JPS5959695A - Novel halogenated benzulphosphonate and manufacture - Google Patents
Novel halogenated benzulphosphonate and manufactureInfo
- Publication number
- JPS5959695A JPS5959695A JP58154247A JP15424783A JPS5959695A JP S5959695 A JPS5959695 A JP S5959695A JP 58154247 A JP58154247 A JP 58154247A JP 15424783 A JP15424783 A JP 15424783A JP S5959695 A JPS5959695 A JP S5959695A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- chlorine
- benzulphosphonate
- manufacture
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 16
- -1 benzyl halides Chemical class 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- OGBVRMYSNSKIEF-UHFFFAOYSA-L benzyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-L 0.000 claims 1
- 239000003205 fragrance Chemical group 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AIPJZPPOFWCJRC-UHFFFAOYSA-N 1,2-dichloro-3-(chloromethyl)benzene Chemical compound ClCC1=CC=CC(Cl)=C1Cl AIPJZPPOFWCJRC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000001177 diphosphate Substances 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- OUKVSHGUWMRMTQ-UHFFFAOYSA-N 1,3,2-dioxaphospholan-2-yl dihydrogen phosphite Chemical compound C1COP(O1)OP(O)O OUKVSHGUWMRMTQ-UHFFFAOYSA-N 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical class OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 description 1
- 229920002821 Modacrylic Polymers 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- LTBRACVJRXLQHC-UHFFFAOYSA-N OP(=O)OCC1=CC=CC=C1 Chemical class OP(=O)OCC1=CC=CC=C1 LTBRACVJRXLQHC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003385 ring cleavage reaction Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical group CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- XKCQNWLQCXDVOP-UHFFFAOYSA-N tris(2-chloropropan-2-yl) phosphate Chemical compound CC(C)(Cl)OP(=O)(OC(C)(C)Cl)OC(C)(C)Cl XKCQNWLQCXDVOP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5337—Esters of phosphonic acids containing also halogens
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は新規なハロゲン化ベンジルポスホン酸エステル
、その好ましい製造方法および易燃性材料を防火性にす
る際のその使用に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel halogenated benzyl phosphonic acid esters, a preferred method of their preparation and their use in rendering fire-retardant flammable materials.
燐と塩素または臭素とを含有する多数の有機化合物がプ
ラスチック材料、合成繊維および他の種々の易燃性物質
のための非官能性防火用添7111剤として過去におい
て提案されている。しかしながら、これらの化合物の内
の幾つかだけが工業的に開発されているに過ぎない。A number of organic compounds containing phosphorus and chlorine or bromine have been proposed in the past as non-functional fire protection additives for plastic materials, synthetic fibers and a variety of other flammable materials. However, only some of these compounds have been developed industrially.
最も良く知らtしておりかり最も古いものはトリスシト
クロロエチル)ホスフェートi’ o coat−r2
011207 ) 3 であることは疑いのないとこ
ろである。The best known and oldest one is tris-cytochloroethyl) phosphate (coat-r2).
There is no doubt that 011207) 3.
トリス(クロロ−イソプロピル)ホスフェートP(J[
0C14(UH20A)C!I■3〕3も挙げることズ
I:できる。Tris(chloro-isopropyl)phosphate P(J[
0C14(UH20A)C! I■3〕Also mention 3 I: I can do it.
純粋な形のまたは部分的に重1111合した形のビス(
,2−クロロエチル)−、z−クロロエチルホスホネー
ト1lcd420H2−P O(00H20H,(1)
2のごときホスホネートも同一の目的で直販されてい
る。Bis (in pure form or in partially combined form)
,2-chloroethyl)-,z-chloroethylphosphonate 1lcd420H2-PO(00H20H, (1)
Phosphonates such as 2 are also sold directly for the same purpose.
