ^ Azodiisobutyronitrile and 1 g of tert-dodecy! Mercaptan
is obtained under nitrogen at 80 ° C after 25 hours and ball with petroleum ether as a colorless powder.

This product corresponds to the formula II, R ₁ , Rp or R- the U-methoxynethylamide group, R ₁ or Rp or R, the carboxybutyl group, R. or Up or R ₇ the phenyl group,

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• 6098.31 / 077Ί

H ¹ s hydrogen or the "• '! Ethyl group,

1 s 1-14.7 or -3 or -9.7

1, = I-9.7 or -14.7 or -8.

■ l _z - 0 -32.4
1 = 32.4

Λ = methyl,

o = 0,

D = trinothylsilyl, q »1, '

b ° dei; th. ,

fV = a product obtained by Mtschpolymerisieren of 79 Z styrene, 16 g of acrylonitrile and 5 g of p-Isopropenylphenylphenylcarbonat (see Patent Vr 1 3 93 o ". 51) in loo <r xylene / Dir.ethylformanid 1: 1 in the presence of 0 , 2 .τ Azodiisobutyronifcril viird obtained under nitrogen at 80 ° C after 11 hours and precipitation with methanol.

This product corresponds to the formula II, where R, or R ₂ = the Phony 1 / ^ ruppe,

R. or Rg = the nitrile group, R ¹ = hydrogen,

1 = 1-38.6 or -15.8.

1 = 1-15.8 or -38.6

I ₇ = 0-54.4.

1 = 54.4

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. 609831/0771 bad original

A ». Methyl, η = O, ο = 0, D = the phenyl carbonate group, q = 1,

mean.

M- = a product obtained by interpolymerizing

Styrene and p-isopropenylphenol in a molar ratio of lo: l w

according to the method of German patent 1 153 is obtained.

This product corresponds to the formula II, in which - ^{% v}

R ₁ = the Pheny! Group,

R ¹ = hydrogen, I ₁ = 1 -m lo,

1 «1,« 0

A = methyl,. . m

η - 0, ο'- Q _s ;

0 β hydrogen,

M ^ s a product made by copolymerizing styrene

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609831/0771

and isopropenylphenol in a molar ratio of 3o: 1 the process of German patent 1,155,527 will.

This product corresponds to formula II, where R ₁ = the phenyl group, R ¹ s = hydrogen, I ₁ -I-? O, I ₂ = .... I ₂ - 0, A - methyl

η β 0, ο 0, D - hydrogen, q »1,

mean.

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609831/07 71:

■ ■ \ -

BATH ORIGINAL

Example 1ϊ

A mixture of 11.9 Z copolymer M ₂ ,, 15 * 96 g 2, .2-bis- (4-hydroxyphenyl) -propane (bisphenol A), 16.5 8 diphenyl carbonate and 0.1 mg disodium salt of the 2, 2-Bis - (^ - hydroxyphenyl) propane is melted in a glass flask equipped with a stirrer and a distillation device after nitrogen equalization twice at IBo ⁰ C. The temperature is increased to 21o °, 24o ° and 27o ° C at intervals of 30 minutes. At the same time, the pressure is reduced to 100 Torr, Io Torr and <1 Torr. The split off phenol and excess diphenyl carbonate distill off. A post-condensation time of 25 minutes is sufficient to achieve the desired toughness. The relative viscosity of the condensation product is 1.41, measured in m-cresol at 25 ° C

with a concentration c = 0.1 g in 100 cm ^y , _ .- ■

This product corresponds to the formula I ₃ in which the meanings of the letters are the same as for M ₂ , D

omitted and ..

Ar. the bisphenol-A residue,

Ar _{2 is} the phenyl radical and

ρ mean 4.2.

Example 2: · _;

A mixture of 5.55 ζ copolymer VU ₉ 15 »9ö S

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■ 609.83170.771. .

Bisphenol-A, .16.5 S diphenyl carbonate and 0.1 πίζ sodium salt of bisphenol A is, as described in Example 1, treated. The relative viscosity of the condensation product is 1.9 ° * measured in m-cresol at 25 ° C with a concentration c = 0.1g in 100 ml.

