CS235885B1 - Method of polymers' fillers and admixtures sizing - Google Patents

Abstract

BACKGROUND OF THE INVENTION The present invention relates to a method for finishing fillers and resins to polymer polymers based on aminoplasts in one manufacturing operation. Finishing is performed with a melamine mixture and / or urea with formaldehyde, optionally melamine precondensates, urea cells or melamine urea resins in an amount of 5 to 30% by weight based on the weight of the peliva. Specified the reagents and resins may optionally be modified with 6-caprolactam in amount 5 - 60% based on amine weight substances. The filler finish is suspended And stirring at 80 to 150 ° C. ; The polycondensation conditions are "To include the finished filler surface "Less than 1% of the methylol groups are reactions, wherein the polykondene finish The milling is carried out in a fluidized bed reactor stirring or in a fluid bed dryer. During preparations finished fillers and polymer additives according to the invention, cheap and commercially available compounds or resins. Conventional fluidization can be used to finish reactors with rotating arms, which provide a homogeneous reaction provided heating and extraction.

Description

The present invention relates to a process for finishing fillers and additives in polymers in a fluidized bed with aminoplast resins in a single manufacturing operation.

Fillers are inorganic or organic, natural or synthetic, often very complex compounds, which are used as additives to polymeric materials to improve the desired properties such as stiffness, thermal conductivity, decrease in extensibility, flame retardancy, etc., or to reduce the cost of plastic. Untreated fillers usually have poor cohesion with polymeric materials, which results in a decrease in physico-mechanical properties, higher water absorption, and elution of the filler during aging. The filler finishes are carried out with various finishing agents to improve the adhesion in the polymer filler system and increase the utility properties. Improvement of properties is achieved abroad by finishing the filler with a substance that changes the surface properties. The known methods so far most commonly used are on the so-called wet route, in which solutions of resins in a solvent are used, which must be removed in a subsequent production process. In the case of finishing with acrylic polymers, the disadvantage is the thermoplastic character, which deteriorates the surface adhesion, moreover, there is swelling on the surface of plastics - sprays and moldings. Solution finish solution is time consuming and energy intensive. The drawbacks of these processes are partially overcome by buoyancy finishing, but using basic silanes, organic tin compounds, aluminum silicates and phosphorocarboxylic acids.

The aforementioned drawbacks are eliminated by a method of finishing fillers and additives in polymers with aminoplasts, which consists in that the finishing is carried out in a single operation in a floating manner at a temperature of 80 to 150 ° C with a 1: 1 molar ratio of melamine or urea with formaldehyde. 2 to 1: 3 and in an amount of 5 to 1: 3

235 885% by weight of the filler or precondensates of melamine, urea or melamine-urea resins prepared by the simultaneous polycondensation of melamine and / or urea with formaldehyde in the said molar ratio and in an amount of 5 to 30% by weight. In another aspect, the finishing agents are optionally modified with 6-caprolactam in an amount of 5 to 60% by weight based on the weight of the amine. The polycondensation conditions are chosen such that the size of the filler surface contains less than 1% of reactable methylol groups, wherein the polycondensation finish is carried out in a fluidized bed reactor with stirring or in a fluidized bed dryer. Cheap and commercially available compounds or resins are used in the preparation of the finished fillers and polymeric additives of the invention. For finishing it is possible to use conventional fluidized bed reactors with rotating arms which ensure a homogeneous reaction, provided with heating and suction.

The process of finishing the fillers and additives in polymers with the aminoplasts according to the invention enables the production of filled plastics with substantially higher strength, better electrical insulation properties and less water absorption. Due to the minimal number of free functional methylol groups on the surface of the filler, no larger amount of reaction water is released, which would negatively affect the curing reaction or the formation of blisters in the epoxide. The process according to the invention allows the formation of a uniform resin surface layer on the filler surface. This layer is non-fusible and insoluble in resin systems and, as a result, does not exudate on the spray surface. The surface of the finished fillers is chemically unreactive and adheres firmly to the filler and to the binder used. Internal separators, moisture, etc. do not precipitate on the filler surface when curing resin binders, which deteriorate the quality of the composite. In the process according to the invention, a layer is formed on the surface of the filler or other polymer additive which prevents a negative effect of the surface of the filler on the rate of curing reaction, reducing corrosion and abrasion of the processing equipment. Another advantage is a reduction in the oil number of the filler and thus an increase in the fill while saving filler.

- 3 Example 1 ^{235 885}

The following components were charged to the stirred reactor at 80 ° C:

ground mica 82.3% by weight · amine 8.2% by weight · formaldehyde technical 36% 9.0% by weight · formic acid p.a. 0.5% by weight ·

Within 20 minutes the resin was treated with 1% free methyl groups, the material was dried under vacuum of 0.05 MPa and after cooling it was ready for use as a filler.

