DE1767128C - Process for the production of wood containing polymensate - Google Patents

Description

3 4

delay and thus the resulting temperature - that it is passed through a cooler in which the

lower tip. Examples of such salts are copper mono-

naphthenate and copper compound made from crystal resin is recovered. For the

resinat. Aim the hardest possible body can after completion

The type and amount of polymerizable substances 5 of the actual polymerization, the temperature in

can vary considerably. So you can as a poly- the chamber for '/ ·> up to 4 hours at 110 to 160 ³ C,

merisierbaren material exclusively as a monomer preferably au ^f are 130 to 150 ^ C, increased.

z. B. use styrene. It is more advantageous that this is necessary to initiate the polymerization

however, together with bridging substances, a temperature of less than 110 C can

set. Low molecular bridging agents are ι. B. io impregnated wooden bodies also by means of high-frequency

Divinylben / ol, the allyl ester of maleic acid. Acrylic heating can be generated. After triggering the poly

late with two or more double bonds and the merization reaction can, depending on requirements,

Methacrylates. Such substances can be used in the impregnation of the gas surrounding the wood body

Applying liquid in amounts of 1 to 10 weight above.

Percent, preferably 1 to 4 percent by weight, are based on the process according to the invention

keep his Unharden, crosslinked polymer-containing wood products can also be added to the monomer.

saturated polymers that react with the monomer are obtained, whereby the

such as B. unsaturated, polyester, polybutadiene, mixed position prevailing, relatively low tempe-

polymers of butadiene and styrene as well as similar temperatures do not destroy the interior of the product and none

Mix in addition polymers. Such substances can cause remarkable changes in shape in the wood body

the impregnation liquid can be produced in quantities of 1 to 50 Ge.

weight percent, preferably 5 to 20 weight percent, The Brinell hardnesses of the wood products obtained

contain. These polymers prevent both that were nac ^ < DIN 50 351 determined. Room dry

Evaporation of the monomer during the polymer birch wood body with 4 to 7 °, "" moisture content

sation and also give the finished product as had an average hardness of 200 kgf / cm ² .

a high degree of hardness. In terms of polymerizable substances, the invention is illustrated below with reference to

the impregnation liquid also explains unsaturated carbon examples in more detail. All wooden bodies

acids. Epoxy compounds, isocyanates or others were used here with holes 15 cm in length

with the constituents of the wood reactive in one provided, in the beginning of the heat treatment

Contains an amount of 1 to 15 percent by weight of substances. 30 thermocouples were introduced.

The bridges listed above make 11

the plastic produced in the wood pores in b c 1 s ρ 1 e I 1

insoluble in organic solvents and cause two dried wooden bodies (5 χ 5 < 50 cm

its hardening. The amount of the radical poly or 2.5 χ 5 ■, 50 cm) were with a solution

merization catalyzing substance impregnated in solution 35 of the following composition:

is 0.2 to 3 percent by weight. Styrene 71 4

The amount of the polymerization retarder in the commercially available 'unsaturated poly-' "

Solution depends on the composition of the solution, ester resin (30 percent by weight styrene

the initial temperature of the polymerization, containing the size) 28 6

the wood body and the desired temperature- 40 methyl ethyl ketone peroxide (60 "/" ig) ". '.'. U5

pointed inside the body during the course crystal resin 5 0

the polymerization. Generally 0.1

up to 15 percent by weight of retarder in the solution. The impregnation was carried out at room temperature

needed. in a steel container of 5.7 l capacity,

As catalysts for radical polymerization 45 which was evacuated to 5 torr pressure; at me-

if ordinary, commercially available catalysis is suitable, the impregnation liquid was poured into the container

goals such as B. methyl ethyl ketone peroxide, benzoyl filled. Over the liquid surface was

peroxide, diazoisobutyronitrile or mixtures thereof. Admitted nitrogen under 5 kp / cm ² pressure, and

The wood material used in the following examples was this pressure for 3 hours 45 minutes

play such used that keep on less than 2% 50. The impregnated body was turned into a

Moisture content was dried. Warming cabinet (90 C) introduced and with a

The impregnation of the fetch / good with the liquid provided thermocouple. Subsequently, the

happens according to a standard procedure under an on-cabinet nitrogen introduced until the air is greatest

application of vacuum or pressure, as it is e.g. B. Part was replaced by nitrogen. The temperature

is used to protect the wood from rot. 55 the body started first as a result of temperature

The maturation of the impregnated wood in the heating cabinet and later as a result of the polymer hardness Product is brought about by increasing the sation reaction. The smaller body Pieces of wood placed in a heating chamber in this way reached its maximum temperature of 136 C in be that between them for the gas circulation 1 hour 43 minutes. The maximum temperature of the required gaps are retained. The 60 larger body of 180 C was after 1 hour Air is reached from the chamber by means of inert gas for 52 minutes. Then an oil was expelled and heating the chamber with a moderate decrease in the temperature of the body Observe circulating gas or by means of through the walls.