This product corresponds to the formula I, where the letters have the same meaning as for However, product M ,, D is not applicable. Ar. means the bisphenol radical, the phenyl radical and

Example 3:

Under the conditions given in Example 1, a mixture of 5.33 g of the copolymer Mg, 15.96 g Bisphenol A, 16.5 g diphenyl carbonate and 0.1 mg disodium salt of bisphenol A condenses. An after-condensation time is sufficient to achieve a relative viscosity of 1.52 of 25 minutes.

The product corresponds to the formula I, in which the letters mean the copolymer Mg, but D is omitted.

Ar ₁ denotes the bisphenol A radical, Arg denotes the phenyl radical and

p "- 5 *". ■; · ■■■ ;.

Γ m Γ ¹

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60983170771.

Within 2 hours at 25 ⁰ C with stirring in 1960 g of phosgene in a mixture of 342o g of bisphenol A, - 72.1 g of p-tert-butylphenol, 2I5o g of sodium hydroxide in 12ooo g .Water, 4 "5ο π of the! The mixed polymer of Mg and 6 g of triethylamine in 45oo g of ethylene chloride are passed in. The viscous organic phase is separated off and washed neutral with water Methylene chloride at 25 ° C with a concentration c «0.05 g / l σ ο enr. W

This product corresponds to the formula I, the letters having the meaning of the copolymer M ₂ , but D is omitted.
Ar ₁ denotes the bisphenol A radical, Ar ₂ denotes the p-tert. Butylphenyl radical and /

p «51.2 ·. ■■■■

Γ m T * -

Examples 5-13 '-,

As described in Example 4, those in the table specified mixtures implemented. The products will also worked according to Example 4 Yields and the viscosities achieved are given in the table

refer to.

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Beir.p. Phosgene
(Ό Bisphe
nol A
Ce) pt «rt.
Butylph.
(Ό sodium
hydroxide
(-.) V / ater
(%) 'Mixed polymer
(g) according to example Methylene
chloride
(ml) Triethyl
amine
(I) yield
Ce) rel
(Methylene chloride
c = 5? / looonl ' 5 64 91.2 2, Io 63 56o 60.3 M ₂ ^ OO " 0.2 100 1,313 6th 5O.5 63.4 2.2o 63 560 127 M ₂ 300 H 123 1.321 7th 57 91.2 1.46 6o 54o Io6,6 Ψ ^ ^ OO η 143 1,3ο5 42 6?, 4 1.54 5o 450 Ιοί, ο M ₁ ^ • 00 η Ι09 1.366 9 33 57, o ¹ ^, 3o 33 3oo 127 \\ 600 Il 312 1,1ο9 * Io 33 57, ο 4,3o 33 3oo 127 M ₅ 600 η 1ο2 1.12ο 11 16.5 2-, 5 16.5 I60 31.7 M ₁ 43ο H 47 1.247 ^ 12th '42 6fl, 4 l, 2o 5o 450 5o, ° · Μ _? . ^ OO η 99 1.277 ^ 13th 42 6G, 4 5o 450 5θ, 3 Μ _? ^! ? οο H 11> 1,339

609831/0771

S Le A 17 073 ο

οο.

These products also correspond to the? C »sleeve T,

where the letters are the same as in 179 5 * 840

the copolymers "^ ₁ to 'V and K ₇ and Mq are, ■' ■

However, D is not applicable. *

Ar ₁ each denotes the bisphenol A radical and

Ar ₂ the p-tert. Butylphenyl radical, or in Example 11 the

Ar ₁ radical with a hydroxyl group ■

r each = r ¹

The V values for ρ are:

for example 5 27.3 for example 6 9.7

for ..example 7 15.5 #

for example. Ί 12.2. *.

for example 9 8.1 ·.

for example Io 8.1 '

for example M 16.2

for example 12 5.5 *. ^

for example 1? 14.3

Example 14:.

