CN101497691A - High activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol and preparation thereof - Google Patents
High activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol and preparation thereof Download PDFInfo
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- CN101497691A CN101497691A CNA2008101877053A CN200810187705A CN101497691A CN 101497691 A CN101497691 A CN 101497691A CN A2008101877053 A CNA2008101877053 A CN A2008101877053A CN 200810187705 A CN200810187705 A CN 200810187705A CN 101497691 A CN101497691 A CN 101497691A
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- epoxy chloropropane
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- 229920002755 poly(epichlorohydrin) Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 63
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 229920000570 polyether Polymers 0.000 claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 150000005846 sugar alcohols Polymers 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- -1 trihydroxyethyl isocyanuric ester Chemical class 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 13
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- LGRDAQPMSDIUQJ-UHFFFAOYSA-N tripotassium;cobalt(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Co+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] LGRDAQPMSDIUQJ-UHFFFAOYSA-N 0.000 claims description 4
- 229940102001 zinc bromide Drugs 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002924 oxiranes Chemical class 0.000 claims description 2
- 229920006250 telechelic polymer Polymers 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 description 11
- 150000001298 alcohols Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000007670 refining Methods 0.000 description 11
- 230000004044 response Effects 0.000 description 11
- 239000004814 polyurethane Substances 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000013535 sea water Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000013016 damping Methods 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000001046 anti-mould Effects 0.000 description 1
- 239000002546 antimould Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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- Polyethers (AREA)
Abstract
The invention relates to high activity hydroxy terminated polyepichlorohydrin polylol with simple preparation technology and good color, and the preparation method thereof. The high activity hydroxy terminated polyether has the molecular structure including a large quantity of methylene lateral chloro groups and terminated by epoxy ethane or propylene oxide, and the high activity hydroxy terminated polyepichlorohydrin polylol has the average relative molecular mass of 500-9000 and the average hydroxide radical functionality of 2-3. The preparation method comprises the following steps: low molecular mass initiator and dual-metal prussiate complex compound catalyst are added in a pressure-proof reaction kettle, volatile components are removed in a vacuumed mode, part of epoxy chloropropane are added in the low molecular mass initiator and dual-metal prussiate complex compound catalyst, all the reactants are heated to 100-140 DEG to react under the nitrogen protection and the high-speed stirring, and the rest part of epoxy chloropropane is added gradually drop by drop after the activation; after the polymerization reaction is finished, the temperature is reduced to 90-120 DEG C, propylene oxide or epoxy ethane is added drop by drop for end capping, and residual monomer is removed in a vacuumed way after the reaction, thus the hydroxy terminated polyepichlorohydrin polylol is obtained.
Description
Technical field
The invention belongs to polymkeric substance synthetic materials polyether glycol technical field, be specifically related to a kind of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol and preparation method thereof.
Background technology
Polyether glycol is one of main raw material of synthesis of polyurethane material, now has been widely used in the synthetic of all respects such as hard polyurethane foam, flexible PU foam, polyurethane elastomer, microporous polyurethane elastomer, polyurethane coating and polyurethane adhesive.The mechanical property that it is excellent and can operate processibility easily and make it in the modern life, have wide development space.At present, the polyether glycol of heavy industrialization and widespread use mostly is to adopt poly(propylene oxide) ether, polyethylene oxide ether, propylene oxide and the oxyethane copolyether of anionoid polymerization and with ethylene oxide-capped poly(propylene oxide) ether.This type of polyether glycol ehter bond internal cohesive energy is lower, is easy to rotation, so good by the polyurethane material low temperature kindliness of its preparation, warping strength performance is good, and has performance such as water tolerance, anti-mould preferably.But its water tolerance is with respect to fresh water, owing to contain each a large amount of metal ion species in the seawater, has very strong corrodibility, makes this polyether glycol have a greatly reduced quality aspect the sea water resistance performance, can not well be applied in the aspect, ocean.Along with deepening continuously of research and application, it is found that terminal hydroxy group Hydrin polyvalent alcohol (PECH) owing to have a large amount of METHYLENE CHLORIDE side groups on its molecular chain, chlorinity is up to 38%, has extraordinary corrosion resistance, the existence of simultaneously a large amount of METHYLENE CHLORIDE side groups has also increased intermolecular internal friction, make the material that contains PECH have very high ratio of damping, can be used as the tackiness agent and the Embedding Material of sea water resistance, oil resistant, damping, thereby infer that it will have application prospects.
