CN1312302A - Continuous prepn of polyether polyol - Google Patents
Continuous prepn of polyether polyol Download PDFInfo
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Abstract
The continuous preparation method of polymer polyether polylol includes the following steps: activating dispersing agent in activating still, copolymerization reaction of phenylethylene, acrylonitrile and activated dispersing agent under the initiation of ATBN in the polyether polylol and solvent to form seed polymer polyether polylol in seed polymerization still, swelling said seed polymer by phenylethylene, acrylonitrile and solvent and polymerizing and growing up to form crude polymer polyether polylol in 1-2 series-connected polymerization still, drying through flash drum, boil-up tower and membrane-reducing evaporator so as to obtain refined polymer polyether polylol. It is high in solid content, low in viscosity, can be extensively used for producing polyurethane foam material.
Description
The present invention relates to a kind of polymer manufacture technology, the continuous preparation method of a kind of polyether polyol of more clearly saying so.
Polyurethane foamed material is a kind of superpolymer with special performance and many-sided purposes.It is a basic raw material with polyether glycol, polyether polyol and diisocyanate, allocate less water, filler, organic silicon surfactant, whipping agent into, under the acting in conjunction of organotin and tertiary amine catalyst, form, can make hard, semi-rigid and flexible urethane foam with it, be applied to the aspects such as saddle of cushion, back cushion, inside gadget and the motorcycle of vehicle mainly as cushioning material, also can be used for making simultaneously civilian industries such as sofa, mattress, finishing material.
Polyether polyol be vinyl monomer in the presence of dispersion agent in polyether glycol diffuse-aggregate product, the used vinyl monomer of polyether polyol at the beginning of the seventies is a vinyl cyanide, its solid content (polymer content) is 5%～25%, viscosity height, look Huang, easily makes the heartburn variable color of polyurethane foam; The mid-80 prepares polyether polyol with vinyl cyanide and vinylbenzene mix monomer, and its solid content is 20%～30%, and styrene content is more than 50%; The initial stage nineties, more external companies release one after another solid content about 40%, the polyether polyol of viscosity about 5500mPas (25 ℃), as Chinese patent CN1067059, CN1087919 and the disclosed polyether polyol of CN1119020, but mode is intermittently all adopted in the preparation of these polyether polyols, and promptly (1) joins dispersion agent, initiator and a part of polyether glycol in the polymerization reaction kettle; (2) join vinylbenzene, vinyl cyanide, initiator, molecular weight regulator and another part polyether glycol in the mixing kettle and be cooled to certain temperature; (3) temperature with polymerization reaction kettle is raised to the material in the back dropping mixing kettle about 115 ℃; (4) treat that monomer reaction finishes, after vacuum, drum nitrogen drying, get polyether polyol.
The polyether polyol that intermittent mode is prepared, have dispersed phase polymer narrow diameter distribution (0.4～0.6 μ), viscosity height (＞5000mpa.s, 25 ℃), residual monomer concentration (〉=characteristics such as 1000ppm) batch difference high, product is big, and preparation cycle is long, and equipment capacity is low.
The continuous preparation method who the purpose of this invention is to provide a kind of polyether polyol, with the prepared polyether polyol of this method, have dispersed phase polymer size distribution moderate (0.3～0.85 μ), the little (＜4000mpa.s of viscosity, 25 ℃), residual monomer concentration (＜150ppm) batch difference low, product is little, and have can continuous production, characteristics such as equipment capacity height.
The polymeric colloid dispersion system that polyether polyol of the present invention is made up of the polyether glycol two-phase of the polymer microballoon of disperse phase and external phase.
Above-mentioned polymer microballoon mainly is made up of two or more the multi-element graft copolymer of polyether glycol of multipolymer, two or more vinyl monomer and vinyl modification of vinyl monomer.
Above-mentioned vinyl monomer can be that vinylbenzene, alpha-methyl styrene, methyl acrylate, ethyl propenoate, butyl methacrylate, vinyl cyanide, vinyl acetate, vinyl acetate between to for plastic, acrylamide etc. have the monomer that carbon-carbon double bond can carry out radical polymerization.
Above-mentioned external phase is propylene oxide ring-opening polymerization or propylene oxide and oxyethane polyether glycol that ring-opening copolymerization forms, the functionality of its polyether glycol is between 2～4, hydroxyl value is between 26mgKOH/g～70mgKOH/g, and proportion of primary OH groups is between 5%～98%.
The weight of the dispersed phase polymer microballoon in the above-mentioned polymeric colloid dispersion system accounts for 15%～55% of whole polymeric colloid dispersion system weight, preferably 25%～45%.
