CA2501371A1 - Flame-proofing agent and means for the production thereof - Google Patents
Flame-proofing agent and means for the production thereof Download PDFInfo
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- CA2501371A1 CA2501371A1 CA002501371A CA2501371A CA2501371A1 CA 2501371 A1 CA2501371 A1 CA 2501371A1 CA 002501371 A CA002501371 A CA 002501371A CA 2501371 A CA2501371 A CA 2501371A CA 2501371 A1 CA2501371 A1 CA 2501371A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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Abstract
The invention relates to a flame-proofing agent based on a modified unsaturated oil to which other flame-inhibiting chemical substances such as boron and phosphorous compounds can be added in order to improve the flame-resistant properties thereof. The fungicidal qualities thereof are improved by adding terpenes to the mixture. The invention also relates to a method for the production of said flame proofing agents and the use thereof.
Description
Flame-proofing agent and means for the production thereof The invention relates to a flame-proofing agent based on a modified unsaturated oil to which other flame inhibiting chemical substances such as boron and phosphorus compounds are added in order to improve the flame-resistant properties thereof. The fungicidal qualities thereof are improved by adding terpenes to the mixture. The invention also relates to a method for the production of said flame-proofing agents and the use thereof.
It is known that native vegetable oils with a high content of unsaturated fatty acids are usable for varied fields by integration of different substances combined with a splitting of the C=C-double bond or with a bonding on the carboxyl group. Particularly, this is right for the so-called quick-drying vegetable oils. The content of unsaturated fatty oils is in case of vegetable oils such as linseed oil, hempseed oil, Iberian dragon head, crambe, and camelina approximately at the same level. The difference is, among other things, the content of different fatty acids and the structure on the triglyceride. With that, also the number of available double bonds as reaction potential is different. For providing selective compositions of unsaturated fatty acids, also mixtures of these native vegetable oils are possible.
In case of linseed oil, for example, there are manifold variations of modification and of optimization because of its properties such as, for example, a high creep ability, a high reactivity, and a high polymerizability, respectively, because of a high content of unsaturated fatty oils with a large number of double bonds. The linseed oil is a ester of glycerine with different long-chain carboxylic acids. In this case, always tree fatty acids are combined by the ester compound and form the triglyceride. The content of unsaturated fatty acids in linseed oil is about 90 %. Native linseed oil has a high flash point (316 - 318 °C).
For development of flame-retardant properties, in addition to the said bromine, boron, and phosphorus compounds, also terpenes, for example in the form of liquid resin or wood oil, are added to the vegetable oil. Liquid resins are classified as essential oils because of its consisting of many different carbon compounds. Mainly, they consist of terpenes (over 60 %) which, on the other hand, consist of CSHg-hydrocarbon units. In correspondence with these units, there are many structures, most frequently monoterpenes with 10 C-atomes including unsaturated, partly doubly or triply unsaturated carbon compounds, for example the terpene alcohol geraniol. These multiple bonds form also a reactive potential for chemical reactions with halogens. A partial halogenation of terpenes can not be precluded. pine oil has polarizing properties which has a positive effect concerning reaction control of a mixture with vegetable oil in case of addition of bromine, for example.
Modified vegetable oil can be used, among other things, as flame-proofing agent. The vegetable oil modified for this use can be used in pure form, for example by spraying on a material, and combined with other substances as additional component and additive. The use of fire-retardant modified vegetable oils is possible in many branches of industry. Above all, in the field of civil engineering, component parts and building materials have to provide with a sufficient flameproofing and by using flame-proofing agents with flame-retardant properties. This is the case, for example, with sealings for building units and with insulations in the building shell. Also in the plastics industry, for PVC products, polypropylene products, and PUR products such as rigid foams or flexible foams, the modified vegetable oil can be used as flame-proofing agent. Here the flame-proofing effect appears, among other things, by an encrustation of the surfaces in case of fire.
Linseed oil, for example, is used in a wide range in the paint industry. By an additional fire-retardant function, the field of application can be extended also to fire protection paints and lacquers.
Further fields of application are, for example, technical textiles and many products made from renewable raw materials, for example chipboards, fiberboards, insulating materials, and fillers. The boron compounds, which are contained in the modified vegetable oil, and the integrated terpenes have in addition to the flame-retardant effect also a fungicidal effect. So there are many possibilities for wood preservation. In particular, the water-soluble boron compounds in products such as chipboards, which are subjected to the external influence of humidity, are because of the bonding with vegetable oil no longer dissolved in the product and washed out. Because of that, these substances maintain their efficiency in these products over a far longer period of time.
The flame-retardant properties can be influenced by the extent of bond formation of the C=C-double bonds of unsaturated fatty acids. The vegetable oil with a high content of unsaturated fatty acids serves in this case as carrier material for the integrated flame-retardant and fungicidal substances. By the complex integration of different flame-retardant substances, different effects in the case of fire are caused. In such a case of fire, because of a release of halogens (bromine) and of the forming HBr, H- and OH-radicals, which are necessary for the combustion process, are caught in the gas phase and converted to HZ and HZO.
This results in a slowing down and a breaking-off of the flame reaction. On the other hand, phosphorus compounds, for example phosphoric acid esters, are active in the condensed phase, support by dehydration of the pyrolizing substrate the carbonizing and reduce so the emission of combustible gases. Moreover, a protective layer, for example in case of plastics, can be formed on the surface. This layer impedes the escaping of combustible decomposition products and can because of its heat-insulating effect prevent an energy input in the product.
The carbonizing of the surface is also promoted by the large C-potential of the fatty acids.
These above-mentioned systems take effect combined with the vegetable oil at temperatures > 200 °C. By an integration of boron compounds, for example disodium octaborate, the effectiveness of flame protection can begin already at temperatures of 90 °C and more.
Particularly, because of that, highly inflammable materials are provided with a protection. The function of the borate is based on the forming of a glass-like protective layer on the surface of a product. By this process, an early thermal barrier is formed and the supply of oxygen is impeded. The water existing in the compound contributes to cooling and to reduction of the flame temperature. In addition to the flame-retardant properties, borates are also effective against insect and fungal attacks.
