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    • 专利摘要:
    oligomeric mixture, process for the preparation of an oligomeric mixture, use of an oligomeric mixture, preparations of flame protection agents, prepared polyurethanes resistant to flame propagation, process for the production of polyurethanes with flameproof finish, molded parts, lacquers, adhesives , coatings, adhesion promoters and polyurethane based fibers and use of polyurethanes the present invention refers to oligomeric misrures free of poly halogen (alkylene phosphates), their production and use as a flame protection agent, as well as polyurechanes with fireproof finish containing halogen free oligomeric mixtures as flame protection agents.
    公开号:BR102013018242B1
    申请号:R102013018242
    申请日:2013-07-17
    公开日:2020-05-05
    发明作者:Tebbe Heiko；Hansel Jan-Gerd
    申请人:Lanxess Deutschland Gmbh；
    IPC主号:
    专利说明:

    OLIGOMERIC MIXTURE, PROCESS FOR THE PREPARATION OF AN OLIGOMERIC MIXTURE, USE OF AN OLIGOMERIC MIXTURE, PREPARATIONS OF FLAME PROTECTIVE AGENTS, POLYURETHANE PREPARED RESISTANCE TO FLAME PROPAGATION, PROCESS FOR 5 PRODUCTION OF POLYURETHANE, POLYURETHANE ADHESIVES, COATINGS, ADHESION PROMOTERS AND FIBERS BASED ON POLYURETHANES AND USE OF POLYURETHANES
    The present invention relates to new oligomeric mixtures of halogen-free poly (alkylene phosphates) and their use for flame protection preparation, in particular polyurethanes, as well as polyurethanes prepared in this way and polyurethane foams and processes for their preparation .
    Polyurethanes are used in many areas, such as furniture, mattresses, transportation, electrical, construction and technical insulation as synthetic materials. In order to obtain high flame protection specifications, as required for materials, among others, for the internal finishing area of automobiles, trains and planes, as well as the insulation of buildings, polyurethanes should, as a rule, be prepared. with flame protection agents. For this purpose, countless different flame protection agents are known and commercially available. However, its use is opposed to several considerable technical problems or toxicological considerations.
    Thus, when using solid flame protection agents, such as, for example, melamine, ammonium polyphosphate and ammonium sulphate, technical dosing problems occur, which often make modifications to the processing systems, that is, remodeling and expensive adjustments.
    Phosphate flame retardants
    2/36 tris (chloroethyl) (molar weight 285 g / mol) and tris phosphate (chloroisopropyl) (molar weight 327 g / mol) frequently used, represent easily dosable liquids. However, in recent times, there is an increasing demand for open cell soft polyurethane foam systems for the interior finish of automobiles, of which gaseous emissions (Volatile Organic Compounds, VOC) and mainly condensable emissions (fogging) these foams should be as low as possible. The liquids mentioned above, due to their relatively low molar weights and the resulting very high volatility, no longer meets those specifications.
    Condensable emission is understood as the undesired condensation of volatile components · evaporated from the internal finish of automobiles in glass, in particular on the windshield. This occurrence can be quantitatively assessed in accordance with DIN 75.201.
    Tris phosphate (2,3-dichloroisopropyl), also liquid, has a molar weight of 431 g / mol, so low a volatility that, like this, it is possible to obtain acceptable condensable emission values. However, from an ecotoxicological point of view, as well as based on better side effects of fires with regard to flue gas density and flue gas toxicity, halogen-free flame protection systems are often preferred. Also for technical application reasons, halogen-containing flame retardants are considered problematic. Thus, for example, when halogen-containing flame protection agents are used, 30 strong corrosion phenomena are observed in the parts of equipment used for flame coating. This can be attributed to the halogen acid emissions that occur in the flame coating of polyurethane foams that
    3/36 contain halogen.
    A flame coating is a process for bonding textiles and foams, in which one side of a foam strip is melted with the aid of a flame and, in a direct connection, is compressed with a textile strip.
    The halogen-free liquid flame retardant systems known to date, such as, for example, triethyl phosphate or other alkyl or aryl phosphates, such as, for example, diphenylcresyl 10 phosphate, are only satisfactory the specifications mentioned above regarding low VOC or low condensable emissions are insufficient or do not show a satisfactory flame protection effect.
    Solutions in the sense of low contributions to the 15 condensable emissions, offer oligomeric phosphoric acid esters. These have long been known, for example, to US 2,952,666 or US 3,228,998. The disadvantage of the substances described in US 2,952,666 is their inherent high content of HO — P (= 0) (OR) 2 acid groups. Substances 20 described in US 3,228,998 have two hydroxyl groups per polymeric chain. Both acids and a high content of hydroxyl groups are undesirable in the production of polyurethanes, since they disrupt isocyanate reactions. For example, the quality of a polyurethane foam depends on the adjustment of the catalyst system for the competitive reactions of polyisocyanates with polyols and optionally water. If, now, another reactive component is introduced with a flame protection agent with hydroxyl groups, then production failures can occur, such as, for example, shrinkage or cracks in the foam. The catalyst system often made up of several components must be adjusted, then considering stabilizers, blowing agents, regulators
    4/36.
    cell phones and optionally other components, to the reactivity of the flame protection agent. This adjustment makes time-consuming development work necessary. In addition, an additional amount of polyisocyanate should be used, which is undesirable for economic reasons.
    In addition, for example, from US 3,767,732 and US 4,382,042, a class of oligomeric phosphoric acid esters is known, which have ethylene bridges and whose structure can be described by the general formula
    / 0 L R '_ln
    In this formula, for example, the substituents R represent alkyl radicals, R 'represents H or alkyl radicals and the index n represents an integer. These poly (ethylene phosphates), due to their good efficiency and low contributions to condensable emissions, have obtained commercial importance. Thus, for example, the product of the above formula with R = ethyl and R '= H, is marketed by the brand Fyrol® PNX through ICL-IP. WO 2002/079315 discloses compositions of flame protection agents, which use that active substance as a flame protection agent.
    However, these known poly (ethylene phosphates) generally have the following disadvantages:
    - high viscosity. The high viscosity, for example, of 1241 mPas Fyrol® PNX at 23 ° C (see comparative examples) makes processing difficult.
    - Formation of secondary components. The use of the ethylene bridge in poly (ethylene phosphates) brings with it, that in its preparation cyclic phosphates, of five
    5/36 members. These are contained as secondary components in poly (ethylene phosphates) and lead to susceptibility to unwanted hydrolysis and acid formation. This problem has been known for a long time and there are numerous tests for resolution (compare, for example, US 3,891,727, US 3,959,415, US 3,959,414, US 4,012,463 and EP-A 0.448,159). According to these resolution suggestions, however, the avoidance or reduction of cyclic phosphates, of five unwanted members always leads to additional expenses in the preparation of poly (ethylene phosphates).
