• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    : The present invention relates to bromine-con-taining oligomeric ethers containing structural units corresponding to the formula in which X = Br, Cl or H, n = 0 to 4, p, the average degree of condensation is from 2 to 10 and y independently of one another represents Br, Cl or H, the sum X+Y containing at least two Br-atoms, and Z represents a direct bond, -CH2-, C(CH3)2 or -SO2-. The invention is also directed to a process for obtaining the above said compounds which are suitable for use as flameproofing agents for numerous plastics.
    公开号:SU713533A3
    申请号:SU772531951
    申请日:1977-10-26
    公开日:1980-01-30
    发明作者:Буркгардт Рудольф；Фолькоммер Норберт
    申请人:Динамит Нобель Аг (Фирма)；
    IPC主号:
    专利说明:

    means hydrogen, methyl, chlorine and bromine, a radical of formula
    where Y and Z are as defined and R is hydrogen or a group of the formula
    where X, l and A have the indicated meanings, B is hydrogen, a group of the formula
    ces hydrocarbons, such as o-xylOL or toluene, or mixtures thereof. In addition, it is possible to use solvents with m.p. 85-150 ° C.
    Reagents are used in a molar ratio of 1: 1-1.35.
    The value of the terminal groups of oligomeric ethers can be influenced by the molar ratio of xylylene and bisphenol. If, for example, a molar excess of bisphenol is used, products are obtained that mainly contain hydroxyl end groups.
    Hg, y
    ,
    pCiCHz-H - (. H2 (ii-i- (fifi) Ho - (} - g
    SNGA
    where A, l and A have the indicated meanings, alkyl GI-C4 unsubstituted or substituted by chlorine or bromine, or the benzyl radical of the formula
    where X, l and R have the indicated values, n is the average degree of condensation, is 2-10, with the following ratio of components, weight. %: Plastic 80-96 Flame retardant 4-20
    The proposed molding composition may also contain conventional additives, such as fiberglass and antimony trioxide.
    Oligomeric ethers or mixtures thereof can be obtained in a simple way and with a good yield.
    A viable method is that the xylylene dihaloids, in particular the dichlorides, are reacted with an alkali or alkaline earth salt, in particular the sodium or potassium salt of bisphenol, in an environment of a suitable solvent. Instead of the bisphenol salt, free bisphenol can also be used and, at the beginning or during the reaction, the necessary amount of basic alkaline or alkaline earth compound, for example, sodium or potassium oxide, hydroxide or carbonate can be added.
    It is advisable to carry out the reaction at a temperature of 85-150 ° C. Preferably 90-120 ° C.
    The reaction can be carried out at atmospheric or elevated (up to 10 bar) pressure.
    A suitable solvent is, for example, dioxane, methyl glycol, aromatics. If an excess of xylylene is used, products that mainly contain chloromethyl terminal groups are obtained.
    Reactive end groups can be blocked by simple esterification with monofunctional halogen-containing alkyl or monophenol. In order to avoid a decrease in the halogen content in oligomeric ethers, blocking of the terminal groups is preferably carried out with a compound with a sufficiently high halogen content. Therefore, for the simple esterification of halomethyl end groups, phenols of the general formula are used that are halogenated in the wood.
    where X, R and l have the indicated value, for example pentachlorophenol, tribromphenol or pentabromophenol, if necessary, also halogenated cresols, and for simple esterification of hydroxyl end groups - haloalkyl compounds, in particular halogenated in benzyl halides of the general formula
    X TL where X, R and L have the indicated value, for example pentachlorobenzyl chloride or pentabromobenzyl chloride.
    The resulting chloromethyl end groups of oligomers are usually blocked in this way.
    The molar amount used for blocking end groups of compounds depends on the content of functional end groups, due to the degree of condensation p.
    For example, if reagents are used in a molar ratio of 4: 5 or 5: 4, a mixture with an average degree of condensation p of about 4 is obtained. At the end of the reaction, 1.5-2 mol of monofunctional compounds to block the end groups and then remove the excess.
    Blocking end groups of the compound are preferably added at the end of the condensation.
    Oligomeric ethers are solids that are insoluble in water. Due to their relatively high molecular weight, they also do not dissolve or only slightly dissolve in lower alcohols, acetone and aliphatic hydrocarbons. Dissolved in aromatic hydrocarbons and chlorohydrocarbons better in dimethylformamide
    and, in particular, in cyclic ethers, for example dioxane and tetrahydrofuran. The solvent, as well as the melting point of oligoethers, depends on the reagents and molecular weights.