introduced heat. After cooling, the temperature of the larger and

Chamber is increased to 60 to 100 C. According to 65 the smaller body has a hardness of 745 or 725 kp /

dissolve the polymerization and when the temperature cm ² dissolve.

of the gas a desired limit, e.g. 120 C, by allowing the bodies to stay at

exceeds, the gas can be cooled by keeping 150 C, an increase in hardness occurred

to 1003 for the larger or 1115kp / cm ² for the temperature of the larger birch wood body (5 χ 5

smaller body one. The polymer content was 50 cm) 18TC in 2 hours 14 minutes, while the

47.8 and 41.6%, respectively. Splitting the body proved that temperature of the smaller body (2.5 χ 5 χ 50 cm)

they were completely usable, although it rose to 148 ° C in 1 hour 58 minutes,

larger body inside darker than the light inside 5 The larger or smaller body had a hardness

of the smaller body was. of 960 or 768 kp / cm "-. After heat treatment

Under the same conditions as above (2 hours at 150 C), the hardness was 1115 and

Implementation, but without the addition of crystal resin 1215 kp / cm ⁸ .

In the impregnation liquid was worked, was Dur.h splitting the body, the maximum temperature in the larger body could be determined, that in both the interior of the smaller body was 216 b / w. 173 C that stayed in 1 hour. although the interior hue was reached at 32 minutes and 1 hour 12 minutes, respectively. the larger body was slightly darker than that of the body was split and found to be smaller. that the larger body inside a blackness ". had experienced and formed cracks and thus became completely unusable. The smaller body The experiment was carried out as in Example 1 but was kept in better condition. where, instead of crystal ^{resin, bis ρ ie 1 2 l parts by weight of 2,6} -dimethyl octatriene was used as a retarder, p. ^? ,, U ₁ -UiUIi- r ^{lm Verl uf polymerization} increased the indoor Trying found with Birkenholzkorpern (5 <5 ■ 20 temperature of the larger body (5 χ 5 χ 50cm) in 50 cm and 2.5 x 5 50 cm) and in the same way 3 hours to the tip of 120 C. The tip in Example 1 took place, but the impregnation temperature of the smaller body of 101 C was liquid instead of crystal resin 5 percent by weight sulfur reached after 2 hours 20 minutes Resin contained. The hardness was 453 kp / cm * for the larger and

The lmpragnierflussigkeit had the following cooperation 25,318 kgf / cm ² for the smaller body.

^{SU / ung After} heat treatment, the hardness increased

Styrene 71.4 ⁵³⁸ ^ ^or 405 kg / cm ² .

Commercially available unsaturated poly ^"6 J S'i'ßere or smaller. Body had 44.7 b / w.

ester resin (30 weight percent styrene- ⁴⁴ ^ Z ₀ polymer content. Both bodies were in

content) 28.5 ³ ° ^inside completely flawless.

Methyl ethyl ketone peroxide 1.5 ^Upon extraction with chloroform, the poly-

Sulfur-containing resin 5.0 mer in the larger body 4,3 ° / ₀ in solution.

During the polymerization of the impregnated Example 5

The body in the heating cabinet (90 C) was the maximum

temperature of the larger body (120 C) in 2 hours as a retarder instead of crystal resin one mV

den50Mmutenundddieesk. a body (110 C) made of 0.5 parts ^ 6-Dime nyloctatr Γ and

reached in 2 hours 35 minutes. Then 2.5 parts of crystal resin were used

The temperature started to drop. The interior would rise during the polymerization

After cooling, the hardness of the 40 temperature in the larger body was 0 mI for 2 hours.

larger body 360 and that of the smaller body grooves at 153 C, and d ^ jenigeSs kline ^ n K ^ prn

11, j Ά- w '" ^{λ hour 58 minutes} at 123 ^f C

If the bodies were then 2 hours after polymerization (3 hours 10 minutes

Held at 150 C, the ^{hardness was set at 488 kp / cm 2} ) the coarser body had a hardness of 865

mi. larger and to 500 kp / cm 'in the smaller body 45 and the smaller body νοΓ ₅ 80ΐρΑ on üfese

elevated. The color of the body held during this e Who came up after WärmebeLJΓΪίηί η «Λ μ

Post-treatment practically unchanged. The larger 150'C) on 8 ^ StS ^{8 (}

Body had a polymer content of 48.5% and the polymer content was 47 6 "/ for the larger

the smaller body of 43.4%. and 46.2% for the smaller body

In the case of chloroform extraction, 8.1% of the poly- 50 was determined by splitting that the

their inner parts are bright and completely flawless Example 6

the n.edrigen peak temperatures, ₅₅ ^^ VJtVZ

obtained in this experiment and their size and instead of crystal resin with 0 < waits

