JPS5915936B2 - Composition for producing phenolic resin foam and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for producing a resol type phenolic resin foam obtained by condensing phenol or a derivative thereof with formaldehyde, and a method for producing the same.

The object of the invention is to obtain foams from thermosetting resins of this type.

According to the present invention, these foams are made by granulating a solid, reactive, and fusible resol type phenolic resin, dispersing an expanding agent (foaming agent) in the granules, and utilizing the action of a catalyst. It can be obtained by expansion hardening by the action of heat alone.

This is an important feature of the present invention, as the novel method results in a chemically neutral foam. On the other hand, acids generated from catalysts used to expand and cure currently known phenolic resin foams remain.
Since the foam of the present invention is thus chemically neutral, it can be used in direct contact with metal parts such as steel and aluminum without fear of attacking these metal surfaces.

These foam bodies therefore have highly desirable characteristics when used in building materials. Further, the foam of the present invention does not discolor, whereas conventional foams with residual acid tend to discolor to a brown-purple color even when not in contact with metal.

5. The present invention further relates to a molded product made from a foam that is chemically neutral at room temperature (15°C to 25°C) obtained from a resol type phenolic resin.

According to another feature of the invention, the solid, reactive and fusible resol-type phenolic resin of the invention is obtained by condensation of phenol 0-lnomole with 1.2 to 3.1 mol of formaldehyde, and is The condensation catalyst is alkaline. This starting resin can be produced by the method described in French Patent No. '57027010, filed on July 22, 1973 in the name of the present application, and the resulting resin is in the form of beads.

The method of the present invention can use beads or particles obtained by grinding these beads. The starting material resin obtained by this method is substantially free of water.

As a result, the foam or product obtained by this method does not need to be dried, whereas conventional phenolic resins with a relatively high water content must be subjected to a drying process. In order to dry, the foam or its product must be heated in order to drive off the moisture as vapor through the foam membrane. If this heating is rapid, the bubbles will be destroyed.
The continuous structure of the foam is also destroyed. These continuous structures must be maintained in order to maintain the properties of the foam. If the heating is too slow, it will take too long to dry. Expansion of the foam and its hardening is achieved by simply heating the resin in beaded or powdered form without the use of additives; the resin is placed in a mold placed in a furnace at a temperature of 100°C or higher. Can be heated. In this case, the resin particles are then catalyzed and fused into a viscous paste that expands very slowly to fill the mold. However, this type of operation only results in objects with highly non-uniform and non-adjustable apparent densities. The pore size itself is highly non-uniform. The resulting product has relatively high thermal conductivity and undesirable mechanical properties. It is therefore necessary to incorporate an expanding agent into the resin before expanding and curing the foam. The amount of swelling agent used is generally 0.5 to 5 of the swelling fat.
% by weight, depending on the desired apparent density of the foam and the nature of the blowing agent. The swelling agent used is an organic liquid that is miscible with the resin and is generally capable of vaporizing at temperatures of about 100-170°C, preferably 120-150°C.

Organic liquids that can be used for this purpose are in particular alcohols and ketones, and more specific examples include the following: Other organisms that can be used as swelling agents include solid organic nitro- and/or organic compounds which are generally known to have azo, nitroso or sulfonyl hydrazide groups and are capable of releasing nitrogen at temperatures above 100°C. Or there are sulfur compounds.

Examples of these compounds include dinitrosopentamethylenetetramine; azoisoptyrodinitrinoreriazo-1,
Cyano-1-cyclohexane; Benzenesulfonylhydrazide; Azodicarbonamide: P,P-oxypis(benzenesulfonyl)hydrazide; Diisopropylazodicarboxylate; Morpholyl-5-thio-1
, 2,3,4-triazole, etc. The inventors have discovered that particularly advantageous results are obtained by utilizing solid swelling agents, particularly powdered swelling agents. On the other hand, it is advantageous and essential to add surfactants to expand the foam more uniformly.

