CN1459452A - Phosphite type liquid alicyclic olefin compound and its preparation method - Google Patents
Phosphite type liquid alicyclic olefin compound and its preparation method Download PDFInfo
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- CN1459452A CN1459452A CN 02119742 CN02119742A CN1459452A CN 1459452 A CN1459452 A CN 1459452A CN 02119742 CN02119742 CN 02119742 CN 02119742 A CN02119742 A CN 02119742A CN 1459452 A CN1459452 A CN 1459452A
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- alicyclic olefin
- phosphite type
- type liquid
- olefin compound
- compound
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- -1 alicyclic olefin compound Chemical class 0.000 title claims abstract description 50
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 title claims abstract description 21
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical group ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000001175 calcium sulphate Substances 0.000 claims description 2
- 235000011132 calcium sulphate Nutrition 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 2
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 9
- 125000002723 alicyclic group Chemical group 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 150000001925 cycloalkenes Chemical class 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000010907 mechanical stirring Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000007792 addition Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000006837 decompression Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- ABZZOPIABWYXSN-UHFFFAOYSA-N cyclohex-3-en-1-ol Chemical compound OC1CCC=CC1 ABZZOPIABWYXSN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical group ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 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
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- PSBABBDEUFNFKJ-UHFFFAOYSA-N cyclopent-2-en-1-ol Chemical compound OC1CCC=C1 PSBABBDEUFNFKJ-UHFFFAOYSA-N 0.000 description 1
- WEIMJSIRDZDHAH-UHFFFAOYSA-N cyclopent-3-en-1-ol Chemical compound OC1CC=CC1 WEIMJSIRDZDHAH-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZWRDBWDXRLPESY-UHFFFAOYSA-N n-benzyl-n-ethylethanamine Chemical compound CCN(CC)CC1=CC=CC=C1 ZWRDBWDXRLPESY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种亚磷酸酯型的液体脂环族烯烃化合物，其结构式如下。本发明还公开了其制备方法，按照下列步骤进行的：1.脂环族烯烃亚磷酸酯的合成：脂环族烯烃醇化物与三卤化磷、叔胺按照3.0∶0.8－1.2∶3.0－6.0摩尔比在－10℃－20℃将三卤化磷滴加到脂环族烯烃醇化物，叔胺的有机溶液中，待滴加完毕后升温至50－80℃，并在此温度反应0.5－2小时，制得脂环族烯烃亚磷酸酯。2.脂环族烯烃亚磷酸酯的纯化。本发明化合物可用作环烯烃聚合反应的单体、合成脂环族环氧树脂的中间体、增塑剂、抗氧剂、阻燃剂或阻燃增塑剂。
The invention discloses a phosphite type liquid alicyclic olefin compound, the structural formula of which is as follows. The invention also discloses its preparation method, which is carried out according to the following steps: 1. Synthesis of alicyclic olefin phosphite: alicyclic olefin alcoholate, phosphorus trihalide and tertiary amine according to the ratio of 3.0:0.8-1.2:3.0-6.0 Add phosphorus trihalide dropwise to the organic solution of alicyclic olefin alcoholates and tertiary amines at a molar ratio of -10°C-20°C, heat up to 50-80°C after the dropwise addition, and react at this temperature for 0.5-2 hours, the cycloaliphatic olefin phosphite was prepared. 2. Purification of cycloaliphatic olefin phosphites. The compound of the present invention can be used as a monomer for cycloolefin polymerization, an intermediate for synthesizing alicyclic epoxy resin, a plasticizer, an antioxidant, a flame retardant or a flame retardant plasticizer.
Description
Technical field:
The present invention relates to a kind of alicyclic olefin compound and preparation method thereof, particularly a kind of phosphite type alicyclic olefin compound and preparation method thereof.
