EP1474465A1

EP1474465A1 - Aminomethylene-functional siloxanes

Info

Publication number: EP1474465A1
Application number: EP03739443A
Authority: EP
Inventors: Oliver SCHÄFER; Wolfram Schindler; Bernd Pachaly; Andreas Bauer
Original assignee: Consortium fuer Elektrochemische Industrie GmbH
Current assignee: Consortium fuer Elektrochemische Industrie GmbH
Priority date: 2002-02-14
Filing date: 2003-01-23
Publication date: 2004-11-10
Also published as: WO2003068845A1; CN1633458A; US20050085612A1; DE10206124A1; JP2005517749A

Abstract

The invention relates to amino-functional organosiloxanes of general formula I [(HO)R2SiO1/2]t[R3SiO1/2]U[R2SiO2/2]p[O1/2SiR12CR22NH2]S (I), in which s represents a whole number, said whole number being at least 1, s + t + u represents the value 2, t or u represent the value 0 or 1, and p represents the value 0 or a whole number from 1 to 100,000, and R, R1, and R2 have the meanings indicated in claim 1, and a method for the production thereof.

Description

Amino et ylenf functional siloxanes

The invention relates to aminomethylene-functional siloxanes and a process for their production using alkoxysilanes.

Aminoalkyl polysiloxanes are useful in many fields of application, including the preparation of polyidene and polyetherimides. However, the commercial use of these compounds on a larger scale is prevented by a relatively expensive manufacturing process.

It is known e.g. the base-catalyzed equilibration of octamethylcyclotetrasiloxane with bisaminopropyltetramethyl-disiloxane as e.g. in US-A-5512650. This reaction has the disadvantage that the expensive bisa inopropyl-tetramethyldisiloxane is used as the starting material. In addition, there are the long reaction times, some of which in the equilibration reaction are longer than 10 hours.

Another method for the production of such polysiloxanes is to produce them by cohydrolysis of difunctional silanes with organofunctional aminosilanes. However, this has the disadvantage that, due to the presence of amino groups, the cohydrolysis cannot be carried out with chlorosilanes, but alkoxysilanes have to be used. This means that the hydrolysis must be preceded by the esterification of the chlorosilanes, with the valuable alcohol being lost in the subsequent hydrolysis.

DE-A-2500020 describes a process for the preparation of aminomethylsiloxanes. Here, OH-terminated siloxanes with secondary aminomethylsilanes with elimination of Alcohol implemented. The advantage of this process is a reaction of a siloxane with an alkoxysilane without equilibrating the reaction mixture, which would lead to the formation of cycles as a by-product and is therefore not wanted. The disadvantage of this process is that, because of the secondary amino function, the silicone oils thus produced cannot be used for the production of, for example, siloxane-polyimide copolymers, since a primary amino function is essential here.

The object was therefore to provide such amino-functional siloxanes with which, inter alia, Polysiloxane-polyimide copolymers can also be produced.

The invention relates to amino-functional organosiloxanes of the general formula I,

[(HO) R ₂ Si0 _1/2] t [R3SiOι / 2] u ^R 2Siθ2 / 2] p [Ol / 2 SiR ¹ ² 2CR 2NH2] _s (I)

in which

R is a hydrogen atom or a monovalent, optionally with -CN, -NCO, -N ^X 2 -COOH, -COOR ^x , -halogen, -acrylic,

Epoxy, -SH, -OH or -CONR ^x 2 substituted Si-C-bonded C] _- C2o hydrocarbon radical or C; ι_-Ci5 hydrocarbonoxy radical in which one or more, not adjacent methylene units by groups -0- , -CO-, - COO-, -OCO-, or -0C00-, -S-, or -NR ^X - can be replaced and in which one or more non-adjacent methine units by groups, -N =, -N = N-, or - P = can be replaced, R- ¹ - a hydrogen atom or a monovalent optionally with -CN, -NCO, -NR ^X 2, -COOH, -COOR ^x , -halogen, -acrylic, -

Epoxy, -SH, -OH or -CONR ^x 2 substituted Si-C-bonded Cη_-C20 ~ hydrocarbon radical in which one or more, not adjacent methylene units by groups -0-, -CO-, -COO-, -OCO- , or -OCOO-, -S-, or -

NR ^X - can be replaced and in which one or more non-adjacent methine units by groups,

N =, - N = N-, or -P = can be replaced, R ^{x is} hydrogen or a C] _- C] _o ^_κ ° hydrogen carbon residue which may be substituted with -CN or halogen,

R ^ hydrogen or an optionally substituted with -CN or halogen C] _- C2o hydrocarbon radical, s is an integer of at least 1, s + t + u the value 2, t, u the values 0 or 1 and p the value 0 or an integer from 1 to 100,000.

