DE3510782A1 - Repellent - Google Patents

Abstract

A repellent against forest pests, in particular bark beetles and curculionids, which contains active ingredients found in crude terpentine obtained by the sulphate method or in a condensate which resembles crude terpentine and which is obtained when tall oil is processed. The composition is obtained as residue when crude terpentine or the condensate are distilled at 0.9-1.2 kPa at temperatures of up to 115 DEG C. The repellent is used for protecting plants, trees and timber against insect attack.

Description

DESCRIPTION

The present invention relates to detergents (Repellants) against forest pests, especially bark beetles and weevils Process of making these repellants and their use to protect Plant zen, trees or wood against insect attack.

Swedish forestry is suffering due to insect attack big losses every year. The greatest losses are caused by insect attacks on forest plants, growing conifers, lying trees and wood. The conifer plant damage are mainly used by weevils (Hylobius abietis and other Hylobius species) caused, as well as black bast beetles (Hylastes species), short weevils (Strophosoma species) and black weevils (Otiorryhnchus species). On living conifers and those that have not been barked Bark beetles in particular, but also other types of insects, cause great damage to wood and losses. The most important bark beetle species in this context are: the eight-toothed bark beetle (Ips typgraphus), the six-toothed bark beetle (Pityogenes chalcographus), the small and large forest gardener (Tomicus piniperda and T. minor) and the striped timber bark beetle (Trypodendron lineatum).

Various preventive measures are used to prevent insect damage Measures taken. Beating calm and ground wounds reduce the risk of damage on coniferous plants. Mechanical protection or treatment with insecticides can also protect the plants.

Preventive protective treatment of trees and wood against bark beetles and other bark- and wood-living insects could up to now in an effective way can only be done using insecticides or water sprinkling. Pheromones, signal substances can currently only in a very limited way Dimensions are used. Insecticide treatment may only occur in special cases, and water irrigation can only be carried out under certain conditions.

Neither in terms of occupational hygiene nor with regard to environmental protection the use of insecticides is desirable.

Repellants used to be tried on plants, trees and wood been. These repellants had different origins and different compositions. It has long been known that turpentine, wood tar, terpenes and the like Substances of wood origin can affect the behavior of various insects. All of these tried and tested repellants for protecting plants against insect attack exhibited an insufficient effect, damaged the plants, i.e. a had phytotoxic effects or were unacceptable for other reasons.

It is known that a fraction of turpentine which mainly consists of a mixture of naturally occurring terpene hydrocarbons and terpene alcohols, obtained as by-products in the paper pulp industry and by Northwest Petrochemical Corporation designated as Norpine 65, the infestation of timber bark beetles can delay and counteract the bark beetle attack on living trees (Nijholt, W.W., Bimonthly Research Notes 29 (6), 36, 1973 and 35 (4), 22-23 1979).

An effective forest insect repellent, especially as a deterrent of bark beetles and weevils based on olfactory and other sensory perceptions, like taste and feeling, and without any harmful effect on the forest tree plants it's not on the market yet. As can be seen from the above, there is a there is a great need to produce such a means.

It has now been shown that the high-boiling part of sulphate turpentine contains one or more components with strong deterrent effects on one Majority of insects without noticeably toxic effects on them.

Light pre-run oil, which is obtained from the crude tall oil during dehydration, before it is further refined by vacuum distillation, a composition which largely corresponds to that of raw turpentine. Also the so-called Ejector condensate obtained from the vacuum system during the distillation of crude tall oil has, for the most part, a composition that corresponds to that of raw turpentine.

Both the light feed oil and the ejector condensate can add more Be sources for the active components.

Form in the manufacture of paper pulp by means of the sulphate process black liquor and a vapor phase with raw turpentine, which are separated and in safekeeping be taken. Raw soft soap is separated from the black liquor Treatment with sulfuric acid results in crude tall oil. Distillation of crude tall oil results Light lead oil, lead oil, fatty acids, resin acids and a residue of tall pitch. The distillation of crude turpentine after separation from the vapor phase results a majority of turpentine fractions as well as a high-boiling residue, which is about 10 % of the original amount. An investigation into the deterrent activity in some of these distillation fractions shows that they are due to the high-boiling turpentine residue is focused.