これらの化合物は容易に入手し得るが、余りにも揮発性
でかつ余ジにも流動性であり従って貯蔵中の蒸発または
移行Vこよりしばしば損失ヶ生じかつ永続性の不十分な
防火効果しかもたらさないという欠点を有する〇
これらの欠点を除去するために、テトラキス(、z−1
0ロエチル)−エチレンジホスフェート(070H20
H2(J )z P (0) −00H2(!H20−
P (0) (OOH20H207)2のごときより高
分子量の化合物も提案されているが、この種の化合物は
、他の類似の化合物と同様、水に対する浴解注が余りに
も大きいかあるいは加水分解性であり、この性質は防火
効果の永続性に対して不利な影響を与えている。Although these compounds are readily available, they are too volatile and too fluid and therefore often suffer losses due to evaporation or migration during storage and provide insufficiently durable fire protection. In order to remove these drawbacks, tetrakis (, z-1
0 loethyl)-ethylene diphosphate (070H20
H2(J)z P (0) -00H2(!H20-
Compounds with higher molecular weights such as P (0) (OOH20H207)2 have also been proposed, but these compounds, like other similar compounds, either have too large a bath dissolution with water or are hydrolyzable. This property has a detrimental effect on the durability of the fire prevention effect.
ジホスフェート(070H20H20) P (U)−
00H2−に(CHz(jjlkh −0H20−P
(C))(OOHzOH20A)2 のごとき、前記
した欠点金石していない2.2−ビス(クロロメチル)
−/、、?−プロパンジオールの誘導体も提案されてい
るが、この種の化合物はその用途の点からしばしば問題
を生じている;例えばポリウレタンフォームを防火性に
する場合、これらの化合物は粘度が余ジに大きいため、
計於ポンゾにより言1量して使用することが因島C′″
Cある・トリス(,2,、?−ジブロモ=/−プ・ロビ
ル)ホスフェ−トPO(OOH20HBrOH2Br
)3のごときブロム化ホスフェートまたはトリス(ノー
プロモー3−クロローコーグロビル)ホスフ:c、 −
11,’O[(JOH(OH2Of!= ) OH2B
r 〕3のごときクロロブロム化ホスフェートも提案
されあるいは使用さtしているが、これらの化合物は発
f7i性を有することが知られるに至ってその使用茫断
念しなければならなくなづた・本発明の新規ハロゲン化
ベンジルホスホネートは前記したごとき欠点を有して訃
らず、特にその防火効果により区別さルるものでらる。Diphosphate (070H20H20) P (U)-
00H2-(CHz(jjlkh -0H20-P
(C)) (OOHzOH20A)2, 2,2-bis(chloromethyl) which does not have the above-mentioned defects
-/、、? - Derivatives of propanediol have also been proposed, but these compounds often pose problems in terms of their use; for example, when making polyurethane foams fireproof, these compounds have too high a viscosity. ,
According to Ponzo, it is said that Innoshima C'''
C-tris(,2,,?-dibromo=/-probil)phosphate PO(OOH20HBrOH2Br
) brominated phosphates such as 3 or tris(nopromo 3-chlorochoglobil) phosph: c, -
11,'O[(JOH(OH2Of!=) OH2B
Chlorobrominated phosphates such as [r]3 have also been proposed or used, but as it became known that these compounds have f7i-producing properties, their use had to be abandoned.The present invention The new halogenated benzyl phosphonates do not suffer from the drawbacks mentioned above and are distinguished in particular by their fire protection effect.
この化合物は次の一般式(I):
0−OTI2−CHzX 0−OH20H2X(
式中、Xは塩素または臭素原子を表わす)で示される。This compound has the following general formula (I): 0-OTI2-CHzX 0-OH20H2X (
In the formula, X represents a chlorine or bromine atom).
芳香族核中の置換基Xの平均値mおよびn(これらは同
一でも異ってもよい〕は0−.1である。The average values m and n (which may be the same or different) of the substituents X in the aromatic nucleus are 0-.1.