The amino-functional organosiloxanes of the general formula I have a primary amino function which is bonded to a silicon atom of the siloxane chain by a carbon atom. The primary

Amino functions are very reactive. For example, polysiloxane-polyimide copolymers can therefore be easily produced with the amino-functional siloxanes.

R can be aliphatic saturated or unsaturated, aromatic, straight chain or branched. R is preferably an unbranched C _] _-C3 alkyl radical, which can be substituted. R is particularly preferably a methyl radical.

The Cι-C20 ~ hydrocarbon residues and C] _- C20 ^-K ° ^{cool en} ~ material oxy residues R ^ can be aliphatic saturated or unsaturated, aromatic, straight-chain or branched. R ^ preferably has 1 to 12 atoms, in particular 1 to 6 atoms, preferably only carbon atoms, or an alkoxy oxygen atom and otherwise only carbon atoms. R - * - is preferably a straight-chain or branched C ^ -Cg-

Alkyl. The radicals methyl, ethyl, phenyl, vinyl and trifluoropropyl are particularly preferred.

The radicals R2 can, independently of one another, also be aliphatically saturated or unsaturated, aromatic, straight-chain or branched. R ^ is preferably a C] _- C3 ~ alkyl radical or hydrogen. R ^ is particularly preferably hydrogen.

The amino-functional organosiloxanes of the general formula I are preferably aminoalkyl-terminated

Polydimethylsiloxanes which carry an aminoalkyl group on at least 90% of the chain ends. In particular, that carries

Aminoalky-terminated polydimethylsiloxane has at least 99% of the chain ends an aminoalkyl group.

T is preferably 0.

P is preferably from 4 to 500.

The invention also relates to a process for the preparation of amino-functional organosiloxane of the general formula I, in which the organosiloxane general formula II

[(HO) R ₂ SiO _1/2] VCR3 ^si0 l / 2] u [R2 ^Si 02/2] qC ^H] ^{<I] [>} '

with alkoxysilane of the general formula III (R ³ 0) R ¹ ₂ SiCR ² 2NH ₂ (III),

is implemented, whereby

R- an optionally cyano- or halogen-substituted <Z - C] _5 hydrocarbon radical, q integer values of at least 0 means v means 0 or 1, u means 0 or 1, v + u = 1 and R, R-- and R ^ have the above meanings.

R-3 can also be aliphatic saturated or unsaturated, aromatic, straight chain or branched. R ^ is preferably a Cχ-C3 alkyl radical. -3 ethyl or methyl is particularly preferred. R ^ is very particularly preferably a methyl radical.

The alkoxysilanes of the general formula III used can be obtained simply and in high yields by amination of the corresponding chloroalkyl (alkoxy) dialkylsilanes e.g. be produced under pressure in an ammonia atmosphere as described in the patent specification SU 395371.

The alkoxysilanes prepared in this way react simply and very quickly with hydroxy-functional siloxanes of the general formula II. The use of special catalysts is not necessary.

In order to enable a reaction between the organosiloxane of the general formula II and the alkoxysilane of the general formula III, the organosiloxane of the general formula II Contain hydroxy groups. The reaction proceeds with elimination of the alcohol R- ^ OH.

In the process for the preparation of amino-functional organosiloxane of the general formula I, the amount of alkoxysilanes of the general formula III used depends on the amount of the silanol groups to be functionalized. However, if the OH groups are to be fully functionalized, the alkoxysilane must be added in at least equimolar amounts.

If the silanes of the general formula (III) are reacted with at least an equivalent amount of water, the hydrolysis product obtained is a disiloxane of the general formula (IV)

^[ 0 ₁ / 2SiR ¹ 2CR ² H ₂ ^] 2 ⁽ I ^V)

where R! and R ^ have the meanings given above.

