CS266045B1 - Lubrication for treatment of glass fibers - Google Patents

Abstract

A lubrication for the treatment of glass fibers, processable by chopping technology with subsequent application for thermoplastic reinforcement, based on polyphenylene oxide contains 0.1 to 3% by weight of a coupling agent formed in situ in the preparation of the lubrication from a compound of the general formula I, where m is an integer of 1 to 5; n is an integer of 1 to 3, X is a hydrolyzable alkoxy group with 1 to 4 carbon atoms or halogen, and from a transition metal acetylacetonate of the general formula II, where R is alkoxy or acetylacetonate, Me is the respective transition metal, Ry is acetylacetonate, x is an integer of 1 to 3 and y is an integer of 1 to 2. The lubrication further contains a film-forming agent, preferably a polyurethane resin, in an amount of 1 to 20% by weight. The lubrication also contains 0.1 to 3% by weight of an antistatic agent, 0.1 to 5% of a pH regulator, and the remainder, up to 100% by weight, is water.

Description

The invention relates to a lubricant for the treatment of glass fibers suitable for the production of a thermoplastic composite material based on polyphenylene oxide. The lubrication consists of a coupling, film-forming, antistatic agent and a pH regulator.

The glass fibers used for the reinforcement of thermoplastic polymers make up 10 to 40% by weight of the composite and are applied in the form of chopped strands of elementary fibers with lengths of 3 to 12 mm. Fiber chopping technology and application conditions require that lubrication impart the desired properties to the fibers.

The repair must ensure a high integrity of the strand of elementary fibers after cutting, and thus ensure a high bulk density of the chopped strands, which is desirable for perfect dosing and mixing of the fiber with the matrix. Another important function of the treatment is to ensure good wettability of the matrix fibers and a satisfactory adhesive bond between the glass fibers and the thermoplastic polymer, thus creating conditions for achieving high physical and mechanical properties of the composite.

In the case of the reinforcement of a thermoplastic based on polyphenylene oxide, the treatment of the fiber must not degrade at the temperature of their mixing with the matrix.

Previously known glass fiber treatments used for the production of conventional thermoplastic composites based on polycarbonate, polyamide, polypropylene, polyethylene terephthalate and polybutylene terephthalate do not meet the requirements for polyphenylene oxide reinforcement, especially in view of the unsatisfactory physical and mechanical properties of the composite. In these lubricants, a bonding agent based on conventional functional organosilicon compounds of the general formula is used to provide an adhesive bond between the fibers and said polymeric matrices.

R-Si- (OR ') ₃ , where

R is an organofunctional group vinyl, amino, epoxy, methacryloxy, glycidoxy, mercapto, ureido and the like.

R 'is a hydrolyzable alkoxy group having 1 to 4 carbon atoms, or halogen and Si is silicon.

Aqueous dispersions of polyvinyl acetate, acrylic and methacrylic acid esters, aqueous emulsions of polyester and epoxy resins and also emulsions of aromatic or aliphatic polyurethanes are used as film-forming components in lubricants, in addition to other components such as pH regulators, lubricating components and wetting agents.

Said disadvantages are eliminated or substantially reduced in the lubrication according to the present invention, the essence of which consists in that the lubrication contains as coupling agent 0.1 to 3% by weight of the reaction product formed in situ in the lubrication preparation process. at least two free electron pairs on the functional atoms of the functional group chain, and from the transition metal acetylacetonate. The lubricant further comprises a film-forming agent, preferably an aqueous dispersion of polyurethane resin, in an amount of 1 to 20% by weight, an antistatic agent in an amount of 0.1 to 3% by weight, a pH adjuster of 0.1 to 5.0% by weight and the remainder up to 100% by weight. water. The polyamino-functional organosilicon compound has the general formula

H- (NH-CH _O -CH 2 -NH- (CH _O ) J SiX., Where 2 2 m 2 Ji n 4-nm is an integer from 1 to 5, n is an integer from 1 to 3 X is a hydrolyzable alkoxy group, having 1 to 4 carbon atoms or halogen Typical polyamino-functional organosilicon compounds are, for example

N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane

N- (beta-dimethylaminoethyl) -gamma-aminopropyltrimethoxysilane N- (beta-aminoethylaminoethyl) -gamma-aminopropyltriethoxysilane N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane Ureidopropyltriethoxysilane.

The transition metal acetylacetonate is a compound of formula (R) _x -Me- (Rpy, where

R is alkoxy or acetylacetonate,

Me is a transition metal such as titanium or zirconium,

R 1 is acetylacetonate, x is an integer from 1 to 3 and y is an integer from 1 to 2.

The content of acetylacetonate of the metal entering the reaction is 5 to 150% of the total weight of the polyamine-functional organosilicon compound, preferably 40 to 60% by weight, when the best physical and mechanical properties of the polyphenylene oxide composite are achieved.