ベンゼン核上の塩素または臭素原子の位置はオルソ、メ
タまたはノξう位であp得る。本発明は一般式(1)の
ホスホネートの2種まだはそれ以上の混合物も包含する
。The position of the chlorine or bromine atom on the benzene nucleus can be in the ortho, meta or ξ position. The present invention also includes mixtures of two or more phosphonates of general formula (1).
本発明のホスホネート’を製造する方法は環式エチレン
ジホスファイト(Illと)・ロゲン化ベンジル側の/
拙またはそれ以上と全10〜200℃の温度で反応させ
ることからなる。The method for producing the phosphonate' of the present invention is based on the cyclic ethylene diphosphite (Ill)/logenated benzyl side/
It consists of reacting with the same or higher temperature at a total temperature of 10 to 200°C.
工 工
0□○
1
+
田
駕〈べきことに、垣化ベンジルまたは臭化ベンジル(I
II)と環式ホスファイト(II)とのミハエリスーア
ルプゾプ(八1 i c h ;+ e目5−Arbu
zov )縮合が、上記反応式(11K従って、環の開
裂を伴って選択的に生起すること、すなわち、反応式(
1)の反応と同43Qに生起しPiイ)と推測される下
記の競合反応(rival reaction X21
が認め得る程に生起することなしに、(11の反応だけ
が生起することが認められた。Engineering Engineering 0□○ 1 + Tago
II) and cyclic phosphite (II) (81 i ch ; + e 5-Arbu
zov ) condensation occurs selectively with ring cleavage, that is, the reaction formula (
The following competitive reaction (rival reaction
Only 11 reactions were observed to occur without any appreciable occurrence of .
(fV)
競争反応(2)は非常に好ましくない反応である;その
理由は一方においてこの反応により副生物としてジハロ
ゲン化炭化水素が生成しそのため、ミハエリスーアルブ
ゾプ縮合の重量収率が低下しかつ最終生成物から、目的
とする防火活性に対して非常に有用なハロゲン原子が、
2個不必要に失われることKあり、他方において(IV
)のごとき環式エチレンホスホネートは一般に非常[7
1部1水分解を受は易いことに4)る。(fV) Competitive reaction (2) is a very unfavorable reaction; this is because, on the one hand, this reaction produces dihalogenated hydrocarbons as by-products, which reduces the weight yield of the Michaelis-Albuzob condensation. Moreover, the final product contains halogen atoms, which are very useful for the desired fire protection activity.
Two pieces may be lost unnecessarily, and on the other hand (IV
Cyclic ethylene phosphonates such as ) are generally very [7
1 part 1 It is easy to undergo water splitting 4).
環式ホスファイト(II)は慣用の既知の方法の一つに
より製造し州る;例えば2モルのトリエチルまたはトリ
フェニルホスファイトと3モルのエチレングリコールと
孕エステル交換させるか、またはコモルの2−ハロー/
、3..2−ジオキサポスホクンと1モルのエチレング
リコールとヲコモルの第3級アミンの存在下で反応させ
ることにより調製し得る。Cyclic phosphites (II) are prepared by one of the conventional known methods; for example, by transesterification of 2 mol of triethyl or triphenyl phosphite with 3 mol of ethylene glycol, or by transesterification of comol of 2- Hello/
, 3. .. It can be prepared by reacting 2-dioxaposphocne in the presence of 1 mole of ethylene glycol and 1 mole of tertiary amine.
反応(1)で使用されるハロゲン化ベンジル(Ill)
はトルエン全塩素化または臭素化しついで場合により蒸
留により分別することにょp製造し得る。Benzyl halide (Ill) used in reaction (1)
may be prepared by total chlorination or bromination of toluene and optionally fractionation by distillation.
mまたはnが/〜3であるハロゲン化ベンジル側が好ま
しい。場合により、使用するハロゲン、化ベア シルu
不活性であるが無害な不純物として、ポリハロトルエン
を5%まで含有し得る。The halogenated benzyl side where m or n is /-3 is preferred. Depending on the case, the halogen used, bare sil u
It may contain up to 5% polyhalotoluene as an inert but harmless impurity.
