DE1084024B - Process for the production of a phenolic resin with a cell structure - Google Patents

Description

The invention represents a further development of the method for producing foam-like phenolic resin products according to the method of patent specification 885 004.

The patent specification 885 004 discloses a method for Production of a foam-forming, heat-generating, acidified, flowable mass by allowing it to react of a phenol-aldehyde reaction product with a water-soluble sulfonic acid and a water-soluble carbonic acid Salt, such as sodium bicarbonate, and allow the reaction mixture to expand to form a cellular Foam product forms. Patent 885,004 also shows the use of surfactants together with other ingredients in performing this procedure. According to the present invention now instead of the carbonate a volatile organic solvent, preferably about 2 to 10%, based on the water-containing mass of the phenolaldehyde reaction product, entered into the reaction mass. The known, cumbersome multistage processes already have volatile organic solvents used, but it is always necessary in this process, externally supplied heat and, if necessary Apply vacuum to remove the solvent again. In the case of the present procedure, it is sufficient but the heat of reaction by itself to completely remove the solvent. That way The resulting phenolic resin foam has a smaller and more uniform cell size than that obtained by the process of the 885 004 patent. In addition, a more uniform one is generally obtained Product with increased mechanical strength, lower moisture absorption and improved thermal insulation properties.

According to an additional feature of the invention, an organic polymerizable compound, in particular a compound which has a polymerizable CH ₂ = C <- or - CH = CH group, can also be incorporated into the reaction mass. The addition of this unsaturated material gives the final foam some toughness and water-repellent properties.

It was also found that instead of the sulfonic acid described in patent specification 885 004, a mixture of sulfonic acid with hydrochloric acid or hydrochloric acid alone can be used as the water-soluble acid. aside from that it has been found that it can be beneficial to use significantly more of the surfactant, than disclosed in Patent Specification 885,004. became.

The following examples are intended to illustrate the manufacture of a Explain product with cell structure according to the invention in more detail. All parts and percentages are in these Examples of weight information. The in the examples

Method of manufacture
a phenolic resin with a cell structure

Addendum to patent 885 004

Applicant:

General Electric Company,
Schenectady, NY (V. St. A.)

Representative: Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse

and Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Bad luck man,

Patent Attorneys, Munich 9, Schweigerstr. 2

Claimed priority:
V. St. v. America April 30, 1953

John Daniel Nelson, Pittsfield, Mass. (V. St. A.),
has been named as the inventor

Applied liquid resin was prepared according to patent specification 885 004 by heating a mixture of synthetic 100% phenol and an aqueous 37.2% formaldehyde solution in a molar ratio of 1 to 1.3 and in the presence of a small amount of an alkaline catalyst such as Barium hydroxide. After heating the mixture under reflux at the boiling point of _^3/4 to 1 hour, it was neutralized and finally partially dewatered under reduced pressure, as described in the patent. The dehydration was preferably carried out until the liquid resin is about had a viscosity of 7000 to lOOOOcP at 25 ⁰ C. This resin was then used to make the various foam-like products in the following manner.

example 1

Common foamed resin product

Resin 30.0 parts

40% phenolsulfonic acid 3.0 parts ..

Sodium bicarbonate, 0.21 parts

»Tween20 << * 0.06 parts

■ * The surface-active substance »Tween 20« is a technical one - Polyethylene ether of the monolaurin sorbitol ester.

The acid and the "Tween 20" are mixed with the phenolic resin, which initially has a temperature of 25 to 28 ° C, vigorously mixed in an open cone-shaped paper container, after which the sodium bicarbonate was added and gets mixed up. After a standing time of 1 to 3 minutes, the mass foams up and hardens

009 5 + 7/447

a solid product. The cell size was good in itself, however, the cells varied in size and significant numbers were interconnected. This product is the previously known resin foam according to patent specification 885 004.

Example 2

Resin 30.0 parts

Isopropyl ether 1.5 parts

»Tween20« 0.4 parts

50 ° / ₀ sodium phenolsulfonic acid 3.0 parts

The ether and the "Tween 20" were mixed with the resin at an initial temperature of 25 to 28 ° C in one, open cone-shaped paper container, whereupon the acid was quickly mixed in. After a standstill from 30 seconds to 1 minute the mass foamed and hardened to a solid foam product. the Foam development was slower compared with Example 1, but stronger in the end result. the Cell size was much finer and more even, and the number of individual cells was much higher.