Background technology:
Alicyclic olefin is to study and use all a compounds very widely.Alicyclic olefin can be used as monomer carries out cyclopolymerization and the ring copolymerization, obtain fused ring polymers system (J.Polym.Sci.:Part A-1,1967,5,1827-1844); Also can be used as intermediate and carry out alkene prepared in reaction olefin resin (U.S.Pat.4849532 and JP Patent 05032647A).Can also generate alicyclic epoxide compound with the peroxy acid oxidation.Synthetic method can be raw material synthetic (GE.Pat.1099733 and U.S.Pat.2848426) with phenol or Resorcinol, can be starting raw material also with divinyl and propenal or crotonaldehyde, through reactions such as diene additions, obtain the ester or the etherate (U.S.Pat.2750395 and U.S.Pat.2745847) of alicyclic ring diolefine.The compound of alicyclic olefin is similar to fatty compounds, owing to have low C/H ratio, and intramolecularly do not have the conjugation rock steady structure, possesses fire retardancy hardly, reaches the practical application purpose for making it, must carry out fire-retardant finish to it.
At present, flame resistant method mainly contains two kinds:
A kind of method of carrying out fire-retardant finish comprises inorganic combustion inhibitor, as aluminium hydroxide, magnesium hydroxide, ammonium polyphosphate, simple substance red phosphorus, borate family for adding fire retardant; Halogen containing flame-retardant such as bromide fire retardant, chlorine-based flame retardant; Phosphonium flame retardant such as phosphoric acid ester, phosphonic acid ester.In order to reach the ideal flame retardant effect, the add-on of fire retardant is generally all bigger, can affect greatly Mechanical Properties of Materials, electrical property, viscosity etc., and the compatibility problem of existence and material.
Another kind of flame resistant method is to adopt reactive flame-retardant system, and promptly material molecule itself has the group of tool fire retardancy.The fire-retardant group of more introducing so far is a halogen atom.This class material also has the total meeting generation hydrogen halide that is heated of halogenated flame retardant, the big shortcoming of being fuming when burning produces Dioxins, burning, and disabled in Europe at present, developed countries such as the Japanese U.S. also reduce the use of bromine-containing compound gradually.
For requirement on environmental protection, present countries in the world are developed country especially, is seeking not halogen-containing flame-retardant system.Normally adopt physical method, in base material, dose a large amount of phosphorated fire retardants.As JP2000-154234, CN1257075 and CN1147517 disclose the manufacture method of 3 kinds of phosphate flame retardants respectively.Fire retardant and base material are dosed calorifics and the bigger decline of mechanical property that fire retardant must cause material in a large number owing to there is the problem of dispersed and interface compatibility.And phosphorus is incorporated in the phosphite type compound molecule with covalent, can when possessing fire retardancy, not reduce the physical and mechanical properties of material.It is the new direction of flame-retarded technology development.
Summary of the invention:
The structural formula of a kind of phosphite type liquid alicyclic olefin compound of the present invention is as follows:
M is 0 to 10 positive integer; R is a hydrogen, C
1-C
5Alkyl (CH
3～-C
5H
11), phenyl, or benzyl; N is the positive integer of 0-5, for example specifically comprises following compound:
Work as R=H, m=0, during n=0, the structural formula of gained compound is
Work as R=H, m=1, during n=0, the structural formula of gained compound
Work as R=H, m=2, during n=0, the gained structural formula of compound
The preparation method of a kind of phosphite type liquid alicyclic olefin compound of the present invention, specifically carry out according to the following step:
1. the alicyclic olefin phosphorous acid ester is synthetic:
Alicyclic olefin alcoholate and phosphorus trihalide, tertiary amine are according to 3.0: 0.8-1.2: the 3.0-6.0 (ratio preferred 3.0 of alicyclic olefin alcoholate and phosphorus trichloride: 0.9-1.1; The ratio preferred 3 of alicyclic olefin alcoholate and tertiary amine: 3.1-4.0.) mol ratio-10 ℃-20 ℃ (preferred-5 ℃-5 ℃) phosphorus trihalide is added drop-wise in the organic solution of alicyclic olefin alcoholate, tertiary amine, every mole of alicyclic olefin alcoholate of solvent load: 75-250ml/, preferred every mole of alicyclic olefin alcoholate of 100-150ml/.Be warming up to 50～80 ℃ after waiting to dropwise, and, make the phosphorous acid ester of alicyclic olefin alcoholate this thermotonus 0.5～2 hour.Selected solvent can be one or more mixed solvents such as benzene,toluene,xylene, tetrahydrofuran (THF), sherwood oil, methylene dichloride, chloroform, tetracol phenixin, acetone, benzene, ethyl acetate, preferred benzene; Selected phosphorus trihalide is phosphorus oxychloride, tribromo oxygen phosphorus, from cost consideration, and preferred phosphorus trichloride; Used tertiary amine is triethylamine, Tri-n-Propylamine, tri-isopropyl amine, triallylamine, pyridine, N, accelerine, N, one or more mixture such as N-Diethyl Aniline, preferred triethylamine, N, accelerine.