The inventive agent is characterized in that it the contains active components contained in a high-boiling residue, which Remainder from the distillation of the raw turpentine from the sulphate process or one at the processing of crude tall oil at 220 "C and 5 kPa or corresponding distillation requirements obtained raw turpentine-like condensate has been obtained, which remainder to makes up 10% by weight of it, and any additives.

By another distillation of the high-boiling turpentine residue under reduced pressure a residue is obtained which is about 2% of the original Sulphate turpentine and in which the active components are concentrated.

As a condensate similar to turpentine, light feed oil, which with the dehydration of crude tall oil at 220 "C and 5 kPa or corresponding reaction conditions can be used.

According to the invention, an agent with a deterrent effect is produced, by using raw turpentine from the sulphate process or in the processing of raw tall oil obtained at 220 "C and 5 kPa or corresponding distillation requirements Turpentine-like condensate is distilled, with a high-boiling residue with active components with a deterrent effect, which accounts for up to 10% by weight, is obtained.

According to a preferred embodiment, an agent with a deterrent Effect produced by the high-boiling residue obtained at up to 115 "C and at a pressure of 0.9 - 1.2 kPa or with appropriate distillation requirements is distilled, with a remainder containing active components with a deterrent effect is obtained, which makes up to 20% by weight thereof, corresponding to up to 2% by weight of the original raw turpentine.

In the fractionation of the distillation residue according to the invention, this being divided into a polar and a non-polar fraction, for example by chromatography or countercurrent partition extraction, the ingredients enriched with deterrent effect in the polar fraction, while the non-polar Hydrocarbon fraction becomes less active.

The active components in the still are not identified been. Gas chromatographic studies of the remainder, which is 2% of the original Turpentine corresponds to suggest that the main part of the retention times of the incoming components on a polar column between the retention times for G -Terpeneo-1 and the methyl esters of dehydroabietic acid.

The agent according to the invention can in addition to the active components also include various additives or diluents in the distillation residue. As an example of additives can. Adhesion-improving agents, such as film formers, Dyes, consistency factors, are called. Except for the inactive components in the distillation residue can be used as diluents or various solvents Use water.

The invention also relates to the use of the inventive Means to protect plants, trees or wood against attack by insects, whereby the Agents according to the invention applied on or next to the plant, the tree or the wood will. The means can be done by brushing, dipping or spraying in any way can be applied before or after planting. It is possible to use dispensers, i.e. some kind of carrier, impregnated with the agent and into which to use Be placed near or on the plant and thereby protect the plant.

Preparation examples a) Raw sulphate turpentine of Scandinavian origin is periodically in a laboratory distillation apparatus equipped with a packed column given. About 90% of the added turpentine is distilled off at normal pressure. The final temperature in the still is about 200 "C. Here, XPQ becomes 32 obtain.

b) The distillation residue from a), XPQ 32, is poured into the one in a) and the pressure was reduced to 0.4 kPa. With this one 80% of the added amount is distilled off in vacuo, the remainder being XPQ 32-4. The final temperature in the still is 1200C at 04 kPa.

From 500 ml XPQ 32, which is passed through a Vigreux column at 0.9 - 1.2 kPa is distilled, after distilling off a fraction at a temperature from 50-115 "C at the distillation head, 120 ml of a residue obtained, which is XPQ 32-4.

c) The distillation residue from b), XPQ 32-4, is placed on a silica column given, which then elutes with low-boiling petroleum ether (boiling point 40-60 "C) is, whereby a non-polar fraction, 61, is excreted. Continuous elution with a mixture of low-boiling petroleum ether and ethyl acetate results in a polar fraction, 62, which is enriched in the active components. From 5.5 g of added XPQ 32-4, 2.5 g of 61 and 2.5 g of 62 are obtained.

The field tests, the deterrent effect of the invention Means show are with the fractions XPQ 32 and XPQ 32-4 been. Comparative experiments between these and other substances are in the laboratory been made.

Experiment 1 Protection of pine wood against the great forest gardener were carried out on 2 places, one place with a fairly high population (Funbo) and one with a smaller population (Länna) of large forest gardeners.

Treated and untreated were 1.5 m long on both places Trunks laid out. The experiments were carried out in pairs so that each A pair of treated and untreated pieces were taken from the same tree. the Pieces were laid out in a line with about six inches between them.

The treatment with XPQ 32 was started about a week before the first day of swarming carried out by the great forest gardener.