    Example 1. In a mixture of 125 g of a 32% sodium hydrochloric acid with 950 ml of dioxane, 272 g of 2, (3,5-dibromo-4-hydroxyphenyl) -iropane (tetrabromo-diane) are dissolved and 196 g of tetrachloro- xylene dichloride. The mixture was heated under reflux at a temperature of 90 to 101 ° C for 4 hours. Then a solution of 63 g of 2,4,6-tribromophenol in 125 ml of dioxane and 32 g of 32% sodium hydroxide and the reaction mixture were added still at boiling point for 1 hour. After distilling off 720 ml of dioxane, the reaction mixture while stirring is fed into 4 l of water and the precipitate is sucked off, washed with water and methanol and dried in vacuum at a temperature of 100-120 ° C.
    458 g (94.3% of theory) of oligomeric tetrachloro-d-xylyltetrabromodianate ether with terminal tribromophenoxy groups are obtained in the form of a brownish-white powder.
    Diane but the characteristics of a simple ether and in the table. one.
    T ab l n c a 1
    Note. The average degree of condensation of p oligomers is 4-6.3, with the majority of individual molecules having a degree of condensation of 4-6, and a small amount of molecules} l has a degree of condensation ranging from 2 to 10.
    Example 2. 123 g of tetrabromo-p-xylylene dichloride and 73.2 g of 2,2-bms- (3,5-dichloro-oxyphenyl) propane in 350 ml of dioxane are heated to boiling with stirring and added dropwise over 1 hour. 39 g of 40% sodium hydroxide. The reaction mixture is then refluxed for 3 hours, a solution of 25 g of 2,4,6-tribromophenol in a mixture of 12 g of 40% sodium hydroxide solution and 50 ml of dioxane is added and the reaction mixture is boiled for another 1 h. Then, 270 ml of water-containing dioxane are distilled off and the viscous distillation residue is placed in 1.8 l of water when placed. The precipitate is filtered off with suction, washed with water and methanol and dried under vacuum at a temperature of 120 ° C.
    186 g (91.1% of theory) of tetrabromo-p-xylyltetrachloroethyl ether with terminal tribromophenoxy groups are obtained in the form of a yellowish-white powder.
    Data on the characteristics of simple ether are given in table. I.
    Example 3. 63 g of tetrachloro-α-xylene dichloride are mixed with 136 g of 2,2-bms-3,5-dibrom-4-hydroxyphenyl) -propane in 350 ml of dioxane and a mixture of 42 g of 40% is added at a boiling point over 1 hour -Naton silk with 25 ml of dioxane. After 3 hours of refluxing, 52 g of pentabromobenzyl chloride and a mixture of 10 g of 40% sodium hydroxide solution with 50 ml of dioxane are added. The mixture is then stirred at boiling for 1 h, 300 ml of dioxane containing water are distilled off, and hot residue is stirred into 1.8 l of water while stirring. After several hours, the precipitate is sucked off, washed with water and methanol and dried in vacuum at a temperature of 100-120 ° C.
    228 g (97.9% of theory) of tetrachloro-L-xylyltetrathiophenyl ether with terminal pentabromobenzyl groups are obtained in the form of a white powder.
    Data on the characteristics of simple ether are given in table. one.
    Example 4. 90.6 g of 3,3,5,5-tetrabromo-4,4-dioxy-diphenylsulfone are dissolved in 400 ml of dioxane and 31 g of 40% sodium hydroxide solution, 98.2 g of tetrabromo-xylilandne chloride are added and the mixture is stirred within 30 min. Then the reaction mixture is slowly heated to boiling and boiled under reflux for 4 hours. After adding the solution, 20 g of 2,4,6-tribromophenol in 40 ml of dioxane and 10 g of 40% sodium cell are boiled for another I h. Then 300 ml of water-containing dioxane are distilled off and, with stirring, the viscous residue is fed into 1.5 liters of water. The precipitate is sucked off, washed with water, pre-dried at 90 ° C, further washed with 350 ml of methanol and dried in vacuum at a temperature of 100-120 ° C.
    169 g (87% of theory) of an oligomeric tetrabromo-l-xylylentetrabromodiphenylsulfone ether with terminal tribromophenyl groups are obtained in the form of a yellowish powder.
    Data on the characteristics of simple ether are given in table. one.
    Examples 5-12. Example 1 is repeated, with the difference that those listed in Table 2 are used. 1 reagents.
    Data on the characteristic oligomeric ethers of examples 5-12 are also given in table. one.
    In tab. 1 shows the following abbreviations:
    K - xylylene radical
    D - diphenoxy radical
    TBC - tetrabromoxylen .. TCC - Tetrachloroxylylene
    K - xylylene (non-halogenated)
    D - 2,2-bis- (4-hydroxyphenyl) -propane (liana)
    LDP - 2,2-byc- (3,5-dibromo-4-hydroxyphenyl) propane
    TCD - 2,2-bis- (3,5 - dnchloro - 4 - hydroxyphenyl) propane
    DFS - 4,4-dioxydiphennsulfone
    TBS - 3,3,5,5-tetrabrom - 4,4 - discsidiphenylsulfone
    TBP - 2,4,6-tribromophenoxy
    PBB - penabrombenzyl
    percentage yield data refers to a total reagent conversion of 100%.