    - Limited use possibilities. In the production of polyurethanes, polyols of different structural classes are used. Particularly important classes are polyether polyols, i.e., polyethers containing hydroxyl groups and polyester polyols, i.e., polyesters containing hydroxyl groups. It turns out, that the known poly (ethylene phosphates), in fact, can be well processed in combination with polyether polyols, however, in combination with polyester polyols, useful foams are not obtained (see comparative examples). This fact represents a serious limitation on the applicability of poly (ethylene phosphates), since machines, which are used for the production of polyether foams using poly (ethylene phosphates), due to the danger of cross contamination, cannot be used either. for the production of polyester foams, even if in this case, other flame protection agents must be used. Producers, who want to produce polyether foams, as well as polyester foams, must therefore, when using poly (ethylene phosphates) must censor not only a dual logistics for two flame protection agents, but also a double machinery.
    WO 96/06885 also deals with the problem of condensable emissions, where phosphoric acid esters in
    6/36 chain form with 2 to 11 groups of phosphoric acid esters are recommended as flame protection agents for polyurethane foams. Oligomeric mixtures are not mentioned there. The phosphoric acid esters of WO 96/06885 preferably used contain aryl groups, for example, phenyl groups. Such aryl phosphates, due to the inevitable release of health-damaging phenols under conditions of use, for example, are no longer accepted in the automobile industry.
    The aim of the present invention was, therefore, to make halogen-free flame protection agents available to polyurethanes, which overcome the mentioned disadvantages of the prior art and which can be processed, in particular, with both polyether polyols and also with polyester polyols and contribute as little as possible to condensable emissions.
    This objective is solved by flame protection agents, which contain certain oligomeric mixtures of halogen-free poly (alkylene phosphates).
    The purpose of the present invention is, therefore, oligomeric mixtures, characterized by the fact that they contain at least three poly (alkylene phosphates) of the formula (I)
    Οχ 4
    R
    2/0
    R
    3 / O
    R Jn in which
    R 1 , R 2 , a Ci ~ radical to a Ci ~ and R 4 radical independently,
    Cg-alkyl chain to C4-alkoxyethyl
    R 3 represent each straight or branched or straight or branched chain,
    A represents a C 2 o-alkylene radical of
    7/36 straight, branched and / or cyclic chain or
    A represents a radical of the formula -CH 2 -CH = CH = CH 2 , a radical of the formula CH 2 -C = C-CH 2 , a radical of the formula CHR 5 CHR 6 - (O-CHR 7 -CHR 8 ) a - a radical of formula -CHR 5 -CHR 6 -S (0) B5 CHR 7 -CHR 8 - , or a radical of the formula - (CHR 5 -CHR 6 -O) CR 9- (O-CHR 7 CHR 8) d-, where a represents an integer from 1 to 5, b represents an integer from 0 to 2, c and independently, represent an integer from 1 to 5,
    R 5 , R 6 , R 7 and R 8 represent a radical of the formula CH 2 -CH = CH-CH 2 -, a radical of the formula -CH 2 -C = C-CH 2 -, a 1,2 - phenylene radical , a 1,3 - phenylene radical, a 1,4-phenylene radical or a radical of the formula (II)
    represents a radical of the formula (III)

    (III), represents a radical of formula (IV)
    or represents (IV) a radical of the formula -C (= O) -R 12 C (= O) -,
    8/36 where
    R 10 and R 11 independently represent each H or Ci- to C 4 -alkyl or R 10 and R 11 together represent a ring with 4 to 8 carbon atoms optionally substituted by alkyl,
    R 12 represents a straight-chain, branched and / or cyclic C2- to Cg-alkylene radical, a 1,2-phenylene radical, a 1,3-phenylene radical or a 1,4-phenylene radical and
    n represents an integer from 0 to 100, with the proviso that the at least three poly (alkylene phosphates) of the formula (I) are distinguished from each other at least in the number n of the repetition units and the average value of the number of the repeat units at least three poly (alkylene phosphates) of formula (I) is greater than 1.10 and less than 2.00.
    Preferably, R 1 , R 2 , R 3 θ R 4 are the same and represent either ethyl, n-propyl, iso-propyl, n-butyl, isobutyl or n-butoxyethyl. Preferably, A is a radical
    C 4 - to C 6 -straight chain alkylene.
    Furthermore, preferably A represents a radical of formula (II), in which R 10 and R 11 are equal and represent methyl or represents a radical of formulas (V), (VI) or (VII)
    H 2 H 2Í ^ Η ^ Η 2
    II 2
    H, C. / CH 2 h 2 h 2 h 2 h 2 (V)
    H, C. , CH 2 2 CH 2 (VI)
    H 2 h 2
    C CH 2
    II 2
    H, C. /Ç. x
    CHC h 2 h 2 (VII)
    In the same way
    CHR 5 -CHR 6 - (O-CHR 7 -CHR 8 ) a -, R 6 , R 7 and R 8 are equal
    A represents where a is one and preferably represents number 1 to 2 and R 5
    H or represent a
    9/36 radical of the formula - (CHR 5 -CHR 6 -O) CR 9 - (O-CHR 7 -CHR 8 ) d-, in which c and d independently, represent an integer from 1 to 2, R 9 represents a radical of formula (II), where R 10 and R 11 are equal and represent methyl.
    Preference is given to oligomeric mixtures containing at least three poly (alkylene phosphates) of the formula (I), one in which
    R 1 , R 2 , R 3 and R 4 independently, represent each linear or branched or C 1- to C 4 -alkyl radical of C 1- or C 2 -alkoxyethyl radical,
    A represents a radical of the radical of the formula -CH 2 -C = C-CH 2 -, a
    CHR 5 -CHR 6 - (O-CHR 7 -CHR 8 ) aS (O) b-CHR 7 -CHR 8 -, or a (O-CHR 7 -CHR 8 ) d-, formula -CH2-CH = CH- CH2, a radical of the formula -CHR 5 -CHR 6 formula radical, a radical of the formula - (CHR 5 -CHR 6 -O) -R 9 where C is an integer of 1 to 5, an integer of 0 to 2, represents d independently, represent an integer of 1
    R 5 , to 5,
    R 6, R 7 and R 8 independently represent H or methyl, formula -CH2-CH _ _ CH-CH 2,
    R 9 a radical of the formula -CH2-CsC-CH 2 -, a 1,2-phenylene radical, a 1,4-phenylene radical or one represents a radical of a 1,3-phenylene radical, radical of the formula (II)
    II) a radical of formula (III)
    10/36 h 2
    H 2
    C CH, H, CC
    II 2 2 II
    H, C. .C. / CH, c hVhc H 2 r io Z R 11 H 2 a radical of the formula (IV)
    (IV) in
    R 10 which and R 11 each independently represent H or
    Ci- or C 2 -alkyl,
    R 12 represents a straight or branched C 2 - to C 6 -alkylene alkylene radical, a 1,2-phenylene radical, 1,3-phenylene radical, a 1,4-phenylene radical and n represents an integer from 0 to 100.