本発明の新規なハロゲン化ペンジルポスホネートは極め
て多くのプラスチックス材料、すなわち例えばポリウレ
タン、ポリスチレン、ABS、ビニル系樹脂およびエポ
キシ樹脂;ニジストマー;ポリエステル、ポリアミド、
アクリル系またはモダクリル系繊維のごとき合成繊維(
これらの合成繊維は単独であるかまたは他の天然繊維と
組合せたものであり得る);塗料;接着剤または火災の
危険から保護することが望ましい他の可燃性材料中にお
いて防火用添加剤として使用し得る。The novel halogenated pendyl phosphonates of the present invention can be used in a wide variety of plastic materials, such as polyurethanes, polystyrenes, ABS, vinyl resins and epoxy resins;
Synthetic fibers such as acrylic or modacrylic fibers (
These synthetic fibers may be used alone or in combination with other natural fibers); as fire protection additives in paints; adhesives or other combustible materials for which it is desirable to protect against fire hazards. It is possible.
本発明のホスホネートの防火特性はポリウレタンフォー
ムにおいて特に有用であり、この場合、防火効果は促進
老化試験において明らかに永久的であることが示されて
いる。The fire protection properties of the phosphonates of the present invention are particularly useful in polyurethane foams, where the fire protection effect has been shown to be clearly permanent in accelerated aging tests.
実施例/
、310gt5(Dトリフェニルホスファイト、73部
のエチレングリコールおよび0.2部部のナトリウムメ
トキシドをフラスコに装入した。Example/ A flask was charged with 310 gt5(D triphenyl phosphite, 73 parts of ethylene glycol, and 0.2 parts of sodium methoxide.
この混合物2iso℃で/、、ll一時間加熱した。エ
ステル交換により生成したフェノールを/ 999..
33Paの真空下で蒸留した後、残渣勿/ j 、3.
、? 、2 Paの真空下、/、2.?℃で蒸留して、
り0部のコ、−2′−、(:/、、2−エタン−ジ−イ
ル−ビス(/、、?。This mixture was heated at 2 iso<0>C for 1 hour. Phenol produced by transesterification/999. ..
After distillation under a vacuum of 33 Pa, the residue is 3.
,? , under a vacuum of 2 Pa, /, 2. ? Distilled at °C,
0 parts of co, -2'-, (:/,, 2-ethane-di-yl-bis(/,,?.
コージオキサホスホラ/)〕を得た。この化合物をフラ
スコに装入し、/弘コ部のジクロロベンジルクロライド
c主として、コ、弘、2.Jおよび3.’1異性体の混
合物)を添加した。混合物を/lO℃で/♂時間7Jl
]熱した後、/999.ざ、? Paの真空下、/AO
℃で蒸留して、下記の式で示さす上る化合物からなる中
性の年明液体、2.23部を得た0屈折率 nら0=7
J!t3
NMR:
’Ti ” δ、?、、? 90I;I): グ、 2
0 (Hb、Ilc )および3.乙Spp+n (l
lrl)
/3c:δ30..2 g −30,77((b+);
乙、!;、/4’−1、A、33 (Ob、Oc)およ
びq、2.7ppm (Cd)標準試料S i (OI
T3)4
実施例コ
実施例/と同様にして1.?70部のトリフェニル ホ
スファイト、り3部のエチレングリコールおよび0.2
.!;部のナトリウムメトキシド?フラスコに装入した
。この混合物を730℃で/、j時間加熱しfC後、エ
ステル交換により生成したフェノールを/ 9 F ?