These surfactants work to mix the ingredients mixed into the resin very uniformly, and in Examples 1 and 2 described below, in which no surfactant is added, more continuous, large, and non-uniform cells are produced. In contrast to the foams obtained, the use of surfactants results in foams that are lighter, yet have better mechanical properties and a better cellular structure, as shown in Examples 3 to 9. These have in their molecules a water-soluble polyoxyalkylene chain bonded to a water-insoluble aliphatic chain or an organosilico chain. Suitable compounds for this purpose include silicone oils such as polyoxyethyl sorbitol laurate, nonylphenol polyoxyethylene, preferably copolymers obtained from dialkyl silicones and alkylene oxides. These surfactants are used in an amount of 0.1 to 5% by weight, preferably 0.2 to 2% by weight, based on the resin. Although not an essential component, in some cases oil lubricant mixtures such as zinc stearate) and amides of long chain fatty acids may be incorporated. These lubricants are used in amounts of 0 to 5% by weight, preferably 0.5 to 2% by weight, based on the resin; the mixing of the resin with swelling agents and other additives according to the invention is very Importantly, in order to obtain a product of desired quality, it is necessary to uniformly disperse the swelling agent and additives in the resin, which is accomplished by one of the following operations.

(a) Using an internal rotary mixer such as a rotating drum or a Y-type mixer, the resin is made into beads or powder together with additives.

Mixing is carried out at normal temperatures. (6) Under the same conditions, a countercurrent mixer called a so-called "reponn blender" is used. (c) Simultaneously grinding the resin and additives at normal temperatures and grinding the mixture into powder in a hammer-type grinder while cooling.

(6) Werner blender with spiral arms (W
The resin is melted in a heated mixer with rotating arms, such as an ernerblender, and the required additives are mixed into the molten resin mass.

The operation in this case takes place at a temperature of approximately 50-80°C. A viscous, homogeneous mass of the mixture is obtained by shaping or sufficiently cooling and pulverizing the mixture before expanding into a foam. The product can be stored in lump or crushed form for several weeks without losing its properties before expanding into a foam. (e
) A rapid mixer, such as a Henschel or Papenmaier blender, consisting of a vertical shaft with an agitator with rotating blades in a cylindrical drum (sometimes a double drum) use.

This mixer is commonly used to densify thermoplastic resin powders. Place the beaded resin into the drum and start stirring. Additives are added during stirring. Stirring is then stopped and the ground additives are added before stirring again. The mixing operation is carried out at a temperature of approximately 15-35°C, and the total operating time is a few minutes. A mixture consisting of resin beads uniformly coated with swelling agent and other additives is obtained.
Particularly good results are obtained when the additives are incorporated by mixing the resin in the molten state using a heated Werna type blender.

The resulting mixture is then heated to expand.

This operation may be carried out in the mold or during extrusion, the extrudate being heated during transport, for example on a conveyor. In the case of molding, the mixture is put into the mold in the form of a powder, a thin rod or a sheet, and the mold is heated to a temperature of 120 to 200°C in a temperature-controlled oven, or an electric resistor or Other suitable molds with uniform heating means may also be used.

In extrusion, the mixture is continuously fed into an extruder, from which it is extruded in strips and conveyed through a conveyor belt into a furnace where foaming takes place. This method results in a foam that is cut to the desired length when it comes out of the furnace. In this way, various shapes (
(for example, sinyl) can be obtained and used as heat insulation and insulation for tubes. Examples of the extruder include a single screw extruder, a double screw extruder, and a rotating plate extruder that extrudes through the center of a fixed plate (utilizing the Weissenberg effect).

Particularly good results have been obtained using a device which has two movements, on the one hand a fixed cycle followed by rotation, and on the other hand a transport and a cycle whose axis is also fixed.

This type of extrusion device has a cylindrical body,
It consists of a shaft with spiral blades and spiral blades inside. An example of this type of device is a bus (
There is a Buss) device. An interesting feature of this type of equipment is that it can continuously homogenize the molten state while heating the mixture of resin and additives, which has been premixed in another type of blender. It can be extruded through a die at the same time. Extrusion machines (bath equipment) are used for band-shaped extruded products.
It is produced by a die with a spout attached to the outlet.

It may be extruded into one or several thin rods at the same time and passed through a tarendar consisting of one or several pairs of cooled rollers.