    Very oligomeric preference containing at least alkylene) of formula (I) is given, in which
    R 1 , R 2 , R 3 and R 4 represent a C 1 to C 4 -alkyl radical of a particular to mixtures three poly (phosphates of each, independently, linear or branched or a butoxyethyl radical,
    A represents a radical
    C 4 - to C 6 -straight chain alkylene or
    A represents a radical of formula -CH 2 _ CH = CH-CH 2, a radical of formula of formula -CHR 5 -CHR 6 a radical of formula -CH2-C = C-CH2, CHR 5 -CHR 6 - (O -CHR 7 -CHR 8 ) a-, a radical
    S (O) b _ CHR 7 -CHR 8 -, or represents a radical of the formula - (CHR CHR 6 -O) cR 9 - (O-CHR 7 -CHR 8 ) d-, in which a represents an integer of 1 to 5,
    11/36 b represents an integer from 0 to 2, c and d each independently represent an integer from 1 to 5,
    R 5 , R 6 , R 7 and R 8 independently represent H or methyl,
    R 9 represents a radical of the formula -CH 2 -CH = CH-CH 2 -, a radical of the formula -CH 2 -C = C-CH 2 -, a 1,2-phenylene radical, a 1,3-phenylene radical , a 1,4-phenylene radical or a radical of formula (II)
    a radical of the formula (III)
    (III), a radical of formula (IV)
    (IV) or a radical of the formula -C (= 0) -R 12 -C (-0) in which
    R 10 and R n each independently represent H or
    Ci- or C 2 -alkyl,
    R 12 represents a straight or branched chain C 2 - to Cg-alkylene, a 1,2-phenylene radical, a 1,3-phenylene radical, a 1,4-phenylene radical and n represents an integer from 0 to 100 .
    12/36
    Particularly preferred are oligomeric mixtures containing at least three poly (alkylene phosphates) of the formula (I), in which
    R 1 , R 2 , R 3 and R 4 are the same and represent ethyl, npropyl, iso-propyl, n-butyl, iso-butyl or n-butoxyethyl,
    A represents a straight chain C1- to Cg-alkylene radical or
    A represents a radical of the formulas h 2 h 2 h 2
    C H CH,
    II 2 H 2 C. / CH 2 o H 2 (V)
    H, Ch / CH 2 h 2 (VI) or h 2 h 2
    C ^ H / C ch 2 c ^ ch 2
    I 2 h 2 h 2 (VII) or
    A represents a -CHR 5 -CHR 6 - (O-CHR 7 -CHR 8) a -, wherein a is an integer from 1 to 2 and R 5, R 6, R and R are
    6 equal and represent H or represent a radical - (CHR -CHR O) C -R 9 - (O-CHR 7 -CHR 8 ) d -, in which c and d represent, independently, an integer from 1 to 2, R, R, R and R are equal and represent H, R 9 represents a radical of formula (II), in which R 10 and R 11 are equal and represent methyl and
    n represents an integer from 0 to 20.
    Preferably, the oligomeric mixtures according to the invention and the poly (alkylene phosphates) contained therein are free of halogen. The term halogen-free in the sense of the present invention means that
    13/36 poly (alkylene phosphates) of the formula (I) do not contain the elements fluorine, chlorine, bromine and / or iodine and that the oligomeric mixtures according to the invention do not contain other substances in an amount, which causes a content of one or more of the elements fluorine, chlorine, bromine and iodine greater than 5000 ppm based on the oligomeric mixture.
    The oligomeric mixtures according to the invention contain at least three, preferably more than three different poly (alkylene phosphates) of the general formula (I), which are distinguished from each other at least in the number n of the repetition units and, with this, in its molar mass. For the description of such oligomeric mixtures, the specialist uses suitable average values, such as, for example, the average numerical molar mass M n and the average value of the number of repeat units n of the molecules of formula (I) contained in the oligomeric mixture .
    According to the invention, the numerical average molar mass M n of the poly (alkylene phosphates) contained in the oligomeric mixtures is determined by means of gel permeation chromatography with tetrahydrofuran as an elution agent against the polystyrene pattern. This method is known to the specialist, for example, from DIN 556721: 2007-08. From M n , considering the stoichiometry of formula (I), the average value of the number of repeat units n of the poly (alkylene phosphates) contained in the oligomeric mixture can be easily calculated (see examples).
    For the present invention it is essential the result
    surprising, what just mixes oligomeric in poly (alkylene phosphates) of the formula ( I) have The wanted combination in properties whose average value of number of units in repetition n of poly (phosphates in alkylene) contained at oligomeric mixture is bigger than
    14/36
    1.10 and less than 2.00. The oligomeric mixtures according to the invention are characterized by good flame protection efficiency, low condensable emissions, low viscosity and good processability with both polyether polyols and polyester polyols.
    Preferably, the poly (alkylene phosphates) of formula (I) contained in the oligomeric mixtures according to the invention have an average value of the number of repetition units n greater than 1.20 and less than 1.90.
    Oligomeric mixtures can be prepared, in principle, by methods known to the skilled person for the production of alkyl phosphates. For example, oligomeric mixtures according to the invention, can be prepared by reacting alkyl dichlorophosphates of the formula MO-POCI2, in which M represents a radical R 1 , R 2 , R 3 or R 4 and R 1 , R 2 , R 3 and R 4 have the general and preferred meanings indicated above, with dihydroxy compounds of the formula HO-A-OH, in which A has the general and preferred meanings indicated above and with one or more monohydroxy compounds M-OH, in the in which M has the meanings indicated above or through the reaction of dihydroxy compounds of the formula HO-A-OH, in which A has the general and preferred meanings indicated above, with phosphoroxy chloride POCI3 and with one or more monohydroxy compounds M-OH, in which M represents a radical R 1 , R 2 , R 3 or R and R, R 2 , R 3 and R 4 have the general and preferred meanings indicated above or through the reaction of one or more trialkyl phosphates (MO) 3 PO, in which M has the meaning indicated above, with phosphorus pentoxide P2O5 and with a cyclic ether.
    According to the invention, the preferred preparation is through the reaction of dihydroxy compounds HO-A-OH, in which A has the general and preferred meanings indicated above, with phosphoroxy chloride POCI3 and with at least one monohydroxy compound M-OH, in which M represents a radical R 1 , R 2 , R 3
    15/36 or R 4 and R 1 , R 2 , R 3 and R 4 have the general and preferred meanings indicated above.
    Another objective of the present invention is a process for the preparation of the oligomeric mixtures according to the invention, which is characterized by the fact that in a first step, a dihydroxy compound of the formula HO-A-OH, in which A has the general meanings and preferred indicated above, is reacted with phosphoroxy chloride POC1 3 , being per mol of dihydroxy compound of the formula HO-A-OH, more than 1.0 mol and less than 2.0 mol of POC1 3 are used and the mixture of oligomeric chlorine phosphates thus obtained from formula (VIII)
    O
    Cl ll
    P
    Cl o
    Οχ X OJI
    A P
    Cl
    Cl (VIII), in which n represents an integer from 0 to 100, is subsequently reacted in a second step with at least one monohydroxy compound of the formula
    M-OH (IX), in which M represents a radical R 1 , R 2 , R 3 or R 4 and
    R 1 , R 2 , R 3 and R 4 have the general and preferred meanings indicated above, to form the oligomeric mixtures according to the invention.
    The monohydroxy compounds of the formula (IX) used for the preparation of the oligomeric mixtures according to the invention can be the same or different.