The structural formula of described alicyclic olefin alcoholate is as follows:
M is 0 to 10 positive integer; R is a hydrogen, C
1-C
5Alkyl (CH
3～-C
5H
11), phenyl, or benzyl; N is the positive integer of 0-5.
2. the purifying of alicyclic olefin phosphorous acid ester
With the carboxylate of top gained,, extremely neutral with deionized water wash again with the sodium hydroxide solution washing to not showing acid, add siccative, siccative is anhydrous sodium sulphate, anhydrous magnesium sulfate, Calcium Chloride Powder Anhydrous, anhydrous calciumsulphate, preferred anhydrous magnesium sulfate.Remove by filter siccative, slough solvent, underpressure distillation or separate with column chromatography can get pure product.
Liquid alicyclic olefin compound of the present invention is through infrared spectra, and elemental analysis method detects, and has confirmed that its structure is the alicyclic olefin compound that contains phosphorous acid ester bond and two keys.See embodiment.
Compound of the present invention can be used as the monomer of cyclopolymerization reaction and the intermediate of synthesis of alicyclic epoxy resin.See the inventor with the same applying date of the present invention in careful patent: a kind of phosphorous alicyclic epoxide compound and preparation method thereof.
Embodiment
Embodiment 1
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 3-cyclohexenol 14.7g (0.15mol), 15.9g (0.165mol) triethylamine, and 25ml benzene, mechanical stirring is bathed with cryosel simultaneously and is cooled to-4 ℃; Drip phosphorus trichloride, the control rate of addition rises temperature of reaction system and is not higher than 5 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 70 ℃, be incubated 2 hours.Reduce to room temperature, add deionized water 30ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous magnesium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 2-cyclohexenol phosphorous acid ester.Column chromatography is separated, and gets product 10.8 grams.Yield 68%.
IR(KBr)：1054cm
-1，762cm
-1(P-O)，；3012cm
-1(H-C＝C-H)；1645cm
-1(H-C＝C-H)
Anal.calcd.For?C，67.08％，H，8.38％.Found：C，67.17％，H，8.31％
Embodiment 2
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 3-cyclopentenol 16.8g (0.20mol), 21.2g (0.21mol) triethylamine, and 30ml benzene, mechanical stirring is bathed with cryosel simultaneously and is cooled to-6 ℃; Drip phosphorus trichloride, the control rate of addition rises temperature of reaction system and is not higher than 5 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 80 ℃, be incubated 2 hours.Reduce to room temperature, add deionized water 30ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous magnesium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 3-cyclopentenol phosphorous acid ester.Column chromatography is separated, and gets product 12.3 grams.Yield 67%.
IR(KBr)：1060cm
-1，754cm
-1(P-O)；3010cm
-1(H-C＝C-H)；1638cm
-1(H-C＝C-H)
Anal.calcd.For?C，64.28％，H，7.50％.Found：C，64.33％，H，7.42％
Embodiment 3
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 2-cyclopentenol 25.2g (0.30mol), 31.8g (0.315mol) triethylamine, and 45m toluene, mechanical stirring is bathed with cryosel simultaneously and is cooled to-5 ℃; Drip phosphorus trichloride, the control rate of addition rises temperature of reaction system and is not higher than 5 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 70 ℃, be incubated 1.5 hours.Reduce to room temperature, add deionized water 30ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With the Calcium Chloride Powder Anhydrous drying; Solvent is sloughed in decompression, gets colourless transparent liquid 3-cyclopentenol phosphorous acid ester.Column chromatography is separated.Get product 17.6 grams.Yield 63%.