Example 3

Resin 30.0 parts

Dipropylene glycol maleic acid polyester in styrene, dissolved at 1.0%

Benzoyl peroxide 1.5 parts

Isopropyl ether 1.5 parts

»Tween20« 0.4 parts

50 ° / ₀ sodium phenolsulfonic acid 3.0 parts

Ether, polyester and "Tween 20" were mixed with the resin at a temperature of 25 to 28 ° C in a container mixed in the manner indicated above, whereupon the acid was quickly stirred in. After a standing time of From 30 seconds to 1 minute the mass foamed and formed the solid foam product. The foam development corresponded to that of example 2, but the cell size was even finer and more uniform than in example 2 and much finer than in example 1.

The unsaturated substance in the above example can be replaced by a corresponding amount of another unsaturated Connection to be replaced, e.g. B. by the allyl carboxylic acid diester of diglycol with the formula

= CH-CH ₂ -CO-CH ₂ CH ₂ OCH ₂ Ch ₂ -OC-CH ₂ -CH =

Other examples of unsaturated compounds are a) polymerizable compounds of the type disclosed in U.S. Patents 2,443,736 to 2,443,741 and obtained by reacting a reactive alkyd resin with a reactive _{compound containing the CH 2} = C <group ; b) styrene itself; c) diallyl phthallate; d) reaction products of epichlorohydrin with a polyhydric alcohol, e.g. B. with glycerol, and e) reaction products of epichlorohydrin with a bis-phenol.

Further examples of unsaturated compounds are those compounds which have a polymerizable CH ₂ = C <atomic group. Examples include diene compounds such as butadiene, isoprene, piperylene and the like; vinyl-substituted aromatic hydrocarbons such as styrene, methyl styrene, divinylbenzene, vinyl fluorene, acenaphthylene and the like; Acrylic acid and its derivatives, such as methacrylic acid, acrylonitrile, acrylamide, methacrylonitrile, methacrylamide, esters of acrylic and methacrylic acids, e.g. Methyl acrylate, ethyl acrylate, methyl methacrylate and the like; ethylenically unsaturated halogenated or unhalogenated aliphatic hydrocarbons, such as ethylene, or the chloroethylene, fluoroethylene, chlorofluoroethylene and similar unsaturated compounds.

Other polymerizable compounds can similarly be used, e.g. B. compounds that have a polymerizable - CH = CH group or CH ₂ = C C group in their molecular structure, ie compounds that have a single CH ₂ = C C group or a plurality, z. B. have two, three, four or more CH ₂ = C C groups in the molecule of the individual compound. Examples of these compounds are esters, nitriles and amides of unsaturated, optionally substituted acids, vinyl esters and vinyl halides, methylenemalonic acid esters, mono- and polyallyl compounds, e.g. B. di-, tri- or tetraallyl derivatives or even higher allyl derivatives and the like. B. also be an unsaturated alkyd resin, or it can be a polyallyl ester of an inorganic polybasic acid, a saturated or unsaturated polycarboxylic acid or an aromatic polycarboxylic acid. Mixtures of these compounds can also be used. Specific examples of compounds or mixtures of compounds which can be used in addition to those already mentioned are shown in the following table.

Table I.

Benzyl acrylate glyceryl triacrylate

Benzyl methacrylate ethylene glycol diacrylate

Methyl ct-chloroacrylate diethylene glycol maleate

Ethyl a-bromoacrylate dipropylene glycol fumarate

Propyl cc-chloroacrylate divinylbiphenyl

p-chlorostyrene diallyl citraconate

Allyl acrylate vinyl methyl ketone

Diethylenitaconate Cyclopentadiene

Diethyl maleate 2-chloro-butadiene-1,3 dimethyl fumarate (chloroprene)

p-chlorobenzyl acrylate 2,3-dimethyl-butadiene-1,3

Diallylsuccinate Chlorinated methyl styrenes

Diallyl fumarate Chlorinated vinyl naphthalenes

Diethyl itaconate hexadiene-1,5

Allyl methacrylate 2-cyano-butadiene-1,3

Tetraallylsilane dimethallyl maleate

Diallyl phthalate dimethallyl itaconate

Methallyl acrylate, dimethallyl phthalate

Di- and tri-chlorostyrenes amyl acrylate chlorinated divinylbenzenes hexyl methacrylate