The viscosity of above-mentioned polymeric colloid dispersion system is at 2000 mPas～6000 mPas (25 ℃), and is preferably at 2000 mPas～5000 mPas (25 ℃), best at 2000 mPas～4000 mPas (25 ℃).
The dispersed phase polymer microballoon of polyether polyol of the present invention is stable existence and is uniformly distributed in the external phase polyether glycol.
The particle diameter of above-mentioned polymer microballoon (scanning electron microscopy particle diameter) is between 0.1 μ m～2 μ m.
The method for continuous production of polyether polyol of the present invention is as follows:
(a) activate still: enter in the activation still that has temperature regulator, nitrogen protection, electric mixer and side overflow discharging with certain input speed (quality) respectively to dispersion agent, solvent, polyether glycol, initiator; the mean residence time of controlled temperature and material is activated dispersion agent at a certain temperature and moves liquid continuously to the seeding polymerization reactor by the side overflow.
(b) seeding polymerization reactor: respectively vinyl monomer; solvent; polyether glycol; initiator enters with certain input speed (quality) with the feed liquid of coming the self activation still and has temperature regulator; nitrogen protection; in the seeding polymerization reactor of electric mixer and side overflow discharging; the mean residence time of controlled temperature and material; under the initiator effect, carry out free radicals copolymerization reaction and form solid (polymkeric substance) content 5～30%; the seed polymer polyether glycol of dispersed phase polymer particle diameter 0.1～0.5 μ moves liquid to polymerization reaction kettle (1) continuously by the side overflow.
(c) polymerization reaction kettle (1): respectively vinyl monomer; solvent; polyether glycol; initiator and enter with certain input speed (quality) from the seed polymer in the seeding polymerization reactor and to have temperature regulator; nitrogen protection; the polymerization reaction kettle (1) of electric mixer and side overflow discharging; the mean residence time of controlled temperature and material; at solvent; the particle diameter of disperse phase seed polymer increases under initiator and the monomeric effect; form solid (polymkeric substance) content 5～30%; the polyether polyol of dispersed phase polymer particle diameter 0.15～0.65 μ moves liquid to polymerization reaction kettle (2) continuously by the side overflow.
(d) polymerization reaction kettle (2): respectively vinyl monomer; solvent; polyether glycol; initiator and enter with certain input speed (quality) from the material in the polymerization reaction kettle (1) and to have temperature regulator; nitrogen protection; in the polymerization reaction kettle (2) of electric mixer and side overflow discharging; the mean residence time of controlled temperature and material; at solvent; the particle diameter of dispersed phase polymer further increases under initiator and the monomeric effect; form solid (polymkeric substance) content 20～42%; the polymkeric substance of dispersed phase polymer particle diameter 0.3～0.85 μ moves liquid to the polyether polyol groove continuously by the side overflow.
(e) drying: polyether polyol in the groove is obtained the exsiccant polyether polyol at certain service temperature and certain working pressure through flash drum, after steaming dryings such as tower and falling-film evaporator.
Polyether glycol among above-mentioned (a) and (b), (c), (d) is homopolymer or the propylene oxide and the ethylene oxide copolymer of propylene oxide, and its functionality is preferably between 2～4 between 2～5; Its hydroxyl value is preferably between 26mgKOH/g～70mgKOH/g between 20mgKOH/g～100mgKOH/g; Proportion of primary OH groups is between 5%～98%; The ratio of the input speed (quality) of polyether glycol in (a) and (b), (c), (d) is (a): (b): (c): (d)=0～25: 10～25: 10～70: between 0～50;
Vinyl monomer among above-mentioned (b), (c), (d) can be that vinylbenzene, alpha-methyl styrene, methyl acrylate, ethyl propenoate, butyl methacrylate, vinyl cyanide, vinyl acetate, vinyl acetate between to for plastic, acrylamide etc. have carbon-carbon double bond and can carry out two or more monomer in the free yl polymerizating monomer, preferably vinylbenzene, vinyl cyanide; Two kinds of monomeric ratios are vinylbenzene: vinyl cyanide=50: 50～90: 10; (b), total vinyl monomer quality input speed total polyether glycol input speed (quality) and 25%～42% of total vinyl monomer input speed (quality) sum in accounting among (c), (d); The ratio of the input speed (quality) of vinyl monomer in (b), (c), (d) is (b): (c): (d)=5～25: 10～85: 0～60;
Dispersion agent in above-mentioned (a) is the polyether glycol of vinyl modification, and molecular weight is between 3000～7000, and its input speed (quality) is 6%～30% of a total vinyl monomer input speed (quality), preferably 8%～25%;
Solvent among above-mentioned (a) and (b), (c), (d) can be ethylbenzene, toluene, Virahol, dimethyl formamide, N,N-DIMETHYLACETAMIDE, uncle's DDM dodecyl mercaptan, dodecyl mercaptan carbon, tert-dodecyl mercaptan and C
5-C
11The mixture of one or more in the mercaptan.Its input speed (quality) is a vinyl monomer input speed (quality) 0.4%～20%, preferably 0.4～15%.
