DE2317985A1 - NITROGEN-CONTAINING POLYMERS - Google Patents

Description

PATENT ANWALTSBORO TlEDTKE - BöHLING - KlNNE

TEL. (MiD 839853-56 TELEXi 524845 ti pat CABLE ADDRESS: Germaniapatem Munich

8000 Munich 2

Bavariaring 4.

P.O. Box 202403 April 10, 1973 B 5329 / case Dv; 24925

Imperial Chemical Industries Limited London (Great Britain)

Nitrogen-containing polymers (addendum to patent application P 19 6 4 609.4)

The invention relates to improved, modified ones Nitrogen-containing polymers and in particular nitrogen-containing Siloxane / oxyalkylene copolymers according to patent application P 19 64 609.4.

In the patent application P 19 64 609.4 of the same applicant nitrogen-containing polymers are described, the organopolysiloxane copolymers containing one or more units of the general formula

R..S1

R ¹ N

° 4-xy 2

wherein

R is a substituted or unsubstituted monovalent Hydrocarbon group,

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Deutsche Bank (Munich) KIo. 51/81070 Dresdner Bank (Munich) Account 3939844 Postacheck (Munich) Account 670 43-804

R ^{1 is} a divalent organic group, R ^{B is} a monovalent hydrocarbon group, R " ^{1 is} a monovalent hydrocarbon group, an acyl group, an N-substituted carbamyl group or a divalent group of the general formula

OR »

Il /

- C - N - R ¹
mean, where the remaining valence of the group R ¹ is saturated by another silicon atom in the same or a different polysiloxane block,

χ 0, 1 or 2,

y 1 or 2,

η 2, 3 or 4 and

ζ mean an integer not less than 2 and not greater than 100,

the remaining units, when in the organopolysiloxane copolymer are present, the general formula

■ V ⁱ⁰ 4-b

where R is as defined above, with the exception that a small portion thereof is hydrogen can and b is 0, 1, 2 or 3.

The present invention relates to improved or modified copolymers of the patent application mentioned P 19 64 609.4. It has now been found that new and valuable co-

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_ 3 -

polymers can be prepared which contain the copolymers described in the patent mentioned, wherein each

p but the group R ″ has been replaced by the group R and in which

2
the group R denotes a hydroxyalkyl or hydroxycycloalkyl group.

The present invention relates to new and valuable organopolysiloxane copolymers which contain one or more Units of the general formula

R Si

R ²

R ¹ NCO (GH 0) R "'

H_

η <xi

contain,
wherein

R is a substituted or unsubstituted monovalent hydrocarbon group,

R ^{r is} a divalent organic group,

2
R is a hydroxyalkyl or hydroxycycloalkyl group,

R ^{'11 is} a monovalent hydrocarbon group, an acyl group, an N-substituted carbamyl group or a divalent group of the general formula

OR ² »/ - C- NR '-

mean, the remaining valence of the group R 'by a different silicon atom in the same or a different polysilicon

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oxane block is saturated,

χ 0, 1 or 2,

y 1 or 2,

η 2, 3 or 4 and

ζ an integer that is not less than 2 and not greater than 100

where the remaining units in the copolymer, if any, have the general formula

V ⁱ⁰ 4-b

wherein R is as defined above, with the exception that a small portion of it will be hydrogen can and b is 0, 1, 2 or 3.

. The groups R can, for example, be alkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkyl or cycloalkenyl groups be or these groups which contain substituents, for example halogen atoms, cyano groups, ether or ester groups. Suitable groups are, for example, methyl, ethyl, propyl, butyl, phenyl, tolyl, benzyl, phenylethyl, Vinyl, allyl, cyclohexyl, chloromethyl, 3-chloropropyl, p-chlorophenyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 4-cyanobutyl, 3-methoxypropyl and 2- (ethoxycarbonyl) -ethyl groups. However, it is generally preferred that at least the majority of the groups R are methyl groups.