The flame-proofing agent made from modified vegetable oil is characterized by the following behavior which has appeared in case of utilization in different applications:
- a fire-retardant and fire-slowing down behavior of the material, - immediate going out of the flames in case of removing the body from the source of the fire, - no complete ashing of the body during the burning out, structure maintaining effect, - no dropping of the burnt material in case of plastics, but a partial encrustation of the surface.
For the above-mentioned wide range of use and effects, modified vegetable oil products are necessary which have a permanent material stability and which are suitable for processing without demixing phenomena according to the technological demands.
The usability of brominated vegetable oils as fire-retardant agents is already mentioned in some patent specifications. In the patent specification DD-PS 230 709 (C 08 G
8/32), a method for the production of bromine-containing oil-modified phenol resins is described which can processed into flame-resistant plastic laminated sheet materials.
For this purpose, a partially brominated vegetable oil with a mass ratio oil/bromine of preferably 10 : 1 is used, which corresponds to a degree of bromination of < 0.1. So only a very small part of the double bonds is bonded with bromine. The flameproofness, achieved with these products, for the above-mentioned plastic laminated sheet materials can be estimated as rather small. Here the addition of, for example, a trialkylphosphate as softener or flame-proofing agent is mentioned.
A part of the remained double bonds in the vegetable oil is needed for the reaction with phenolic resins. The plastic laminated sheet materials are treated with heat and with pressure and are hardened by these treatments. As a result, the bromine-containing addition products are embedded in the plastic laminated sheet materials. In case of heat treatment, flameproof ness is achieved. Because of these embedding the effective components in the hardened plastic laminated sheet material, a fast-acting use as flame-proofing agent can not be achieved.
In the patent specification DE-OS 3936 394 (C 08 G 8132), a method for production of modified phenolformaldehyde resols is described. By alkylation of phenol with unsaturated bromine-containing oils, an oil-modified phenolformaldehyde impregnation resin is made.
The resin is used for circuit boards but it is not suitable for a universal use as flame-proofing agent. In this patent specification, as prior art the limited storage stability of a partially brominated tong oil or of other oils are stated as disadvantage. As reason for this, the isomerization of the cis double bonds of a elaeosteric acid which were not converted with bromine into the more stable trans configuration of [3 elaeosteric acid is regarded. After exceeding the saturation concentration, a precipitating from the oil can be obtained already a few days later. By addition of a certain amount of an additional reactive unsaturated hydrocarbon, for example 20 percentages by weight styrene, the storage stability is improved.
However, this addition can, among other things, results in a negative effect on the flameproofing function and can only be compensated with a higher level of bromination.
In the patent specification DE-OS 196 19 421 A1 (C 07 C 59/62), a method for bromination of unsaturated vegetable oils is presented, in which the addition reaction is carried out in the presence of a trialkylphosphate or trialkylphosphonate. In this patent specification is described that 50 - 100 parts by weight for the trialkylphosphate or trialkylphosphonate in proportion to the oil are used and that the reaction temperature for the bromination is up to 84 °C, but preferably is in the range of 25 °C - 50 °C.
However, examinations have demonstrated that stable and homogeneous solutions can not be expected for the whole given area of the mixing ratio and at reaction temperatures over 20 °C.
Reaction temperatures above the boiling temperature of bromine with free feed conditions into the given mixture are not understandable. The proceeding reaction is exothermic. In the reaction center of bromination, it has considerably higher temperatures to reckon with. So the higher temperatures promote not only parallel reactions which, among other things, results in higher acid values of the reaction products, but also changes regarding viscosity and homogeneity of the product. In the mentioned mixing ratios, it comes to demixing phenomena between brominated fatty acids and partially brominated or non-brominated fatty acids. This instable solution ratios are a fundamental disadvantage of the given claims.
It is purpose of the invention to develop a brominated modified unsaturated oil, which regarding its effectiveness in case of a fire forms a surface protection already in a low temperature range and has fungicidal properties and as a result of its technological production process a stable homogeneous material condition.
This problem is solved by the flame-proofing agent according to the desired type with the characteristic features of claim l and the method for production of the flame-proofing agent according to the desired type with the characteristic features of claim 12.
The concerning subclaims indicate advantageous further developments. The use of the flame-proofing agent is described in the claims 18 - 22.
According to the invention, a flame-proofing agent on the basis of a brominated and modified oil is provided which comprises the following components:
a) at least one quick-drying unsaturated oil, b) an essential terpene-containing oil, c) a phosphoric acid ester and d) a boron-containing compound as fungicidal component.
The oils are here at least partially brominated.
A vegetable oil is preferred used as quick-drying vegetable oil. Among these oils, linseed oil, hempseed oil, Iberian dragon head, crambe, and camelina are preferably used.
The share of component a) in the flame-proofing agent is preferably 20 - 60 percentages by weight.
The essential terpene-containing oil is preferred selected among liquid resin, pine oil, fir-needle oil, fennel-seed oil, geranium oil, eucalyptus oil, camphor oil, laurel leaves oil, mustardseed oil, citrus oil, or a mixture from these oils. The share of terpenes in component b) is preferred over 30 percentages by weight. The share of component b) in the flame-proofing agent is preferably 5 - 50 percentages by weight.
As phosphoric acid esters are preferred used trimethylphosphate, triethylphosphate, tributyl-phosphate, triphenylphosphate, tricresylphosphate, trismonochloro isopropyl phosphate, diethylethanephosphonate, dimethylmethanephosphonate, or a mixture from these compounds. The share of component c) in the flame-proofing agent is preferably percentages by weight.
As boron-containing component the mixture preferred comprises a borate with the general formula I
Rn-2Bn02n-I
with n = 1 to n = 12. R is selected among the methyl group, alkali metals, alkaline-earth metals, and disodium octaborate tetrahydrate. The concentration of this boron-containing is preferred from 2 - 30 percentages by weight.
The method for production of flame-proofing agent according to the invention is based on four elementary steps:
I. At first, a mixture made from a quick-drying unsaturated oil, a terpene-containing essential oil, a phosphoric acid ester, and a boron-containing compound is given in a reaction vessel, II. the mixture is cooled at a temperature of less than 20 °C by a cooling device, III. bromine is fed by means of a plunge pipe which is quite close to the stirrer, IV. the temperature is kept under the boiling temperature of bromine during feeding of the bromine.