At present, the development and use of relevant terminal hydroxy group Hydrin ether are less relatively, and domestic almost do not have, and have suitability for industrialized production on a small scale abroad.This may be relevant with present catalyst system.Owing to contain a chlorine atom on the epoxy chloropropane monomer molecule structure, therefore can not be with its polymerizations of negatively charged ion catalyst system catalysis such as traditional NaOH or KOH.The synthetic of current terminal hydroxy group Hydrin ether all is to adopt BF
3, SnCl
4Realize Deng cationic polymerisation catalyst.As everyone knows, cationoid polymerisation has a lot of disadvantages, for example reaction is acutely wayward, very easily chain transfer taking place and makes the polymkeric substance relative molecular mass not high, molecular weight distribution is wide, polymkeric substance degree of unsaturation height, the polymer end hydroxy radical content is few or the like, and this is totally unfavorable to preparation high performance polyurethane material.Moreover, adopt the synthetic terminal hydroxy group Hydrin ether of cationoid polymerisation to also have a lot of otherwise shortcomings at present, for example among patent US4340749, US4391970, US4431845, US2327053, the US2380185 with metal halide SnCl
4For catalyzer can synthesize terminal hydroxy group Hydrin ether, but the polyethers that this cationoid polymerisation generates is a black, has seriously restricted its application.And with SnCl
4For catalyzer synthetic PECH contains the impurity of 10-20%, as oligopolymer, the byproducts such as functional group of hydroxyl not, and the preparation molecular weight is big more, and impurity the more.Producing cyclic oligomer is big characteristics of cationoid polymerisation.Remove impurity as need, then must carry out time-consuming distillation and extraction.In addition, adopt the product molecular weight distribution of cationic polymerization wide, influence the physicals of material.Patent US4879419 adopts SnCl
4Being Primary Catalysts, is that co-catalyst synthesizes PECH with the carboxylic acid.The molecular weight distribution of product has narrowed down, and generally is lower than 1.5 (molecular weight was less than 2000 o'clock), good reaches (when adopting co-catalyst) below 1.2.And cyclic oligomer content is below 2% in the product of 1000 molecular weight, and when adopting co-catalyst even do not have oligopolymer (when the molecular weight of product when not being too big), and color shoals.But, still have by product to produce, and molecular weight distribution also can broaden gradually along with the increase of molecular weight.
Institute's these terminal hydroxy group Hydrin ethers of synthetic all are end capped with secondary hydroxyl mostly at present, the relative primary hydroxyl of its reactive behavior will be low a lot, and, make the active of hydroxyl further reduce because the terminal hydroxy group next door has sterically hindered great METHYLENE CHLORIDE group.Introduced it in the contribution of being done aspect end group activity of the poly-ECH ether of improvement terminal hydroxy group at these question patents EP0042505, US5164521 etc., it utilizes oxyethane etc. to carry out termination process, thereby obtains having the terminal hydroxy group Hydrin ether of primary hydroxyl.This type of catalyzer is when the polymerization of catalysis epoxy chloropropane, and the reaction times reaches more than 20 hour, carries out termination process, and the reaction times also can further increase.
Summary of the invention
At above problem, this patent has been invented a kind of new method for preparing high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol.This method is to adopt bimetallic cyanide complex catalyst (DMC) by the incompatible preparation high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol of polycomplexation.This method catalytic efficiency height, the content of catalyzer in polymkeric substance is few, metal ion neutralization product Zn
2+And Co
3+Residual quantity is low, thus postprocessing working procedures such as the purification of release product, catalyst separating, and preparation technology is simple, product colour good (for slightly yellow or yellowish green transparence thick liquid), the molecular weight height can be regulated arbitrarily, narrow molecular weight distribution, and do not have the by product generation in the polymerization process.
Technical scheme of the present invention is: a kind of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol, it is characterized in that this polyether glycol molecular structure is the end hydroxy polyether polyvalent alcohol that has a large amount of METHYLENE CHLORIDE side groups, its average molecular mass 500～9000, the average hydroxy functionality is between 2～3.