The divalent organic group R ¹ is preferred

an alkylene group having not more than 20 carbon atoms.

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-, 5 -

Suitable alkylene groups are, for example, ethylene, 1,3-propylene, 1,4-butylene, 2-methyl-13-propylene and 1,11-undecylene groups.

It is generally preferred that the group R contain no more than 8 carbon atoms. Suitable groups include, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, i-methyl-2-hydroxypropyl, 1,3-dihydroxypropyl, 2-hydroxy-2-phenylethyl and 2-hydroxycyclohexyl. In many

In two cases it is preferred that the group R is a 2-hydroxypropyl group means.

The group R "'can be a monovalent hydrocarbon group such as an alkyl, aryl, aralkyl, alkaryl or cycloalkyl group, an ayl group, a carbamyl group substituted on the nitrogen atom by one or two monovalent hydrocarbons groups such as alkyl or aryl groups or a divalent group of the general formula

O R ² η / - C NO'-

where the remaining valence of the group R ¹ is saturated by another silicon atom in the same or a different polysiloxane block. However, it is generally preferred that this group means a monovalent hydrocarbon group having not more than 10 carbon atoms. Suitable groups are, for example, methyl, ethyl, propyl, butyl, phenyl, benzyl, ToIyI and cyclohexyl groups.

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t.

The oxyalkylene units (C _n H _2n O) can be oxyethylene, oxypropylene or oxybutylene units or a mixture of two or more of these units. However, it is usually preferred to use oxyethylene units with or without oxy-1,2-propylene units.

The ratio of units of the formula II to those of the formula I can be high in the copolymers according to the invention vary. The products that are most valuable are those in which the ratio is from 0: 1 to 100: 1. The chosen Ratio will depend on the end use for which the copolymers are intended. The invention Products can be used as emulsifiers and dispersants in a variety of systems. The copolymers which are water-soluble due to the oxyethylene content are special useful. In general, products with a high SiI-oxane content are, for example, as lubricants for fibers and Plastics valuable and products with a higher polyoxyalkylene content are useful as nonionic surfactants, latex coagulants, and the like. The preferred copolymers which contain only oxyethylene units or these together with oxy-1,2-propylene units are particularly important for the production of polyurethane foam as a means to control the cells and useful as stabilizers. They are particularly valuable in the manufacture of polyether-based polyurethane foams. The general rule is that Products with a weight ratio of oxy-1,2-propylene

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Units to oxyethylene units in the range of 1: 1 to 0.4: '1 are particularly useful in the manufacture of rigid Polyurethane foam, whereas products where this ratio is from 0.6: 1 to 1.5: 1 are particularly valuable in the production of flexible polyurethane foams. Are the copolymers according to the invention in the production of When polyurethane foams are used, it is preferred that the polyoxyalkylene portion be within a range of 50 to 85 wt. #, Based on the total, lies. These products are naturally used in the production of polyurethane foams in a known manner, and they can be added, by adding them separately at the mixing stage or one can premix it with one or more of the other ingredients.

The products according to the invention have a high degree of hydrolytic and chemical stability. You can thus, for example, for long periods in aqueous amine solutions, how to use them to make polyurethane foams.

The stability is also in other applications, especially in those applications in which the copolymers used in aqueous solutions, valuable. The copolymers according to the invention also have an improved one Solubility in water and they dissolve more rapidly in water than the copolymers of British Patent 1,257,650.

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This is particularly advantageous when the copolymers in an aqueous medium can be used, for example when you get them from aqueous solutions as a lubricant or antistatic Means for fibers used during processing and during the subsequent removal from the fiber by washing with V / ater.

