The process for semicontinuous preparation of organo-fluorine polymer grafted polyether polyolTechnical field
The present invention relates to a kind of fluoro-resin technology of preparing, is a kind of process for semicontinuous preparation of organo-fluorine polymer polyether glycol, the process for semicontinuous preparation of more clearly say so a kind of organo-fluorine polymer and polyether glycol graft copolymer.
Background technology
Fluorine carbon lacquer is a kind of coating with special performance and many-sided purposes.It is a basic raw material with the fluoro-resin, and it is formed through being uniformly dispersed to allocate filler, pigment, dispersion agent and other auxiliary agent into, can realize self-vulcanizing and have stronger sticking power as solidifying agent with the aliphatics diisocyanate.Fluorine carbon lacquer has performances such as good weather-proof, acidproof, alkaline-resisting, resistance to chemical attack and ultraviolet resistance, is widely used in the application of aspects such as external wall, chemical industry equipment, steel construction, vehicle, freeway guardrail, power equipment.
The organo-fluorine polymer polyvalent alcohol is a kind of of fluoro-resin, normally trifluorochloroethylene (or tetrafluoroethylene), the basic monomer of ethene (or propylene) carry out the product of solution copolymerization with third and fourth monomer in organic phase in the presence of initiator for it, used ethene (or propylene) monomer of nineteen nineties organo-fluorine polymer polyvalent alcohol is an acrylate, and third and fourth monomer is respectively vinylcarbinol and C3～C12Unsaturated acid, its solid content (polymer content) is 45%～65%; Its preparation technology all adopts mode intermittently, that is: 1 mixed solvent such as dimethylbenzene, hexone and vinyl or propenyl ester, vinylcarbinol, C3～C12Olefin(e) acid, initiator, trifluorochloroethylene (or tetrafluoroethylene) join in the polymerization reaction kettle; 2 are warming up to 70～73 ℃ of reactions obtained in 18～20 hours.
The organo-fluorine polymer polyvalent alcohol that intermittent mode is prepared has that molecular weight distribution is wide, viscosity is high, monomer conversion is low and preparation cycle is long, and equipment capacity is low; Fluorine carbon lacquer poor adhesive force, hardness of paint film with its production are low.
The objective of the invention is to be to provide a kind of process for semicontinuous preparation of preparation method-organo-fluorine polymer grafted polyether polyol of fluoro-resin, its synthesis technique be adopt graft polymerization method promptly: unsaturated polyether polyol is as macromonomer and trifluorochloroethylene (or tetrafluoroethylene), vinyl acetate, C3～C12Monomers such as unsaturated acid carry out solution graft copolymerization and close method preparation in organic phase under the initiator effect; Its production technique adopts semi-continuous method promptly: 1 joins the mixed solvent feed liquid in the polymerization reaction kettle; 2 mix monomer feed liquids are vinyl or propenyl ester, unsaturated polyether polyol macromonomer, C3～C12Unsaturated acid, initiator, molecular weight regulator etc. mix constitute the mix monomer feed liquid and organic fluorine monomer feed liquid adds in the polymerization reaction kettle with certain speed respectively, carry out graft copolymerization, obtain organo-fluorine polymer grafted polyether polyol product.With the prepared fluoro-resin of this method, has narrow molecular weight distribution, viscosity is low, monomer conversion is high and preparation cycle is short, the equipment capacity height; Characteristics such as the fluorine carbon lacquer sticking power with its production is big, hardness of paint film height.
Summary of the invention
The polymers soln homogeneous system that organo-fluorine polymer grafted polyether polyol of the present invention is made up of fluororesin polymer and mixed solvent.
Above-mentioned fluororesin polymer is the graft copolymer of organo-fluorine polymer and unsaturated polyether polyol, and it is to carry out solution graft copolymerization by one or more organic fluorine monomer and two or more vinyl monomer and unsaturated polyether polyol macromonomer in the presence of initiator, molecular weight regulator in organic phase to close method prepared.
Above-mentioned organic fluorine monomer can be one or more the monomer mixture in trifluorochloroethylene, the tetrafluoroethylene.
Above-mentioned vinyl monomer can be two or more the monomer mixture in vinyl acetate, methyl acrylate, ethyl propenoate, butyl methacrylate, the undecylenic acid.
Above-mentioned unsaturated polyether polyol is that vinyl carbinol is an initiator, bimetallic cyanide complex (DMC) is formed unsaturated polyether polyol by catalyzer through propylene oxide ring-opening polymerization or propylene oxide, oxyethane ring-opening copolymerization, the functionality of its polyvalent alcohol is between 1～4, hydroxyl value is between 30mgKOH/g～500mgKOH/g, and proportion of primary OH groups is between 5%～98%.