A unsaturated a vegetable oil is preferred used, for example linseed oil, hempseed oil, Iberian dragon head, crambe, and camelina. As essential terpene-containing oil is preferred used liquid resin, pine oil, fir-needle oil, fennel-seed oil, geranium oil, eucalyptus oil, camphor oil.
laurel leaves oil, mustardseed oil, citrus oil, or a mixture from these oils.
As phosphoric acid esters are preferred used trimethylphosphate, triethylphosphate, tributylphosphate, triphenyl-phosphate, tricresylphosphate, trismonochloro isopropyl phosphate, diethylethane-phosphonate, dimethylmethanephosphonate, or a mixture from these compounds. As boron-containing component is preferred used a borate with the general formula 1 Rn-2Bn~2n-I
with n = 1 to n = 12. R is selected among the methyl group, alkali metals, alkaline-earth metals, and disodium octaborate tetrahydrate.
In the method according to the invention, linseed oil with an iodine value >
180 g iodine /
I00 g, liquid resin, triethylphosphate, and disodium octaborate are given in the reaction vessel, are thoroughly mixed and are cooled at a temperature of 10 °C.
In order to obtain an optimal product, two basic prerequisites are needed in the reactor.
Neither concentration gradient nor temperature gradient are permissible in the reactor, in other words, in order to prevent parallel reactions, mainly substitution reactions forming hydrobromic acid, at no point of the reaction mixture, a surplus of bromine related to the existing free double bonds is permissible. The risk of a surplus of bromine is very high in the feeding position of bromine in the reaction vessel, and so the bromine streaming into the reaction vessel has to be separated fastest possible and distributed evenly.
Because the reaction temperature has a deciding influence on the quality of the reaction product, the developed reaction heat has to carry off the reaction mixture. In order to avoid a boiling away and so pressure impacts in the feed pipe on the feeding point because of the very quickly proceeding exothermic reaction of bromine with linseed oil, also an immediate dispersion and mixing thoroughly within the reactor is needed on the bromine feeding point.
The temperature on the feeding point has to maintain lower than the boiling temperature of bromine (58.8 °C).
A rise in temperature promotes also occurring parallel reactions.
Consequently, in addition to the temperature in the reactor, the dispersion of the incoming stream of bromine and the mixing thoroughly in the reactor play an important role.
The dynamic viscosity of the giving mixture exponentially rises with the degree of bromination, and with rising of the viscosity also the mixing time in the reactor rises by which is impeded the heat transfer from the reactor to the cooling jacket. In order to solve this problem and to come up to the demands to achieve a sufficient mixing thoroughly, the velocity of dosage of bromine is changed in dependence on the viscosity of the product existing in the reactor at the concerning moment. The dosage rate at the beginning of the reaction is essentially determined by the cooling performance of the reactor cooling The dosage rate is reduced with higher degree of bromination. Experiments have indicated that reaction temperatures over 20 °C promote not only parallel reactions of bromine, which are perceptible by a rise of the acid value, but also a demixing of the product.
When, for example, a bromination is carried out at a temperature of 40 °C, the product tends to demixing within a few hours. On the other hand, a product, which was manufactured using identical parts by weight of the basic materials and of bromine but at temperatures <_ 20 °C, has no demixing phenomena. The viscosity of a product which was prepared at 40 °C is clearly lower than the viscosity of a product which was prepared at 20 °C.
The C=C-bonds of the fatty acids in the glyceride unit of the untreated linseed oils are mainly cis(Z)-configurated. Because of the presence of halogens, it is possible that a isomerization takes place to trans(E)-configurated C=C-bonds, as described in the patent specification DE-OS 39 36 394. In case of a addition of bromine onto C=C-bonds finally predominates the product formed by trans addition. Completely brominated linseed oil is a solid which is only sparingly soluble in triethylphosphate. Consequently, brominated linseed oil is precipitated in the form of crystals with a size of 10 pm above a certain concentration of the given substances in triethylphosphate. A colloid-disperse system is formed. When the brominated vegetable oil exist in the triethylphosphate in a high concentration, it does not come to a sedimentation because the rate of sedimentation of the particles goes toward zero. In this way, it is possible to adjust the viscosity of the product by means of a variation of the parts by weight the substances concerned. A product, in which the equilibrium is on the side of the trans(E)-configurated CBr-CBr-bonds, is nearer on the crystalline state than a product with cis(Z)-configurated CBr-CBr-bonds. Thus, this equilibrium influences the viscosity of the product decisively. A transfer and so a displacement of the equilibrium from trans(E)-configurated CBr-CBr-bonds to cis (Z)-configurated CBr-CBr-bonds is possible by energy input, here a rising in temperature. The cis(Z)-configurated double bonds are nearer to the liquid state. So can be explained the decrease of viscosity and of sedimentation of the remaining solid resulting from that. The effect of the decrease of viscosity occurs also in that case when products, which are resistant against sedimentation, a few hours long are subjected to a heat treatment, for example at > 50 °C - 100 °C. A pure linseed oil without additives, in which all C=C-bonds were brominated, has the same effect after heating of several hours at 100 °C.
As a result of heating up over prolonged periods of time, the viscosity is clearly reduced. l~his process can not be reversed by a thermal aftertreatment, for example a quick cooling or melting of the product combined with a subsequent quick cooling. There is no change of the acid value by heating up. Therefore, it can be excluded that the triglyceride unit is disintegrated because the amount of the free fatty acids is constant.
The bromine is fed by means of a plunge pipe into the reactor. This plunge pipe is led vertically into the reactor and is bent at its lower end. The discharge opening is close over the stirring unit in the direction of rotation of the stirrer. This method of feeding achieves that the feed pipe is sucked out by the suction and the underpressure caused by the stirrer, and so a clogging up of the feed pipe with product is prevented. Moreover, this method of feeding of the bromine below the surface of liquid that the bromine can not rise into the atmosphere of the reactor because of its density and the immediately running chemical reactions and so this atmosphere is kept free of bromine vapors.
A reduction of the acid value is preferred carried out by addition of a base.
Because of that the dosage and adding are simplified compared with a deacidification with solids, and in this process no solid are formed in the product which has to be removed by means of a processing aftertreatment such as centrifugation. Here hydroxides, oxides, carbonates, or hydro-carbonates of alkali metals or alkaline-earth metals are preferred used as bases.