    For the preparation of the oligomeric mixtures according to the invention, preferably 1.45 to 1.8 mol of POC1 3 are used per mol of dihydroxy compound of the formula HO-A-OH.
    The favorable molar ratio for the preparation of
    16/36
    Ir oligomeric mixture according to the invention with an average value of the number of repetition units n greater than 1.10 and less than 2.00, within the range indicated above, of dihydroxy compounds HO-A-OH for chloride phosphoroxy POCI3, 5 can be easily determined by serial assays, such as are entrusted to the specialist.
    The process according to the invention can be carried out over a wide temperature range. In general, the process according to the invention is carried out in a temperature range of 0 to 100 ° C. Preferably, in the first stage it is worked at a temperature of 5 to 40 ° C and in the second stage, in general, at a temperature of 5 to 30 ° C.
    The process according to the invention can be carried out over a wide pressure range. Preferably, the first stage is performed at a pressure of 10 to 1000 mbar and the second stage, at atmospheric pressure.
    In the case of oligomeric mixtures according to the invention, these are preferably liquid compounds at the processing temperature. Process temperature must be understood here as the temperature at which the polyurethane raw materials are added to the dosing and mixing aggregates of the production systems. As a rule, depending on the viscosities of the components and the dimensioning of the dosing aggregates, 25 temperatures between 20 and 80 ° C are selected.
    The oligomeric mixtures according to the invention have a viscosity of less than 1000 mPas at 23 ° C. Most preferably, the viscosity at 23 ° C matters less than 500 mPas.
    Preferably, the oligomeric mixtures according to the invention have low volatility.
    Preferably, the oligomeric mixtures according to the invention, compared with the other materials of
    17/36 used for the production of polyurethanes, are not reactive, in particular, compared to isocyanates.
    The oligomeric mixtures according to the invention are suitable for use as flame protection agents and for the production of flame protection agent preparations.
    The aim of the present invention is to use the oligomeric mixtures according to the invention as flame retardant agents.
    The oligomeric mixtures according to the invention can be used, in general, in all applications known to the specialist for flame protection agents. Preferably, the oligomeric mixtures according to the invention are used as flame protection agents for synthetic polymers, such as polyolefins, polycarbonates, styrene-based (co-) polymers, polyamides, polyesters and epoxy resins, for materials based on plants, such as wood, wood composites and synthetic materials, paper and cardboard and for materials of animal origin, such as leather.
    2Q The object of the present invention are also preparations of flame protection agents containing at least one oligomeric mixture according to the invention, at least one other flame protection agent B) and optionally one or more adjuvants C), selected from the group consisting of solvents, antioxidants, stabilizers and dyes.
    Preferably, flame retardant preparations according to the invention contain as another flame retardant B) at least one flame retardant selected from the group consisting of triethyl phosphate, triphenyl phosphate, diphenylcresyl phosphate , tricresyl phosphate, isopropylated or butylated aryl phosphates, bisphenol bis (diphenylphosphate) 18/36
    A, resorcinol bis (diphenylphosphate), neopentylglycol bis (diphenylphosphate), tris (chloroisopropyl) phosphate, tris (dichloropropyl) phosphate, dimethyl methanphosphonate, diethyl ethanophosphonate, diethylphosphonate and propanephosphonate derivatives other oligomeric phosphates or phosphonates, phosphorus compounds containing hydroxyl groups, derivatives of 5,5-dimethyl-2-oxide, 3,2dioxaphosphorinane, 9,10-dihydro-9-oxa-10 phosphaphenanthrene oxide (DOPO) and its derivatives, ammonium phosphate, 10 ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melamine, melamine cyanurate, alkyl esters of a tetrabromobenzoic acid, bromine-containing diols prepared from tetrabromophthalic acid anhydride, polyols containing bromine, ethers diphenyls containing bromine, 15 aluminum hydroxide, boehmite, magnesium hydroxide, expandable graphite and clay minerals.
    As adjuvants C) include, for example, solvents, such as, for example, water or alkyl esters of aliphatic or aromatic di- or tricarboxylic acids, antioxidants and stabilizers, such as, for example, sterically hindered trialkylphenols, alkyl esters 3- (3,5-di-terc.-butyl-4-hydroxyphenyl) -propionic acid, benzofuran — 2 — one, secondary aromatic amines, phosphites, phenothiazines or tocopherols and dyes, such as, for example, pigments of iron oxide or soot.
    The object of the present invention is, moreover, also fireproof polyurethanes containing at least one oligomeric mixture according to the invention.
    The flame-protected polyurethanes according to the invention can be produced, in which organic polyisocyanates are reacted with compounds with at least two hydrogen atoms capable of reacting with isocyanates, optionally with blowing agents,
    19/36 stabilizers, conventional activators and / or with other conventional adjuvants and / or additives and in the presence of at least one oligomeric mixture according to the invention.
    The oligomeric mixtures according to the invention are used in an amount of 0.5 to 30 parts by weight, preferably 3 to 25 parts by weight, based on 100 parts by weight, of the polyol component.
    In the case of polyurethanes, these are isocyanate-based polymers, which mainly have urethane and / or isocyanurate and / or allophanate and / or uretodione and / or urea and / or carbodiimide groups. The production of isocyanate-based polymers is itself known and described, for example, in DE OS 16 94 142, DE-OS 16 94 215 and DE-OS 17 20 768, as well as in Kunststoff-Handbuch volume VII, Polyurethane , edited by G.
    Oertel, Carl-Hanser-Verlag Munich, Vienna 1993.
    In the case of the polyurethanes according to the invention, it is thermoset polyurethanes, polyurethane foams, polyurethane elastomers, thermoplastic polyurethanes, Trench ments and polyurethane lacquers, binders and adhesives or polyurethane 20 , polyurethane fibers.
    In a preferred embodiment of the invention, in the case of polyurethanes according to the invention, these are polyurethane foams.
    Polyurethane foams are roughly differentiated into soft and hard foams. In fact, soft and hard foams can fundamentally have approximately the same spatial density and composition, however, soft polyurethane foams are only slightly cross-linked and at the pressure request they have only low resistance to deformation. On the other hand, the structure of hard polyurethane foams consists of highly cross-linked units and on request for pressure the hard polyurethane foam shows very high resistance to deformation
    High 20/36. The typical hard polyurethane foam has closed cells and has only a low heat conductive index. Primarily, in the production of polyurethanes, which occurs through the reaction of polyols with isocyanates, the posterior structure of the foam and its properties are influenced by the structure and molar mass of the polyol, as well as by the reactivity and number (functionality) of the hydroxyl groups contained in the polyol. . Other particularities regarding the foam of hard and soft foam, the starting materials usable for their production, as well as processes for their production, are found in Norbert Adam, Geza Avar, Herbert Blankenheim, Wolfgang Friederichs, Manfred Giersig, Eckehard Weigand, Michael Halfmann, FriedrichWilhelm Wittbecker Donald-Richard Larimer, Udo Maier, Sven Meyer-Ahrens, Karl-Ludwig Noble und Hans-Georg Wussow, "Polyurethanes, Ullmann's Encyclopedia of Industrial Chemistry Release 2005 Electronic Release, 7th ed, chap.. 7 (Foams), Wiley-VCH, Weinheim 2005.