、♂3 Paの真空下で蒸留した0/り0部のジクロロ
ベンジルクロライド(異性体の混合物)を直扇フラスコ
に添加した。得られた混合′JgJを/1.O’C:、
で20時間と加熱した後、720℃まで放冷した。つい
で75部のメールン蟻酸エチルで30分間処理して、生
成物の僅かな酸性度を中和した。かく得らt′1.た生
成物を/、399.ざJPaの真空下、ito℃で蒸留
したO主として実1m例の生成物からなる迅明液体、2
ざ0部が得られた。Cordioxaphosphora/)] was obtained. This compound was charged into a flask, and dichlorobenzyl chloride c of /Hiroko part was mainly mixed with Ko, Hiroko, 2. J and 3. '1 mixture of isomers) was added. Mixture /l at 0°C/♂hr 7Jl
] After heating, /999. The,? Under vacuum of Pa, /AO
Distilled at ℃ to obtain 2.23 parts of a neutral liquid consisting of the following compound with a refractive index of 0 = 7
J! t3 NMR: 'Ti'' δ,?,,? 90I;I): Gu, 2
0 (Hb, Ilc) and 3. OtsuSpp+n (l
lrl) /3c:δ30. .. 2 g −30,77((b+);
Otsu,! ;, /4'-1, A, 33 (Ob, Oc) and q, 2.7 ppm (Cd) standard sample S i (OI
T3) 4 Example 1. ? 70 parts triphenyl phosphite, 3 parts ethylene glycol and 0.2 parts
.. ! Part of sodium methoxide? The flask was charged. This mixture was heated at 730 °C for /,j hours and after fC, the phenol produced by transesterification was transferred to /9F?
, ♂ 0 parts of dichlorobenzyl chloride (mixture of isomers) distilled under a vacuum of 3 Pa was added to the straight fan flask. The obtained mixture 'JgJ is /1. O'C:,
After heating for 20 hours, the mixture was allowed to cool to 720°C. The product was then treated with 75 parts of ethyl formate for 30 minutes to neutralize the slight acidity of the product. Thus obtained t'1. /, 399. A liquid containing mainly the product of Example 1, distilled at 1° C. under a vacuum of
0 copies were obtained.
実施例3
下記の組成物を使用して軟質ポリウレタンフォーム ブ
ロックを製造した:
ポリオール UGIP(JL//、20(分子骸4to
ooまでのトリオール) 100 部水
3.S 部アミン触i(N、N−ジメチルエタノー
ルアミン) に1.、? o y金顔触s:(カ
ゾリル鍛第1錫?基材とするもの) orsl
’市販の長面活性剤シリコーン o、g
o tt防火用添加剤 10
“トルエン ジイソシアネート
LILTらNE TgoC,インデックス10t)
173 //自由膨張により
得られたポリウレタンブーツクの嵩密度は約、? 01
c7/iでめった。Example 3 A flexible polyurethane foam block was produced using the following composition: Polyol UGIP (JL//, 20 (molecular skeleton 4to
triol up to oo) 100 parts water
3. S part amine contact i (N,N-dimethylethanolamine) 1. ,? o y gold face touch s: (cazolyl forged stannous tin? base material) orsl
'Commercial long surface active agent silicone o, g
o tt Fire protection additive 10
“Toluene diisocyanate LILT et al NE TgoC, index 10t)
173 //The bulk density of polyurethane boot socks obtained by free expansion is approximately? 01
I had a hard time with c7/i.
フオームの耐火性は下記のごとき供用の芙験室試験によ
り測定した。The fire resistance of the foam was determined by the following commercial laboratory test.
