JPS5916704A - Impregnating composition for thermochemically denaturing wood and its manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the thermochemical modification of wood for use in the manufacture of ski edges, substrates, or other products in which it is necessary to improve the physical and mechanical properties and weather resistance of wood. More particularly, the present invention relates to an impregnating composition suitable for thermochemical modification of wood and a method for producing the composition.

Currently, there are low molecular weight, oligomeric and polymeric substances with different properties that can improve the physical and mechanical properties, biological resistance, water resistance, chemical resistance and other properties of wood, depending on the application. The first one is ready for use.

The weatherability of wood can be improved by adding small amounts of certain cypress heptenols and other toxic compounds. For example, U.S. Pat.
No. 95,077 describes the use of polychlorophenol, nitrophenol, chloronaphthalene, and zinc oxide, butyltin, and copper compounds dissolved in a petroleum-based solvent as preservatives. West German Patent No. 2,555,984 suggests the use of polyphenols in combination with quinolines and thiophosphate compounds. U.S. Patent No. 4,013,8
No. 04 describes that a polychlorophenol composition is modified with paraffin wax in a polyester of polyhydric alcohol. British Patent No. 1.528,
No. 041 discloses MeSOs as an antifungal preservative.
It has been suggested to use N (P h )-sal, CGlt F (where Me is F), and US Pat.
, 993,752, the use of alkali metal cyanides was proposed, and West German Patent No. 2,622,0
No. 28 proposes a preparation based on boric acid and alkylene oxide for the insect control of wood. Sara K.

British Patent No. 1,467,420 proposes a solution of an organotin compound and a quaternary ammonium base. Soviet inventor certificate No. 537814 and same No. 571376
No. 1, a composition containing OuO and rosin in turpentine (oil) or OuSo in acetic acid.

Compositions containing Na, 0rtO, and H3BO are taught.

During the past few decades, efforts have been made to improve the properties of low-quality wood varieties by impregnating them with synthetic resins containing monomers and oligomers and polycondensing them by thermochemical methods. Ta.

For example, according to US Pat. No. 4,194,033, low quality wood is treated with alkylamines.

According to Japanese Patent Application No. 53-30764, an aqueous solution of formaldehyde is further used for treatment. In order to cause the wood to absorb free formaldehyde, boric acid is further added to the aqueous solution (Reference No. 55-117611).

In the USSR, phenolic alcohols (
USSR Inventor's Certificate No. 404,620) and its multi-ridged modified products such as 30% solution of maleic anhydride (USSR Inventor's Certificate No. 6)
20373), condensates of ethylene and higher fatty alcohols (USSR Inventor's Certificate No. 536044), and urea formaldehyde resin (USSR Inventor's Certificate No. 575218) have been successfully used.

% Application No. 49-35401, No. 52-79004 and 4
! No. 9-43126 and Borland Patent No. 411178
According to the specifications of the above publications, satisfactory results are obtained using low molecular weight polycondensates of phenol and formaldehyde. In order to absorb formaldehyde A, it has been proposed to treat wood with a solution containing sodium sulfite and ammonium salts (Japanese Patent Application No. 49-43126).

The disadvantage of the method of modifying wood with fue-based flucol or phenol/formaldehyde oligomer is that the impregnation is not homogeneous, and the wood becomes corrugated and cracked.
The problem lies in the instability of the impregnating composition.

For this reason, impregnation and subsequent curing of the impregnation composition are carried out under pressure.
Drying must be carried out by gradually increasing the temperature from 30-45°C to 100-120°C. However, curing must be carried out at a temperature of 160 to 180°C (Japanese Patent Application No. 49-20483).

However, this curing temperature deteriorates the properties of the modified wood.

Impregnation compositions containing a methylol derivative of carbamide, formaldehyde and a polymerization initiator are also known (West German Patent No. 2,063,1 'I 1).

Furthermore, in Japanese Patent Application No. 52-24082, phenol,
Impregnating compositions containing dihydroxybenzene and melamine or urea and with added fire-retardant salts are taught. The wood is treated in two steps. That is, 160
After evaporating the bath agent at a temperature of °C, the wood is treated with formaldehyde while simultaneously curing the impregnating composition.

On the other hand, in Japanese Patent Application No. 52-24082, a cellulose derivative is blended into a starting mixture of monomers, and wood is modified with an impregnating composition based on phenol resin, urea resin, melamine resin, or urea/melamine/formaldehyde resin. It is taught to improve physical strength properties.

A prior art composition which is close to the impregnating composition of the present invention in terms of composition and results obtained is U.S. Pat.
This is the impregnating composition described in No.

The impregnating composition is made by mixing the monomers resorcinol and dimethylol urea.

Although the impregnating composition described in U.S. Pat. No. 3,832,251 has some advantages, it also has some disadvantages.