    In tetrabromoxylylene and pentabromobenzyl residues, a small content of bromine in the core is replaced by chlorine. Therefore, the total halogen content is lower than the calculated value.
    All products melt completely, but they do not have a precise melting point, as they are mixtures of oligomers.
    To determine the heat resistance, the temperature is indicated at which the weight loss is 1 and 5% of thermobalance, the heating rate is 80 ° C / min.
    The proposed molding composition is explained by the following examples 13-15. The fire resistance of the products obtained was determined according to the following UL-94 method.
    The 1.6x12.7x127 mm specimen is fixed in a vertical position so that the front edge of 9.5 mm protrudes above the tip of the Bunsen burner with a diameter of 9.5 mm.
    The burner is mounted on a blue flame of 19 mm and is centrically guided under the lower end of the sample for 10 seconds. After the flame has been removed, the duration of the afterburning or dusting is determined. After complete attenuation, the sample is re-ignited for 10 s.
    The second duration of afterburning or dosing is also determined. Evaluation of flame-retardant materials is produced in two classes:
    1.SE1 (self-extinguishing I).
    The average burnout time should be 25 seconds and the maximum should not exceed 30 seconds.
    2.SEO (self-extinguishing 0).
    This average burnout time should be 5 seconds and the maximum should not exceed 10 seconds.
    The material subjected to this enhanced SEI class test, in particular SEO, is a good passive fire protection for electrical appliances that may have an insulating substance ignited when disturbed.
    Example 13. 86 wt. % indicated in the table. 2 plastics, 10 wt. % oligomeric simple ether according to examples 1, 2, 9-12 and 4 weight. antimony trioxide% intense
    mixed in a screw extruder and processed into samples.
    Note. The first values were obtained without pretreatment of the samples, and the second values (after the oblique stroke) after storage at 70 ° C for 7 days.
    After storage at 200 ° C for 28 days, no coating was formed on the surface of all samples.
    Example 14. 94 wt. % indicated in the table. 3 ilastmass, 4 wt. % flame retardant
    The first values were obtained without pretreatment of the samples, and the second values (after the oblique stroke) after storage at 70 ° C for 7 days.
    After storage at 200 ° C for 28 days, no coating was formed on the surface of all samples. The first values were obtained without pretreatment of the samples, and the second values (after skewing), after storage at 70 ° C for 7 days.
    The test results are given in table. 2
    table 2
    means but examples 2, 4 and 11 and 2 weight. % antimony trioxide and similarly, prmeru 13 is processed into samples.
    The results of the test are given in Table. 3
    Table 3
    Fire retardant according to example Example 15. 80 wt. % indicated in the table. 4 plastics and 20 wt. % fire retardant, itn means but examples 2, 4 and 11 analogously to example 13 are processed into samples.
    The test results are given in table. four.
    Table 4
    Flame retardant by primer.} After storage at 200 ° C for 28 days no coating was formed on the surface of all samples. Comparative tests.
    Examples 13-15 are repeated with the difference that 4-20 wt.% Are used as flame retardants in the compositions. % of simple brominated diphenyl ethers.
    After storage at 70 ° C for 7 days, the fire resistance of all samples was SEI.
    After storage at 200 ° C for 28 days, a coating formed on the surface of the samples, which consisted of an appropriate flame retardant.
    权利要求:
    Claims (1)
    [1]
    1. USSR patent for application number 1821047 / / 23-05 with attached to it No. 1998980/28, cl. From 09К 3/28, 08.21.72, according to which a decision was made to issue a patent.
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    同族专利:
    公开号 | 公开日
    DE2650117A1|1978-05-03|
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    IL53255D0|1977-12-30|
    BE860251A|1978-04-28|
    FR2369312A1|1978-05-26|
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    GB1578359A|1980-11-05|
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    AT351773B|1979-08-10|
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    FR2369312B1|1984-06-29|
    DE2650117C2|1983-08-04|
    NL178070C|1986-01-16|
    ES463704A1|1978-06-01|
    JPS5356636A|1978-05-23|
    DK481877A|1978-05-01|
    SE7712101L|1978-05-01|
    CA1129889A|1982-08-17|
    引用文献:
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    DE3504169A1|1985-02-07|1986-08-07|Bayer Ag, 5090 Leverkusen|BROMIC OLIGOMERS ETHERS OF BIS-CHLORMETHYL-DIPHENYLETHERS|
    CN110914338A|2017-07-07|2020-03-24|东曹株式会社|Halogen-containing polymer and process for producing the same|
    法律状态:
    优先权:
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    DE19762650117|DE2650117C2|1976-10-30|1976-10-30|Bromine-containing oligomeric ethers|
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