Described terminal hydroxy group Hydrin ethoxylated polyhydric alcohol is that a kind of end group is the telechelic polymer of primary hydroxyl or secondary hydroxyl.
High activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol of the present invention is to adopt bimetallic cyanide complex catalyst (DMC) to come the homopolymerization of catalysis epoxy chloropropane by polycoordination mechanism, and then the polyether polyol with high activity that obtains with oxyethane or propylene oxide end-blocking.
The average molecular mass of this terminal hydroxy group Hydrin ethoxylated polyhydric alcohol 500～2000, the average hydroxy functionality is between 2～3 the time, can be used as the raw material of synthesis of polyurethane and toluene and one or more mixture reaction in the vulcabond, diphenylmethanediisocyanate, poly methylene poly phenyl poly isocyanate, polyisocyanates performed polymer prepares oil resistant, sea water resistance, acid-and base-resisting polyurethane adhesive, polyurethane coating etc.
The average molecular mass of this terminal hydroxy group Hydrin ethoxylated polyhydric alcohol 2000～9000, the average hydroxy functionality is between 2～3 the time, can be used as the raw material of synthesis of polyurethane and toluene and one or more mixture reaction in the vulcabond, diphenylmethanediisocyanate, poly methylene poly phenyl poly isocyanate, polyisocyanates performed polymer prepares seal gum, damping polyurethane elastomerics, damping polyurethane coating of various sea water resistances, grease-proof cable plug etc.
The preparation method of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol of the present invention is as follows:
(1) in withstand voltage reactor, adds small molecular weight initiator, bimetallic cyanide complex catalyst, vacuum is deviate from volatile component, add the part epoxy chloropropane, be heated to 100～140 ℃ then, under the condition of nitrogen protection and high-speed stirring, react; Progressively drip the residual epoxide chloropropane behind the reacting activation.
After the epoxy chloropropane polymerization is finished in (2) (1) steps, reactor temperature is reduced to 90～120 ℃, drip propylene oxide or oxyethane again and carry out end-blocking, reaction finishes, vacuum is deviate from residual monomer, obtain average molecular mass 500～9000, the average hydroxy functionality is at 2～3 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
Small molecular weight initiator in the above-mentioned steps (1) is a propylene glycol, 1,4-butyleneglycol, 4,4-dihydroxy-diphenyl propane, relative molecular mass are that 400 two functionality polyether glycols, glycerol, trihydroxyethyl isocyanuric ester, relative molecular mass are that 250 three-functionality-degree polyether glycol, relative molecular mass are one or more the mixture in 700 the three-functionality-degree polyether glycol.
The a part of epoxy chloropropane in the above-mentioned steps (1) and the mass ratio of remainder epoxy chloropropane are between 100:0～1:99.
The mol ratio of small molecular weight initiator and epoxy chloropropane is between 1:4～1:100 in the above-mentioned steps (1).
Bimetallic cyanide complex catalyst is that the trimethyl carbinol is that the bimetallic cyanide complex catalyst of one of part is a disperse phase, the oligomer polyol that contains reactive hydrogen is the emulsion form bimetallic cyanide complex catalyst of external phase in the above-mentioned steps (1).Wherein the bimetallic cyanide complex catalyst consumption accounts for 300～800ppm. of institute's synthetic polyether glycol quality
Bimetallic cyanide complex catalyst is that potassium hexacyanocobaltate and zinc salt prepare through operations such as complexing reaction, washing, dryings in the presence of water, the trimethyl carbinol, polyether glycol in the above-mentioned steps (1).
The preparation method of above-mentioned bimetallic cyanide complex catalyst, it is characterized in that above-mentioned zinc salt is one or more the mixture in zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, zinc phosphate, zinc carbonate, the zinc oxalate, the mol ratio of zinc salt and Cobalt Potassium Cyanide is between 1.5:1～20:1, and wherein the mol ratio of zinc bromide and Cobalt Potassium Cyanide is between 1.8:1～15:1.
The mol ratio of Hydrin ether and oxyethane or propylene oxide is between 1:1～1:3 in the above-mentioned steps (2).