The process is preferably carried out at 0.degree. C. to 100.degree. C., particularly preferably at least 10.degree. C. to at least 40.degree. C. The process can be carried out either with the inclusion of solvents or else without the use of solvents in suitable reactors. If necessary, the process is carried out under vacuum or under superatmospheric pressure or at normal pressure (0.1 MPa). The alcohol formed can then be removed from the reaction mixture under reduced pressure at room temperature or at elevated temperature.

When using solvents are inert, especially aprotic solvents such as aliphatic hydrocarbons, such as. B. Heptane or decane and aromatic hydrocarbons such as toluene or xylene preferred. Ethers such as THF, diethyl ether or MTBE can also be used. The amount of solvent should be sufficient to ensure adequate homogenization of the reaction mixture. Solvents or solvent mixtures with a boiling point or boiling range of up to 120 ° C. at 0.1 MPa are preferred.

If the alkoxysilane of the general formula III is added to the organosiloxane of the general formula II in deficit, residual unreacted Si-OH groups can remain in the amino-functional organosiloxane of the general formula I or with other compounds which react with Si-OH groups, are implemented so that a further reduction in the Si-OH content can be achieved and, for example unreactive end groups can be introduced into the silicone oil mixture, which can be used to limit the molecular weight in later copolymerizations. Isolation of the intermediate product is not absolutely necessary.

All of the above symbols of the above formulas each have their meanings independently of one another.

In the following examples, unless otherwise stated, all quantities and percentages are based on weight, all pressures are 0, 10 MPa (abs.) And all temperatures are 20 ° C.

Experiment 1: 100 g were placed in a 1 liter steel autoclave

Chlormethyldimethylmethoxysilan (Starfire Systems, Troy, USA) in an autoclave with 300 g of liquid ammonia at a temperature of 100 ° C to react. After 5 hours was allowed to cool to room temperature, the autoclave was depressurized to normal pressure and 500 ml of dry heptane were added. The precipitated ammonium chloride was filtered off, the heptane was removed by distillation and the product was purified by distillation. 56 g of aminomethyldimethylmethoxysilane were obtained.

Example 1 :

1000 g of bishydroxy-terminated polydimethylsiloxane with an average molecular weight of 3000 g / mol were reacted at room temperature with 79.2 g (1-aminomethyl) dimethylmethoxysilane. ^ H-NMR and ² ^ Si-NMR showed that after 30 minutes all OH groups had been converted to aminomethyl units and a bisaminomethyl-terminated polydimethylsiloxane had been obtained. The by-product methanol was removed in vacuo and 1050 g were obtained

Bis (aminomethyl) polydimethylsiloxane.

Example 2:

1000 g of bishydroxy-terminated polydimethylsiloxane with an average molecular weight of 3000 g / mol were added

Room temperature reacted with 83.2 g (1-aminomethyl) dimethylmethoxysilane. ^ H-NMR and ² ^ si-NMR showed that after 30 minutes all OH groups had been converted to aminomethyl units. Residual silane was reacted by adding a few milliliters of water and the resulting

Bis (aminomethyl) tetramethyldisiloxane) removed in vacuo. The by-product methanol also distilled off.

Example 3: 100 g of bishydroxy-terminated polydimethylsiloxane with an average molecular weight of 13000 g / mol were mixed at 50 ° C. with

1.85 g of A inomethyldimethylmethoxysilan implemented. ^ H NMR and ^ Si NMR showed that after 1 hour all OH groups had been converted to aminomethyl units.

Example 4:

100 g of bishydroxy-terminated polydimethyl siloxane with an average molecular weight of 28000 g / mol were at 50 ° C.

0.85 g of aminomethyldimethylmethoxysilane reacted. ^ H NMR and

29si-NMR showed that after 2 hours all OH groups had been converted to aminomethyl units.

Example 5:

100 g of bishydroxy-terminated polydiphenyl siloxane with an average molecular weight of 1000 g / mol were at 100 ° C.

23.8 g of aminomethyldimethylmethoxysilane reacted. ^ H-NMR and ² 9si-NMR showed that after 1 hour all OH groups had been converted to aminomethyl units.