一酸累指数のか11定:フランス標準試験法NFT、3
107/
一水平燃焼試+6;s : ASTM IJ−/l
q、z−7a1i’Z ”A指’Ml (oxygen
1ndex )の測定は/ 2.J X/2.S−の
断面を有する垂直試験片上で、少なくとも3分I)11
(または7Iwの長さに亘って)燃焼全行わせるのに必
要な酸素と窒累との混合物の最少濃度葡測定することに
よυ行わ扛るO耐火性の改良の程度は酸素指数の値が大
きければ大きい程、大きいことが認められた。Monoacid Cumulative Index 11: French Standard Test Method NFT, 3
107/ One horizontal combustion test +6;s: ASTM IJ-/l
q, z-7a1i'Z ``A finger'Ml (oxygen
1ndex) measurement is /2. JX/2. on a vertical specimen with a cross section of S- for at least 3 minutes I) 11
The degree of improvement in O refractoriness achieved can be determined by measuring the minimum concentration of the mixture of oxygen and nitrogen necessary for complete combustion (or over a length of 7 Iw). It was recognized that the larger the
ASTM D /lYコー7qには水平試験片(5
0x1.50x/3van)3金網上に載せ、試験片の
端部茫30秒間ガスバーナーの焔に接触させることが規
定されている。この試験法においては燃焼により破損し
た長さく多くとも、垣に接触させた端部から727節の
位置にある基準線まで)と燃焼時間とを測定する。試験
片が完全に破損する前に燃焼が自然に止りかつこのこと
が5個の試験片について起った場合、この材料は試験条
件下で”自己消火性”(SB)であるとさnる。ASTM D/lY Co.7q has a horizontal test piece (5
0x1.50x/3van) 3 placed on a wire mesh, and the end of the test piece is placed in contact with the flame of a gas burner for 30 seconds. In this test method, the length of damage caused by combustion (at most, from the end in contact with the fence to a reference line located at node 727) and burning time are measured. If combustion ceases spontaneously before complete failure of the specimen and this occurs for five specimens, the material is said to be "self-extinguishing" (SB) under the test conditions. .
防火性試験は試験片に促進老化を行う前と後とに行った
(促進老化は70℃、相対湿度qo9(、の密閉好器内
に3一時間または2り時間放置して行う)。The fire resistance test was carried out before and after the specimens were subjected to accelerated aging (accelerated aging was carried out by leaving them in a sealed container at 70° C. and relative humidity qo9 for 31 or 2 hours).
実施例/およびコの化合物の防火効果を下記の2種の市
販の防火剤と比較することにより評価しrc 。The fire retardant effects of the compounds of Example/C were evaluated by comparing them with the following two types of commercially available fire retardants.
−2−クロロエチルホスホン酸(AN’l’1BLAZ
B”7ざ、 Mobil Chemica1社製品)−
トリス(2−10ロエチル)ホスフェートすなわちT
Og P 。-2-chloroethylphosphonic acid (AN'l'1BLAZ
B”7za, Mobil Chemica1 product)
Tris (2-10 loethyl) phosphate or T
OgP.
試験結果を表中に示す。促進老化試験は特に本発明の化
合物の利点(防火効果の持続性)′ff:示している。The test results are shown in the table. Accelerated aging tests particularly demonstrate the advantages (durability of fire protection effect) of the compounds according to the invention.
