CS238995B1 - Method of phenolic pressing and injection materials making - Google Patents

Abstract

The invention relates to a process for the production of phenolic compounds and injection materials in one operation suspended in vigorous stirring in the temperature range of 60 to 170 ° C from the primary raw materials or semi-products. Short achieved production time and physical-mechanical manufacturing properties - flexural strength higher than 80 MPa, shape stability according to Martens higher than 145 oC greater than 0.7 J / cm. Semiproducts floated in this way they contain less than 0.5% free mass phenols.

Description

MAREK OLDRICH ing.,

ΜΑΪΑΤΚ0 JAN ing., PARDUBICE,

MAREK PETR ing., CELAKOVICE,

HAJICEK 0D0N ing.,

PRIMLOVA BLANKA ing., PARDUBIČE, TATÍČEK JAROSLAV, SVÍTKOV

Process for producing phenolic molding and injection molding compositions

BACKGROUND OF THE INVENTION The present invention relates to a process for the production of phenolic and injection molding materials in a single fluidized-bed operation with intensive mixing in the temperature range of 60-170 ° C from primary raw materials or semi-products. Short production times and physical and mechanical properties achieved - flexural strength higher than 80 MPa, Martens shape stability higher than 145 ^o C. _? Impact toughness greater than 0,7 J / cm.

The semi-products floated in this way contain less than 0.5% by weight of free phenols.

? 38 995 (51) Int Cl?

OJ C 08 G 8/00

- 4,238,995

The invention relates to a process for the production of phenoplasts suitable for compression, extrusion, injection molding as well as intermediate products intended for further processing processes. The phenoplasts according to the invention are produced in one production plant in one or more successive manufacturing operations.

Phenoplasts are thermosetting thermosetting plastics, mass-produced for processing into a wide variety of technical and consumer products. The processes known to date for the production of these thermosetting plastics work in several separate, mutually independent manufacturing operations; differing technological process and production equipment with high space requirements. In a first operation, approximately 50% phenol-formaldehyde resin is prepared in an acidic or alkaline environment at temperatures below 100 ° C. Due to the exothermic process, the condensation process is very lengthy (in the order of several hours) to avoid an explosive uncontrollable condensation process. After reaching the desired condensation stage and stabilizing the intermediate product, excess water is removed by separation or evacuation, the free phenol is removed by steam vapor or the like. The anhydrous resin - a semi-product - must be quenched as, for example, on a flaker, in the form of solid particles, granules, which are intended for the next operation. In a second essential operation, in a homogenizer, this solid resin is mixed with organic or inorganic fillers, lubricants, catalysts, colorants, and preferably lubricants. The homogenized mixture is melted, kneaded, further homogenized and converted to its final chemical form - the processable thermosetting material is batch-processed on steam-heated double-cylinders, where the temperature, friction and pressure produce a continuous form of plastic.

238 99S

The entire state of the process can be carried out by continuous (Raschig) or batch kneading. A unit for granulation, crushing and cooling of the final product is connected. All these methods require high costs of machinery, construction and space.

Organic and inorganic fillers for these dry technologies must be surface treated and stabilized in order to achieve good physico-mechanical and electrical properties.

These drawbacks are eliminated by a process for the production of phenolic molding and injection materials as well as by-products of polycondensation from primary raw materials, ie phenols, aldehydes, organic and / or inorganic fillers, lubricants and catalysts, which is based on the fact that polycondensation is carried out stirring in the temperature range from 60 ° C to 170 ° C.

novolaks and / or resole-based semi-products can be used as primary raw materials.

The preparation of phenol-formaldehyde resin by condensation of phenols and formaldehyde in the presence of organic and / or inorganic fillers, including other additive components, allows rapid condensation to occur at any temperature conditions due to the large surface area of fillers, significantly reducing condensation time without explosive polycondensation.

Precise control of the polycondensation process allows even the strongest catalysts to be used in the most economical and reactive kinetics possible.

- 3 238 995

By starting from the monomeric reaction raw materials, the condensation makes it ideal for impregnating all fillers and auxiliary components, thereby achieving highly homogeneous products of excellent physical-mechanical and electrical properties.

This raw material fluid system allows any initial condensation temperature, depending on the degree of preheating of the raw materials, before the addition of formalin and catalysts.

During the manufacturing process, the material is in the form of x fine particles or granules which are dried after the condensation operation is completed, preferably under reduced pressure Ahmota, capable of being processed by any processing technology.

Due to the simplicity of technology and low production equipment, the large-scale production unit _f • requires significantly lower machine and construction investment costs.

The preproducts of the present invention exhibit zero or minimal free phenol content, so that for further use, e.g. when used for epoxy / novolak resins, no further treatment thereof is necessary.

Example 1

The reactor is heated to 160 ° C and charged with:

wood flour 23.0 kg stearin 1.0 kg phenol 28.0 kg p-toluenesulfonic acid 1> kg ^Fe 2 ° 3 0.5 kg fitting wax 1.0 kg After 2 min, vigorous stirring is released formalin (36.5%) 24.0 kg

followed by condensation under reflux at 110 ° C for 15 min. The resulting novolak semi-product contains 5% free phenol in the resin.