Within 60 minutes at 25 C 9.8 ζ phosgene in a mixture of 26 g Φ, <^ '-Bis-Cp-hydroxyphonyiy-p-diiso propylbenzene, 0.7o g of p-tert-butylphenol, 9.5 R sodium hydroxide in ίοο ml of water, 4 * 5.5 r, of the table polymer K _? and 0.05 ρ tristhylamir. Riethyl chloride is introduced into 400 ml. The organic phase is then separated off and washed with neutral water. By filling with petroleum ether, nan 42 is obtained, a condensation product with a relative viscosity of 1.168, measured in methylene chloride (c 0.1 G5 / loo cn),

609831/0771> 1 17 073 - 39 -

3 ° 17958A0

This product corresponds to the formula I, the letters having the same meaning; have the same as for the copolymer M ₂ , D but not applicable.

Arj means the OC, o £ '-Bis-Cp-hydroxyphenylI-p-diisopropylbenzene radical,

Ar _{2 is} the p-tert-butyl radical and

P = 6.8

r - r *.

Example 15ί '

Within 50 minutes at 25 C with stirring 7.5 Z of phosgene in a mixture of 16.75 ζ 1,1-bis (hydroxyphenyl) cyclohexah, I.o6 r, phenol, 7.2 <τ sodium hydroxide in loo ml V / ater, 46.5 ß copolymer M ₀ and 0.02 (T ₁ 4oo triethylamine in ml of methylene chloride introduced. by precipitation with methanol from the ^r with V. ater neutral washed organic phase Z 37 is obtained a condensation product having a relative viscosity 1.144 (methylene chloride, c = 0.05 z / '^ - oo cm').

This product corresponds to the formula X, where the letters have the same meaning; have the same as for the copolymer M ₂ , D but not applicable.

Ar ₁ denotes the 1,1-bis (4-hydroxyphenyl) cyclohexane radical, Ar «denotes the phenyl radical and

P = 5.5

r »r ¹

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. . BATH ORIGINAL

Example 16: ^ i

Within 70 minutes at 25 ° C with stirring 12.0 g of phosgene in a mixture of 2o, 5 S bisphenol A, 3.7 g of 2,2-bis- (4-hydroxy-3,5-dichlorophenyl) propane, 0.12 g 2,6-dichlorophenol, 11.16 g sodium hydroxide in 2oo ml of water, 23.0 g of the copolymer Mp and

0.02 g of triethylamine introduced into 3oo ml of methylene chloride «

The organic phase is separated and washed with water washed neutral and from this by adding acetone

31 g of a condensation product with a relative w

Viscosity of 1.241 (methylene chloride, 0 «= 0.05 g / l00 cnr ⁵ )

failed.

This product corresponds to the formula I, the "letters" having the same meaning as for the copolymer M ₂ , but D being omitted.

Ar ₁ denotes the bisphenol A and the tetrachlorobisphenol ¹ A radical,

Ar _{2 is} the 2,6-dichlorophenyl _{radical or the Ar 1} radical with a hydroxyl group. '™

ρ = 17.9

r «r ¹ ■ '. ■ ·

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Claims (1)

Claim; 1. New polymeric compounds that statistically have the • Formula I Le A 17 073 - 22 60 9 831/0771 BATH ORIGINAL where R ₁ , R ₂ ··· R _{x can be the} same or different and are hydrogen or halogen or a lower alkyl or aryl radical, an ester group of a monohydric alcohol, an amide, a nitrile, a carboxylic acid ester or a Alkyl ether group, R 'is hydrogen or the methyl group A is hydrogen or the methyl group B is halogen or the methyl group = a divalent, optionally ring-substituted one aromatic residue,
₂ = a monovalent, optionally ring-substituted one aromatic residue I a number from about 5 to about 200, I _I + I ₂ + ·. I ₂ = 1 m = 0 or 1 η = 0 or 1 ο = 0, 1 or 2 ρ is an integer from 5 to 100, q = 1 or 2 and r is an integer from about 5 to about 1000 mean. Le A 17 075 - 23 - 609831/0771 ORIGINAL.