Initiator among above-mentioned (a) and (b), (c), (d) is azo-initiator or peroxide initiator or the mixture of the two.
Above-mentioned azo-initiator is one or both mixtures in Diisopropyl azodicarboxylate, the 2,2'-Azobis(2,4-dimethylvaleronitrile).
Above-mentioned peroxide initiator is one or more mixtures in dicumyl peroxide, dibenzoyl peroxide, the peroxidized t-butyl perbenzoate.
Temperature of reaction among above-mentioned (a) and (b), (c), (d) is more than 90 ℃, preferably 115 ± 15 ℃.
The mean residence time of material is 5～30 minutes in above-mentioned (a), preferably 10 minutes;
The mean residence time of material is 50～150 minutes among above-mentioned (b), (c), (d), preferably 50～130 minutes;
Service temperature in above-mentioned (e) should be not less than 70 ℃, preferably is not less than 95 ℃, is not higher than 140 ℃; Working pressure should not be higher than-70kPa, preferably is not higher than-90kPa;
The present invention has the following advantages compared with prior art:
1. the preparation technology of whole polyether polyol can realize serialization;
2. under identical solid content condition, the viscosity of system is low, is 42% polyether polyol as solid content, and the viscosity of system is lower than 4000mPa.s (25 ℃);
3. the distribution of dispersed phase polymer microspherulite diameter is moderate, between 0.3 μ m～0.85 μ m;
4. residual monomer concentration in the polyether polyol (＜150ppm) low;
5. batch difference of product is little.
With polymer polyatomic alcohol of the present invention is that basic raw material can prepare urethane foam, be mainly used in automobile, train, motorcycle cushion, back cushion, the lining of Spring mattress carpet, wrapping material and finishing material have the bearing capacity height, rebound resilience is good and cost is low.Its foam process can adopt traditional foam process such as manual foaming, flat-top foaming, vertical foaming and molding foaming.Its basic raw material consists of common polyether glycol, polyether polyol of the present invention, diisocyanate, water, pneumatogen, tensio-active agent, oxidation inhibitor, anti-aging agent, organotin catalysts and tertiary amine catalyst.
Embodiment nomenclature polyether glycol 551C (being called for short 551C): glycerine or TriMethylolPropane(TMP) are initiator, KOH is a catalyzer, the propylene oxide ring-opening polymerization, and 15% left and right sides is ethylene oxide-capped, hydroxyl value is between 52mgKOH/g～58mgKOH/g, about viscosity 440mPa.s (25 ℃).Polyether glycol 3050:(is called for short 3050): glycerine or TriMethylolPropane(TMP) are initiator, and KOH is a catalyzer, the propylene oxide ring-opening polymerization, hydroxyl value is between 52mgKOH/g～58mgKOH/g about viscosity 440mPa.s (25 ℃).Polyether glycol 330N:(is called for short 330N): glycerine or TriMethylolPropane(TMP) are initiator, KOH is a catalyzer, the propylene oxide ring-opening polymerization, about 15% ethylene oxide-capped, hydroxyl value is between 34mgKOH/g～37mgKOH/g about viscosity 830mPa.s (25 ℃).Dispersion agent 1: the polyether glycol of vinyl modification, molecular weight is about 3000; Dispersion agent 2: the polyether glycol of vinyl modification, molecular weight is about 6500; Solvent 1 (EB): ethylbenzene; Solvent 2 (n-C12SH): dodecyl mercaptan carbon; Solvent 3 (DMF): dimethyl formamide; Initiator (AIBN): Diisopropyl azodicarboxylate;
Embodiment 1:
(a) activate still: respectively dispersion agent 1, input speed 218 Grams Per Hours; Ethylbenzene, input speed 60 Grams Per Hours; Polyether glycol 551C, input speed 200 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 4.2 Grams Per Hours enter in 80 milliliters of activation stills that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is 10 minutes at 112 ± 5 ℃, the mean residence time of material, dispersion agent is activated at a certain temperature and moves liquid continuously to the seeding polymerization reactor by the side overflow;
(b) seeding polymerization reactor: respectively vinylbenzene, input speed 117.3 Grams Per Hours; Vinyl cyanide, input speed 63.2 Grams Per Hours; Dodecyl mercaptan carbon, input speed 1.8 Grams Per Hours; Polyether glycol 551C, input speed 287.2 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 2.16 Grams Per Hours; With come the feed liquid in the self activation still to enter in 900 milliliters of seeding polymerization reactors that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 19.5%, the seed polymer polyether glycol of dispersed phase polymer particle diameter 0.1～0.5 μ, move liquid continuously to polymerization reaction kettle (1) by the side overflow;