The copolymers according to the invention can be prepared by adding an organopolysiloxane containing one or more units of the general formula

(III)

° 4-x-y

contains, either alone or with one or more other units of the general formula

_ _b (II)

wherein R, x, y and b have the definitions given above, with an unsaturated polyoxyalkylene carbamate of the following formula _R 2 _Q

R ^V NC 0 (C _n H _2n O) ₂ R '"(IV) converts, wherein R ^{v is} the ethylenically unsaturated precursor

(= Precursor) of R 'and R, R " ¹ , η and ζ have the meanings given above. This gives copolymers in which R" ^{1 is} a monovalent hydrocarbon group, an acyl group or a substituted carbamyl group. In order to prepare copolymers in which R " ^{1 is} divalent, the organopolysil-

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oxane with a polyoxyalkylene dicarbamate of the general formula

2 p2

ι 0 Ov ι R ^V NC ° C ^c _n ^H 2n ° ^ z ^CNRV ^

implemented.

The copolymers according to the invention can also be prepared by reacting the organopolysiloxanes with a mixture of two or more carbamates, which do not all have to be of the same type. The siloxane used in the process of the invention can be linear, cyclic or branched. The linear organopolyisloxanes which have at least one unit of the formula (RHSiO) with or without one or more terminal (RpHSiO) ₁ / p units are particularly valuable. It is generally preferred that no more than one hydrogen atom be bonded to any silicon atom. The siloxane used can also contain one or more branching units RSiO, / p or SiOp. However, these should not be present in such an amount that strong branching is effected, ie there should not be more than one branching unit per 10 SilQxan units. If the reaction is not carried out to completion, the product will of course contain a small proportion of hydrogen atoms bonded to silicon.

Are the polymers according to the invention by coupling reaction between an organopolysiloxane, the units

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of the formula III, and an unsaturated polyoxyalkylene carbamate of the formula IV by conventional processes in which is catalyzed with platinum metal salts or complexes, as described above, it is found that a small proportion of the available Si-H groups of the Units of the formula III (generally less than 5%) react with the hydroxyl groups of the R substituents of the polyoxyalkylene carbamate, with hydrogen being formed.

The following examples illustrate the invention without restricting it. Unless otherwise noted, all are Parts and percentages expressed by weight.

example 1

580 parts of a polyoxyethylated 2-Methoxyäthanols having an average molecular weight of 580 are stirred in a glass reaction vessel at 35 ⁰ C while 109 parts of gaseous phosgene in the course of one hour are introduced into the liquid. The temperature of the reaction mixture is kept in the range from 35 to 40 ^° C. by external cooling during the addition. Then continue stirring. The temperature of the reaction mixture v / hile held for 2 hours at 30 to 40 ⁰ C. Infrared spectroscopic examination of the reaction mixture then indicated that the conversion of the hydroxyl groups to the chloroformate was complete, which could be inferred from the absence of a hydroxyl absorption band in the region of 2.8 / µ. Solved, not implemented

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Phosgene and hydrogen chloride were then removed by purging with a stream of nitrogen and then the product is distilled at 65 to 70 ° C and 20 mm Hg pressure, the polyether chloroformate having the average composition CKL (OCH ₂ GH ₂ ) ₁ 2 ₅ OC (O) C1 is obtained as a clear, colorless liquid.

610 parts of the polyether chloroformate thus prepared are gradually added over 30 minutes to a stirred mixture of 700 parts of toluene, 115 parts of N-2-hydroxypropylallylamine and 159 parts of anhydrous sodium carbonate. During the addition process, the temperature of the reaction mixture is maintained at 28-30 ° C by external cooling. Thereafter the mixture is stirred at 29 to 30 ° C for 15 minutes, then it is gradually increased over the course of 30 minutes Heated to reflux temperature. 20 parts of an aqueous distillate are by azeotropic distillation using a Dean and Stark separators removed. The mixture is then cooled to 60 ° C, 35 parts of an acidic ion exchange resin (Amberlite IR 120 (H)) are added and the mixture is stirred while maintaining the temperature over the following 2 hours can drop to 25 ° C. The mixture is filtered through a pad of silica, leaving 1410 parts of a 48% solution of the polyether-N-allyl-N-2-hydroxypropylcarbamate obtained in toluene as a clear, light yellow solution.