According to the invention, the compliance of a narrow temperature range between 10 °C and 20 °C, the reduction of the dosage rate of bromine in dependence on the increasing viscosity, the feeding the bromine near the stirrer below the surface of liquid, and the use of a liquid deacidification agent result in a product with a high material stability.
The flame-proofing agent according to the invention are used as component of insulating materials and fillers or of sealings. These flame-proofing agents can preferred used in chipboards or fiberboards. However, also a use as component of plastics such as polyvinyl chloride (P~1C), polypropylene (PP), polyamide (PA), polyethylene (PE), acrylonitrile-butadiene-styrene copolymer (ABS), or polyurethane (PUR) is possible. In addition, the flame-proofing agent can also be used as component of paints or lacquers in the paint industry and in wood preservatives.
On the basis of the following example the method of preparation of the flame-proofing agent is to be more detailed explained. The subject of the invention is not limited by this example.
Example l:
25.0 kg (27.0 1) linseed oil with a iodine value of 192 g iodine/100 g, S.0 kg (5.8 1) liquid resin, 1.5 kg disodium octaborate, and 16.4 kg (15.5 1) triethylphosphate are given in a reaction vessel. For a better solubility, the mixture can be warmed up to a temperature of 60 °C, mixed intensively during this time and afterwards cooled at a temperature of 10 °C.
The reactor is cooled by a combination of cooling coil and cooling jacket. The total amount of bromine, which is to dose, is 23.4 kg (7.5 l). The degree of bromination of the mixture can be adjusted according to the demands on the flameproofness. The degree of bromination is BG = 0.80 in this example, that is, that 80 % of the most addable amount of bromine are chemically added.
After reaching the start temperature, bromine is dosed. The bromine is fed by means of a plunge pipe the end of which is bent and the mouth of which is arranged right over the stirrer.
This arrangement results in a sucking out the feed pipe for the bromine.
Because the viscosity with increasing degree of bromination exponentially increases and also the mixing time in the reactor with increasing viscosity increases, the dosage rate is adapted these circumstances during the process of bromination. The first dosage rate is. for e~cample.
35 ml/min, and it is reduced in dependence on the degree of bromination in 10 steps to 8.5 ml/min during the bromination. The reduction of the dosage follows an exponential function. Consequently, the plotting of log (dosage rate) over the degree of bromination results in a straight line through the points (BG = 0, dosage rate = 35 ml/min) and (BG = 0.80, dosage rate = 7.3 ml/min).
By this method of chemical reaction engineering, the reactor temperature remains in the range between 10 °C and 18 °C. The product has a acid value of SZ = 4 mg KOH/g, has a dynamic viscosity of ~ = 950 mPa~s (at 20 °C), has a light-orange color, and is stable against demixing.
It is known that native vegetable oils with a high content of unsaturated fatty acids are usable for varied fields by integration of different substances combined with a splitting of the C=C-double bond or with a bonding on the carboxyl group. Particularly, this is right for the so-called quick-drying vegetable oils. The content of unsaturated fatty oils is in case of vegetable oils such as linseed oil, hempseed oil, Iberian dragon head, crambe, and camelina approximately at the same level. The difference is, among other things, the content of different fatty acids and the structure on the triglyceride. With that, also the number of available double bonds as reaction potential is different. For providing selective compositions of unsaturated fatty acids, also mixtures of these native vegetable oils are possible.
In case of linseed oil, for example, there are manifold variations of modification and of optimization because of its properties such as, for example, a high creep ability, a high reactivity, and a high polymerizability, respectively, because of a high content of unsaturated fatty oils with a large number of double bonds. The linseed oil is a ester of glycerine with different long-chain carboxylic acids. In this case, always tree fatty acids are combined by the ester compound and form the triglyceride. The content of unsaturated fatty acids in linseed oil is about 90 %. Native linseed oil has a high flash point (316 - 318 °C).
For development of flame-retardant properties, in addition to the said bromine, boron, and phosphorus compounds, also terpenes, for example in the form of liquid resin or wood oil, are added to the vegetable oil. Liquid resins are classified as essential oils because of its consisting of many different carbon compounds. Mainly, they consist of terpenes (over 60 %) which, on the other hand, consist of CSHg-hydrocarbon units. In correspondence with these units, there are many structures, most frequently monoterpenes with 10 C-atomes including unsaturated, partly doubly or triply unsaturated carbon compounds, for example the terpene alcohol geraniol. These multiple bonds form also a reactive potential for chemical reactions with halogens. A partial halogenation of terpenes can not be precluded. pine oil has polarizing properties which has a positive effect concerning reaction control of a mixture with vegetable oil in case of addition of bromine, for example.
Modified vegetable oil can be used, among other things, as flame-proofing agent. The vegetable oil modified for this use can be used in pure form, for example by spraying on a material, and combined with other substances as additional component and additive. The use of fire-retardant modified vegetable oils is possible in many branches of industry. Above all, in the field of civil engineering, component parts and building materials have to provide with a sufficient flameproofing and by using flame-proofing agents with flame-retardant properties. This is the case, for example, with sealings for building units and with insulations in the building shell. Also in the plastics industry, for PVC products, polypropylene products, and PUR products such as rigid foams or flexible foams, the modified vegetable oil can be used as flame-proofing agent. Here the flame-proofing effect appears, among other things, by an encrustation of the surfaces in case of fire.
Linseed oil, for example, is used in a wide range in the paint industry. By an additional fire-retardant function, the field of application can be extended also to fire protection paints and lacquers.
Further fields of application are, for example, technical textiles and many products made from renewable raw materials, for example chipboards, fiberboards, insulating materials, and fillers. The boron compounds, which are contained in the modified vegetable oil, and the integrated terpenes have in addition to the flame-retardant effect also a fungicidal effect. So there are many possibilities for wood preservation. In particular, the water-soluble boron compounds in products such as chipboards, which are subjected to the external influence of humidity, are because of the bonding with vegetable oil no longer dissolved in the product and washed out. Because of that, these substances maintain their efficiency in these products over a far longer period of time.