The present invention compared with prior art has the following advantages:
High activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol of the present invention is to adopt bimetallic cyanide complex catalyst catalysis epoxy chloropropane polymeric, belongs to polycoordination mechanism, and it is different from traditional cationoid polymerisation.Utilize the big I of this catalyst system polymericular weight to regulate arbitrarily, narrow molecular weight distribution, degree of unsaturation is low, can be used for polyurethane material synthetic of high performance requirements; No coupling product produces in the polymerization process, the catalytic activity height of catalyzer, and the add-on of catalyzer is few in the polymerization process, metal ion neutralization product Zn
2+And Co
3+Residual quantity is low, thus postprocessing working procedures such as the purification of release product, catalyst separating, and preparation technology is simple; Institute's synthetic polymkeric substance is with primary hydroxyl or the end capped terminal hydroxy group Hydrin of secondary hydroxyl ethoxylated polyhydric alcohol, reactive behavior height during with isocyanate reaction; Polymeric articles is slightly yellow or yellowish green transparence thick liquid, and the black or the amber terminal hydroxy group Hydrin ether that obtain than cationoid polymerisation have had great change on color.Be easy to realize suitability for industrialized production and reach the requirement of Industrial products colourity.
Embodiment
The preparation method of 1. 1 kinds of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohols of embodiment.In withstand voltage reactor, add 15g 4,4-dihydroxy-diphenyl propane, 0.099g bimetallic cyanide complex catalyst (DMC), vacuum is deviate from volatile component, adds the 90g epoxy chloropropane, be heated to 128 ℃ then, under the condition of nitrogen protection and high-speed stirring, react; Question response progressively drips remaining 92.4g epoxy chloropropane after activating.After the epoxy chloropropane polymerization is finished, reactor temperature is reduced to 115 ℃, drip the 17.6g reacting ethylene oxide and carry out end-blocking.After reaction was finished, vacuum was deviate from residual monomer, refining obtained that average molecular mass is 3264, the average hydroxy functionality is 2 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
The preparation method of 2. 1 kinds of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohols of embodiment.In withstand voltage reactor, add 15g 4,4-dihydroxy-diphenyl propane, 0.132g DMC, vacuum is deviate from volatile component, adds the 90g epoxy chloropropane, is heated to 128 ℃ then, reacts under the condition of nitrogen protection and high-speed stirring; Question response progressively drips remaining 224g epoxy chloropropane after activating.After the epoxy chloropropane polymerization is finished, reactor temperature is reduced to 115 ℃, drip the 17.6g reacting ethylene oxide and carry out end-blocking.After reaction was finished, vacuum was deviate from residual monomer, refining obtained that average molecular mass is 5264, the average hydroxy functionality is 2 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
The preparation method of 3. 1 kinds of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohols of embodiment.In withstand voltage reactor, add 15g 4,4-dihydroxy-diphenyl propane, 0.099g DMC, vacuum is deviate from volatile component, adds the 90g epoxy chloropropane, is heated to 128 ℃ then, reacts under the condition of nitrogen protection and high-speed stirring; Question response progressively drips remaining 92.4g epoxy chloropropane after activating.After the epoxy chloropropane polymerization is finished, reactor temperature is reduced to 115 ℃, drip the 23.2g propylene oxide reaction and carry out end-blocking.After reaction was finished, vacuum was deviate from residual monomer, refining obtained that average molecular mass is 3348, the average hydroxy functionality is 2 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
The preparation method of 4. 1 kinds of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohols of embodiment.Adding 30g relative molecular mass is 400 two functionality polyether glycols, 0.162g DMC in withstand voltage reactor, vacuum is deviate from volatile component, add the 60g epoxy chloropropane, be heated to 135 ℃ then, under the condition of nitrogen protection and high-speed stirring, react; Question response progressively drips remaining 113g epoxy chloropropane after activating.After the epoxy chloropropane polymerization is finished, reactor temperature is reduced to 115 ℃, drip the 23g propylene oxide reaction and carry out end-blocking.After reaction was finished, vacuum was deviate from residual monomer, refining obtained that average molecular mass is 3000, the average hydroxy functionality is 2 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
The preparation method of 5. 1 kinds of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohols of embodiment.Add 20g trihydroxyethyl isocyanuric ester, 0.138g DMC in withstand voltage reactor, vacuum is deviate from volatile component, adds the 80g epoxy chloropropane, is heated to 135 ℃ then, reacts under the condition of nitrogen protection and high-speed stirring; Question response progressively drips remaining 130g epoxy chloropropane after activating.After the epoxy chloropropane polymerization is finished, reactor temperature is reduced to 115 ℃, drip the 30.4g reacting ethylene oxide and carry out end-blocking.After reaction was finished, vacuum was deviate from residual monomer, refining obtained that average molecular mass is 3400, the average hydroxy functionality is 3 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