To 165.0 parts of the solution prepared in this way, the 79.3 parts of methoxypolyoxyethyl-N-allyl-N-2-hydroxypropylcarb-

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contains amate, a further 27 parts of toluene are added. The solution is stirred and refluxed under a small stream of nitrogen heated and dried by azeotropic distillation. The solution is cooled to 90 ° C and a solution of 0.023 parts Bis (diethyl sulfide) platinum (II) chloride in 5 parts of toluene is added. In the course of 5 minutes it becomes 27.4 parts a polysiloxane having an average composition of the following formula

Me.JSiO (Me ₀ SIOL ,. - (MeSiO) _{1 oo} SiMe ,,

added, while the temperature of the reaction mixture in the range from 90 to 100 ⁰ C is kept. The reaction mixture is then heated under reflux conditions (116 to 118 ° C.) for 5 hours. The toluene is then ^{distilled off by heating to 100 °} C. at a pressure of 0.1 mm Hg. This gives 106 parts of a clear, light brown, liquid copolymer with a viscosity of 2050 cSt. at 25 ° C, which is readily soluble in water at 20 ⁰ C.

This product was tested as follows during the production of a polyurethane foam:

100 parts of an oxypropylated glycerol with a average molecular weight of 312, 178 parts of crude 4,4'-di-isocyanatodiphenylmethane, 30 parts of trichlorofluoromethane, 30 parts of tri- (ß-chloroethyl) phosphate, 4 parts of Pluronic L61 (registered trademark), 2 parts of N, N-dimethylcyclohexylamine, 1 part water and 1 part polysiloxane-polyoxyalkylene-

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Copolymers prepared as described above were blended together and foamed. This gave a rigid polyurethane foam with a fine, uniform texture and a density of 0.0272 g / cm ³ (1.7 lb / cu.ft.).

Example 2

316 parts of a 48% solution of a polyether carbamate in toluene from Example 1 are dried by azeotropic distillation under nitrogen, the solvent returns to the solution. The solution is cooled to 90 ° C. and a solution of 0.045 parts of bis (diethyl sulfide) platinum (II) chloride in 5 parts of toluene is added. 141 parts of methyl hydrogen polysiloxane are then added terminal triraethylsilyl groups of the general formula

Me ₁ SiO (SiKe ₀ O) ._ _ (SiMeO) _r

added. The cloudy mixture that is obtained is stirred and refluxed. Within 5 minutes, upon reaching the reflux temperature (118 ⁰ C), the solution is clear and homogeneous. The mixture was then refluxed for a further 4 hours and then all materials which were volatile up to a temperature of 110 ° C. at 0.5 mm Hg pressure were removed from the solution by distillation. 292 parts of a clear, light, liquid copolymer with a viscosity of 1172 cSt were obtained in this way. at 25 ⁰ C

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Example 3

610 parts of a polyoxyalkylated 2-methoxyethanol the average composition

produced by oxyalkylation of 2-methoxyethanol3 with a mixture of ethylene oxide and propylene oxide, treated with 109 parts of phosgene in the same way as described in Example 1 to convert it into the corresponding polyether chloroformate _{with the average composition CH 3 COCH 2} CHg] ₁₀ ^ COCH ₂ CH ( CH _to convert _{3)] 2e1} 0C (0) Cl.

54-0 parts of the polyether chloroformate thus prepared are added over a period of 1 hour to a stirred mixture of 550 parts of toluene, 97.3 parts of N-2-hydroxypropylallylamine and 135 parts of anhydrous sodium carbonate. During the addition process, the temperature of the reaction mixture is kept below 40 ^° C. by external cooling. The mixture is then stirred at 40 ° C. for 30 minutes and then it is heated to reflux temperature. 13 parts of an aqueous distillate are removed by azeotropic distillation using a Dean and Stark separator. The mixture is then cooled to 25 ° C. 140 parts of an acidic ion exchange resin (Amberlite IR 120H) is added and the mixture is stirred for 16 hours at 20 to 25 ⁰ C. It is filtered through a layer of kieselguhr and 1140 parts of a 51.8% solution of the are obtained

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.lyether-N-allyl-N-2-hydroxypropylcarbaniate.