The flame-retardant properties can be influenced by the extent of bond formation of the C=C-double bonds of unsaturated fatty acids. The vegetable oil with a high content of unsaturated fatty acids serves in this case as carrier material for the integrated flame-retardant and fungicidal substances. By the complex integration of different flame-retardant substances, different effects in the case of fire are caused. In such a case of fire, because of a release of halogens (bromine) and of the forming HBr, H- and OH-radicals, which are necessary for the combustion process, are caught in the gas phase and converted to HZ and HZO.
This results in a slowing down and a breaking-off of the flame reaction. On the other hand, phosphorus compounds, for example phosphoric acid esters, are active in the condensed phase, support by dehydration of the pyrolizing substrate the carbonizing and reduce so the emission of combustible gases. Moreover, a protective layer, for example in case of plastics, can be formed on the surface. This layer impedes the escaping of combustible decomposition products and can because of its heat-insulating effect prevent an energy input in the product.
The carbonizing of the surface is also promoted by the large C-potential of the fatty acids.
These above-mentioned systems take effect combined with the vegetable oil at temperatures > 200 °C. By an integration of boron compounds, for example disodium octaborate, the effectiveness of flame protection can begin already at temperatures of 90 °C and more.
Particularly, because of that, highly inflammable materials are provided with a protection. The function of the borate is based on the forming of a glass-like protective layer on the surface of a product. By this process, an early thermal barrier is formed and the supply of oxygen is impeded. The water existing in the compound contributes to cooling and to reduction of the flame temperature. In addition to the flame-retardant properties, borates are also effective against insect and fungal attacks.
The flame-proofing agent made from modified vegetable oil is characterized by the following behavior which has appeared in case of utilization in different applications:
- a fire-retardant and fire-slowing down behavior of the material, - immediate going out of the flames in case of removing the body from the source of the fire, - no complete ashing of the body during the burning out, structure maintaining effect, - no dropping of the burnt material in case of plastics, but a partial encrustation of the surface.
For the above-mentioned wide range of use and effects, modified vegetable oil products are necessary which have a permanent material stability and which are suitable for processing without demixing phenomena according to the technological demands.
The usability of brominated vegetable oils as fire-retardant agents is already mentioned in some patent specifications. In the patent specification DD-PS 230 709 (C 08 G
8/32), a method for the production of bromine-containing oil-modified phenol resins is described which can processed into flame-resistant plastic laminated sheet materials.
For this purpose, a partially brominated vegetable oil with a mass ratio oil/bromine of preferably 10 : 1 is used, which corresponds to a degree of bromination of < 0.1. So only a very small part of the double bonds is bonded with bromine. The flameproofness, achieved with these products, for the above-mentioned plastic laminated sheet materials can be estimated as rather small. Here the addition of, for example, a trialkylphosphate as softener or flame-proofing agent is mentioned.
A part of the remained double bonds in the vegetable oil is needed for the reaction with phenolic resins. The plastic laminated sheet materials are treated with heat and with pressure and are hardened by these treatments. As a result, the bromine-containing addition products are embedded in the plastic laminated sheet materials. In case of heat treatment, flameproof ness is achieved. Because of these embedding the effective components in the hardened plastic laminated sheet material, a fast-acting use as flame-proofing agent can not be achieved.
In the patent specification DE-OS 3936 394 (C 08 G 8132), a method for production of modified phenolformaldehyde resols is described. By alkylation of phenol with unsaturated bromine-containing oils, an oil-modified phenolformaldehyde impregnation resin is made.
The resin is used for circuit boards but it is not suitable for a universal use as flame-proofing agent. In this patent specification, as prior art the limited storage stability of a partially brominated tong oil or of other oils are stated as disadvantage. As reason for this, the isomerization of the cis double bonds of a elaeosteric acid which were not converted with bromine into the more stable trans configuration of [3 elaeosteric acid is regarded. After exceeding the saturation concentration, a precipitating from the oil can be obtained already a few days later. By addition of a certain amount of an additional reactive unsaturated hydrocarbon, for example 20 percentages by weight styrene, the storage stability is improved.
However, this addition can, among other things, results in a negative effect on the flameproofing function and can only be compensated with a higher level of bromination.
In the patent specification DE-OS 196 19 421 A1 (C 07 C 59/62), a method for bromination of unsaturated vegetable oils is presented, in which the addition reaction is carried out in the presence of a trialkylphosphate or trialkylphosphonate. In this patent specification is described that 50 - 100 parts by weight for the trialkylphosphate or trialkylphosphonate in proportion to the oil are used and that the reaction temperature for the bromination is up to 84 °C, but preferably is in the range of 25 °C - 50 °C.
However, examinations have demonstrated that stable and homogeneous solutions can not be expected for the whole given area of the mixing ratio and at reaction temperatures over 20 °C.
Reaction temperatures above the boiling temperature of bromine with free feed conditions into the given mixture are not understandable. The proceeding reaction is exothermic. In the reaction center of bromination, it has considerably higher temperatures to reckon with. So the higher temperatures promote not only parallel reactions which, among other things, results in higher acid values of the reaction products, but also changes regarding viscosity and homogeneity of the product. In the mentioned mixing ratios, it comes to demixing phenomena between brominated fatty acids and partially brominated or non-brominated fatty acids. This instable solution ratios are a fundamental disadvantage of the given claims.
It is purpose of the invention to develop a brominated modified unsaturated oil, which regarding its effectiveness in case of a fire forms a surface protection already in a low temperature range and has fungicidal properties and as a result of its technological production process a stable homogeneous material condition.
This problem is solved by the flame-proofing agent according to the desired type with the characteristic features of claim l and the method for production of the flame-proofing agent according to the desired type with the characteristic features of claim 12.
The concerning subclaims indicate advantageous further developments. The use of the flame-proofing agent is described in the claims 18 - 22.
According to the invention, a flame-proofing agent on the basis of a brominated and modified oil is provided which comprises the following components:
a) at least one quick-drying unsaturated oil, b) an essential terpene-containing oil, c) a phosphoric acid ester and d) a boron-containing compound as fungicidal component.
The oils are here at least partially brominated.
A vegetable oil is preferred used as quick-drying vegetable oil. Among these oils, linseed oil, hempseed oil, Iberian dragon head, crambe, and camelina are preferably used.
The share of component a) in the flame-proofing agent is preferably 20 - 60 percentages by weight.