IR(KBr)：1050cm
-1，748cm
-1(P-O)；3010cm
-1(H-C＝C-H)；1638cm
-1(H-C＝C-H)
Anal.calcd.For?C，64.28％，H，7.50％.Found：C，64.22％，H，7.59％
Embodiment 4
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 3-cyclohexenol 39.2g (0.40mol), 31.8g (0.42mol) triethylamine, and 50ml benzene, mechanical stirring is bathed with cryosel simultaneously and is cooled to-4 ℃; Drip phosphorus trichloride, the control rate of addition rises temperature of reaction system and is not higher than 5 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 65 ℃, be incubated 1 hour.Reduce to room temperature, add deionized water 30ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous sodium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 3-cyclohexenol phosphorous acid ester.Column chromatography is separated.Get product 30.3 grams.Yield 70%.
IR(KBr)：1047cm
-1，757cm
-1(P-O)；3014cm
-1(H-C＝C-H)；1641cm
-1(H-C＝C-H)
Anal.calcd.For C, 67.08%, H, 8.38%.Found:C, 67.17%, H, 8.33% embodiment 5
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 2,3-cyclohexenyl methyl alcohol 33.6g (0.30mol), 38.1g (0.315mol) N, N-dimethyl benzylamine, 60ml benzene, mechanical stirring are bathed with cryosel simultaneously and are cooled to-7 ℃; Drip phosphorus trichloride, the control rate of addition rises temperature of reaction system and is not higher than 10 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 60 ℃, be incubated 1 hour.Reduce to room temperature, add deionized water 30ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous sodium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 2,3-cyclohexenyl methyl alcohol phosphorous acid ester.Column chromatography is separated.Get product 26.1 grams.Yield 72%.
IR(KBr)：1044cm
-1，759cm
-1(P-O)；1257(P＝O)；3010cm
-1(H-C＝C-H)；1651cm
-1(H-C＝C-H)
Anal.calcd.For?C，69.23％，H，9.07％.Found：C，69.27％，H，9.15％
Embodiment 6
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 3,4-cyclohexenyl methyl alcohol 33.6g (0.30mol), 45.7g (0.315mol) N, N-diethyl benzylamine, 50ml benzene, mechanical stirring are bathed with cryosel simultaneously and are cooled to-6 ℃; Drip phosphorus trichloride, the control rate of addition rises temperature of reaction system and is not higher than 10 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 60 ℃, be incubated 1 hour.Reduce to room temperature, add deionized water 30ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous sodium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 2,3-cyclohexenyl methyl alcohol phosphorous acid ester.Column chromatography is separated.Get product 24.7 grams.Yield 69%.
IR(KBr)：1061cm
-1，748cm
-1(P-O)；3019cm
-1(H-C＝C-H)；1645cm
-1(H-C＝C-H)
Anal.calcd.For?C，69.23％，H，9.07％.Found：C，69.20％，H，9.03％
Embodiment 7
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 2-suberene alcohol 22.4g (0.20mol), 21.2g (0.21mol) triethylamine, and 45ml dimethylbenzene, mechanical stirring is bathed with cryosel simultaneously and is cooled to-5 ℃; Drip phosphorus trichloride, the control rate of addition rises temperature of reaction system and is not higher than 10 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 55 ℃, be incubated 1.5 hours.Reduce to room temperature, add deionized water 25ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous sodium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 2-suberene alcohol phosphoric acid ester.Column chromatography is separated.Get product 14.12 grams.Yield 58%.
IR(KBr)：1025cm
-1(P-O)；3014cm
-1(H-C＝C-H)；1643cm
-1(H-C＝C-H)
Anal.calcd.For?C，69.23％，H，9.07％.Found：C，69.20％，H，9.11％
Claims (9)
1. the liquid alicyclic olefin compound of a phosphite type, its structural formula is as follows:
M is 0 to 10 positive integer; R is a hydrogen, C
1-C
5Alkyl (CH
3～-C
5H
11), phenyl, or benzyl; N is the positive integer of 0-5.