Above-mentioned mixed solvent can be two or more a solvent mixture such as N-BUTYL ACETATE, dimethylbenzene, toluene, hexone, pimelinketone.
Above-mentioned initiator can be an azo-initiator.
Above-mentioned azo-initiator is one or both mixtures in Diisopropyl azodicarboxylate, the 2,2'-Azobis(2,4-dimethylvaleronitrile).
Above-mentioned molecular weight regulator can be dodecyl mercaptan carbon, tert-dodecyl mercaptan and C5-C11The mixture of one or more in the mercaptan.
The semicontinuous manufacture method of organo-fluorine polymer grafted polyether polyol of the present invention is as follows:
(a) mixing kettle: respectively vinyl acetate, methyl acrylate, ethyl propenoate, butyl methacrylate, C3～C12The vinyl monomer of two or more in the olefin(e) acid etc. and unsaturated polyether polyol macromonomer, initiator, molecular weight regulator join and have in temperature regulator, the electric mixer mixing kettle, and mixing also, controlled temperature is lower than 15 ℃.
(b) polymerization reaction kettle: two or more solvent in N-BUTYL ACETATE, dimethylbenzene, toluene, hexone, the pimelinketone etc. is joined have in temperature regulator, nitrogen protection, the electric mixer polymerization reaction kettle respectively; nitrogen replacement three times; the content of control oxygen and is warming up to temperature of reaction less than 60ppm.
(c) continuously feeding: material in the mixing kettle and organic fluorine monomer feed liquid are entered in the polymerization reaction kettle with certain input speed (quality) respectively, carry out solution graft copolymerization at a certain temperature and close reaction, the reaction times is 3～12.
(d) isothermal reaction: continue reaction 3～6 hours after continuously feeding is finished.
(E) drying: after reaction is finished unreacted organic fluorine monomer removed and obtain the organo-fluorine polymer grafted polyether polyol.
Unsaturated polyether polyol in above-mentioned (a) is that vinyl carbinol is an initiator, bimetallic cyanide complex (DMC) is formed unsaturated polyether polyol by catalyzer through propylene oxide ring-opening polymerization or propylene oxide, oxyethane ring-opening copolymerization, the functionality of its polyvalent alcohol is between 1～4, be preferably between 1～2, hydroxyl value is between 30mgKOH/g～500mgKOH/g, be preferably between 56mgKOH/g～300mgKOH/g, proportion of primary OH groups is between 5%～98%, be preferably between 35%～85%, its consumption be organic fluorine monomer consumption 7%～100% between.
Vinyl monomer in above-mentioned (a) is vinyl acetate, methyl acrylate, ethyl propenoate, butyl methacrylate, C3～C12The vinyl monomer of two or more in the olefin(e) acid, preferably vinyl acetate and undecylenic acid, its consumption is respectively 1～70% and 0.1～10% of an organic fluorine monomer consumption, preferably 15～58% and 1～5%.
Initiator in above-mentioned (a) is one or both mixtures in Diisopropyl azodicarboxylate, the 2,2'-Azobis(2,4-dimethylvaleronitrile), and its consumption is 0.3～2% of whole monomer consumptions, preferably 0.8～1.5%.
Molecular weight regulator in above-mentioned (a) can be dodecyl mercaptan carbon, tert-dodecyl mercaptan and C5-C11The mixture of one or more in the mercaptan, preferably dodecyl mercaptan carbon, tert-dodecyl mercaptan, its consumption is 0.2～2% of whole monomer consumptions, preferably 0.2～1%.
Solvent in above-mentioned (b) can be two or more the solvent in N-BUTYL ACETATE, dimethylbenzene, toluene, hexone, the pimelinketone etc., be preferably dimethylbenzene, hexone, its consumption is 10～80% of an organo-fluorine polymer grafted polyether polyol, preferably 30～50%, the ratio of the two is a dimethylbenzene: hexone=0.2: 1～1: 0.2.
Temperature in above-mentioned (b) is 65～95 ℃, is preferably 70～74 ℃
Organic fluorine monomer in above-mentioned (C) can be one or more the monomer mixture in trifluorochloroethylene, the tetrafluoroethylene, and its consumption is 15～80% of whole monomer consumptions, preferably 40～70%.
Material and organic fluorine monomer feed liquid enter in the polymerization reaction kettle continuously with certain input speed (quality) respectively in the mixing kettle in above-mentioned (C), carry out the successive soln graft copolymerization at a certain temperature.