The test material consisted of 15 linear meters of wood with an average 13 cm in diameter under the bark. The approach to the logs was with Adhesive-treated (Stickem-Special) metal nets - placed next to the pieces - measured.

In June all the pieces were debarked and the number of attacks noted.

Average number of large forest gardeners caught per piece (trap) Average number of prisoners / unit control 60 (21-101) * (n = 5) Länna XPQ 32 4 (0-14) * (n = 5) Control 333 (295-399) * (n = 3) 49 (43-57) * Funbo XPQ 32 (n = 3) n = number of repetitions * minimum and maximum values number of attacks by large ones Forest gardeners on average per m2 of jacket area Number of attacks on average / m2 Shell area First day of swarming * Total swarming control 61 (26-109) ** Länna XPQ 32 0.3 (0-1.7) ** Control 142 (92-196) ** 372 (308-455) ** Funbo XPQ 32 0 41 (0-127) ** * Each 1.5 m piece was cut in the middle and one half removed after the first day of swarming while the other during the entire swarming remained lying.

** Minimum and maximum values The treatment thus had a strong deterrent to forest gardener brood attack and also frightened the approach.

Experiment 2 Protection of pine wood from spruce bark beetles Field trials in Uppland were carried out on a fresh spruce cut area 1.5 m long of spruce put down in 10 groups with 3 pieces per group. The pieces in each Groups were divided among themselves at intervals of 2 m. On May 9th was in everyone Group treated one piece with XPQ 32 and one with XPQ 32-4, while one unprocessed remained. The swarming of the bark beetles began around May 15th.

As early as May 16, 8 of the 10 untreated pieces were attacked. As can be seen from the table, the treated pieces became slower and attacked to a much lesser extent.

Pine medullary beetle attack on XPQ treated pieces Number attacked number of drillings pieces average May 16 May 24 May 12 June Control: I typographus 8 10 A60 P chalcographus 6 9> 60 XPQ 32 I typographus 3 8 5 P chalcographus 0 4 3 XPQ 32-4 I typographus 0 3 4 P chalcographus 0 2 1 The trials clearly show that the remedies have a strong deterrent effect on the eight-toothed (Ips typographus) and the six-toothed bark beetle (Pityogenes chalcographus).

Experiment 3 Protection of plants from weevils In field tests were Pine plants (Pinus sylvestris) on felling areas that were cut down last winter had been planted in different places in Uppland and Östergötland. The experiments were done in blocks, with each block one machined and one Contained unprocessed parcel. The number of blocks per attempt is 3-7 pieces.

Bar roots were planted with a hoe, with a smaller one Ground wound mark was recorded. All cover root plants were with Pipes or drills and planted without previous soil wounding. Most of the plants happened in May to early June according to the recommendations made in forestry are valid.

The treatment consisted of applying the agent with a brush became. The lower half of the above-ground part of the plant was under special Taking into account that the root neck is covered, treated.

The treatment was carried out before (Mögstorp) or immediately after planting performed.

When reading, the plant was rated on a 5-degree scale. The damage level 0 means that there was no damage, the damage level 5 that the whole trunk was eaten bald by the end of the year. For the dead plants it was records whether they were killed by weevils or for some other reason or perished from some combination of weevils and some other cause are. "Other reasons" could be phytotoxic effects or drought, for example.

The results in the table partly show the attack situation after 11 to 16 days, partly the death rate of the plants during the autumn inspection. This clearly shows the deterrent and protective effect of XPQ 32-4.

I n s p e k t i o n H e r b s t i n s p e k t i o n test facility test equipment Number Number of days Damage% Died P f l a n z e n Plants the degree / griffe- number of days of off from rus- + total zen planting plant After planting the weevil beetle plants, Selren and Andekä- greens Green far from the Mögstorp control 63 16 1.8 73 101 43 0 0 43 XPQ 32-4 63 16 0.2 6 101 2 0 0 2 Odens control 180 12 1.4 41 91 61 0 0 61 l and I XPQ 32-4 180 12 0.5 21 91 46 0 1 47 Kohlhagen control 180 15 2.5 66 91 80 0 0 80 XPQ 32-4 180 15 0.4 15 91 23 2 8 33 Odens control 108 11 2.9 75 48 74 1 0 74 l and II XPQ 32-4 108 11 1.0 35 48 26 4 2 32 Comparative experiment investigation the deterrent effect of some agents on weevils using a rodent test In a comparative test, light feed oil, raw turpentine, Norpine 65 and tried the XPQ 32-4 for its deterrent effect.