(1) Free formaldehyde (up to 2%) is present in the impregnating composition, and this formaldehyde is therefore present in the modified wood in an amount determined by the equilibrium of the dimethylol urea formation/decomposition reaction; Secondly, safety and health issues remain when processing ski materials.

(2) Due to the low stability of the impregnating composition, the drying temperature was
℃ or higher, and the dry solid content cannot be increased to 30% or more (the dry solid content is 50% only when producing a small amount of the impregnating composition).

(3) Due to the low stability of an aqueous solution of dimethylol urea in ethanol, dimethylol urea must be prepared on-site, in other words directly at the site of use. For this reason,
The impregnating composition cannot be manufactured centrally.

(4) Due to its brittleness, wood modified by impregnating compositions with (4) poses problems in mechanical strength when manufacturing ski edges and ski bases.

The object of the present invention is to provide an impregnating composition for the thermochemical modification of wood consisting of a monomer resorcinol and a donor of formaldehyde in an alcoholic aqueous solution containing ethanol, in which the monomer resorcinol and formaldehyde donor contain a hydrophosyl group content. is 12.0-13
．． 3 mθq/f water-soluble oil shale crude phenol, urea, hexamethylenetetramine, and a molecular complex in equilibrium between the phenol and urea and hexamethylenetetramine, and also contains ethylene glycol, its homolog, or glycerin, The composition is 100 parts by weight of water-soluble oil shale crude phenol, 28-3 parts by weight of urea.
6 parts by weight, 35 to 40 mft parts of formaldehyde, 13 to 15 parts by weight of ammonia, 3 to 10 parts by weight of ethylene glycol or its homologues or glycerin, 5 parts by weight of ethanol.
An object of the present invention is to provide an impregnating composition characterized in that it contains 17,501 parts by weight and 100 to 3,370 parts by weight of water.

The dry solids content of the impregnating composition according to the invention is within the range of 3 to 60 parts by weight. This is one of the advantages of the impregnating composition according to the invention, which improves the physical and chemical properties of modified wood. It is undesirable to use impregnating compositions with a dry solids content of less than 3% by weight. This is because the impregnating composition loses its modifying effect.

When the dry solid content exceeds 60% by weight, the viscosity increases suddenly and the modification effect does not become large.

The impregnating composition (which has high stability and dry solids content and is free of free formaldehyde) is characterized in that the impregnating composition contains a molecular combination of water-soluble oil shale crude phenol, urea and hexamethylenetetramine in an alcoholic water bath solution. The overall properties of the system are improved primarily by the fact that the system is in equilibrium with the following equilibrium reaction acid:

Note that the required reactivity under curing conditions is that the hydroxyl group content is 12.0 to 13.0%, which is highly reactive as a phenol component.
Obtained using 3 mequiv/f of Sierre water-soluble total phenols. Here, [Water-soluble oil shale crude phenol J] means that obtained by heat treatment of Estonian oil shale.

During heat treatment of combustible shale, part of the phenol (2-z, 5iit% based on oil shale) is recovered together with ghatal water. On the other hand, the remaining part can be obtained by further washing the oil shale with water. Phenol content is approximately 1o
When y/l of these waters are extracted with an organic bath agent, 240-3
A shale water-soluble total phenol boiling at a melting temperature in the range of 60°C is obtained. These phenols contain about 10% by weight -Jj phenol and about 90% by weight dihydric phenol. It was also discovered that dihydric phenols are alkylresorcinols.

Recent research has led to the ability to determine the chemical composition of crude oil shale phenols. The chemical composition is summarized in Table 1.

Table 1 Some phenols
8.6-10.4 resorcinol
1,6-2.32-94-
Methylresorcinol 2.6-31
5-Methylresorcinol 28
0-3032.4-Dimethylresorcinol
01-Q, 8-16-dimethylresorcinol 1,1-1.52.5-dimethylresorcinol 5.8-6.45-
Ethylresorcinol 10.2
~10.72-ethyl-5-methylresorcinol
1.7-1.8 4.5-Dimethylresorcinol 5. T~7.55-ethynylresorcinol 1.3~1. γ2
-Methyl-5-ethylresorcinol 1.
9-2.02.4.5-trimethylresorcinol
2.1-3.05-propylresorcinol
1.9-2.14-methyl-5-
Ethylresorcinol 1.1-1.5 Other alkylresorcinols 18.4
~22.6 However, 4 types of basic components including the following 50 ~ 555
-Substituted alkylresorcinol 6o
~68 hydroxy group content
12.0~13.3maquiv/? As can be seen from Table 1, the main components are 5-methylresorcinol, 5-ethylresorcinol, 2,5-dimethylresorcinol, and 4,5-dimethylresorcinol, and the metal lid has a narrow range (50 to 55 resorcinol). n%) of which 28-30% is 5-methylresorcinol.