A furnace is attached to a horizontal conveyor that transports the extrudate strips, where they are foamed.

This oven is preferably attached to a second conveyor placed parallel to the lower conveyor belt and is set to maintain the shape of the foam at a constant thickness during expansion. In this way a panel of foam of constant thickness is obtained at the outlet. The conveyors may be placed evenly to the sides of the oven, with their vertical faces parallel to each other, so that a parallelepiped panel is obtained. The present invention enables the production of intermediate products that can be easily stored, making it possible to easily produce resol type phenolic resins.

More specifically, the present invention enables the production of an industrial intermediate of a solid, reactive, fusible, granular resol type phenolic resin having an average and homogeneous dispersion of a blowing agent, which granular resol type phenolic resin is It can be foamed and hardened simply by the action of .

The particulate resin preferably consists of beads of phenolic resin coated with a swelling agent or surfactant or lubricant. The present invention provides an industrial intermediate of a solid, reactive, and fusible resol-type phenolic resin with an evenly uniform dispersion of a swelling agent, which resin is stable and only resistant to the action of heat. It can be foamed and hardened.

The present invention further provides a resol type phenolic resin in which a surfactant and optionally a lubricant are uniformly dispersed.

The inventors have found it particularly advantageous to introduce the swelling agent in powder form.

The invention is better explained by the following examples (Examples 1 and 2 are comparative examples and the others are examples).

The starting resin used in the examples below is prepared as follows.

4 in a 20 t stainless steel reactor equipped with a stirrer having "impeller" type blades, i.e. opposite corresponding blades, and a variable speed motor to vary the stirring speed.
Phenol 6366V1 Hydrazine hydrate 109y1 Formaldehyde 36% by weight solution 7900t and water 3320t at 5-50℃ and rotation speed 95rpn1
Continuously charge water (distilled water, decationized water, double deionized water, untreated water, etc.).

After raising the reaction mixture to 60° C., 30(f) ammonia solution 6667 is added.

After raising the temperature to 80°C and keeping it constant, 20t of carboxymethyl cellulose was added to NaCConal9OF (Alle
Sodium dodecylbenzene sulfonate (produced by edChemical) 157 is added to stabilize the suspension. After 3 hours of polycondensation, the mixture is cooled to normal temperature, washed with water, centrifuged and dried in an oven with circulating air at 40° C. to give resin 75009. The resin thus obtained was shaped into spheres with a diameter of 0.3 to 1.2 m [average diameter (Gauss size) = 0.8 Tm].

Example 1 Heating of resin and liquid expansion agent 6f of n-amyl alcohol was added to 200f of the resin, and the mixture was rotated at 23r on one side and 40r on the other.
In a blender with Z-shaped blades rotating at pm, 5
Mix for 5 minutes at 0°C.

The molten paste thus obtained is calendered into a strip with a thickness of 7 TmL. The strip is placed in a parallelepiped container measuring 30 x 30 x 10 cm and the whole is heated in an oven at 140°C for 30 minutes (or 160°C for 20 minutes, or 130°C for 40 minutes). Average density is 10
A foam with continuous cells having a diameter of 1 to 30 rfm was obtained at 0 kf/R.

Example 2 Powdered azo-1,1 instead of heated n-amyl alcohol for resin and solid expansion agent
Example 1 was repeated using '-cyano-1-dichlorohexane 67.

After heating in the mold at 140° C. for 30 minutes, a foam with very fine cells (average diameter = 1-37 m) and an apparent density of 40 kf/d was obtained.

The presence of non-uniform areas in the foam with diameters greater than 3 WWL was also observed. Example 3 The bead-shaped resin 100 is mixed with a solid swelling agent in a drum and placed in a cylindrical container containing 57
I put in 07.