(c) polymerization reaction kettle (1): respectively vinylbenzene, input speed 234.6 Grams Per Hours; Vinyl cyanide, input speed 126.4 Grams Per Hours; Dodecyl mercaptan carbon, input speed 3.6 Grams Per Hours; Polyether glycol 551C, input speed 487.2 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 4.3 Grams Per Hours; With enter in the 1700 milliliters of polymerization reaction kettles (1) that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed from the feed liquid in the seeding polymerization reactor, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 30%, the polyether polyol of dispersed phase polymer particle diameter 0.15～0.65 μ, move liquid continuously to polymerization reaction kettle (2) by the side overflow;
(d) polymerization reaction kettle (2): respectively vinylbenzene, input speed 429.7 Grams Per Hours; Vinyl cyanide, input speed 231.4 Grams Per Hours; Dodecyl mercaptan carbon, input speed 6.6 Grams Per Hours; Polyether glycol 551C, input speed 648 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 7.93 Grams Per Hours; With come the feed liquid in the polymerization reaction kettle (1) to enter in the 3100 milliliters of polymerization reaction kettles (2) that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 42%, the polyether polyol of dispersed phase polymer particle diameter 0.3～0.85 μ, move liquid continuously to the polyether polyol groove by the side overflow;
(e) drying: with polyether polyol in the groove 110 ℃ of service temperatures ,-95kPa working pressure, nitrogen protection under through flash drum, steam tower and falling-film evaporator etc. and obtain dried polyether polyol.Dried polyether polyol performance sees Table 1.Embodiment 2: except " ethylbenzene, input speed 60 Grams Per Hours " in (a) become outside " DMF, input speed 70 Grams Per Hours ", all the other are with embodiment 1.Dried polyether polyol performance sees Table 1.Embodiment 3: except " dispersion agent 1, input speed 60 Grams Per Hours " in (a) become outside " dispersion agent 2, input speed 80 Grams Per Hours ", all the other are with embodiment 1.Dried polyether polyol performance sees Table 1.Embodiment 4: except (a) (b) (c) " polyether glycol 551C " in (d) become " polyether glycol 3050 ", all the other are with embodiment 1.Dried polyether polyol performance sees Table 1.
Embodiment 5:
(I) seeding polymerization reactor: respectively respectively dispersion agent 1, input speed 218 Grams Per Hours; Ethylbenzene, input speed 60 Grams Per Hours; Vinylbenzene, input speed 117.3 Grams Per Hours; Vinyl cyanide, input speed 63.2 Grams Per Hours; Dodecyl mercaptan carbon, input speed 1.8 Grams Per Hours; Polyether glycol 551C, input speed 487 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 6.36 Grams Per Hours, enter in 900 milliliters of seeding polymerization reactors that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 19.5%, the seed polymer polyether glycol of dispersed phase polymer particle diameter 0.1～0.5 μ, move liquid continuously to polymerization reaction kettle (1) by the side overflow;
(II) polymerization reaction kettle (1): respectively vinylbenzene, input speed 234.6 Grams Per Hours; Vinyl cyanide, input speed 126.4 Grams Per Hours; Dodecyl mercaptan carbon, input speed 3.6 Grams Per Hours; Polyether glycol 551C, input speed 487.2 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 4.3 Grams Per Hours; With enter in the 1700 milliliters of polymerization reaction kettles (1) that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed from the feed liquid in the seeding polymerization reactor, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 30%, the polyether polyol of dispersed phase polymer particle diameter 0.15～0.65 μ, move liquid continuously to polymerization reaction kettle (2) by the side overflow;
(III) polymerization reaction kettle (2): respectively vinylbenzene, input speed 429.7 Grams Per Hours; Vinyl cyanide, input speed 231.4 Grams Per Hours; Dodecyl mercaptan carbon, input speed 6.6 Grams Per Hours; Polyether glycol 551C, input speed 648 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 7.93 Grams Per Hours; With come the feed liquid in the polymerization reaction kettle (1) to enter in the 3100 milliliters of polymerization reaction kettles (2) that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 42%, the polyether polyol of dispersed phase polymer particle diameter 0.3～0.85 μ, move liquid continuously to the polyether polyol groove by the side overflow;
(IV) drying: with polyether polyol in the groove 110 ℃ of service temperatures ,-95kPa working pressure, nitrogen protection under through flash drum, steam tower and falling-film evaporator etc. and obtain dried polyether polyol.Dried polyether polyol performance sees Table 1.