Water-bathable oil shale crude phenol has a high reactivity and is highly reactive compared to resorcinol. This can be explained by the presence of 5-substituted alkylresorcinols in the composition of the oil shale crude phenol.

The final temperature increase of the material from impregnated wood is due to the increased stability of the impregnating composition according to the invention.

The dry solids content of the impregnating composition increases to 60% by weight because the mixture of molecular complexes formulated in the equilibrium solution is dissolved in a solvent, i.e., an alcoholic water bath solution (a mixture of ethanol and ethylene glycol, their congeners, or glycerin in water). )
This is because homogeneity is maintained even in small amounts.

The improved elasticity of modified wood is due to the condensation reaction between hexamethylenetetramine and water-soluble oil shale crude phenol and urea that occurs under drying and compression conditions of the impregnated wood, resulting in the generation of ammonia, which has a high boiling point. This is because together with alcohol (ethylene glycol, its congeners or glycerin) it has a plasticizing effect on wood.

An improvement in the safety and health aspects of the working environment during wood modification results from the fact that the impregnating composition according to the invention is free of free formaldehyde.

The dry isomorphic content of the impregnating composition is increased, and the final drying temperature of the material from the impregnated wood can also be increased, making it possible to increase the production rate of the modification and wood drying process.

The present invention also has a hydroxy group content of 12.0 to 13.3.
meq# watered oil shale crude phenol 10
0 parts by weight, 28-36 parts of urea, 3-3 polyhydric alcohols (ethylene glycol, its congeners or glycerin)
10. A mixture consisting of 6 to 1,025 parts by weight of ethanol, and 3 to 1,492 parts by weight of water is heated at a temperature within the range of 60 to 95°C to produce the above-mentioned water bath oil shale crude phenol, urea, and these phenols and urea. In addition to obtaining an alcoholic aqueous solution containing a molecular complex, separately add 95 to 107 parts of a 31% water solution of formaldehyde, 54 to 62 parts of a 2γ% ammonia water solution, 1 to 125N of ethanol, and 1 to 1,764M of water. and maintaining this mixture at a temperature within the range of 20-60° C. to form an alcoholic aqueous solution of hexamethylenetetramine, which contains the water-bathable oil shale crude phenol, urea and molecules of these phenols and urea. The present invention also relates to a method for producing an impregnating composition for thermochemical modification of wood, characterized in that an alcoholic aqueous solution containing the complex is mixed with the alcoholic water bath solution of hexamethylenetetramine in a weight ratio of 1=1. As a result of mixing the above two alcoholic aqueous solutions, hydroxyl groups are present; df 12. Q
~13.3 maq #' tD water fafi, tIlcher crude phenol, urine s, hexamethylenetetramine, and an impregnating composition consisting of an equilibrium alcoholic aqueous solution containing hexamethylenetetramine and a molecular complex of the phenol, urea, and hexamethylenetetramine is produced. do.

When preparing an alcohol-based aqueous solution (hereinafter referred to as a solution) containing water-bathable oil shale crude phenol, urea, and molecular complexes of these phenols and urea, make sure that each component (phenol and urea) is in the solvent. The temperature needs to be maintained within the range of 60-95°C to ensure co-dissolution.

When preparing an ethanol aqueous solution of hexamethylenetetramine (hereinafter referred to as Solution IB), the temperature is 6.5°C because the starting components (formaldehyde and ammonia) are volatile.
It is necessary to ensure that the temperature does not exceed 0°C.

In order to simplify the production of the impregnating composition, the mixing weight ratio of solution M and B is selected to be 1:1. However, compositions with other proportions can also be produced, but this would complicate the process.

There is no limit to the storage period of the alcohol-based aqueous solution and B, and their production can be carried out intensively.

Therefore, the synthesis of dimethylol urea (formaldehyde donor), which was not limited in the woodworking field, can be performed in a limited manner, and the impregnating composition can be produced intensively.

Impregnating compositions for thermochemical modification of wood are produced by a three-step mechanical and chemical process.

(1) A water-soluble alcoholic compound is prepared in a reactor equipped with a stirrer, a thermometer, a cooler, and a cooling/heating jacket. Hydroxy group content is 12.0-13.3 meq/
The water-soluble oil shale crude phenol of Stir until formed and add polyhydric alcohol [ethylene glycol, its homologs (diethylene glycol, triethylene glycol) or glycerin], water and ethanol. The solution is stirred and cooled before being removed from the reactor. It has an unlimited shelf life and can be produced intensively.

(2) Alcoholic aqueous solution B is produced in a similar reactor, but a 3T% aqueous solution of formaldehyde is introduced into this reactor. With continuous stirring and cooling, a 24% aqueous solution of ammonia is added in such a proportion that the temperature of the mixture does not exceed 60°C. Cool the solution and remove from the reactor.