Relatively long training periods with the parts of copper naphthenate as a lower level

corresponding values of example 1 or the one below, whereby the impregnation fluidity Sb

described experiment (without delay) can the Die SpitenletpeUSr ^ η ^^ ϋ

Retarding effect one made of plastic resin and 60 in 2 hours 26 minutes

Sulfur formed compound can be detected. The hardness of the body was

Example 3 mensation 1115 and after heat treatment 1290 kp /

γλ χ, χ. j · · " ^cm ■ ^The polymer content was 44 8 ° /

The experiment was carried out as in Example 1. By columns de * änft.ri; 5, ■? ^: u t- u *

wherein in place of crystal resin as delaying Körpin 65 k «£ nth FSE ÄTwf ^ H ^ ^ß h η

0.5 -.w.ch.stei.e ^ D.-methyloctatrien used lur- InnSL röSbraS Ä ΐ £ Γ'γ ^ ρΑ was

^e ^ The course of the polymerization reached the inner

r ^ iecle those of info.ge high temperature 45 £% polymer

dark-hardened wood. 5 Jeim Sprite ^ were ^ Jje

B e i s ρ i e 1 7 The graph shows the development

ISSÄHSS

"IS5SäH; S

* ^ufwies: had been impregnated. The curve la shows the

Styrene. ¹⁰ Y temperature development when the wooden body with

Methyl ethyl ketone peroxide (60 ° / _O ig) ·· * »·> the one _{at the} end of the example! 1 mentioned solution without

Sulfur-containing resin ² O retarders were impregnated. Curves 1 to 6

In.VeHaufderPo.y ^^ the following were found., ^^ <^^ ΐ ^ ΖΧ ™ ^

Peak temperatures and standby points. were impregnated Looking at the curves

Larger body ·, _c α shows that when using the retarder the

(5 x 5 x 50 cm) \ WC in 2 hours _{inside the} wooden body, peak temperature

Smaller body. _ao rature significantly lower than without retarder gc-

(2.5 5 50 cm) 108 ¹ C in hour _{staUet haf}

30 minutes. _{In the} attempts according to the preceding examples

χι u f! „!» r Pnivmerization had the larger one was a relatively high initial temperature

After P ⁰ ^^ ' ⁰ "" ^^ used after the polymerization (90 ° C). If the poly-

Body eme hardness of 365kpcm and na r. _merisat fonstemperat _U r reduced to 65 ° C.

Heat treatment (2 transmissions at KW ^) ⁴ ^ ¹ ^ ^ the polymerization time is considerably extended.

while the corresponding W ^ for councils to Z ^ peak temperatures down

^K nS ^r ^ r ^b e ^Z Kör ⁴ _p ° er Sfit %?! & * The k.einere In the experiments in the example ^ I b »6 was aIs

- "» * puiyiHCI l> ici uaic oüusiaiii cm uiiu uiuciuv muvuu.'t

Ä · VS ^ were completely flawless inside. 30 taken from styrene and unsaturated polyester.

The bodies were inside e _{On Qrund these tests can effectively dje} J _{first r}

. . _R different polymerization retarders can be assessed

Example » _{den One can firmest} || _{en> that} crystal resin is a die

c a ..; » Edited in Reisniel 1, the polymerisation clearly slowing down the effect

As in the example, ^ J »™ = ·. _{which, however, is} significantly less than the effect

Impregnation nutty following composition J ₂₆ . _{Dimethyloctatrieni} ^g _the ^B _reaction p _r od _U kt

^{pointed out:} of sulfur and crystal resin and of copper

Styrene. Λ is naphthenate. By using suitable

Commercially available polybutadiene Iw retarders or combinations thereof as well as through

Divinylbenzene (53%> g) . 40 suitable choice of the initial temperature of the polymer

Acrylic acid · ■ · ·. ₁ , sation you have the opportunity to

Methyl ethyl ketone peroxide (60 / _o ig) - O · gnierten wood body during the polymerization

Crystal resin forming temperature at the desired level

rv τ «.ntnr ^ nitzen to regulate in the course of the polymer. This in turn influences numerous

»En JS ¹ KSSS were as follows: 45 properties of the product, such as B. its hardness

Bigger body. The effect of the above-mentioned polymerization

(5 χ 5 x 50 cm) 177 C ml ^ ^nü ^ retarder is also at ordinary temperature

52 minutes perceptible. The mixture mentioned in Example 1

Smaller body. 50 of styrene, unsaturated polyester and catalyst

(2.5 5 x 50 cm) 139 C in 1 mouth _without crystal resin gels at 15 to 2O ⁰ C in 2 to

Minutes. ^ Days to a mixture unsuitable for impregnation,

A larger body according to the poly- whereas with 5% crystal resin additive 7 bis

after heat treatment - 10 days usable.