Claims (1)
は同一でも異ってもよく、かつ、芳香族核中の置換基X
の平均数であってか90〜jを表わす)で衣わされる新
規なハロゲン化ベンジルホスホネート。 1mおよびnが/、コまたは3を表わす特許請求の範囲
第1項記載の化合物。 3 mおよびnがコを表わす特許811求の範囲第1項
記載の化合物。 gXが塩素原子を表わす特許請求の範囲第項記載の化合
物。 y 一般式: C6H,−mXm−CH2XおよびC
6H6−nX nQH2X(式中のX 、 mおよびn
は後記の意義を有する)のハロゲン化ベンジルの7種ま
7jHそれ以上と、一般式(■): の環式ホスファイトと全反応させることを特徴とする、
一般式(■): 0−OT42−0H2)C0−CI■2−0H2X(式
中、Xは塩素または臭累原子盆表わし、mおよびnは同
一でも異ってもよく、かつ、芳香族核中の置換基Xの平
均数であってかつ0〜J?茨わす)で表わされる新規な
ノ・ロゲン化ベンジルホスホネートの製造方法。[Claims] / General formula (I): (wherein, X represents a chlorine or bromine atom, m and n
may be the same or different, and the substituent X in the aromatic nucleus
90 to j). A compound according to claim 1, wherein 1m and n represent /, co or 3. 3. A compound according to item 1 of the scope of patent No. 811, wherein m and n represent ko. A compound according to claim 1, wherein gX represents a chlorine atom. y General formula: C6H, -mXm-CH2X and C
6H6-nX nQH2X (X, m and n in the formula
is characterized in that seven or more of 7 or more benzyl halides (having the meanings given below) are reacted with a cyclic phosphite of the general formula (■):
General formula (■): 0-OT42-0H2)C0-CI■2-0H2X (wherein, X represents chlorine or an odorant, m and n may be the same or different, and A method for producing a novel urogenated benzylphosphonate, which is the average number of substituents X in the compound and is expressed by 0 to J?
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8214727A FR2532317A1 (en) | 1982-08-27 | 1982-08-27 | NOVEL HALOGENATED BENZYL PHOSPHONIC ESTERS, THEIR MANUFACTURING METHOD AND THEIR APPLICATION AS FLAME RETARDANTS |
FR8214727 | 1982-08-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS5959695A true JPS5959695A (en) | 1984-04-05 |
Family
ID=9277091
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58154247A Pending JPS5959695A (en) | 1982-08-27 | 1983-08-25 | Novel halogenated benzulphosphonate and manufacture |
Country Status (9)
Country | Link |
---|---|
JP (1) | JPS5959695A (en) |
BE (1) | BE897453A (en) |
CA (1) | CA1196008A (en) |
DE (1) | DE3330934C2 (en) |
FR (1) | FR2532317A1 (en) |
GB (1) | GB2126233B (en) |
IL (1) | IL69194A0 (en) |
IT (1) | IT1162940B (en) |
NL (1) | NL8302991A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2228939B (en) * | 1989-03-09 | 1992-05-20 | Ciba Geigy Ag | Flame retardant compositions |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3547842A (en) * | 1969-08-05 | 1970-12-15 | American Cyanamid Co | Flame-retardant polyurethanes |
-
1982
- 1982-08-27 FR FR8214727A patent/FR2532317A1/en active Granted
-
1983
- 1983-07-11 IL IL69194A patent/IL69194A0/en unknown
- 1983-08-03 BE BE0/211292A patent/BE897453A/en not_active IP Right Cessation
- 1983-08-25 JP JP58154247A patent/JPS5959695A/en active Pending
- 1983-08-26 CA CA000435422A patent/CA1196008A/en not_active Expired
- 1983-08-26 GB GB08322986A patent/GB2126233B/en not_active Expired
- 1983-08-26 IT IT67902/83A patent/IT1162940B/en active
- 1983-08-26 NL NL8302991A patent/NL8302991A/en not_active Application Discontinuation
- 1983-08-27 DE DE3330934A patent/DE3330934C2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
GB2126233B (en) | 1987-08-12 |
DE3330934C2 (en) | 1985-06-20 |
IT8367902A0 (en) | 1983-08-26 |
FR2532317B1 (en) | 1984-12-21 |
BE897453A (en) | 1984-02-03 |
GB8322986D0 (en) | 1983-09-28 |
DE3330934A1 (en) | 1984-04-05 |
IT1162940B (en) | 1987-04-01 |
CA1196008A (en) | 1985-10-29 |
GB2126233A (en) | 1984-03-21 |
IL69194A0 (en) | 1983-11-30 |
NL8302991A (en) | 1984-03-16 |
FR2532317A1 (en) | 1984-03-02 |
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