It has an unlimited shelf life and can be produced intensively.

(3) At the neck where the molecular complex is in equilibrium in the impregnating solution, mix the alcoholic aqueous solution obtained at a temperature within the range of 20-30°C for 15-30 minutes and B in a weight ratio of 1=1. .

The shelf life of the resulting impregnating composition is 20 days at 20-25°C, and the composition is free of free formaldehyde.

The method of manufacturing impregnating compositions according to the invention is further illustrated in Examples 1-5 of Table 2.

Table 3 shows various embodiments of the impregnating compositions of the present invention prepared according to Examples 1-5 of Table 2.

Table 4 shows impregnating compositions according to the invention and U.S. Pat.
A comparison of various properties of conventional impregnating compositions described in Publication No. 832,251 will be shown.

Thermochemical modification of wood with the impregnating composition of the present invention is carried out preliminarily in an open bath or autoclave. The process consists of impregnating the wood under pressure with dry air and then drying the impregnated wood at a temperature of 20 DEG to 90 DEG C., thereby causing polycondensation of the composition used. Furthermore, polycondensation 1ti O, 2-6.0
MPa ノ)E under power? +) 11-180℃ preferably 1
It is carried out at 00-120°C.

Table 5 shows the physical and mechanical properties of modified wood obtained using the impregnating composition of the present invention and modified wood obtained using the known composition described in U.S. Pat. No. 3,832,251. Compare and show.

As can be seen from Table 5, when the dry solids content of the impregnating compositions is equal, the physical and mechanical properties of wood modified using the impregnating composition according to the present invention are better than those of U.S. Pat.
．． 832.2 s 1 (1.1 to 1.1 times better than those of wood modified with impregnating compositions No. 832.2 s 1).

A-4 poem -- Nun
.

Continued from page 1 to I/1 Poem -Claim of priority @October 22, 1982ΦSoviet Union (SU)
■349921 0 Inventor Night Karlovich Kapusovjet Federation Tallinn Ulyitsa Letke Ti 24 K.V. 55 0 Inventor Miialt Augustovitch Riistovsovjet Federation Tallinn Ulyitsa Fisi 20 Kev. 1 0 Author: Yuri Hindrekovych Lok Soviet Union Pialnu Ulyitsa Oia 112 B.K. 41 0 Inventors Tomas Lovych Matov. Author: Yuri Edgarovitch Prabon Soviet Union Pyarnu Ulytsa Oia 61 Cavy10 Bateivayastii Complex 1 Vijsnurku 6 Soviet Union Piialnu Uliitsa Suureziye 48

Claims (2)

[Claims] (1) An impregnating composition for thermochemical modification of wood comprising a monomer resorcinol and a formaldehyde donor in an alcoholic aqueous solution containing ethanol, wherein the monomer resorcinol and the formaldehyde donor have a hydroxyl content of 12. 0-13.3m
eq/y of water-soluble oil shale containing crude phenol, urea, hexamethylenetetramine, and molecular complexes in equilibrium with the phenol and urea and hexamethylenetetramine, and also containing ethylene glycol, its congeners, or glycerin. and the composition is 100ml of water-soluble oil shale crude phenol, 1 part of urea, 28-3
6 parts by weight, 35-40 parts by weight of formaldehyde, 13-15 parts by weight of Ammoev, 3-10 parts by weight of ethylene glycol, its homolog or glycerin, 5-10 parts by weight of ethanol.
An impregnating composition comprising 1150 parts by weight and 100 to 33 TO parts by weight of water. (2) Hydroxy group content is 12.0 to t3.3m
eq/r water soluble oil shale crude phenol 100
Heavy storage part, 28-36 parts by weight of urea, 3-1 polyhydric alcohol (ethylene glycol, its congeners or glycerin)
0! parts by weight, 6 to 1025 parts by weight of ethanol and 3 to 1 part by weight of water
Heating a mixture consisting of 492 Dobe at a temperature within the range of 60 to 95°C to obtain an alcoholic aqueous solution containing the water-soluble oil shale crude phenol, urea, and molecular complexes of these phenols and urea, Separately, 95 to 107 parts by weight of a 31% aqueous solution of formaldehyde, 54 to 62 parts by weight of a 27% aqueous solution of ammonia, and 1 part by weight of ethanol.
~725 parts by weight and 1~1764 parts by weight of water were mixed, and the mixture was maintained at a temperature within the range of 20~60°C to prepare an alcoholic aqueous solution of hexamethylenetetramine, and the above-mentioned oil shale crude phenol was prepared. , an alcoholic aqueous solution containing urea and a molecular complex of the phenol and urea is mixed with the alcoholic water falFM of hexamethylenetetramine in a weight ratio of 1:1. A method for producing an impregnating composition for thermochemical modification of wood as described in 2.