The preparation method of 6. 1 kinds of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohols of embodiment.Add 20g trihydroxyethyl isocyanuric ester, 0.138g DMC in withstand voltage reactor, vacuum is deviate from volatile component, adds the 80g epoxy chloropropane, is heated to 135 ℃ then, reacts under the condition of nitrogen protection and high-speed stirring; Question response progressively drips remaining 130g epoxy chloropropane after activating.After the epoxy chloropropane polymerization is finished, reactor temperature is reduced to 115 ℃, drip the 40g propylene oxide reaction and carry out end-blocking.After reaction was finished, vacuum was deviate from residual monomer, refining obtained that average molecular mass is 3500, the average hydroxy functionality is 3 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
The preparation method of 7. 1 kinds of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohols of embodiment.Adding 20g trihydroxyethyl isocyanuric ester, 0.153g DMC, vacuum are deviate from volatile component in withstand voltage reactor, add the 80g epoxy chloropropane, are heated to 128 ℃ then, react under the condition of nitrogen protection and high-speed stirring; Question response progressively drips remaining 296.4g epoxy chloropropane after activating.After the epoxy chloropropane polymerization is finished, reactor temperature is reduced to 115 ℃, drip the 40g propylene oxide reaction and carry out end-blocking.After reaction was finished, vacuum was deviate from residual monomer, refining obtained that average molecular mass is 4500, the average hydroxy functionality is 3 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
The preparation method of 8. 1 kinds of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohols of embodiment.Add 20g trihydroxyethyl isocyanuric ester, 0.192g DMC in withstand voltage reactor, vacuum is deviate from volatile component, adds the 80g epoxy chloropropane, is heated to 128 ℃ then, reacts under the condition of nitrogen protection and high-speed stirring; Question response progressively drips remaining 283.1g epoxy chloropropane after activating.After the epoxy chloropropane polymerization is finished, reactor temperature is reduced to 115 ℃, drip the 30.4g propylene oxide reaction and carry out end-blocking.After reaction was finished, vacuum was deviate from residual monomer, refining obtained that average molecular mass is 5400, the average hydroxy functionality is 3 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
The preparation method of 9. 1 kinds of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohols of embodiment.Add 20g trihydroxyethyl isocyanuric ester, 0.192g DMC in withstand voltage reactor, vacuum is deviate from volatile component, adds the 80g epoxy chloropropane, is heated to 128 ℃ then, reacts under the condition of nitrogen protection and high-speed stirring; Question response progressively drips remaining 283.1g epoxy chloropropane after activating.After the epoxy chloropropane polymerization is finished, reactor temperature is reduced to 115 ℃, drip the 40g propylene oxide reaction and carry out end-blocking.After reaction was finished, vacuum was deviate from residual monomer, refining obtained that average molecular mass is 5500, the average hydroxy functionality is 3 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
The preparation method of 10. 1 kinds of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohols of embodiment.Adding 20g relative molecular mass is 700 three-functionality-degree polyether glycol, 0.114g DMC in withstand voltage reactor, vacuum is deviate from volatile component, add the 60g epoxy chloropropane, be heated to 135 ℃ then, under the condition of nitrogen protection and high-speed stirring, react; Question response progressively drips remaining 63g epoxy chloropropane after activating.After the epoxy chloropropane polymerization is finished, reactor temperature is reduced to 115 ℃, drip the 40g propylene oxide reaction and carry out end-blocking.After reaction was finished, vacuum was deviate from residual monomer, refining obtained that average molecular mass is 5500, the average hydroxy functionality is 3 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
The preparation method of 11. 1 kinds of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohols of embodiment.Add 15g trihydroxyethyl isocyanuric ester, 0.230g DMC in withstand voltage reactor, vacuum is deviate from volatile component, adds the 80g epoxy chloropropane, is heated to 128 ℃ then, reacts under the condition of nitrogen protection and high-speed stirring; Question response progressively drips remaining 365g epoxy chloropropane after activating.After the epoxy chloropropane polymerization is finished, reactor temperature is reduced to 115 ℃, drip the 40g propylene oxide reaction and carry out end-blocking.After reaction was finished, vacuum was deviate from residual monomer, refining obtained that average molecular mass is 8500, the average hydroxy functionality is 3 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
Claims (10)
1. high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol, it is characterized in that its molecular structure be have a large amount of METHYLENE CHLORIDE side groups with oxyethane or the end capped end hydroxy polyether polyvalent alcohol of propylene oxide, average molecular mass 500～9000, the average hydroxy functionality is between 2～3.