1 sheet of drawings

Claims (3)

1 2 prevents the world of heat more effectively than one of the patent claims: the impregnating liquid and wood alone. 1. Process for the production of polymer object of the invention is to provide a containing Hc ¹ ; with impregnation of the wood 5 process using catalysts with a radical-polymerizable monomer and heat, which verrenverbindungen the above-mentioned disadvantages. d'e contains a catalyst which avoids and in which, in particular, after the start of the polymerization at a temperature with a polymerization reaction, an increase in the polymeri-110 C is able to classify, so that the characteristic temperature is set to a temperature for charring, etc. ζ eic Ii η e ι that an impregnating liquid is prevented from leading to temperature. is used as a polymerization retarder. This object is achieved according to the invention by a 0.1 to 15 weight percent unsaturated resin process for the production of polymer-containing or fatty acids with at least two conjugated wood with impregnation of the wood with a catalytic Double bonds, terpene derivatives with three Dop- lysatorhaltigen, free-radical-polymerisierbfren mono- pel bonds and / or reaction products of 15 mer mixture and subsequent polymerization Contains sulfur with terpenes or resin acids. dissolved in heat, which is characterized by 2. The method according to claim 1, characterized in that an impregnating liquid is used which is characterized by the fact that 0.1 to 1.5 weight stable resins, tall oils or fatty oils are used as polymerization retarders. percent unsaturated resin or fatty acids boiling at least above 100 C, at least two 20 at least two conjugated double bonds, terpene di'ppel bonds in conjugated position - derivatives with three double bonds and / or: detours and under the action of the polymerization settlement products of sulfur with Terpenes or catalyst · * highest; Experience dimerization. Contains resin acids. 3. The method according to claim 1, characterized according to the invention, this is the wood on the draws that as a polymerization retarder Kup- 25 polymerization temperature either by means of Hochfernaphthenat or frequency heating made from crystal resin or in a heating chamber Copper resinate is used. heated under inert gas and after inserting the poly- merization reaction the rise in temperature of the the inert gas surrounding the body above 120 C 30 prevents. Since this makes it possible to keep the polymerization temperature low, the aforementioned occur Disadvantages do not arise. The invention relates to a process for producing the polymer which can be used according to the invention of polymerizathhaltigem wood, in which the ion retarder can be divided into three classes Wood with a catalyst-containing, radical-poly- 35 be. The first class includes compounds that are two then subjected to a heat treatment or several double bonds in conjugated positions will. position or easily with the help of heat in such a Free radical polymerizing monomers, such as. B. lung contain convertible and under action Methyl methacrylate or styrene or their mixtures of the catalysts used no polymerization with unsaturated polyesters can be experienced as a result of their or at most dimerization. As a result of low viscosity without difficulty in wood occurring temperatures must be the boiling point bring. The initiation of the polymerization reaction of these substances is above 100 ^J C. Polymerization can either with the help of radiant energy, in the retarder of this type are numerous unsaturated special with the help of y-ray or with the help of 45 resin and fatty acids that are found in technical resins, a catalytic converter in the heat. Crystal resins, tall oil and fatty oils occur. There are various methods using 2,6-dimethyl-octatriene is a preferred example known from ^ radiation, which, however, is an expensive polymer containing three double bonds Radiation source and extensive safety device retarder. conditions require. From the USA. Patents 50 The second class includes sulfur-containing 3 077 417 to 3 077 420 processes are known in the case of bonds consisting of terpenes such as, for. B. auj dipenten those wood with polymerizable solutions under or from resin acids such as from crystal resin and sulfur Addition of catalysts is impregnated. can be obtained. The production takes place on In processes of this kind, the polymerization play dadurc ^h that (C 200 ^1), reaction with the aid of externally supplied heat 55 stirred crystal resin slow 2 ° / "sulfur is added to hot introduced energy. A disadvantage of this method is that an exothermic reaction occurs. In the case of wood materials of greater thickness, the stirring is continued for a few minutes, the inside becoming clear due to the influence of the thermal dissolution. Such a sulfur-containing polymerisation reaction released heat crystal resin has a significantly greater degree of charring and splitting, so that a change in the degree of the retarding effect occurs as the starting material. This phenomenon is partially serving crystal resin. due to the fact that the third class includes metal resins of some initial supply of heat by means of heat radiation organic acids, which also in small quantities as or with the help of hot gas, the polymer is a mild accelerator of radical polymerization sation reaction first in which can be known on the surface. These salts can affect the Layers used, the liquid thereby in merization of the liquid introduced into the wood Polymer is transferred, which in turn accelerate the in the initial phase, however, the The polymerisation generated inside the wood escapes when the gel hardens