After completion of the condensation, the suspension is metered in;

238 995

triethanolamine 2,0 kg formalin (36.5%) 5.0 kg hexamethylenetetramine 5.0 kg MgO 0.2 kg CaO 1.0 kg CaC0 ₇ 10.0 kg

After stirring vigorously under reflux for 2 min

dried under vacuum at 0.01 MPa in 5 min * to give a final product in the form of uniform fine granules suitable for final processing. The resulting product exhibits a bulk density of 65 < RTI ID = 0.0 > fr / l, < / RTI > bending strength of 85 MPa, impact strength of 0.7 J / e, and Martens shape stability of 140 ° C.

Example 2

The reactor is charged with intensive stirring, the walls of which are heated to 120 ° C.

Cellulose fibrous 30.0 kg waste wood flour 40.0 kg stearin 2.0 kg assembly wax 1.0 kg phenol 56.0 kg formalin (36.5%) 49.0 kg

HCl (36.5%) 1.4 kg asbeet fibrous 90.0 kg

Condensation of the filled novolak takes place within 8 min, with a free phenol content of 1% in the resin. Triethanolamine 10.0 kg formalin 15.0 kg ammonia (25%) 15.0 kg hexamethylenetetramine 8.0 kg

CeCO ₃ 10,0¾

After 6 min. With vigorous stirring under reflux at 120 ° C, the resulting fine granulated product is dried under a vacuum of 0.02 MPa for 4 min. The resulting material exhibits a weight of 850 g / l, a bending strength of 95 MPa, an impact strength of 0.87 J / cm @ 2 and a Martens shape stability of 155 ° C.

-5 238 995

Example 3

The following are fed to a 140 ° C reactor:

40.0 kg 25.0 kg 30.0 kg

1.5 kg 2.0 kg

1.5 kg 1.0 kg

1,5 kg phenol cellulose beech mica ground magnesium stearate MgO ozokerite carbon black KOH

While stirring high-speed stirrers at 25 m / s, the raw materials are heated for 4 min before formalin (36.5%) 45.0 kg is introduced into the mixing system.

The condensation mixture was maintained at 120 ° C for 15 min. The reaction mixture is dried under a vacuum of 0.03 MPa for 8 min. The bulk density of the plastic * is 850 g / l, the bending strength is 80 MPa, the Martens shape stability is 145 ° C, the specific surface electrical resistance is 10 ³ ^ (? _0).

Example 4

Intensively mixed thermosetting plastics are dosed with:

beech wood flour 20.0 kg asbestos micronized 20.0 kg stearin 1.5 kg phenol 15.0 kg cresol technical 15.0 kg oxalic acid 2.0 kg formalin (36.5%) 22.0 kg

The reaction mixture is heated to 160 ° C over a few minutes with stirring at the rotational speed of the main stirring system of 30 m / s and the condensation of the filled novolak is complete within 25 minutes. The temperature of the reaction mixture was lowered to 100 ° C. To stabilize the novolak, add:

triethanolamine 2.0 kg

CaCO 2 - 5.0 kg

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Immediately after stabilization, the novolak is dried under a vacuum of 10 bar for 10 min. Free phenol content in resin is less than 0.5%, drop point is 89.5 ° C, degradation temperature

197 ° Go

Example 5

The reactor is heated to 150 [deg.] C. with the following intensive stirring:

beech wood flour 40.0 kg asbestos fibrous 10.0 kg magnesium stearate 1.5 kg magnesium oxide 2.0 kg assembly wax 1.5 kg phenol-formaldehyde resol (50%) 100.0 kg

The temperature of the duplicated reactor is maintained at 150 ° C / 16 ° C, the main mixing system is maintained at an orbital speed of 20 m / s. After 3 minutes of interaction, the product is dried over 5 minutes to form a fine granulate of bulk density

800 g / l, flexural strength 90 MPa, impact strength 0.95 J / cm and Martens shape stability 160 ° C.

Example 6

The heated reactor at 60 ° C is charged with stirring:

phenol 60.0 kg hydrochloric acid, 36.5% 1.5 kg formalin (36.5%) * 45.0 kg stearin 1.5 kg

Within 40 min. polycondensation is carried out under constant stirring at 30 m / s and triethanolamine 4.0 kg is added.

Within 5 min.je _(novolak stabilized dried 10 min.za vacuum of 0.07 MPa and discharged with a novolak in the form of crumbs on a free phenol content of 0.3% pour point of 85 ° C and a degradation temperature of _about 188 ° C

Claims (2)

SUBJECT OF THE INVENTION 238 995 1 / Method for producing phenolic molding and injection weight by polycondensation of primary raw materials, i.e. _the phenols, aldehydes, organic and / or inorganic fillers, lubricants, and catalysts / wherein polykondenzaee takes place in one operation, in suspension with vigorous stirring in a temperature range 60 <> C to 170 ° C _o 2. Process according to claim 1, characterized in that novel raw materials based on novolaks or resols _e can be used as primary raw materials.