CH ₉ CH (OK) CH,

1 '■ ^

in toluene.

382 parts of the toluene solution prepared in this way, which contains 197.5 parts of polyether-N-allyl-N-2-hydroxypropyl carbamate, are heated to reflux and dried by azeotropic distillation. The solution is cooled to 90 ° C and a Solution of 0.09 parts of bis (diethyl sulfide) platinum (II) chloride in 5 parts of toluene is added. In the course of 14 minutes, 256.3 parts of a polysiloxane become the average Composition of the formula

Ko ₃ SiO (Ho ₂ SiO) _{25 8} (lfeSi0) ₂ 3SiMe ₃

added while the temperature of the reaction mixture in the range from 90 to 100 ⁰ C is kept. Thereafter, the mixture stood for 4 at reflux (116 to 118 ⁰ C) is heated. The toluene is then stripped from the product by heating to 10O ⁰ C at a pressure of 0.1 mm Hg. 440 parts of a clear, light brown oil with a viscosity of 451 cSt are obtained. at 25 ° C. The oil was easily soluble in water at 20 ^{° C.}

Example 4

150 parts of the polyether chloroformate from Example 3

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are in the course of 30 minutes to a stirred mixture of 150 parts of toluene, 41.5 parts of N- (2-hydroxy-2-phenyl) ethylallylamine (CH ₂ = CHCh ₂ NHCH ₂ CH (OH) C ₆ H ₅ ) and 36 parts of anhydrous sodium carbonate were added. During the addition process, the temperature of the reaction mixture is maintained in the range of 25-30 ° C. The mixture is then heated to reflux and 3.6 parts of water are removed by azeotropic distillation using a Dean and Stark separator. The mixture is then cooled ^{to 25 ° C.} 20 parts of an acidic ion exchange resin (Amberlite IR 120H) are added and the mixture is stirred at 20 to 25 ° C. for 16 hours.

Filtration of the mixture through a layer of silica and subsequent removal of the toluene by distillation at 100 ^° C. and 0.1 mm Hg yield 180 parts of the polyether-N-allyl-N- (2-hydroxy-2-phenyl) ethyl carbamate

CH ₂ CH (OH) C ₆ H

CH, COCH ₀ CH ₀ ] ^, COCH ₀ CH (CHj] ₀ , OCIICH CH = ^ H,

81.4 parts of the polyether-N-allyl-N- (2-hydroxy-2-phenyl) ethyl carbamate thus prepared are dissolved in 80 parts of toluene and the solution is heated to reflux and azeotroped Dried distillation. The solution is then cooled to 90 ° C. and 0.0338 part of bis (diethyl sulfide) platinum (II) chloride are added in 4 parts of toluene. Over the course of 7 minutes

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97.5 parts of a polysiloxane become the average Composition of the formula

added while the temperature of the reaction mixture in the range from 90 to 100 ⁰ C is kept. The mixture is then heated to reflux (120 ° C.) for 4 1/2 hours. The clear, brown solution is then ^{stripped from the toluene by heating to 100 °} C. at a pressure of 0.1 mm Hg. 174 parts of a clear, brown oil with a viscosity of 435 cSt are obtained in this way. at 25 ⁰ C.