While rotating the container, powdered azo-1,1/-cyano-1-cyclohexane 307 and silicone oil (U
L534O) 57 manufactured by niOnCaride was added. The vessel continued to rotate at 60 rpm and 20° C. for 15 minutes. The resulting mixed composition was removed and placed into a parallelepiped mold. The mold was heated to 140° C. for 35 minutes. As a result, a foam was obtained which had an apparent density of 38 kf/M3 and had cells with a diameter of 0.1 to 2 Tm, although some had a diameter of 3 to 7 Tm extending in the direction of expansion. Example 4 The bead-like resin 4007, powdered Azo-1,17 was mixed while melting with the solid swelling agent and surfactant in a Werner blender.
12V of -cyano-1-cyclohexane and 2f of silicone oil (UniOnCarbide L534O) were continuously added.

The contents were melted into a continuous mass at 70° C. for 6 minutes. This mass was taken out and pressed into a strip 3w1n thick, after which it was put into a mold and the whole was 1.
Heated at 40°C for 30 minutes. The result is 0.2~2wrm
A very homogeneous foam was obtained with cells having a diameter of .
Its apparent density was 35 cells/d. This foam is N
FT56. It required 1.0 Bar. to compress by 5% according to the IOl test method.

According to the standard ASTM D1692-68 test method, the propagation index was O. Thermal conductivity is 0.030ka1 at 23.9℃
! Example 5 Rapid mixing and extrusion with a single screw extruder 1
The bead-shaped resin 4 is placed in the 0t rapid mixer DIOSNA.
20 tons of 00t1 silicone oil (L534O manufactured by UniOnCardide) and 120 tons of powdered azo-1,1-cyano-1-cyclohexane were continuously added.

Mixing was carried out for 3 minutes at ambient temperature. The resulting mixture was transferred to a single screw extruder CO with a constant pitch screw of 20 Tm in diameter and 360 wn in length.
I put it in the first hotspot of TTFERT. The temperature in the three areas of the body was adjusted to 90°C. Extrusion was carried out through a rectangular 18 x 10 TWL die maintained at 90°C at a rate of 1 hour/hour, and then calendered through two rollers cooled to 20°C with water for 3 hours. of thickness and the strip was transported continuously on a conveyor belt fitted with an oven. After heating at 150° C. for 30 minutes, a foam with the same properties as those of Example 4 was obtained.

Example 6 Rapid mixing with bath mixer The rapid mixing procedure of Example 5 was repeated.

The mixed composition was placed in the hopper of a two-motion PR46 mixer.

Mixing was carried out in the body of the mixer in three zones of the screw at a temperature of 65-70°C. Extrusion is done using a circular 15Tfr kept at 80℃! n die at a speed of 17 h/hr. The thin bars obtained were then transferred to a calender with two rolls cooled to 20° C. with water and then transferred to a conveyor belt. The 4wn thick strip thus obtained was passed into an oven where it was foamed and cured. After continuous heating at 150° C. for 20 minutes in a furnace tunnel, a band-shaped foam was obtained. The resulting foam has the same properties as in Example 4 and is cut into panels so that it can be used as insulation in building materials, in particular as insulation in steel roofs. The foam is neutral and non-corrosive, so there is no need to worry about it corroding metal over a long period of time. In this regard, when the cooled foam 5f was taken, crushed, and placed in 45 tons of doubly deionized water and allowed to stand in a CO2 atmosphere, the pH of this water was 5.95-6.10. The foam was found to be nearly neutral and non-corrosive. Example 7 Mixing of powders In a FORPLEX hammer mill maintained at ambient temperature,
The bead-shaped resin 1007, silicone oil (L534O
)0.5f and powdered benzenesulfonyl hydrazide 3
I put 7.

After 3 minutes a powder with an average diameter of about 200 microns was obtained.

Take out this powder immediately or after 8 days, put it in a mold and
It was heated at 50°C for 20 minutes. A homogeneously structured foam with an apparent density of 30 phantom/d and a diameter of 1 to 3 wn was obtained.

NFT56. 3. This foam was tested according to the lOl test method.
It took 0.75 bar to compress 8(11). EXAMPLE 8 The powder left in the mill of Example 7 was placed in a single screw GOTTFERT extruder as used in Example 5.

Adjust the temperature of the three areas of the main body to 90℃ to 1kf/H
After extrusion at a speed of Moved to target. The foam obtained after heating at 150° C. for 30 minutes had the same properties as those obtained in Example 7.