In addition to the reaction product, other known binders, such as low molecular weight polyether-modified diaminosilane, gamma-aminopropyltriethoxisilane, can be applied in the lubrication in cases where it is desired to further enhance or suppress any of the functional properties of the glass fibers.

Wetting agents and lubricants, such as oxyethylenated nonylphenol and fatty acid amides, may also be used if it would be desirable to process the fibers in uncut form.

The advantage of the lubrication formed according to the invention is the use of the reaction product as a binder which, together with the film-forming agent represented by the polyurethane resin, provides improved physical and mechanical properties of the polyphenylene oxide composite, for example its increased tensile, flexural and impact strength, improved . The fibers treated with this lubrication are also suitable for reinforcing polyamides, polyethylene terephthalate, polybutylene terephthalate, polycarbonate and polyacrylonitrile / butadiene / styrene.

The invention is further elucidated in the form of exemplary lubrication compositions applied to the surface of glass fibers during the drawing process, the content of the individual components of the lubrication being given in% by weight.

Example 1

Coupling agent: reaction product which is formed in situ from 6 parts

N- / beta-aminoethyl (-gamma-aminopropyltrimethoxysilane and parts of di-iso-propoxy-Ti-acetylacetonate 0.90%

Film-forming agent: aqueous dispersion of aliphatic polyurethane resin 33% 13.00%

PH regulator:

acetic acid 10% 2.50%

Antistatic:

lithium chloride 50% aqueous solution water

0.30% to 100.00%

Preparation process:

In a stainless steel vessel, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane is reacted with diisopropoxy-Ti-acetylacetonate at normal temperature. This produces a reaction product which is hydrolyzed with stirring with one-fifth of the water required to prepare the lubrication. After the addition of water, the solution thus formed is neutralized with acetic acid. An aqueous dispersion of polyurethane resin is metered into the vessel for the final preparation of the lubrication, which is diluted with half of the water required for the preparation of the lubrication. The reaction product prepared in the previous operation and a 50% lithium chloride solution are metered into the diluted dispersion and made up to the total lubrication content with water.

Example 2

Fastener:

reaction product formed in situ from 6 parts of ureidopropyltriethoxysilane and 3 parts of diisopropoxy-Ti-acetylacetonate 0.90% ’

Film-forming agent:

aqueous dispersion of aliphatic polyurethane resin 33% 13.00%

PH regulator:.

acetic acid 10% 2.50%

Antistatic:

lithium chloride 50% aqueous solution 0.30% water up to 100.00%

The preparation procedure is identical to Example 1.

The content of transition metal acetylacetonate entering the reaction in Examples 1 and 2 is 50% by weight of the polyamino-functional organosilicon compound.

Example 3 '

Fastener:

reaction product, which is formed in situ from 7 parts

Of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and 3 parts of di-iso-propoxy-Ti-acetylacetonate 0.70% aminosilane modified with a low molecular weight polyether 0.30%

Film-forming agent:

aqueous dispersion of aliphatic polyurethane resin 33% 13.00%

Antistatic:

lithium chloride 50% aqueous solution 0.30% water up to 100.00%

The transition metal acetylacetonate content of the reaction in Example 3 is 42.85% by weight of the polyamino-functional organosilicon compound.

The preparation procedure is the same as in Example 1, except that both silanes are metered into the vessel for the preparation of the reaction product. However, the polyether-modified diaminosilane does not react.

According to Examples 1, 2 and 3, the prepared lubrication is applied to the surface of the elementary glass fibers by means of known applicators, directly in the process of drawing them out of the platinum furnace. The lubricated fibers are wound on a paper spool and passed on for drying at 130 ° C. Drying is continued until the weight of the coil remains constant.

Claims (2)

Lubricant for the treatment of glass fibers suitable for the production of a thermoplastic composite material based on polyphenyl oxide, consisting of a binder, film-forming, antistatic agent and pH regulator, characterized in that it contains 0.1 to 3% by weight of reaction product formed in situ in the process of preparing a lubrication, from a polyamine-blowing organosilicon compound having at least two free electron pairs of the general formula on the atoms of the functional group chain, of the general formula H- (NH-CH ₂ -CH ₂ ) _m -NH- (CH ₂ ) _n SiX _{4 -n} , where m is an integer from 1 to 5, n is an integer from 1 to 3 X is a hydrolyzable alkoxy group, with 1 to 4 carbon or halogen atoms, and from a transition metal acetylacetonate of the general formula (R) -Me- (R.), In which X iy R is alkoxy or acetylacetonate, Me is the appropriate transition metal, is acetylacetonate, x is an integer from 1 to 3, y is an integer from 1 to 2, and the film-forming agent, which is preferably a polyurethane resin in aqueous dispersion, contains 1 to 20% by weight, of antistatic agent 0, 1 to 3% by weight, a pH adjuster 0.1 to 5% by weight and the remainder up to 100% by weight is water. 2. The lubrication according to item 1, characterized in that the content of acetylacetonate of the transition metal entering the reaction is 5 to 150% of the total weight of the polyamine-blowing organosilicon compound.