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Claims (1)

Patents n.s ρ back e 1. Organopolysiloxane copolymers containing one or more units of the general formula , 2 R ¹ NCO (CH ₀ 0): (D R is a substituted or unsubstituted monovalent hydrocarbon group, R ^{1 is} a divalent organic group, 2
R is a hydroxyalkyl or hydroxycycloalkyl group, R "'is a monovalent hydrocarbon group, an acyl group, an N-substituted carbamyl group or a divalent group of the general formula 0 R ² Il mean, in which the remaining valence of the group R ^f is saturated by another silicon atom in the same or a different polysiloxane block,
χ 0, 1 or 2,
X 1 or 2,
η 2, 3 or 4 and - ζ an integer that is not less than 2 and is not greater than 100, mean, with the remaining 309843/0890 Units in the Cppolyraeren, if such are present, the general formula ■ '-7- have, wherein R has the definition given above, with with the exception that a minor portion of it may be hydrogen and b is 0, 1, 2 or 3. 2. Copolymers according to claim 1, wherein the groups R are alkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkyl or cyeloalkenyl groups, with or without substituents such as halogen atoms, cyano, ether and ester groups. 3. Copolymers according to claim 2, wherein the group R is an ethyl, propyl, butyl, phenyl, tolyl, benzyl, phenylethyl, Vinyl, allyl, cyclohexyl, chloromethyl, 3-chloropropyl, p-chlorophenyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 4-cyanobutyl, 3-methoxypropyl and 2- (ethoxycarbonyl) -ethyl groups means. 4. Copolymers according to claim 2, wherein at least a major part of the groups R are methyl groups. 5. Copolymers according to one of the preceding claims, p
wherein the group R contains no more than 8 carbon atoms. 6. Copolymers according to claim 5, wherein the group R is a 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, 1-methyl 309843/0890 2-hydroxypropyl, 1,3-dihydroxypropyl, 2-hydroxy-2-phenylethyl or a 2-hydroxycyclohexyl group. 7. Copolymers according to one of the preceding claims, wherein the group R "'is an alkyl, aryl, aralkyl, alkaryl or a cycloalkyl group or a carbamyl group on the nitrogen atom by one or two alkyl and / or aryl groups, means. 8. Copolymers according to one of the preceding claims, wherein die.Oxyalkylen-units (C _n H _2n O) consist of oxyethylene units with or without oxy-1,2-propylene units. 9. Copolymers according to any one of the preceding claims, wherein the ratio of the units of the formula II to those of the formula I is 0; 1 to 100: 1. \ §J Process for the preparation of organopolysiloxane copolymers according to one of Claims 1 to 9, characterized in that an organopolysiloxane which has one or more units of the general formula ^R x? ^iH y '° 4-xv
2 ~ either alone or with one or more other units the general formula ^R b ^Si0 4-b 309843/0890 contains, wherein R, χ, y and b have the meanings given above, with an unsaturated polyoxyalkylene carbamate ρ
of the formula R 0 R ^V NC 0 (CLO) R ¹¹ condensed, where R ^{v is} the ethylenically unsaturated precursor of R 'and R, R "', η and ζ have the definitions given above to obtain copolymers in which R" ^{f is} a monovalent hydrocarbon group, an acyl group or a substituted carbamyl group. 11. Process for the preparation of organopolysiloxane copolymers according to one of claims 1 to 9, characterized in that an organopolysiloxane, the one or several units of the general formula ° 4-xy 2—- either alone or with one or more other units of the general formula ^R b ^Si0 4-b contains, in which R, x, y and b have the meanings given above, with a dicarbamate of the general formula fj, of ) ^v converts, wherein R ^{v is} the ethylenically unsaturated precursor of R ¹ ρ
and R, η and ζ have the definitions given above. 309843/0890 12. The method according to claim 10 or 11, characterized in that a linear organopolysiloxane is used and that this contains at least one unit of the formula (RHSiO) with or without one or more terminal (RpHSiO) _1. ^ - units, wherein R contains the above given definition has * 13. Use of an organopolysiloxane copolymer of Claims 1 to 9 in a process for the production of polyurethane foams j, characterized in that one in the Reaction mixture incorporates part of an organopolysiloxane copolymer according to one of Claims 1 to 9. 14. Polyurethane foams which are part of an organipolysiloxane copolymer according to any one of claims 1 to 9 incorporated. 309843/0890