Example 6:

1000 g of bishydroxy-terminated polymethylvinyl-co-polydimethylsiloxane with a vinyl: methyl ratio of 1: 4 and an average molecular weight of 2500 g / mol were reacted at room temperature with 95.4 g of aminomethyldimethylmethoxysilane. ^ H-NMR and ² ^ Si-NMR showed that after 0.5 hours all OH groups had been converted to aminomethyl units and no further aminomethyldimethylmethoxysilane was detectable.

Example 7:

100 g bishydroxy-terminated polymethyl-trifluoropropylsiloxane with a trifluoropropyl: methyl ratio of 1: 1 and with an average molecular weight of 900 g / mol were at room temperature with 26.6 g of aminomethyldimethylmethoxysilane implemented. ¹ H-NMR and ²⁹ Si-NMR showed that after 2 hours all OH groups had been converted to aminomethyl units and no residual aminomethyldimethylmethoxysilane was detectable.

Example 8:

1000 g of bishydroxy-terminated polydimethylsiloxane with an average molecular weight of 3000 g / mol were reacted at room temperature with 87.2 g (1-aminomethyl) dimethylethoxysilane. ^ H-NMR and ²⁹ Si-NMR showed that after 0.5 hours all OH groups had been converted to aminomethyl units and a bisaminomethyl-terminated polydimethylsiloxane had been obtained. The by-product ethanol was removed in vacuo and 1050 g of bis (aminomethyl) polydimethylsiloxane were obtained.

Example 9:

1000 g of bishydroxy-terminated polydimethylsiloxane with an average molecular weight of 3000 g / mol were reacted at room temperature with 71.2 g (1-aminomethyl) dimethylmethoxysilane. ^ H-NMR and ²⁹ Si-NMR showed that after 30 minutes 90% of the OH groups had been converted to aminomethyl units and an aminomethyl-terminated polydimethylsiloxane had been obtained in this way. The by-product methanol was removed in vacuo and 1050 g of aminomethyl-functional polydimethylsiloxane were obtained.

Example 10:

215 g of bishydroxy-terminated polydimethylsiloxane with an average molecular weight of 860 g / mol were added

Room temperature with 59.8 g (1-aminomethyl) dimethylmethoxysilane implemented. 1 H NMR and ²⁹ Si NMR showed that after 30 minutes all OH groups had been converted to aminomethyl units and a bisaminomethyl terminated polydimethylsiloxane was obtained. The by-product methanol was removed in vacuo and 1050 g were obtained

Bis (aminomethyl) polydimethylsiloxane.

Example 11:

119 g (1-aminomethyl) dimethylmethoxysilane were dissolved in 200 ml

Dissolved methanol and reacted with 10 g of distilled water.

After stirring for 30 minutes, the methanol was removed and the product was distilled. 93 g (97%

Yield) bis (aminomethyl) tetramethyldisiloxane.

Example 12:

180 g of an onohydroxy-terminated polydimethylsiloxane (produced by anionic polymerization of C3-Cycles) with an average molecular weight of 1800 g / mol were reacted with 12.0 g (1-aminomethyl) dimethylmethoxysilane at room temperature. ^ H-NMR and ⁹ Si-NMR showed that after 30 minutes all OH groups had been converted to aminomethyl units and a mono-inomethyl-terminated polydimethylsiloxane had been obtained. The by-product methanol was removed in vacuo and 190 g of aminomethylpolydimethylsiloxane were obtained.

Claims

claims

1. amino-functional organosiloxanes of the general formula I,

[(HO) R ₂ Si0 ₁ 2] t [R3SiOι / 2] u [R2Siθ2 / 2] p [0 ₁ / 2SiR ¹ 2CR ² ₂ NH ₂ ] _s (I

where R is a hydrogen atom or a monovalent, optionally with -CN, -NCO, -NR ^X 2, -COOH, -COOR ^x , -halogen, -acrylic,

Epoxy, -SH, -OH or -CONR ^x 2 substituted Si-C-bonded C] _- C2o ~ hydrocarbon residue or C ^ -C ^ hydrocarbon-oxy residue in which one or more, not adjacent methylene units by groups -0- , -C0-, - COO-, -OCO-, or -OCOO-, -S-, or -NR ^X - can be replaced and in which one or more non-adjacent methine units by groups, -N =, -N = N-, or - P = can be replaced,