2. according to the described high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol of claim 1, it is characterized in that described terminal hydroxy group Hydrin ethoxylated polyhydric alcohol is that a kind of end group is the telechelic polymer of primary hydroxyl or secondary hydroxyl.
3. according to the described high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol of claim 1, it is characterized in that described terminal hydroxy group Hydrin ethoxylated polyhydric alcohol is to adopt bimetallic cyanide complex catalyst catalysis synthetic.
4. the preparation method as the described high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol of above-mentioned each claim is characterized in that comprising the steps:
(1) in withstand voltage reactor, adds small molecular weight initiator, bimetallic cyanide complex catalyst, vacuum is deviate from volatile component, add the part epoxy chloropropane, be heated to 100～140 ℃ then, under the condition of nitrogen protection and high-speed stirring, react; Progressively drip the residual epoxide chloropropane behind the reacting activation;
After the epoxy chloropropane polymerization is finished in (2) (1) steps, reactor temperature is reduced to 90～120 ℃, drip propylene oxide or oxyethane again and carry out end-blocking, reaction finishes, vacuum is deviate from residual monomer, obtain average molecular mass 500～9000, the average hydroxy functionality is at 2～3 terminal hydroxy group Hydrin ethoxylated polyhydric alcohol.
5. the preparation method of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol according to claim 4, it is characterized in that the small molecular weight initiator in the described step (1) is 4,4-dihydroxy-diphenyl propane, 1,4-butyleneglycol, relative molecular mass are that 400 two functionality polyether glycols, trihydroxyethyl isocyanuric ester, relative molecular mass are that 250 three-functionality-degree polyether glycol, relative molecular mass are one or more the mixture in 700 the three-functionality-degree polyether glycol.
6. the preparation method of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol according to claim 4, the mass ratio that it is characterized in that a part of epoxy chloropropane in the described step (1) and remainder epoxy chloropropane is between 100:0～1:99; The mol ratio of small molecular weight initiator and epoxy chloropropane is between 1:4～1:100 in the described step (1).
7. the preparation method of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol according to claim 4 is characterized in that bimetallic cyanide complex catalyst in the described step (1) is that the trimethyl carbinol is that the bimetallic cyanide complex catalyst of one of part is a disperse phase, the oligomer polyol that contains reactive hydrogen is the emulsion form bimetallic cyanide complex catalyst of external phase.Wherein the bimetallic cyanide complex catalyst consumption accounts for 300～800ppm. of institute's synthetic polyether glycol quality
8. the preparation method of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol according to claim 4 is characterized in that bimetallic cyanide complex catalyst is that potassium hexacyanocobaltate and zinc salt prepare through operations such as complexing reaction, washing, dryings in the described step (1) in the presence of water, the trimethyl carbinol, polyether glycol.
9. the preparation method of bimetallic cyanide complex catalyst according to claim 8, it is characterized in that described zinc salt is one or more the mixture in zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, zinc phosphate, zinc carbonate, the zinc oxalate, the mol ratio of zinc salt and Cobalt Potassium Cyanide is between 1.5:1～20:1, and wherein the mol ratio of zinc bromide and Cobalt Potassium Cyanide is between 1.8:1～15:1.
10. the preparation method of high activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol according to claim 4, the mol ratio that it is characterized in that Hydrin ether and oxyethane or propylene oxide in the described step (2) is between 1:1～1:3.
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