Vinyl methyl ether triallyl citrate

Vinyl ethyl ether triallylaconitate

Divinyl ether vinyl acetate

Methylene methyl malonate vinyl propionate

Methylene ethyl malonate vinyl butyrate vinyl chloride
Vinylidene chloride
Diethylene glycol dimethacrylate

Example 4

Resin 100.0 parts

Isopropyl ether 4.0 parts

»Tween20« 4.0 parts

50 ° / ₀ sodium phenolsulfonic 10.0 TEEE

5 6

In this example, using 4 ° / ₀ using that in the previous examples

Surface-active substance, based on the liquid processing technology mentioned, was a very good one

Resin and made using the process of pre-foam, which has a lower shrinkage

Following examples, a very good foam was obtained, which showed than that made with phenol sulfonic acid alone

possessed an even finer cell size than that in the previous resin product.

The following examples using a lower amount of the isopropyl ether of the above examples can be used Amount of surfactant produced foam by a corresponding amount of another solute. . . be replaced by, with comparable results Example 5 can be obtained. Usually the solvent resin is 30.0 parts in an amount of 2 to 10 percent based on the weight of the liquid

Isopropyl ether 1.5 parts resin. In the absence of an unsaturated substance

"Tween 20" 0.4 parts and using those mentioned in Example 2

50 ° / ₀ phenolsulfonic strength and quantity ratios were in replacement of 1.5 parts of iso

30% hydrochloric acid in a ratio of 1: 1 1.5 parts of propyl ether obtained the following results.

Table II Comparison of different solvents as glass formers *

solvent Percentage amount, Foam results example on the liquid Solvatone A ** Resin related Good development, coarser 6th (Mixture of 80 ° / ₀ 5 Cell size. Acetone, 10% isopropyl alcohol, 10% toluene) Dioxane ** Good development, rough 7th 5 Cell size. Methyl ethyl ketone ** Very firm foam, no 8th 5 Shrinking, coarse cell size. Methylal ** Quick response, no 9 5 Shrink, bigger cell size. Methyl acetate ** Fast reaction, 10 5 larger cell size, low shrinkage. Carbon tetrachloride Very good development, fine 11 5 Cell structure, similar to Iso propyl ether. Carbon tetra Very good, even finer ones 12th chloride** 5 Cell size. Ethylene dichloride Good foam, a little bigger 13th 5 Cells than with the ether. Butanol Pretty good foam, 14th 5 coarse cells. n-propyl acetate Decent foam, 15th 5 medium development, coarser cell size. toluene Very coarse. 16 n-butyl ether 5 Good foam, fine cells, 17th 5 however development is lower than isopropyl ether. Carbon tetra Very good development, very 18th chloride (1) 6 ² / s fine cells as well as Isopropyl ether. Carbon tetra Very good, but minor 19th chloride (1) 10 Shrinkage. n-butyl ether (1) Fast development, coarser 20th 4th Cells than isopropyl ether.

Comment:
The mixtures also contained a further 10 ° / o of 50 ° / _o owned Phenolsulf onsäurelösung and 0.4 parts of "Tween 20".

* Comparison refers to 5 ° / ₀ isopropyl ether.

** In addition, 5 ° / ₀ of the unsaturated compound of Example 3. Fig.

(1) Use of 5 ° / ₀ instead of 0.4 parts of "Tween 20".

It should be mentioned that it is necessary for the implementation of the invention It is essential for the process that the foam-forming composition contains both a water-soluble acid, e.g. B. contains a water-soluble sulfonic acid as well as a solvent that is volatile under the reaction conditions, If z. B. the solvent alone with the liquid resin in the proportions and below those in the above If the conditions described in the examples are mixed, then no foam formation or any other visible occurrence occurs Signs of reaction to. On the other hand, if ζ. Β. ίο an aqueous solution of one of the acids that can be used for this purpose with the liquid phenolic resin in the proportions and is mixed alone under the conditions described in the examples, it does indeed occur a violent reaction and also little foaming, and the resin hardens in a somewhat extended manner State. The product obtained in this way is relatively dense, the density and the appearance within the mass is very different because of a certain stratification and no uniform development occurs. It is therefore unsuitable as a foam material for technical purposes.