The essential terpene-containing oil is preferred selected among liquid resin, pine oil, fir-needle oil, fennel-seed oil, geranium oil, eucalyptus oil, camphor oil, laurel leaves oil, mustardseed oil, citrus oil, or a mixture from these oils. The share of terpenes in component b) is preferred over 30 percentages by weight. The share of component b) in the flame-proofing agent is preferably 5 - 50 percentages by weight.
As phosphoric acid esters are preferred used trimethylphosphate, triethylphosphate, tributyl-phosphate, triphenylphosphate, tricresylphosphate, trismonochloro isopropyl phosphate, diethylethanephosphonate, dimethylmethanephosphonate, or a mixture from these compounds. The share of component c) in the flame-proofing agent is preferably percentages by weight.
As boron-containing component the mixture preferred comprises a borate with the general formula I
Rn-2Bn02n-I
with n = 1 to n = 12. R is selected among the methyl group, alkali metals, alkaline-earth metals, and disodium octaborate tetrahydrate. The concentration of this boron-containing is preferred from 2 - 30 percentages by weight.
The method for production of flame-proofing agent according to the invention is based on four elementary steps:
I. At first, a mixture made from a quick-drying unsaturated oil, a terpene-containing essential oil, a phosphoric acid ester, and a boron-containing compound is given in a reaction vessel, II. the mixture is cooled at a temperature of less than 20 °C by a cooling device, III. bromine is fed by means of a plunge pipe which is quite close to the stirrer, IV. the temperature is kept under the boiling temperature of bromine during feeding of the bromine.
A unsaturated a vegetable oil is preferred used, for example linseed oil, hempseed oil, Iberian dragon head, crambe, and camelina. As essential terpene-containing oil is preferred used liquid resin, pine oil, fir-needle oil, fennel-seed oil, geranium oil, eucalyptus oil, camphor oil.
laurel leaves oil, mustardseed oil, citrus oil, or a mixture from these oils.
As phosphoric acid esters are preferred used trimethylphosphate, triethylphosphate, tributylphosphate, triphenyl-phosphate, tricresylphosphate, trismonochloro isopropyl phosphate, diethylethane-phosphonate, dimethylmethanephosphonate, or a mixture from these compounds. As boron-containing component is preferred used a borate with the general formula 1 Rn-2Bn~2n-I
with n = 1 to n = 12. R is selected among the methyl group, alkali metals, alkaline-earth metals, and disodium octaborate tetrahydrate.
In the method according to the invention, linseed oil with an iodine value >
180 g iodine /
I00 g, liquid resin, triethylphosphate, and disodium octaborate are given in the reaction vessel, are thoroughly mixed and are cooled at a temperature of 10 °C.
In order to obtain an optimal product, two basic prerequisites are needed in the reactor.
Neither concentration gradient nor temperature gradient are permissible in the reactor, in other words, in order to prevent parallel reactions, mainly substitution reactions forming hydrobromic acid, at no point of the reaction mixture, a surplus of bromine related to the existing free double bonds is permissible. The risk of a surplus of bromine is very high in the feeding position of bromine in the reaction vessel, and so the bromine streaming into the reaction vessel has to be separated fastest possible and distributed evenly.
Because the reaction temperature has a deciding influence on the quality of the reaction product, the developed reaction heat has to carry off the reaction mixture. In order to avoid a boiling away and so pressure impacts in the feed pipe on the feeding point because of the very quickly proceeding exothermic reaction of bromine with linseed oil, also an immediate dispersion and mixing thoroughly within the reactor is needed on the bromine feeding point.
The temperature on the feeding point has to maintain lower than the boiling temperature of bromine (58.8 °C).
A rise in temperature promotes also occurring parallel reactions.
Consequently, in addition to the temperature in the reactor, the dispersion of the incoming stream of bromine and the mixing thoroughly in the reactor play an important role.
The dynamic viscosity of the giving mixture exponentially rises with the degree of bromination, and with rising of the viscosity also the mixing time in the reactor rises by which is impeded the heat transfer from the reactor to the cooling jacket. In order to solve this problem and to come up to the demands to achieve a sufficient mixing thoroughly, the velocity of dosage of bromine is changed in dependence on the viscosity of the product existing in the reactor at the concerning moment. The dosage rate at the beginning of the reaction is essentially determined by the cooling performance of the reactor cooling The dosage rate is reduced with higher degree of bromination. Experiments have indicated that reaction temperatures over 20 °C promote not only parallel reactions of bromine, which are perceptible by a rise of the acid value, but also a demixing of the product.
When, for example, a bromination is carried out at a temperature of 40 °C, the product tends to demixing within a few hours. On the other hand, a product, which was manufactured using identical parts by weight of the basic materials and of bromine but at temperatures <_ 20 °C, has no demixing phenomena. The viscosity of a product which was prepared at 40 °C is clearly lower than the viscosity of a product which was prepared at 20 °C.
The C=C-bonds of the fatty acids in the glyceride unit of the untreated linseed oils are mainly cis(Z)-configurated. Because of the presence of halogens, it is possible that a isomerization takes place to trans(E)-configurated C=C-bonds, as described in the patent specification DE-OS 39 36 394. In case of a addition of bromine onto C=C-bonds finally predominates the product formed by trans addition. Completely brominated linseed oil is a solid which is only sparingly soluble in triethylphosphate. Consequently, brominated linseed oil is precipitated in the form of crystals with a size of 10 pm above a certain concentration of the given substances in triethylphosphate. A colloid-disperse system is formed. When the brominated vegetable oil exist in the triethylphosphate in a high concentration, it does not come to a sedimentation because the rate of sedimentation of the particles goes toward zero. In this way, it is possible to adjust the viscosity of the product by means of a variation of the parts by weight the substances concerned. A product, in which the equilibrium is on the side of the trans(E)-configurated CBr-CBr-bonds, is nearer on the crystalline state than a product with cis(Z)-configurated CBr-CBr-bonds. Thus, this equilibrium influences the viscosity of the product decisively. A transfer and so a displacement of the equilibrium from trans(E)-configurated CBr-CBr-bonds to cis (Z)-configurated CBr-CBr-bonds is possible by energy input, here a rising in temperature. The cis(Z)-configurated double bonds are nearer to the liquid state. So can be explained the decrease of viscosity and of sedimentation of the remaining solid resulting from that. The effect of the decrease of viscosity occurs also in that case when products, which are resistant against sedimentation, a few hours long are subjected to a heat treatment, for example at > 50 °C - 100 °C. A pure linseed oil without additives, in which all C=C-bonds were brominated, has the same effect after heating of several hours at 100 °C.