Example 2

The following components were introduced into the stirred reactor at 150 ° C:

% kaolin floated 73.2% by weight

melamine 22.0% by weight ·

6-caprolactam 2.2% by weight * formaldehyde technical 36% 2.5% by weight · sodium hydroxide 0.1% by weight ·

Within 10 minutes the filler was finished with a resin containing zero content of free methylol groups, the finished filler was dried under vacuum 0.10 MPa and after cooling it was ready for further use ·

Example 3

The following reactants were introduced into the stirred reactor at 100 ° C:

glass fiber 95,1% by weight · urea-formaldehyde resin containing 20% methylol groups 4,8% by weight ammonium oxides 0,1% by weight

Within 15 minutes the filler was treated with resin and the content of free methylol groups fell below 0.5%. The material was then dried under a vacuum of 0.03 MPa and after cooling it was ready for further use.

Example 4

To the stirred reactor at the temperature of the component:

235 885 ° C were added following wood flour spruce urea formaldehyde technical 36% triethanolamine versal red phthalic anhydride

50.8% by weight ·

10.2% by mass ·

13.2% wt. 0.2% by weight ·

25.4 wt. 0.2% by weight ·

Within 40 minutes the filler was finished and colored with 0.2% free methylol groups, the material was dried under a vacuum of 0.08 MPa and after cooling it was ready for further use.

Example 5

A mixture of the following components was fed to a fluidized bed dryer at 110 ° C:

precipitated calcium carbonate 68.8 % wt. mel amine 13.8 % wt. formaldehyde technical 36% 17.2 % wt. sodium tetraborate 0.1 % wt. potassium hydroxide 0.1 % wt.

The process mode was set so that the mixture was finely pulverized and held fluid for 50 minutes, obtaining a powdered filler containing 0.45% free methylol groups.

pin, which after cooling was ready for further use. Example 6 Into a stirred reactor at temperature 85 ° C were introduced as follows: Additional components: asbestos 76.8 % wt. melamine 4.6 % wt. urea 4.6 % wt. formaldehyde technical 36% 13.6 % wt. Sodium hydroxide, technical 0.1 % wt. triethanolamine 0.3 % wt.

The filler was treated with a resin containing 0.35% free metalol groups over 45 minutes, dried under a vacuum of 0.06 MPa and cooled.

Example 7 235 885

The following components were charged to a stirred reactor at 100 ° C:

ammonium phosphate 60.1 wt.

melamine 17.4 wt.

phenol 0.6 wt.

technical formaldehyde 36% 21.6% wt.

Formic acid 0.3 wt.

The filler was treated with a resin containing 0.17% of free methylol groups within 40 minutes while drying the material under a vacuum of 0.05 MPa and cooling.

Example 8

The following components were charged to a stirred reactor at 90 ° C:

lithopone aqueous solution of mixed melamine-urea-formaldehyde resin prepared by polycondensation in a 2: 1: 5 molar ratio containing 21,5% of methylol ammonium trioxide groups

84.5 wt.

15.5 wt. 0.1 wt.

After 17 minutes, finishing was carried out, the material with free methylol groups below 0.4% was dried under vacuum of 0.06 MPa and ready for further use.

Example 9

The following components were introduced into a stirred reactor at 95 ° C:

chalk ground 80.5 wt.

aqueous solution of melamine urea-formaldehyde resin prepared by polycondensation in a 1: 1: 4 molar ratio in the presence of 10 wt. 6-caprolactam (based on the weight of melamine) having a content of 22% of methylol groups of 19.4% by weight;

- 6 ammonium oxalate 0,1% m / m · ^{235 883}

After 20 minutes, the material having a free methylol content below 0.4% was dried in a vacuum of 0.05 MPa and ready for further use.

Claims (2)

1. A process for finishing fillers and additives in polyinoplastics, characterized in that the finishing is carried out in a single VB-drift operation with stirring at 80-150 [deg.] C. with a 1: 1 molar ratio of melamine and / or urea with formaldehyde. , 2 to 1 and 3 and in an amount of 5 - 30% by weight based on the weight of the filler or precondensates of melamine, urea or melamine urea resins prepared by simultaneous polycondensation of melamine and / or urea with formaldehyde in the stated molar ratio and in an amount of 5 - 30% 2. A process for finishing fillers and additives according to claim 1, characterized in that the finishing agents and resins are modified with 6-caprolactam in an amount of 5-60% by weight based on the weight of the amine substance.