    Preferably, the polyurethane foams according to the invention have spatial weights of 10 - 150 kg / m 3 . Particularly preferably, they have spatial weights of 20 - 50 kg / m 3 .
    For the production of isocyanate based foams, the following starting components are used:
    1. aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates (for example, W. Siefken in Justus Liebigs Annalen der Chemie, 562, page 75 136), for example, those of the formula Q (NCO) n z in which n is 2 to 4, preferably 2 to 3 and Q represents an aliphatic hydrocarbon radical of 2 to 18, preferably 6 to 10 carbon atoms, a cycloaliphatic hydrocarbon radical of 4 to 15, preferably 5 to 10 carbon atoms, an aromatic hydrocarbon radical with 6 to 15,
    21/36 preferably 6 to 13 carbon atoms or an araliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13 carbon atoms. Particular preference is given, as a rule, to technically easily accessible polyisocyanates, which are derived from 2,4 - and / or 2,6-toluylenedi — isocyanate or from 4,4 - and / or 2,4'-diphenylmethanedi -isocyanate.
    2. Compounds with at least two hydrogen atoms capable of reacting to isocyanates, with a molecular weight of 400 to 8,000 g / mol (polyol component). Among these, we understand, in addition to amino groups, compounds that have thio groups or hydroxyl groups, in particular, compounds that have 2 to 8 hydroxyl groups. If the polyurethane foam should be a soft foam, then polyols with molar masses from 2,000 to 8,000 g / mol and 2 to 6 hydroxyl groups per molecule are preferably used. If, on the contrary, a hard foam is to be produced, then highly branched polyols with molar masses of 400 to 1,000 g / mol and 2 to 8 hydroxyl groups per molecule are preferably used. In the case of polyols, these are polyethers and polyesters, as well as polycarbonates and polyester amides, as they are known in themselves for the production of homogeneous and cell-shaped polyurethanes and as described, for example, in DE- OS 28 32 253. Polyethers and polyesters having at least two hydroxyl groups are preferred according to the invention.
    The polyurethane foams according to the invention can therefore be produced, by means of the corresponding selection, easily deduced by the state of the art, of the starting materials, such as hard or soft foams.
    Other starting components are optionally composed of at least two hydrogen atoms capable of reacting with isocyanates and with a molecular weight of 32 to 399 g / mol. In this case too, it is understood
    22/36 compounds having hydroxyl groups and / or amino groups and / or thio groups and / or carboxyl groups, preferably compounds having hydroxyl groups and / or amino groups, which serve as chain-extending agents or cross-linking agents. These compounds have, as a rule, 2 to 8, preferably 2 to 4 hydrogen atoms capable of reacting in relation to isocyanates. Examples of these are also described in DE-OS 28 32 253.
    3. Water and / or slightly volatile organic substances as blowing agents, for example, n-pentane, pentane, cyclopentane, acetone, halogen-containing alkanes, such as trichloromethane, methylene chloride or chlorofluoralkanes, CO2 and others.
    4. Optionally, coadjuvants and additives, such as catalysts of the known type, surfactant additives, such as emulsifiers and foam stabilizers, reaction retarders, for example, acid reaction substances, such as hydrochloric acid or halides, are co-used. organic acids, in addition, cell regulators of the type known per se, such as paraffins or fatty alcohols and dimethylpolysiloxanes, as well as pigments or dyes and other flame protection agents, in addition, stabilizers against aging and weathering, nuclear fading, plasticizers and substances with fungistatic and bacteriostatic action, as well as fillers such as barium sulphate, infusoria soil, soot or prepared cré (DE — OS 27 32 292). Nuclear fade inhibitors may contain, in particular, sterically hindered trialkylphenols, alkyl esters of 3- (3,5di-terc.-butyl-4-hydroxyphenyl) -propionic acid, benzofuran-2-ones, aromatic secondary amines, phosphites , phenothiazines or tocopherols.
    23/36
    Like other flame-retardant agents, in addition to the oligomeric mixtures according to the invention, they can be contained in the polyurethanes according to the invention
    a) organic phosphorus compounds, such as, for example, triethyl phosphate, triphenyl phosphate, diphenylcresyl phosphate, tricresyl phosphate, isopropylated or butylated aryl phosphates, aromatic bisphosphates, neopentyl glycol acid bis (diphenylphosphate) esters containing chlorine, such as, for example, tris phosphate (chloroisopropyl) or tris phosphate (dichloropropyl), dimethylmethane phosphate, diethyl ethane phosphonate, dimethylpropane phosphonate, derivatives and salts of diethylphosphinic acid, other phosphates or phosphonates of oligomeric compounds phosphorus containing hydroxyl groups, 5,5-dimethyl-1,2,3-dioxaphosphorinane 2-oxide derivatives, 9,10-dihydro-9oxa-10-phosphaphenanthrene-10 oxide (DOPO) and their derivatives,
    b) organic phosphorus compounds, such as, for example, ammonium phosphate, ammonium polyphosphate, melamine phosphate, melamine polyphosphate,
    c) nitrogen compounds, such as, for example, melamine, melamine cyanurate,
    d) bromine compounds, such as, for example, alkyl esters of a tetrabromobenzoic acid, diols containing bromine prepared from tetrabromophthalic acid anhydride, polyols containing bromine, diphenyl ethers containing bromine,
    e) inorganic flame protection agents, such as aluminum hydroxide, boehmite, magnesium hydroxide, expandable graphite and clay minerals.
    Other examples of surfactant additives and foam stabilizers, as well as cell regulators, reaction retardants, stabilizers, flame-inhibiting substances, plasticizers, dyes and
    24/36 fillers to be optionally co-used according to the invention, as well as substances with fungistatic and bacteriostatic action, as well as details about the use and effect of these additives are described in Kunststoff-Handbuch, volume VII, Carl-Hanser -Verlag, Munich, 1993, on pages 104 to 123.
    Another objective of the present invention is a process for the production of flame retardant polyurethanes through the reaction of organic polyisocyanates with compounds with at least two hydrogen atoms capable of reacting in relation to conventional isocyanates and blowing agents, stabilizers, catalysts, activators and / or other conventional adjuvants and additives, in the presence of at least one oligomeric mixture according to the invention. In this case, the oligomeric mixture according to the invention is used, in general, in an amount of 0.5 to 30 parts by weight, preferably in an amount of 3 to 25 parts by weight, in each case based on 100 parts by weight, of polyol component. The process is preferably carried out at a temperature of 20 to 80 ° C.
    In order to carry out the process for the production of polyurethanes according to the invention, the reaction components described above are carried out by the single step process known per se, by the prepolymer process or by the semi-prepolymer process, being frequently mechanical equipment is used, for example, those which are described in US 2,764,565. Particularities about processing equipment, which are also included according to the invention, are described in Kunststoff-Handbuch volume VII, Polyurethane, edited by G. Oertel, Carl-HanserVerlag, Munich, Vienna, 1993, on pages 139 to 192.