A weevil was punched in a test chamber with a fresh Bark set. The exposed bark area, 100 mm2, becomes 20 yl of the current Treated test substance. Each treatment is repeated 40 times. The test chambers are then placed in a desiccator (one per treatment). Any desiccator a humid stream of air was fed in for proper ventilation. The treatment the bark surface is made twice in 24 hours before the animals are admitted in order to avoid too great an impact on the animals. The test animals will be taken out of the cold room (10 "C) and stored at 20" C for two days before take-off. The animals starve one day before the start. The nibbling area (cumulative) and number Animals that gnaw were noted. In the experiment, there were 40 animals in each experimental course used.

The following results were obtained: Number of hours of light feed oil Raw turpentine Norpine 65 XPQ 32-4 Check after start Nage number Nage number Nage- Number Nage- Number Nage- Number area eat- area eat- area eat- area eating area eating mm² de animals mm² de animals mm² de animals mm² de animals mm² de animals 24 170 5 410 13 60 3 40 4 1690 35 48 440 13 1360 21 230 10 380 9 2390 36 72 1020 15 2010 26 620 15 680 14 96 1310 17 2320 26 900 16 740 15 120 1640 20 2460 27 1640 22 1090 17 144 2330 27 2680 29 2050 26 1180 18 168 2560 29 2820 29 2380 28 1400 18 * * This value differs significantly from the values for the other funds at the same time.

In a second attempt under the same conditions, the effect of XPQ 32-4 compared with the effect of the polar 62 or non-polar 61 fraction thereof, which have been obtained according to preparation example c).

The following results were obtained: XPQ 32-4 61 62 hours- gnawing- Number of nails Number of nails Number of area eat- area eat- area eat after mm2 de animals mm2 de animals mm2 de animals Start 24 175 10 415 19 115 5 48 690 16 1605 27 325 7 72 1325 22 2550 29 720 16

Claims (6)

DETERGENT 1. Agents with a deterrent effect (repellants) against forest pests, in particular bark beetles and weevils, characterized in that they comprise the active components contained in a high-boiling residue, which remainder from the distillation of the raw turpentine from the sulphate process or one from processing of crude tall oil at 220 ° C and 5 kPa or corresponding distillation requirements obtained crude turpentine-like condensate, and the remainder up to 10% by weight thereof, and any additives. 2. Means according to claim 1, characterized in that g e k e n n z e i c h -n e t, that the high-boiling remainder is up to 2% by weight of the raw turpentine or the raw turpentine-like Condensate and by distillation at up to 115 "C at a pressure of 0.9 - 1.2 kPa or equivalent distillation requirements has been obtained. 3. Process for the preparation of an agent with a deterrent effect against forest pests, especially bark beetles and weevils, thereby g e k e nn z e i c h n e t that raw turpentine from the sulphate process or one at the Processing of crude tall oil at 220 "C and 5 kPa or corresponding distillation requirements obtained raw turpentine-like condensate is distilled, with a high-boiling Rest with active components with a deterrent effect, which is up to 10% by weight of which matters is obtained. 4. The method according to claim 3, characterized in that g e k e n n z e i c h -n e t that the high-boiling remainder at up to 115 "C and at a pressure of 0.9 - 1.2 kPa or with appropriate distillation conditions is distilled, wherein a remainder with active components with a deterrent effect, which is up to 20% by weight of which makes up and which corresponds to up to 2% by weight of the original raw turpentine, is obtained. 5 The method according to claim 4, characterized in that there is no e n n n z e i c h -n e t that the high-boiling remainder by removing a non-polar hydrocarbon fraction is enriched in active components. 6. Use of an agent with a deterrent effect against forest pests, in particular bark beetles and weevils, for the protection of plants, trees or wood against the attack of such forest pests, being the means that the active Contains components that contain up to 10% by weight in a high-boiling residue are that in the distillation of raw turpentine from the sulphate process or from one when processing crude tall oil at 220 "C and 5 kPa or equivalent Distillation requirements obtained raw turpentine-like condensate obtained is applied on or next to the plant, tree or wood.