Example 9 The powder obtained from the mill outlet of Example 7 was transferred continuously onto the conveyor belt of Example 8.

This foam had the same properties as Example 7. The gist of the invention is as follows.

(a) A resol type phenolic resin foam characterized by being chemically neutral.

(6) A molded product obtained using the foam described in item a) of the previous edition.

(c) Consists of a granular solid, reactive, and fusible resol-type phenolic resin in which an expanding agent, a surfactant, and/or a lubricant are uniformly dispersed, and the phenolic resin foams and hardens only by the action of heat. The above-mentioned (
Intermediate product for producing the foam of item a). (d) consisting of a solid, reactive, fusible, resol-type phenolic resin having a uniformly dispersed swelling agent, surfactant and/or lubricant, said phenolic resin being chemically stable at ambient temperatures; , an intermediate product for producing the foam according to item (a) above, characterized in that it can be foamed and hardened only by the action of heat.

(e) The intermediate product of item αd), which is characterized by being in the form of an extruded thin rod. (f) Before e is characterized by being calendered and having a band-like shape.
) term intermediate product.

(consists of beads of reactive, fusible resol type phenolic resin coated with a blend of Q-expanding agents, surfactants and/or lubricants, said beads of resin being chemically oxidized at ambient temperature). An intermediate product for producing the foam described in item (a) above, which is stable and can be foamed only by the action of heat. (h) In items c) to (ω), the expanding agent is granular. An intermediate product characterized in that it is a solid substance.

(1) An intermediate product characterized in that the swelling agent in (6) to (O) above is a liquid. (j) A granular solid, substantially anhydrous, and containing 1 mole of phenol and 1 to 3 .1
The swelling agent is a reactive, fusible resol-type phenolic resin obtained in a known manner by condensation with preferably 1.2 to 1.8 moles of formaldehyde. Front ridge c) characterized in that it is brought into contact with a surfactant and/or a lubricant
A method for producing the intermediate product of item (i).

(k) Preceding αj) At the top, the resin is heated to 50 to 80°C.
The manufacturing method according to the preceding item αj), characterized in that the mixture is mixed with the expansion agent at a temperature in the range of .

(1) The manufacturing method according to item 12(J) above, characterized in that in item αj), the swelling agent, the surfactant, and/or the lubricant are mixed together with the resin.

(e) The manufacturing method according to item (j) above, characterized in that in item 6), the resin is mixed with the expanding agent, the surfactant, and/or the lubricant at ambient temperature. (n) In the above (e), the temperature of the mixture is 65 to 90°C.
The manufacturing method according to item (e) above, which is characterized by increasing the temperature to .

(B) The method for producing items αj) to (E) above, wherein the reactive and fusible phenolic resin is in the form of beads.

(B) The method for producing items (J) to (E) above, wherein the reactive and fusible phenolic resin is in powder form.

(q) The method for producing items (j) to (p) above, wherein the surfactant is a copolymer made of dialkyl silicone and alkylene oxide.

(r) In the above items (J) to (c), the expansion agent used is solid, particularly powdery.
) to (q).

(s) The manufacturing method according to items (j) to (1) above, wherein the swelling agent is a liquid.

Claims (1)

[Scope of Claims] 1. A granular solid, reactive, substantially anhydrous, and fusible resol-type phenolic resin in which a swelling agent and a surfactant are uniformly dispersed, or a blend of a swelling agent and a surfactant. It is a granular solid coated with a reactive, substantially anhydrous, and fusible resol-type phenolic resin that is chemically stable at room temperature and foams and hardens under the action of heat to form a chemically neutral phenolic resin. A composition for producing a foam, which is characterized in that it becomes a foam. 2. A granular solid, substantially anhydrous, reactive and fusible resol type phenolic resin obtained by condensing 1 mole of a phenolic compound and 1 to 3.1 moles of formaldehyde in a conventional manner. It is characterized by bringing the swelling agent and the surfactant into contact with each other. A method for producing a composition for producing a foam that is chemically stable at room temperature and that foams and hardens into a chemically neutral foam just by the action of heat.