CS215229B1 - BLa (trialkoxysilyl / amidoammonium salts and methods for their preparation) - Google Patents

Abstract

The invention describes new silanes suitable for treating fibers of the general formula conh-/c2h4nh/x-/ch2/-jSí/o2r5/3 C00 HjNH2/C2H4NH^-/CH2/3Si/Ó2R5/. where x is 0.1 or 2 and R is methyl or ethyl. The preparation of these compounds can be carried out by adding solid phthalic anhydride to solutions of the appropriate aminosilanes in a molar ratio of 1:2 at a temperature of 0 to 70 °C, in an environment of a water-soluble organic diluent. Silanes are effective as binding agents for e.g. polyamides.

Description

The invention relates to new bis/trialkoxysilyl/amidoammonium salts and the method of their preparation.

The development of fiber surface treatments is closely related to the continuous growth of the production of glass fiber reinforced plastics and the development of fiberglass production technologies. Lubrication, which is used to treat glass fibers, must give them properties that allow them to be processed into the desired type of reinforcement. Organosilicon compounds have found wide application in the formulation of lubricating compositions, where they are filled with variously substituted trimethoxysilanes, the application of which is constantly being expanded by the preparation of new derivatives with new application properties.

Disilanes of the structural formula /R/^Si-M-Si/R^ where R is alkyl, alkoxyl, aryl, etc. and so on and M is a double bond group are known.

CS car. etc. Nos. 156,986, 177,559, 171,572 and 177,563 describe compounds where M is an aliphatic polyamide residue and R is, for example, butoxyl. The preparation of compounds in which M is an arylene residue is described in ČS aut. etc. No. 160 397, USSR auto. etc. No. 316,334, fluoroaromatic residue in US Pat. No. 3,627,801, imide residue in US Pat. No. 3,901,913. Organosilicon sulfides and polysulfides are described in US Pat. No. 3 946 059.3 997 581. A binding agent for the treatment of glass fibers based on the compound of the formula /hcoo/ ₃ si/ch ₂ / ₂ -o-/ch ₂ / ₂ si/ooch/ ₃ « is covered by the US Pat. No. 4 028 391. Compounds where M is alkylene and R is alkyl are described in ZŠSR'osv. No. 598,908.

Preparation of amidosilanes of the structural formula

R ₁ CONH/CH ₂ / _n Si/OR/ ₃ where R-^ is alkyl, alkenyl, aryl and the like and R is alkyl by the action of acyl chlorides on the corresponding aminosilanes is described in Japanese Patent No. 76,108,022.

general formula

The invention describes novel bis/trialkoxysilyl/amidoammonium salts

co-nh-/c ₂ h ₄ nh/ _x _/ch ₂ / ₃ -sí/or/ ₃

-η

C00 H (NH ₂ -/C ₂ H ₄ NH/ _x -/CH ₂ / ₃ -SÍ/OR/,Í where x is an integer of 0, 1 or 2 and R is methyl or ethyl. The preparation can be carried out by reacting solid phthalic anhydride with the amino silanes of these common compounds with the formula ^NH 2 ^/C 2 ^H 4 ^NH / ^/ x ^/CH 2 ^/ 3 ^Si/OR/ 3 ť

e.g.:

3-aminopropyltriethoxysilane,

M-(2-Ethyldiaminoethyl)-3-aminepropyltrimethoxysilane,

3-/2-aminoethyl/iminopropyltrimethoxysilane a

3-(2-aminoethyl/aminopropyltriethoxysilane).

The addition is possible in the environment of a water-soluble organic solvent such as acetone, dioxane, ethyl alcohol, talanhydride and aminosilanes in a ratio of 1:2 at a temperature of 0 to 70 °C. The course of the reaction is considerably exothermic, therefore it is advantageous to carry out by slowly adding the anhydride, either in solid form or as a solution to the aminosilane solution. Because water is the most common diluent in the preparation of lubricating compositions! it does not have the industrial significance of isolating silanes, but of preparing them in water-soluble solvents. This method, i.e. in the form of solutions, enables their automatic dosing and weighing.

Preparation compounds are effective as means of increasing the rigidity of glass fibers, which is necessary for their processing by cutting, mainly for lengths below 15 mm, or as reinforcement of thermosets, mainly epoxy resins, or thermoplastics, mainly polyamides, where they also fulfill the function of a binding agent.

The advantage of these derivatives is that they are water-soluble, can be prepared from commonly available raw materials in a simple, energy-efficient procedure.

The invention is further explained by way of examples.

Example 1

Preparation of silane with formula conh/ch ₂ sí(oc ₂ h ₅ / ₃ © ® c

C00 H ^H ₂ /CH ₂ / ₃ Si/0C2ÍÍ ₅ / ₃

Handle:

14.8 g /0.1 mol/ of phthalic anhydride

44.3 g /0.2 mol/ 3-aminopropyltriethoxysilane

59.1 g dioxane

The silane and diluent were placed in a flask. The solid anhydride was slowly added with vigorous stirring so that the temperature did not exceed 40 °C (50 minutes).

Analyzes for ^C 26 ^H 5O°9 ^N 2 ^Si 2/ ^τβ1 ·®όΐ. weight- 590.98/ > no. acidity no. amino mg KOH/g mg KOH/g calculated 94.94 94.94 9.50 determined 94.38 94.56 9.61

Example 2

Preparation of silane of the formula

conh/ch ₂ / ₂ nh/ch ₂ / ₃ sí/och ₃ / ₃ β & ť

COO H NH ₂ /CH ₂ / ₂ NH/CH ₂ /.jSi/OCH

3 ^of 3

Handle:

14.8 g/0.1 mol/phthalic anhydride

44.4 g /0.2 mol/ 3-2-aminoethyl/aminopropyltrimethoxysilane 59.2 g dioxane

Preparation procedure as in example 1.