2. according to a kind of phosphite type liquid alicyclic olefin compound of claim 1, it is characterized in that R=H, m=0, n=0.
3. according to a kind of phosphite type liquid alicyclic olefin compound of claim 1, it is characterized in that R=H, m=1, n=0.
4. according to a kind of phosphite type liquid alicyclic olefin compound of claim 1, it is characterized in that R=H, m=2, n=0.
5. according to a kind of phosphite type liquid alicyclic olefin compound of claim 1, it is characterized in that R=CH
3, m=1, n=1.
6. the preparation method of a phosphite type alicyclic olefin compound, carry out according to the following step:
(1) the alicyclic olefin phosphorous acid ester is synthetic:
Alicyclic olefin alcoholate and phosphorus trihalide, tertiary amine are according to 3.0: 0.8-1.2: the 3.0-6.0 mol ratio is added drop-wise to the alicyclic olefin alcoholate at-10 ℃-20 ℃ with phosphorus trihalide, in the organic solution of tertiary amine, every mole of alicyclic olefin alcoholate of solvent load: 75-250ml/; Be warming up to 50-80 ℃ after waiting to dropwise, and, make the alicyclic olefin phosphorous acid ester this thermotonus 0.5-2 hour;
Solvent for use can be one or more mixed solvents of benzene,toluene,xylene, tetrahydrofuran (THF), sherwood oil, methylene dichloride, chloroform, tetracol phenixin, acetone, benzene, ethyl acetate;
Selected described phosphorus trihalide is phosphorus trichloride, phosphorus tribromide;
Described tertiary amine is triethylamine, Tri-n-Propylamine, tri-isopropyl amine, triallylamine, pyridine, N, accelerine, N, N-dimethyl benzylamine, N, N-Diethyl Aniline, N, the mixture of one or more of N-diethyl benzylamine;
The structural formula of described alicyclic olefin alcoholate is as follows:
M is 0 to 10 positive integer; R is a hydrogen, C
1-C
5Alkyl (CH
3～-C
5H
11), phenyl, or benzyl; N is the positive integer of 0-5;
(2). the purifying of alicyclic olefin phosphorous acid ester
With the carboxylate of top gained,, extremely neutral with deionized water wash again with the sodium hydroxide solution washing to not showing acid, add siccative, siccative is anhydrous sodium sulphate, anhydrous magnesium sulfate, Calcium Chloride Powder Anhydrous, anhydrous calciumsulphate, preferred anhydrous magnesium sulfate.Remove by filter siccative, slough solvent, underpressure distillation or separate with column chromatography can get pure product.
7. according to the preparation method of a kind of phosphite type liquid alicyclic olefin compound of claim 6, it is characterized in that the described alicyclic olefin alcoholate and the ratio of phosphorus trichloride are 3.0: 0.9-1.1.
8. according to the preparation method of a kind of phosphite type liquid alicyclic olefin compound of claim 6, it is characterized in that the described alicyclic olefin alcoholate and the ratio of tertiary amine are 3: 3.1-4.0.
9. according to the preparation method of a kind of phosphite type liquid alicyclic olefin compound of claim 6, it is characterized in that described solvent is a benzene; Described phosphorus trihalide is a phosphorus trichloride; Described tertiary amine is triethylamine, N, accelerine.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177504B (en) * | 2006-11-10 | 2012-04-18 | 住友化学株式会社 | Phosphite composition and its preparation method |
| CN113174283A (en) * | 2021-04-02 | 2021-07-27 | 安徽中天石化股份有限公司 | High-performance phosphate flame-retardant hydraulic oil |
-
2002
- 2002-05-14 CN CN 02119742 patent/CN1459452A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177504B (en) * | 2006-11-10 | 2012-04-18 | 住友化学株式会社 | Phosphite composition and its preparation method |
| CN113174283A (en) * | 2021-04-02 | 2021-07-27 | 安徽中天石化股份有限公司 | High-performance phosphate flame-retardant hydraulic oil |
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