    The process according to the invention allows the production of flame-protected polyurethane foams
    25/36 as hard or soft foams in continuous or batch production or with molded foamed articles. The process according to the invention is preferred for the production of soft foams, which are produced by a block defoaming process.
    The polyurethanes according to the invention, obtained by the process according to the invention, are preferably used in furniture upholstery, textile inserts, mattresses, car seats, armrests, construction elements, seat coverings and frames, insulation cables, seals, coatings, lacquers, adhesives, adhesion promoters and fibers.
    The oligomeric mixtures according to the invention, contained in the polyurethanes according to the invention, respectively, used in the process according to the invention, can be prepared, in a manner analogous to the known methods, according to the process described above. In this case, it is particularly advantageous that oligomeric mixtures according to the invention of a given composition can be obtained by choosing the appropriate conditions of synthesis as direct products of the process. In this case, starting materials available on an industrial scale are used, which allow to produce the desired final products in a simple way.
    The liquid oligomeric mixtures according to the invention, can be well dosed. These do not react with the other starting materials used for the production of polyurethane foams and, therefore, can be processed very easily as additives. Surprisingly, these can be processed with both polyether polyols and polyester polyols. Foams produced with the oligomeric mixtures according to the invention
    26/36 correspond not only to the flame resistance specifications, but also show particularly low condensable emission values.
    Based on the following examples, the invention is illustrated in detail, without causing a restriction of the invention.
    Examples
    General synthesis prescription for oligomeric mixtures (examples of synthesis SI to S5)
    A reactor with agitator, drip funnel, reflux condenser and vacuum system, was filled with the amount (parts by weight) of phosphoroxy chloride indicated in table 1. The phosphoroxy chloride was quenched at 10-20 ° C. With a vacuum of 500 - 700 mbar, the amount of diethylene glycol shown in table 1 was added by dripping. Upon completion of the drip, the pressure was further decreased until finally 5-15 mbar and the temperature was raised to 20 - 30 ° C. There remained a liquid residue, almost colorless.
    In another reactor with agitator, drip funnel and reflux condenser, the amount of ethanol indicated in table 1 was previously introduced at 20 - 30 ° C and this was mixed with the residue obtained above. The mixture was further stirred at 20 - 30 ° C until the reaction subsided and then it was neutralized by the addition of concentrated caustic soda. Then, both dichloromethane and water were added, which resulted in two transparent liquid phases. These were separated and the organic phase was released from dichloromethane, excess ethanol and water through distillation. As a residue, the oligomeric mixtures according to the invention remained in the form of colorless liquids. The viscosities of the prepared products were determined with a spherical viscometer commercially available at 23 C and
    27/36 listed in table 1.
    Determination of the average value of the number of repeat units n of the molecules contained in the oligomeric mixture according to formula I
    The prepared products, after analysis by means of gel permeation chromatography (GPC), proved to be oligomeric mixtures. The numerical mean molar masses M n of the oligomeric mixtures were determined using GPC with tetrahydrofuran as an elution agent against the polystyrene standard based on the method of DIN 55672-1: 2007-08. The average value of the number of repeat units n of the poly (alkylene phosphates) contained in an oligomeric mixture according to formula (I) was calculated from the numerical average molar mass M n according to the following formula:
    ή = (M n - M e ) / M r with η: average value of the number of repeat units of the poly (alkylene phosphates) of formula (I) contained in the oligomeric mixture,
    M n : numerical average molar mass in g / mol determined by gel permeation chromatography,
    M e : sum of the molar masses of the end groups in g / mol and
    M r : molar mass of the repetition unit in g / mol.
    For oligomeric mixtures of poly (alkylene phosphates) of the formula (I) with R 1 = R 2 = R 3 = R 4 = ethyl and A = -CH2CH2OCH2CH2- M E = 182.16 g / mol and M R = 194.14 g / mol. The results are listed in Table 1.
    Table 1: Raw materials used and parts by weight for the preparation of oligomeric mixtures from poly (alkylene phosphates) of the formula (I) with R = R = R = R 4 = ethyl and A = -CH2CH2OCH2CH2- of the examples synthesis SI a
    28/36
    S5 and properties
    example SI S2 S3 S4 S5 diethylene glycol 235, 3 428.2 466, 4 118.7 118.7 phosphoroxy chloride 476.9 736, 0 1214 306, 7 269, 9 ethanol 1225 2230 2428 618.2 618.2 viscosity [mPas] 190 1423 40 58 85 M n 592 655 429 462 495 n 2, 11 2.44 1.27 1.44 1.61 according to theinvention not not yea yea yea
    Production of soft polyurethane foams
    Table 2: Raw materials used for the production of soft polyether foams for the compositions of examples Bl, B2 and B3 according to the invention, as well as comparative examples VI to V6 according to the invention (according to table 4)
    component occupation description THE polyol Arcol® 1105 (Bayer Materialscience), polyether polyol with OHZ 56 mg KOH / g B expansion agent Water Ç catalyst Addocat 108® (Rhein Chemie), solution a70 bis (2-dimethylaminoethyl) ether in dipropylene glycol D catalyst Addocat® SO (Rhein Chemie), tin 2-ethylhexanoate-II AND stabilizer Tegostab® B 8232 (Degussa), silicone stabilizer F1 protection agentto the flames tris (2,3dichlorisopropyl) phosphate phosphate, TDCP F2 protection agentto the flames diphenylcresyl phosphate F3 protection agentto the flames bis (diethylphosphate) of diethylene glycol according to EP 1 746 129 Al F4 protection agentto the flames Fyrol® PNX from ICL-IP (oligomeric phosphate ester of formula I with R 1 = R 2 = r 3 = R 4 = ethyl and A = ethylene, CAS
    29/36
    component occupation description Reg.-No 184538-58-7), M n = 640 g / mol of GCP (see above), considering formula (I), n is = 3.01; viscosity 1241 mPas at 23 ° C. F5 protection agentto the flames product of the synthesis example Sl, not according to the invention F7 protection agentto the flames product of the S3 synthesis example, according to the invention F8 protection agentto the flames synthesis example product S4, according to the invention F9 protection agentto the flames product of the S5 synthetic example according to the invention G diisocyanate Desmodur® T 80 (Bayer Materialscience), toluylenediisocyanate, isomeric mixture
    Production of soft polyether foams
    The raw materials for the production of soft polyether foams are specified in table 2. The components indicated according to the type and quantity in table 4, with the exception of diisocyanate (component G), have been mixed to form a mixture homogeneous. Then, the diisocyanate was added and mixed briefly intensively. After a start time of 15 - 20 s and an increase time of 170 - 200 s, a soft polyurethane foam 10 with a space weight of 33 kg / m 3 was obtained . In all tests, uniformly fine pore foams were obtained.