Temperature of reaction in above-mentioned (C) is 65～95 ℃, is preferably 70～74 ℃.
Temperature of reaction in above-mentioned (D) is 68～95 ℃, is preferably 72～76 ℃.
The present invention has the following advantages compared with prior art:
With the prepared fluoro-resin of this method, has narrow molecular weight distribution, viscosity is low, monomer conversion is high and preparation cycle is short, the equipment capacity height; Big, the characteristics such as weathering resistance is good, hardness of paint film height of fluorine carbon lacquer sticking power with its production.
With organo-fluorine polymer grafted polyether polyol of the present invention is basic raw material, allocate filler, pigment, dispersion agent and other auxiliary agent into and can be mixed with fluorine carbon lacquer through being uniformly dispersed, can realize self-vulcanizing and have not flavescence and stronger sticking power as solidifying agent with the aliphatics diisocyanate.This fluorine carbon lacquer has performances such as good weather-proof, acidproof, alkaline-resisting, resistance to chemical attack and ultraviolet resistance, is widely used in the application of aspects such as external wall, chemical industry equipment, steel construction, vehicle, freeway guardrail, power equipment.
Embodiment
Nomenclature
Unsaturated polyether polyol macromonomer I: vinyl carbinol is an initiator, and DMC is a catalyzer, the propylene oxide ring-opening polymerization, and 15% left and right sides is ethylene oxide-capped, and hydroxyl value is between 330mgKOH/g～350mgKOH/g.
Unsaturated polyether polyol macromonomer II: vinyl carbinol is an initiator, and DMC is a catalyzer, the propylene oxide ring-opening polymerization, and 15% left and right sides is ethylene oxide-capped, and hydroxyl value is between 190mgKOH/g～210mgKOH/g.
Unsaturated polyether polyol macromonomer III: vinyl carbinol is an initiator, and DMC is a catalyzer, the propylene oxide ring-opening polymerization, and 15% left and right sides is ethylene oxide-capped, and hydroxyl value is between 160mgKOH/g～180mgKOH/g.
Unsaturated polyether polyol macromonomer IV: vinyl carbinol is an initiator, and DMC is a catalyzer, the propylene oxide ring-opening polymerization, and 15% left and right sides is ethylene oxide-capped, and hydroxyl value is between 100mgKOH/g～120mgKOH/g.
Unsaturated polyether polyol macromonomer V: vinyl carbinol is an initiator, and DMC is a catalyzer, the propylene oxide ring-opening polymerization, and 15% left and right sides is ethylene oxide-capped, and hydroxyl value is between 70mgKOH/g～90mgKOH/g.
Unsaturated polyether polyol macromonomer VI: the polyether glycol of vinyl modification, molecular weight is about 3000;
Molecular weight regulator: dodecyl mercaptan carbon (n-C12SH);
Initiator: Diisopropyl azodicarboxylate (AIBN);
Trifluorochloroethylene: CTFE
Tetrafluoroethylene: TFE
Embodiment 1:
(a): mixing kettle: respectively vinyl acetate 268g, undecylenic acid 16g, unsaturated polyether polyol macromonomer I 117g, initiator A IBN 13g, molecular weight regulator n-C12SH 4g join have temperature regulator, the electric mixer useful volume is in 1 liter of mixing kettle, mix and controlled temperature at 10～15 ℃.
(b) polymerization reaction kettle: respectively dimethylbenzene 350g, hexone 150g equal solvent are joined that to have temperature regulator, nitrogen protection, electric mixer useful volume be in 2 liters the withstand voltage stainless steel polymerization reaction kettle; nitrogen replacement three times; the content of control oxygen and is warming up to 72 ± 2 ℃ less than 60ppm.
(c) continuously feeding: enter the material in 1 mixing kettle in the polymerization reaction kettle with 52.2g/ hour input speed (quality) and 2 organic fluorine monomer feed liquid CTFE simultaneously with 75g/ hour input speed (quality) respectively, carry out solution graft copolymerization and close reaction under 72 ± 2 ℃ of temperature, the charging reaction times is 8 hours.
(d) isothermal reaction: under 74 ± 2 ℃ of temperature, continue reaction 6 hours after charging is finished.
(E) drying: after reaction is finished unreacted organic fluorine monomer removed and obtain the organo-fluorine polymer grafted polyether polyol.Dried organo-fluorine polymer grafted polyether polyol performance sees Table 1.
Embodiment 2: change into except " CTFE with 75g/ hour input speed " in (C) " TFE with 65g/ hour input speed ", all the other are with embodiment 1.Dried organo-fluorine polymer grafted polyether polyol performance sees Table 1.