The addition of a small amount of a finely divided filler leads to a refinement of the final Foam structure as described in patent specification 885,004. During the foam formation they are used Fillers as development nuclei for gas formation. So the fire resistance, especially when moving Air, significantly improved by adding clay. If you also use inorganic fillers, such as those in the patent 885 004 were mentioned, in particular because of the increase in fire resistance, is preferred, so may however, organic fillers can also be used.

In addition to sulfonic acid, the acids used according to the invention also include hydrochloric acid and hydrochloric acid-sulfonic acid mixtures. When using a hydrochloric acid-sulfonic acid mixture can be taken, like parts of a 50 ° / ₀ ° solution of phenol sulfonic acid and a 30 / "by weight hydrochloric acid.

Further examples of other water-soluble sulfonic acids that can be used in place of or in addition to those in the patent 885 004 acids mentioned are: p-toluenesulfonic acid, benzenesulfonic acid, p-naphthalenesulfonic acid, Camphor sulfonic acid, m-benzene disulfonic acid or butyl sulfonic acid.

The amount of surface-active agent can in most cases be _{varied between 0.5 and 10 ° / 0} , based on the weight of the liquid resin, without substantial change in the effectiveness. The preferred range is 3 to 7 percent by weight based on the liquid resin.

Suitable surface-active agents are in addition to the substances already mentioned in patent specification 885 004 the sulfonated ethers and their quaternary ammonium salts and the oxazalin of oleic acid and des 2-Amino-2-methyl-1,3-pentadiols and its corresponding coconut fatty acid derivative.

Although the order in which the ingredients are mixed depends on your preference or depending on the given The usual procedure is to first use the volatile solvent and conditions to mix the surfactant with the resin to form a novel component of the reaction mass and then add the selected acid in question as a second component. The different other ingredients can be mixed together in any appropriate manner. When adding an unsaturated Material can do this with the volatile solvent, surfactant and resin first premixed to form the first novel component, followed by the acid as the second component separately adds. But the reaction can also be set in motion by the various Ingredients mixed together as soon as they are to be used.

The phenolic resin compositions with cell structure according to the invention have excellent buoyancy. The following table shows the percentage buoyancy of a sample of the foam produced according to Example 3 and a sample made according to the method of the main patent.

Table III

Percentage of remaining lift Sample after the
Patent specification
885 004 Dive duration Sample after
Example 3 100 0 100 79.8 ITag 97 74.7 2 days 94 66.7 7 days 91.2 56.2 14 days 85

The foam products according to the invention have a wide field of application. You can e.g. B. for filling of empty tanks in ships for the purpose of temporarily securing buoyancy, for buoyancy purposes, ζ. Β. ία Rafts or pontoons, as thermal insulation materials for refrigerators, air conditioning systems, scientific apparatus, Equipment for oil refineries, in which wax is separated from oil at low temperatures, as sound insulation compounds, used as building materials for certain electrical insulation purposes.

Claims (3)

Patent claims: 1. A process for the production of a phenolic resin with cell structure according to patent 885 004, wherein a water-containing, acid- and thermosetting, liquid phenolic resin is reacted with a water-soluble sulfonic acid and optionally in the presence of a surface-active agent, characterized in that in place of the carbonic acid salt a volatile organic solvent, preferably in an amount of 2 to 10 ° / ₀ , based on the weight of the liquid resin, is added to the reaction mass, which evaporates due to the heat of reaction resulting from the condensation. 2. The method according to claim 1, characterized in that there is a volatile solvent lower aliphatic ether, especially isopropyl ether, a chlorinated aliphatic hydrocarbon, a lower aliphatic ester, an aliphatic monohydric alcohol or an aliphatic monovalent ketone used. Considered publications:
Angewandte Chemie, 1952, No. 3, p. 74. © 009 547/447 6.60