    30/36
    Table 3: Raw materials used for the production of soft polyester foams for the compositions of examples B4, B5 and B6 according to the invention, as well as comparative examples V7 to V13 according to the invention (according to 5 table 5 )
    component occupation description THE polyol Desmophen® 2200 B (BayerMaterialscience),polyester polyol with 60 mg KOH / g oxyhydryl induce B expansion agent Water Ç catalyst Niax® A-30 (Momentive), Amin D catalyst Addocat® 117 (Rhein Chemie), aminetertiary AND stabilizer Tegostab® B 8324 (Degussa), stabilizersilicone El flame protection agent tris (2,3dichlorisopropyl) phosphate phosphate, TDCP,CAS Reg.-No. 13674-87-8 F2 flame protection agent diphenylcresyl phosphate, CAS Reg.-No.26444-49-5 F3 flame protection agent bis (diethylphosphate) of diethylene glycolaccording toEP 1 746 129 Al F4 flame protection agent Fyrol® PNX der ICL-IP (oligomeric phosphate ester of formula I with R = R = R = R 4 = ethyl and A = ethylene, CAS Reg.-No 184538-58-7), M n = 640 g / mol of GCP (see above.), considering formula (I), n is = 3.01; viscosity 1241 mPas at 23 ° C. F5 flame protection agent product of the SI synthesis example F6 protection agent product of the synthesis example. S2
    31/36
    component occupation descriptionflamesF7 flame protection agent product of the S3 synthesis example, according to the invention F8 flame protection agent synthesis example product S4, according to the invention F9 flame protection agent product of the S5 synthetic example according to the invention G diisocyanate Desmodur® T 80 (Bayer Materialscience), toluylenediisocyanate, isomeric mixture H diisocyanate Desmodur® T 65 (Bayer Materialscience), toluylenediisocyanate, isomeric mixture
    Production of soft polyester foams
    The raw materials to produce the soft polyester foams are specified in table 3. The components specified according to the type and quantity in table 5, 5 with the exception of the two diisocyanates (component G and H), were mixed to form a homogeneous mixture. Then, the two diisocyanates previously mixed were added and mixed briefly in an intense manner.
    After a start time of 10 - 15 s and an increase time of 80 - 90 s, a soft polyurethane foam was obtained with a space weight of 29 kg / m. The foam structure of soft polyester foams depended on the flame protection agents used. This is shown in Table 5 as homogeneously thin pores (gf) or heterogeneously thick pores (ug).
    Test results for soft polyurethane foams
    - Determination of resistance to flame propagation
    Soft polyurethane foams have been tested
    32/36 according to Federal Motor Vehicle Safety Standards FMVSS-302 and assigned to fire classifications SE (self-extinguishing), SE / NBR (self-extinguishing / no fire rate), SE / BR 5 (self-extinguishing / fire rate) ), BR (fire rate) and RB (fast combustion). Fire tests for each example were performed five times. The worst result of each series of five was shown in table 4 or table 5.
    - Condensable emission determination] _q The behavior of the condensable emission of soft polyurethane foams was investigated in accordance with DIN 75201 B. The condensed quantities measured after 16 hours storage at 100 ° C are shown in table 4.
    Table 4: Composition (parts by weight) and test results of examples Bl to B3 according to the invention and comparative examples VI to V6 not according to the invention for soft polyether foams
    example 1 2 3 4 5 6 1 2 3 THE 100 100 100 100 100 100 100 100 100 B 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Ç 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 D 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.16 AND 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 F16 F2 6 F3 6F4 6 F56 F7 6_ F8 6F9 6 G 40.9 40.9 40.9 40.9 40.9 40.9 40.9 40.9 40, 9
    33/36
    class ofFMVSS RB SE BR SE SE SE SE SE SE condensable condensate emission [mg] according to DIN 75201 B 0, 19 0.72 0.59 0.37 0.33 0.21 0.32 0.31 0.28
    Evaluation of the results of soft polyether foams
    In the absence of a flame retardant (comparative example VI), the soft polyurethane foam 5 burns quickly (fire rating FMVSS RB), but shows a very low condensable emission value. A foam with tris phosphate (dichlorisoisopropyl) (comparative example V2) shows a substantial contribution to the condensable emission of the protective agent additive to 10 flames and can obtain the best fire rating FMVSS SE (self-extinguishing) in all test repetitions of fire. However, tris phosphate (dichlorisoisopropyl) brings with it the disadvantages described above of a flame retardant containing halogen. This problem is circumvented, in fact, with the use of the halogen-free diphenylcresyl phosphate-free flame retardant (comparative example V3) and a low condensable emission value is also obtained, but the flame protection effect is insufficient with the fire classification FMVSS BR. The 20 flame protection agents used in comparative examples V4 to V6 have a very good flame protection effect (all self-extinguishing) and provide even lower condensable emission values.
    Examples Bl to B3 show that the soft polyurethane foams 25 according to the invention also obtain the
    34/36 best SE fire rating (self-extinguishing) in all repetitions of the fire test and stand out for the lowest values of condensable emissions. In particular, the condensable emission in Bl to B3 is lower than in comparative example V4, in which the flame retardant bis (diethylphosphate) of diethylene glycol (F3) was processed. F3 is structurally related to the oligomeric mixtures according to the invention, which corresponds to formula II with R 1 = R 2 = R 3 = R 4 = ethyl and A = -CH2CH2OCH2CH2- en = 1.00.
    i
    35/36
    Table 5: Composition (parts by weight) and test results of examples B4 to B6 according to the invention and comparative examples V7 to V13 not according to the invention for soft polyester foams
    example 7 8 9 10 11 12 13 4 5 6 THE 100 100 100 100 100 100 100 100 100 100 B 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Ç 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 D 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 AND 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1, the F14 F2 4 F3 4 F4 4F54 F6 4 F7 4 F8 4F94 G 24.1 24.1 24, 1 24.1 24, 1 24.1 24.1 24.1 24.1 24.1 H 24.1 24.1 24.1 24.1 24.1 24.1 24.1 24.1 24.1 24.1 structure offoam gf gf gf gf ug ug ug gf gf gf class ofFMVSS RB SE BR SE SE SE SE
    Results evaluation for soft polyester foams
    In the absence of a flame retardant (comparative example V7), the soft polyurethane foam 10 burns quickly (fire classification FMVSS RB). A foam with tris phosphate (dichloroisopropyl) (comparative example V8) obtains the best fire rating FMVSS SE (self-extinguishing) in all repetitions of the fire test. But tris phosphate (dichlorisopropyl) brings
    36/36 with the disadvantages described above of a flame retardant containing halogen. Using the halogen-free diphenylcresyl phosphate-free flame retardant (comparative example V9), this problem is in fact circumvented, but the flameproof effect is insufficient with the fire classification FMVSS BR. The comparative example V10 also obtains the best rating in the fire test. Flame protection agents F4 (n ~ 3.01), F5 (n = 2.11) and F6 (n - 2.44) (comparative examples Vil to V13) proved to be incompatible with polyester polyols. These incompatibilities were verified in soft polyester foams in an irregular foam structure, with thick pores. Such foams are useless for typical applications of soft foams.
    For this reason, no FMVSS classifications were also determined for comparative examples Vil to V13.
    Examples B4 to B6 show that the oligomeric mixtures according to the invention can also be processed with polyester polyols without problems for soft polyurethane foams 20 and these also obtain the best fire classification SE (self-extinguishing) in all repetitions of the test of fire.
    Comparing the results of soft polyether and polyester foams, it appears that, with the oligomeric mixtures according to the invention, both soft polyether and polyester foams can be produced, which at the same time have very good resistance the spread of flames and low values of condensable emissions. None of the comparative products have this combination of properties.