R! a hydrogen atom or a monovalent, optionally with -CN, -NCO, -NR ^X 2, -COOH, -COOR ^x , -halogen, -acrylic,

Epoxy, -SH, -OH or -C0NR ^X 2 substituted Si-C-bonded C2_-C20 ~ hydrocarbon radical in which one or more, not adjacent methylene units by groups -O-, -CO-, -COO-, -OCO- , or -OCOO-, -S-, or - NR ^X - can be replaced and in which one or more non-adjacent methine units can be replaced by groups, - N =, - N = N-, or -P =,

R ^{x is} hydrogen or a C] _- C g hydrocarbon residue which is optionally substituted with -CN or halogen, R ^{2 is} hydrogen or a C -C 20 ^-K ° hl ^water residue which is optionally substituted with -CN or halogen, s is an integer of at least 1, s + t + u is 2, t, u is 0 or 1 and p is 0 or an integer of 1 to 100,000.

2. Amino-functional organosiloxanes according to claim 1, in which R is an unbranched Cχ-C3 ~ alkyl radical.

3. amino-functional organosiloxanes according to claim 1 or 2, in which R ^ is selected from the radicals methyl, ethyl, phenyl, vinyl and trifluoropropyl.

4. Amino-functional organosiloxanes according to Claims 1 to 3, in which R ^{2 is} selected from C 1 -C 3 -alkyl radicals and hydrogen.

5. Amino-functional organosiloxanes according to Claims 1 to 4, which carry an aminoalkyl group on at least 90% of the chain ends.

6. Process for the preparation of amino-functional organosiloxane of the general formula I,

^{^[(H0)} R2Si0 _^1/2] t ^[R3Si ⁰ ₁ ^2] _u ^[R2 ^S i ⁰ ₂ ^2] p ^[O _{_1/2} ^{C 2} 2SiRl ^2NH2] s ^(D

in the organosiloxane of the general formula II

^{^[(HO)} R ₂ Si0 _1/2] _v CR3SiOι / ^2] u ^[R2 ^S i ⁰ ₂ ^/] q ^{^[H] ^(II),}

with alkoxysilane of the general formula III

(R ³ 0) R ¹ ₂ SiCR2 ₂ NH ₂ (III), is implemented, wherein R is a hydrogen atom or a monovalent optionally substituted with -CN, -NCO, -NR ^X ₂ , -COOH, -COOR ^x , -halogen, -acrylic, -epoxy, -SH, -OH or -CONR ^x ₂ Si-C bound

C] _- C20 ~ hydrocarbon radical or Cι_-C] _5-hydrocarbon oxy radical in which one or more, not adjacent methylene units by groups -0-, -CO-, -

COO-, -OCO-, or -OCOO-, -S-, or -NR ^X - can be replaced and in which one or more non-adjacent methine units are replaced by groups, -N =, -N = N-, or - P = can be replaced, l is a hydrogen atom or a monovalent, optionally with -CN, -NCO, -NR ^X ₂ , -COOH, -COOR ^x , -halogen, -acrylic, - epoxy, -SH, -OH or -C0NR ^X 2 substituted Si-C bonded

C] _- C20 ~ hydrocarbon radical in which one or more methylene units which are not adjacent to one another are formed by groups -0-, -CO-, -COO-, -OCO-, or -OCOO-, -S-, or -

NR ^X - can be replaced and in which one or more non-adjacent methine units can be replaced by groups, - N =, - N = N-, or -P =,

R ^{x is} hydrogen or a C] _- CiQ hydrocarbon radical which is optionally substituted by -CN or halogen,

R ^{2 is} hydrogen or a Cχ-C2 _Q hydrocarbon radical which is optionally substituted by -CN or halogen,

R-3 is an optionally cyano- or halogen-substituted 0χ-

C _] _5 ~ hydrocarbon residue, q integer values of at least 0, v a value of 0 or 1, VL a value of 0 or 1, v + u = 1 and p is 0 or an integer from 1 to 100,000.

7. The method according to claim 6, wherein R ^ is a C_-C3 alkyl radical.

8. Process for the implementation of silanes of the general formula

(III) with water to siloxanes of the general formula (IV)

^[0 ₁ / ^2NO iR ¹ ₂ ₂ NH2-2 CR2 ^(IV) '

where R! and R ^{2 have} the meanings given in claim 6.