As a result of heating up over prolonged periods of time, the viscosity is clearly reduced. l~his process can not be reversed by a thermal aftertreatment, for example a quick cooling or melting of the product combined with a subsequent quick cooling. There is no change of the acid value by heating up. Therefore, it can be excluded that the triglyceride unit is disintegrated because the amount of the free fatty acids is constant.
The bromine is fed by means of a plunge pipe into the reactor. This plunge pipe is led vertically into the reactor and is bent at its lower end. The discharge opening is close over the stirring unit in the direction of rotation of the stirrer. This method of feeding achieves that the feed pipe is sucked out by the suction and the underpressure caused by the stirrer, and so a clogging up of the feed pipe with product is prevented. Moreover, this method of feeding of the bromine below the surface of liquid that the bromine can not rise into the atmosphere of the reactor because of its density and the immediately running chemical reactions and so this atmosphere is kept free of bromine vapors.
A reduction of the acid value is preferred carried out by addition of a base.
Because of that the dosage and adding are simplified compared with a deacidification with solids, and in this process no solid are formed in the product which has to be removed by means of a processing aftertreatment such as centrifugation. Here hydroxides, oxides, carbonates, or hydro-carbonates of alkali metals or alkaline-earth metals are preferred used as bases.
According to the invention, the compliance of a narrow temperature range between 10 °C and 20 °C, the reduction of the dosage rate of bromine in dependence on the increasing viscosity, the feeding the bromine near the stirrer below the surface of liquid, and the use of a liquid deacidification agent result in a product with a high material stability.
The flame-proofing agent according to the invention are used as component of insulating materials and fillers or of sealings. These flame-proofing agents can preferred used in chipboards or fiberboards. However, also a use as component of plastics such as polyvinyl chloride (P~1C), polypropylene (PP), polyamide (PA), polyethylene (PE), acrylonitrile-butadiene-styrene copolymer (ABS), or polyurethane (PUR) is possible. In addition, the flame-proofing agent can also be used as component of paints or lacquers in the paint industry and in wood preservatives.
On the basis of the following example the method of preparation of the flame-proofing agent is to be more detailed explained. The subject of the invention is not limited by this example.
Example l:
25.0 kg (27.0 1) linseed oil with a iodine value of 192 g iodine/100 g, S.0 kg (5.8 1) liquid resin, 1.5 kg disodium octaborate, and 16.4 kg (15.5 1) triethylphosphate are given in a reaction vessel. For a better solubility, the mixture can be warmed up to a temperature of 60 °C, mixed intensively during this time and afterwards cooled at a temperature of 10 °C.
The reactor is cooled by a combination of cooling coil and cooling jacket. The total amount of bromine, which is to dose, is 23.4 kg (7.5 l). The degree of bromination of the mixture can be adjusted according to the demands on the flameproofness. The degree of bromination is BG = 0.80 in this example, that is, that 80 % of the most addable amount of bromine are chemically added.
After reaching the start temperature, bromine is dosed. The bromine is fed by means of a plunge pipe the end of which is bent and the mouth of which is arranged right over the stirrer.
This arrangement results in a sucking out the feed pipe for the bromine.
Because the viscosity with increasing degree of bromination exponentially increases and also the mixing time in the reactor with increasing viscosity increases, the dosage rate is adapted these circumstances during the process of bromination. The first dosage rate is. for e~cample.
35 ml/min, and it is reduced in dependence on the degree of bromination in 10 steps to 8.5 ml/min during the bromination. The reduction of the dosage follows an exponential function. Consequently, the plotting of log (dosage rate) over the degree of bromination results in a straight line through the points (BG = 0, dosage rate = 35 ml/min) and (BG = 0.80, dosage rate = 7.3 ml/min).
By this method of chemical reaction engineering, the reactor temperature remains in the range between 10 °C and 18 °C. The product has a acid value of SZ = 4 mg KOH/g, has a dynamic viscosity of ~ = 950 mPa~s (at 20 °C), has a light-orange color, and is stable against demixing.
Claims (15)
1. Flame-proofing agent on the basis of a brominated and modified oil made from a mixture comprising a) at least one quick-drying unsaturated oil, b) an essential terpene-containing oil, c) a phosphoric acid ester and d) a boron-containing compound as fungicidal component, where the oils are at least partially brominated.
2. Flame-proofing agent according to claim 1, characterized by the fact that the component a) is a vegetable oil.
3. Flame-proofing agent according to at least one of the preceding claims, characterized by the fact that the component a) is selected from the group linseed oil, hempseed oil, Iberian dragon head, crambe, and camelina.
4. Flame-proofing agent according to at least one of the preceding claims, characterized by the fact that the share of the component a) is 20 - 30 percentages by weight.
5. Flame-proofing agent according to at least one of the preceding claims, characterized by the fact that the component b) is selected from liquid resin, pine oil, fir-needle oil, fennel-seed oil, geranium oil, eucalyptus oil, camphor oil, laurel leaves oil, mustardseed oil, citrus oil, or a mixture from these oils.
6. Flame-proofing agent according to at least one of the preceding claims, characterized by the fact that the share of the component b) is more than 30 percentages by weight.
7. Flame-proofing agent according to at least one of the preceding claims, characterized by the fact that the share of the component b) is between 5 and 50 percentages by weight.
8. Flame-proofing agent according to at least one of the preceding claims, characterized by the fact that the component c) is selected from the group trimethylphosphate, triethylphosphate, tributylphosphate, tricresylphosphate, trismonochloro isopropyl phosphate, diethylethanphosphonate, dimethylmethanphosphonate, or a mixture from these substances.
9. Flame-proofing agent according to at least one of the preceding claims, characterized by the fact that the share of the component c) is between 5 and 30 percentages by weight.
10. Flame-proofing agent according to at least one of the preceding claims, characterized by the fact that the component d) is a borate with the general formula I
Rn-2Bn O2n-1 with n = 1 to n = 12 and R = methyl group, alkali metal, alkaline-earth metal, and/or disodium octaborate tetrahydrate.