    权利要求:
    Claims (7)
    [1]
    1. OLIGOMERIC MIXTURE, characterized by containing at least three poly (alkylene phosphates) of the formula (I)
    [2]
    2/0 R
    1/0. II
    R P

    [3]
    3/0 r Jn
    5 in which
    9 R 1, R 2, R 3 and R 4 independently represent each a C _ straight - chain Cg-alkyl or a branched radical or a Cl - C 4 -alcoxietila straight chain or branched] _Q A is radical C 4 - to C 20 -straight chain, branched and / or cyclic alkylene or
    A represents a radical of the formula -CH 2 -CH = CH = CH 2 , a radical of the formula CH 2 -C = C-CH 2 , a radical of the formula CHR CHR 6 - (O-CHR 7 -CHR 8 ) a- a radical of formula -CHR 5 -CHR -S (0) b _ 15 CHR 7 -CHR 8 - , or a radical of the formula - (CHR 5 -CHR 6 -O) CR - (O-CHR CHR 8) d , where a represents an integer from 1 to 5,. b represents an integer from 0 to 2,
    2Q c and d independently, represent a number
    Λ integer from 1 to 5,
    R 5 , R 6 , R 7 and R 8 independently, represent H or methyl,
    R 9 represents a radical of the formula -CH 2 -CH = CH-CH 2 -, 25 a radical of the formula -CH 2 -CsC-CH 2 -, a 1,2-phenylene radical, a 1,3-phenylene radical, a 1,4-phenylene radical or a radical of the formula (II)
    2/7

    [4]
    OLIGOMERIC MIXTURE according to at least one of claims 1 to 3, characterized in that it is halogen free.
    [5]
    5. OLIGOMERIC MIXTURE according to at least one of claims 1 to 4, characterized in that it has a dynamic viscosity of 20 to 1000 mPas at 23 ° C.
    [6]
    6. PROCESS FOR THE PREPARATION OF AN OLIGOMERIC MIXTURE as defined in at least one of the 10 claims 1 to 5, characterized in that in the first step a dihydroxy compound of the formula HO-A-OH, in which A has the meanings indicated in claim 1, be reacted with phosphoroxy chloride POC1 3 , with more than 1.0 mol and less than 2.0 mol of the dihydroxy compound of the formula HO-A-OH and the mixture thus obtained of phosphates per phosphoroxy chloride chlorine oligomers of the formula (VIII)
    Cl
    O. X OJI AP
    Cl
    Cl _ n (VIII), integer from 0 to 100, represents a number in which to be reacted in a second step with at least one
    20 monohydroxy compound of the formula
    M-OH (IX), in which M represents R 1 , R 2 , R 3 or R 4 and
    R 1 , R 2 , R 3 and R 4 have the meanings indicated in claim 1.
    7. USE OF AN OLIGOMERIC MIXTURE as defined in at least one of claims 1 to 5, characterized by being a flame protection agent.
    8. FLAME PROTECTIVE AGENTS PREPARATIONS, characterized by containing at least one mixture
    Oligomeric 5/7 as defined in at least one of claims 1 to 5, one or more flame protection agents B) other than the oligomeric mixture and optionally one or more auxiliary C).
    9. PREPARATION OF FLAME PROTECTIVE AGENTS according to claim 8, characterized in that the flame protection agent B) is selected from the group of triethyl phosphate, triphenyl phosphate, diphenylcresyl phosphate, tricresyl phosphate, aryl phosphates isopropylated or
    10 butylated, bisphenol-A bis (diphenylphosphate), resorcinol bis (diphenylphosphate), neopentylglycol bis (diphenylphosphate), tris (chloroisopropyl) phosphate, tris (dichloropropyl) phosphate, methanophosphate, methanophosphate, methanophosphate of dimethyl,
    15 derivatives and salts of diethylphosphonic acid, other phosphates or oligomeric phosphonates, phosphorus compounds containing hydroxyl groups, derivatives of 5,5-dimethyl-1-oxide, 3,2dioxaphosphorinane, 9,10-dihydro-9-oxide -oxa-10 7 * ~ phosphaphenanthrene (DOPO) and its derivatives, ammonium phosphate,
    20 ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melamine, melamine cyanurate, alkyl esters of a tetrabromobenzoic acid, diols containing bromine prepared from tetrabromophthalic acid anhydride, polyols containing bromine, diphenyl ethers containing bromine,
    25 aluminum hydroxide, boehmite, magnesium hydroxide, expandable graphite and clay minerals.
    10. PREPARED POLYURETHANES RESISTANT TO FLAME PROPAGATION, characterized by containing at least one oligomeric mixture as defined in at least one
    30 of claims 1 to 5.
    POLYURETHANES according to claim 10, characterized in that they are polyurethane foams, preferably based on polyether polyols or based on <ό / Ί polyester polyols.
    12. PROCESS FOR THE PRODUCTION OF IGNIFICENT FINISHED POLYURETHANES as defined in claim 10, characterized in that at least one organic polyisocyanate is
    5 reacted with at least one compound, which has at least two hydrogen atoms capable of reacting with isocyanates, in the presence of at least one oligomeric mixture as defined in at least one of claims 1 to 5 ,. optionally in the presence of one or more
    10 compounds selected as standard from the blowing agents, stabilizers, catalysts, activators, adjuvants and additives.
    13. PROCESS according to claim 12, characterized in that it uses 100 parts by weight of compost,
    15 which has at least two hydrogen atoms capable of reacting with isocyanates, 3 to 25 parts by weight, of oligomeric mixture.
    14. PROCESS according to claims 12 and
    13, characterized by using as a compound, which has at least
    20 minus two hydrogen atoms capable of reacting to isocyanates, a polyether polyol.
    15. PROCESS according to claims 12 and
    13, characterized by using as a compound, which has at least two hydrogen atoms capable of reacting in relation to isocyanates, a polyester polyol.
    16. MOLDED PIECES, SPARKS, ADHESIVES,
    COATINGS, ADHESION PROMOTERS AND POLYURETHANE-BASED FIBERS characterized by being as defined in at least one of claims 10 and 11.
    17. USE OF POLYURETHANES as defined in at least one of claims 10 and 11, characterized by being a component in furniture upholstery, textile inserts, mattresses, car seats, armrests, elements
    [7]
    7/7 construction, seat coverings and cable insulation, seals, adhesive coatings, adhesion promoters and fibers.
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    EP2687535A1|2014-01-22|
    TWI572678B|2017-03-01|
    CA2821152A1|2014-01-20|
    KR102143657B1|2020-08-11|
    CN103570972B|2019-02-01|
    PL2687535T3|2017-06-30|
    PT2687535T|2016-11-23|
    CA2821152C|2020-07-21|
    TW201425483A|2014-07-01|
    BR102013018242A2|2015-08-04|
    US9920081B2|2018-03-20|
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    法律状态:
    2015-08-04| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-16| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-03-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-05-05| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/07/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP20120177287|EP2687534A1|2012-07-20|2012-07-20|Halogen-free poly|
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