Analysis for ^C 24 ^H 48°9 ^N 4 ^Si 2 /mol. mass- 592.84/

δ. acidity No. amine Si (mg KOH/g} (mg KOH/g} (%) calculated 94.64 283.93 determined 94.73 279.86

Example-d 3

Preparation of silane of formula

9.48

9.54

- CONH/CH ₂ / ₂ NH/GH ₂ / ₂ NH/CH ₂ / ₃ Si/OCH ₃ / ₃ ^x COO HjNH ₂ /CH _a / ₂ NH/CH ₂ / ₂ NH/CH ₂ / ₃ Si/0CH ₃ / ₃

Handle:

14.8 g /0.1 mol/ of phthalic anhydride

53.1 g /0.2 mol/ N-(2-ethylenediaminoethyl/3-aminopropyltrimethoxysilane)

67.9 g dioxane

Preparation procedure as in example 1.

Analyses for CggH^gO^NgSig / mol. mass- 679.0/

Acidity No. Amine No. (mg KOH/g} (mg KOH/gJ

Si w

determined calculated

81.74 405.28

82.63 413.17

8.40

8.27

Example 4

Preparation of silane of formula

C ONH/CH ₂ / ₃ Si/OCH^ _/3

COO h[^ ₂ /CH ₂ / ₃ SÍ/QCH ₃ / ₃

Handle:

14.8 g/0.1 mol/phthalic anhydride

35.9 g /0.2 mol/ of 3-aminopropyltrimethoxysilane

50.7 g acetone

Silane, diluent was introduced into the bank and immersed in a dewar container with ice. After cooling to 0°C, stirring slowly, according to the dissolution rate, solid phthalic anhydride was added so that the temperature did not exceed 25°C /40 minutes/.

Analysis by C^gO^Si,, weight 506.72/

acidity (mg KOH/g]

No. amine [mg KOH/g}

Si [%)

H ^NH ₂ /CH ₂ / ₂ NH/CH ₂ / ₃ Si/OC ₂ H ₅ / ₃ j of phthalic anhydride calculated 110.73 110.73 11.09 determined 112.04 111.30 10.87

Example 5

Preparation of a silane of the formula conh/ch ₂ / ₂ nh/ch ₂ / ₃ sí/oc ₂ h ₅ / ₃ xe COO

Handle:

14.8 g /0.1 mol/

53.0 g/0.2 mol 3-(2-aminoethyl)aminopropyltriethoxysilane

The stock was submitted to the bank at normal temperature. The phthalic anhydride suspension dissolved during 10 minutes of stirring and the temperature rose to 60°C due to the exothermic course of the reaction. The reaction was terminated after 30 minutes by cooling the handle.

Analysis for C^H^O^Si,, _/mo 'l.weight - 677.00/

No. of acidity No. of amine Si mg KOH/g mg KOH/g % calculated 82.88 248.64 8.30 determined 83.20 251.18 8.19

Example 6

Preparation of silane of formula

- conh/ch ₂ / ₂ nh/ch ₂ / ₂ mh/ch ₂ / ₃ sí/oc ₂ h _53/

COO Η [nH ₂ /CH ₂ / ₂ NH/CH ₂ / ₂ NH/CH ₂ / ₃ Si/OC ₂ H ₅ /3!

Handle:

14>8 g /0.1 mol/ of phthalic anhydride

61.5 g /0.2 mol/N-/2-ethylenediaminoethyl/ 3-aminopropyltriethoxysilane

76.3 g dimethylformamide

Preparation procedure as in the example? 5. Exothermic temperature rise to 70 °C.

Analysis for ^C 34 ^H 7o°9 ^N 6 ^Si 2 /mol·. _weight st- 763.50/

No. of acidity No. of amine Si mg KOH/g mg KOH/g % calculated 73.49 367.45 7.36 calculated 75.02 370.14 7.29

Example 7

The silane according to example 1 was used to prepare glass fibers from E-glass with a thickness of 13 micrometers in the form of a lubricant containing 0.25% by weight of s.oli. The treated fibers were used as a polyamide reinforcement with a content of 30% by weight of the fibers. A 0.5% solution of 3-aminopropyltriethoxysilane was also evaluated in a similar way and the results obtained are shown in the table, where treatment No. 1 is polyamide without fibers, No. 2 with Isosilane according to the invention and No. 3 with 3-aminopropyltriethoxysilane.

Modification No. 1 2 3

fortress in tension MPa 56 113 112 ductility % 220 6.5 6.0 hardness mean Brinell MPa 117 146 146 fortress in bending MPa 70 143 139

The use of silanes according to the invention is not only of economic importance, i.e. the possibility of reducing the concentration of adhesion promoters, but their use increases the bulk weight of the fibers, which has a positive effect during handling, transport and processing.

Claims (2)

OBJECT OF THE INVENTION 1. Bis / trialkoxysilyl / amidoammonium salts of the general formula O-NH- / C ₂ H ₄ NH / _X - / CH _2/3 -Si / OR e © Γ COO H / NH ₂ - / C ₂ H ₄ NH / _x - / CH _2/3 -Si / OR / ₃ wherein x is an integer of 1 or 2 and R is methyl or style. 2. Process for preparing compounds according to claim 1, characterized in that the solid is treated with phthalic anhydride at the aminosilanes of formula HN / C ₂ H ₄ NH / / CH / ₃ Si / or / ₃ in which X 8 is as defined in point 1 %, a water-soluble diluent, and a molar ratio of phthalic anhydride: aminosilane of 1: 2, p: 0 to 70 ° 0. organic temperature