Rn-2Bn O2n-1 with n = 1 to n = 12 and R = methyl group, alkali metal, alkaline-earth metal, and/or disodium octaborate tetrahydrate.
11. Flame-proofing agent according to at least one of the preceding claims, characterized by the fact that the share of the component d) in the flame-proofing agent is between 2 and 30 percentages by weight.
12. Method for preparation of a flame-proofing agent in which I. a mixture made from a quick-drying unsaturated oil, an essential terpene-containing oil, a phosphoric acid ester, and a boron-containing compound is given in a reaction vessel, II. the mixture is cooled by means of a cooling device at a temperature of less than 20 °C, III. bromine is fed by means of a plunge pipe near to a stirring system and IV. the temperature of the mixture is maintained below the boiling temperature of bromine by cooling during the feeding bromine.
13. Method according to claim 12 characterized by the fact that a mixture comprising a) a vegetable oil as unsaturated oil, for example linseed oil, hempseed oil, Iberian dragon head, crambe, and/or camelina, b) as essential oil for example liquid resin, pine oil, fir-needle oil, fennel-seed oil, geranium oil, eucalyptus oil, camphor oil, laurel leaves oil, mustardseed oil, citrus oil.
or a mixture from these oils.
c) as phosphorous acid ester for example trimethylphosphate, triethylphosphate, tributylphosphate, tricresylphosphate, trismonochloro isopropyl phosphate, diethylethanphosphonate, dimethylmethanphosphonate, or a mixture from these substances.
d) as boron-containing compound for example a borate with the general formula I
Rn-2BnO2n-1 with n = 1 to n = 12 and R = methyl group, alkali metal, alkaline-earth metal, and/or disodium octaborate tetrahydrate.
or a mixture from these oils.
c) as phosphorous acid ester for example trimethylphosphate, triethylphosphate, tributylphosphate, tricresylphosphate, trismonochloro isopropyl phosphate, diethylethanphosphonate, dimethylmethanphosphonate, or a mixture from these substances.
d) as boron-containing compound for example a borate with the general formula I
Rn-2BnO2n-1 with n = 1 to n = 12 and R = methyl group, alkali metal, alkaline-earth metal, and/or disodium octaborate tetrahydrate.
14. Method according to at least one of the claims 12 or 13 characterized by the fact that the viscosity is adjusted by the mass ratio of mixture and added bromine.
15. Method according to at least one of the claims 12 to 14 characterized by the fact that the plunge pipe, which is bent in the direction of rotation of the stirrer, is dipped into the mixture directly over the stirrer blades.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/DE2002/002925 WO2004016712A1 (en) | 2002-08-02 | 2002-08-02 | Flame-proofing agent and means for the production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2501371A1 true CA2501371A1 (en) | 2004-02-26 |
Family
ID=31723991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002501371A Abandoned CA2501371A1 (en) | 2002-08-02 | 2002-08-02 | Flame-proofing agent and means for the production thereof |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1537191A1 (en) |
| AU (1) | AU2002320942A1 (en) |
| CA (1) | CA2501371A1 (en) |
| DE (1) | DE10297806D2 (en) |
| WO (1) | WO2004016712A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI312795B (en) * | 2002-10-29 | 2009-08-01 | Dai Ichi Kogyo Seiyaku Co Ltd | Flame retardants for plastics |
| EP2207841B1 (en) * | 2007-11-02 | 2011-09-14 | Dow Global Technologies LLC | Extruded polymer foams containing brominated fatty acid-based flame retardant additives |
| DE102013113463B4 (en) | 2013-12-04 | 2017-06-22 | Strohlosproduktentwicklung Gmbh | Powder with fire protection properties |
| PL240079B1 (en) | 2017-10-31 | 2022-02-14 | Wojskowa Akad Tech | Smectic material with high photochemical stability and wide temperature range of monolayer smectic phase A (SmA1) and the device that uses such material |
| US10590152B2 (en) | 2017-12-14 | 2020-03-17 | International Business Machines Corporation | Pinene-based flame retardant compounds |
| CN118660948A (en) * | 2022-02-25 | 2024-09-17 | Swimc有限公司 | Wood treatment comprising phosphate esters |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD230709A3 (en) * | 1983-12-30 | 1985-12-11 | Adw D Ddr Zi F Org Chemie | METHOD FOR THE PRODUCTION OF BROMINOUS OIL-MODIFIED PHENOL RESINS FOR FLAME-RESISTANT PROSPECTS |
| DE3610374A1 (en) * | 1986-03-27 | 1987-10-01 | Desowag Materialschutz Gmbh | WOOD PRESERVATIVES |
| DD280534A1 (en) * | 1989-03-10 | 1990-07-11 | Sprela Werke Spremberg Veb | METHOD FOR PRODUCING MODIFIED PF RESOLES |
| US5540762A (en) * | 1995-01-13 | 1996-07-30 | Mischutin; Vladimir | Flame retardants for linseed oil formulations and applications |
| DE19619421A1 (en) * | 1996-05-14 | 1997-11-20 | Rathor Ag | Process for the bromination of natural unsaturated oils |
| DE10020957A1 (en) * | 2000-04-28 | 2001-10-31 | Jobeck Gmbh | Biological wood preservation solution based on herbal extracts |
| DE10123584C2 (en) * | 2001-05-15 | 2003-09-11 | Hawo Oekologische Rohstoffe Gm | Flame retardants and process for their manufacture |
-
2002
- 2002-08-02 DE DE10297806T patent/DE10297806D2/en not_active Expired - Fee Related
- 2002-08-02 EP EP02754505A patent/EP1537191A1/en not_active Withdrawn
- 2002-08-02 CA CA002501371A patent/CA2501371A1/en not_active Abandoned
- 2002-08-02 WO PCT/DE2002/002925 patent/WO2004016712A1/en not_active Application Discontinuation
- 2002-08-02 AU AU2002320942A patent/AU2002320942A1/en not_active Abandoned
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| Publication number | Publication date |
|---|---|
| WO2004016712A1 (en) | 2004-02-26 |
| EP1537191A1 (en) | 2005-06-08 |
| AU2002320942A1 (en) | 2004-03-03 |
| DE10297806D2 (en) | 2005-06-30 |
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