Embodiment 3:
(a): mixing kettle: respectively vinyl acetate 185g, undecylenic acid 16g, unsaturated polyether polyol macromonomer II 200g, initiator A IBN 13g, molecular weight regulator n-C12SH 4g join have temperature regulator, the electric mixer useful volume is in 1 liter of mixing kettle, mix and controlled temperature at 10～15 ℃.
(b) polymerization reaction kettle: respectively dimethylbenzene 350g, hexone 150g equal solvent are joined that to have temperature regulator, nitrogen protection, electric mixer useful volume be in 2 liters the withstand voltage stainless steel polymerization reaction kettle; nitrogen replacement three times; the content of control oxygen and is warming up to 72 ± 2 ℃ less than 60ppm.
(c) continuously feeding: enter the material in 1 mixing kettle in the polymerization reaction kettle with 52.2g/ hour input speed (quality) and 2 organic fluorine monomer feed liquid CTFE simultaneously with 75g/ hour input speed (quality) respectively, carry out solution graft copolymerization and close reaction under 72 ± 2 ℃ of temperature, the charging reaction times is 8 hours.
(d) isothermal reaction: under 74 ± 2 ℃ of temperature, continue reaction 6 hours after charging is finished.
(E) drying: after reaction is finished unreacted organic fluorine monomer removed and obtain the organo-fluorine polymer grafted polyether polyol.Dried organo-fluorine polymer grafted polyether polyol performance sees Table 1.
Embodiment 4: change into except " CTFE with 75g/ hour input speed " in (C) " TFE with 65g/ hour input speed ", all the other are with embodiment 3.Dried organo-fluorine polymer grafted polyether polyol performance sees Table 1.
Embodiment 5: except " respectively vinyl acetate 185g, undecylenic acid 16g, unsaturated polyether polyol macromonomer II 200g " in (a) changes into " respectively vinyl acetate 150g, undecylenic acid 16g, unsaturated polyether polyol macromonomer III235g ", all the other are with embodiment 3.Dried organo-fluorine polymer grafted polyether polyol performance sees Table 1.
Embodiment 6: except " respectively vinyl acetate 185g, undecylenic acid 16g, unsaturated polyether polyol macromonomer II 200g " in (a) changes into " respectively vinyl acetate 130g, undecylenic acid 16g, unsaturated polyether polyol macromonomer IV 255g ", all the other are with embodiment 3.Dried organo-fluorine polymer grafted polyether polyol performance sees Table 1.
Embodiment 7: except " respectively vinyl acetate 185g, undecylenic acid 16g, unsaturated polyether polyol macromonomer II 200g " in (a) changes into " respectively vinyl acetate 130g, undecylenic acid 16g, unsaturated polyether polyol macromonomer V 255g ", all the other are with embodiment 3.Dried organo-fluorine polymer grafted polyether polyol performance sees Table 1.
Embodiment 8: except " respectively vinyl acetate 185g, undecylenic acid 16g, unsaturated polyether polyol macromonomer II 200g " in (a) changes into " respectively vinyl acetate 130g, undecylenic acid 16g, unsaturated polyether polyol macromonomer VI255g ", all the other are with embodiment 3.Dried organo-fluorine polymer grafted polyether polyol performance sees Table 1.
Organo-fluorine polymer grafted polyether polyol performance sees Table 1
| Project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
| Solid content % | 66 | ?64 | ?66 | ?64 | ?66 | ?66 | ?66 | ?66 |
| Hydroxyl value mgKOH/g | 37 | ?43 | ?40.5 | ?44 | ?38 | ?28 | ?20.3 | ?14.1 |
| Acid number mgKOH/g | 4.3 | ?4.5 | ?4.3 | ?4.5 | ?3.9 | ?3.7 | ?4.1 | ?4 |
| Fluorine content % | 30.3 | ?43 | ?30.3 | ?43 | ?30.1 | ?29.1 | ?28.9 | ?29.4 |
| Viscosity (being coated with-4 glasss) (25 ℃) second | 55 | ?60 | ?51 | ?60 | ?61 | ?66 | ?68 | ?76 |
| Molecular weight Mn | 12350 | ?14658 | ?14325 | ?13578 | ?15300 | ?18560 | ?19450 | ?25680 |
| Second-order transition temperature ℃ | 41 | ?39 | ?35 | ?35 | ?51 | ?57 | ?61 | ?53 |
| Monomer conversion % | 95 | ?94 | ?97 | ?97 | ?97 | ?96 | ?96 | ?95 |