Embodiment 6:
(a) activate still: respectively dispersion agent 1, input speed 218 Grams Per Hours; Ethylbenzene, input speed 60 Grams Per Hours; Polyether glycol 551C, input speed 200 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 4.2 Grams Per Hours enter in 80 milliliters of activation stills that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is 10 minutes at 112 ± 5 ℃, the mean residence time of material, dispersion agent is activated at a certain temperature and moves liquid continuously to the seeding polymerization reactor by the side overflow;
(b) seeding polymerization reactor: respectively vinylbenzene, input speed 135.3 Grams Per Hours; Vinyl cyanide, input speed 45.1 Grams Per Hours; Dodecyl mercaptan carbon, input speed 1.8 Grams Per Hours; Polyether glycol 551C, input speed 287.2 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 2.16 Grams Per Hours; With come the feed liquid in the self activation still to enter in 900 milliliters of seeding polymerization reactors that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 19.5%, the seed polymer polyether glycol of dispersed phase polymer particle diameter 0.1～0.5 μ, move liquid continuously to polymerization reaction kettle (1) by the side overflow;
(c) polymerization reaction kettle (1): respectively vinylbenzene, input speed 270.7 Grams Per Hours; Vinyl cyanide, input speed 90.3 Grams Per Hours; Dodecyl mercaptan carbon, input speed 3.6 Grams Per Hours; Polyether glycol 551C, input speed 487.2 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 4.3 Grams Per Hours; With enter in the 1700 milliliters of polymerization reaction kettles (1) that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed from the feed liquid in the seeding polymerization reactor, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 30%, the polyether polyol of dispersed phase polymer particle diameter 0.15～0.65 μ, move liquid continuously to polymerization reaction kettle (2) by the side overflow;
(d) polymerization reaction kettle (2): respectively vinylbenzene, input speed 495.8 Grams Per Hours; Vinyl cyanide, input speed 165.3 Grams Per Hours; Dodecyl mercaptan carbon, input speed 6.6 Grams Per Hours; Polyether glycol 551C, input speed 648 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 7.93 Grams Per Hours; With come the feed liquid in the polymerization reaction kettle (1) to enter in the 3100 milliliters of polymerization reaction kettles (2) that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 42%, the polyether polyol of dispersed phase polymer particle diameter 0.3～0.85 μ, move liquid continuously to the polyether polyol groove by the side overflow;
(e) drying: with polyether polyol in the groove 110 ℃ of service temperatures and-the 95kPa working pressure through flash drum, steam tower and falling-film evaporator etc. and obtain dried polyether polyol.Dried polyether polyol performance sees Table 2.
Embodiment 7:
(a) activate still: respectively dispersion agent 1, input speed 218 Grams Per Hours; Ethylbenzene, input speed 60 Grams Per Hours; Polyether glycol 551C, input speed 200 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 4.2 Grams Per Hours enter in 80 milliliters of activation stills that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is 10 minutes at 112 ± 5 ℃, the mean residence time of material, dispersion agent is activated at a certain temperature and moves liquid continuously to the seeding polymerization reactor by the side overflow;
(b) seeding polymerization reactor: respectively vinylbenzene, input speed 117.3 Grams Per Hours; Vinyl cyanide, input speed 63.2 Grams Per Hours; Dodecyl mercaptan carbon, input speed 1.8 Grams Per Hours; Polyether glycol 551C, input speed 287.2 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 2.16 Grams Per Hours; With come the feed liquid in the self activation still to enter in 900 milliliters of seeding polymerization reactors that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 19.5%, the seed polymer polyether glycol of dispersed phase polymer particle diameter 0.1～0.5 μ, move liquid continuously to polymerization reaction kettle (1) by the side overflow;
(c) polymerization reaction kettle (1): respectively vinylbenzene, input speed 664.3 Grams Per Hours; Vinyl cyanide, input speed 357.8 Grams Per Hours; Dodecyl mercaptan carbon, input speed 10.2 Grams Per Hours; Polyether glycol 551C, input speed 1135.2 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 12.23 Grams Per Hours; With enter in the 4800 milliliters of polymerization reaction kettles (1) that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed from the feed liquid in the seeding polymerization reactor, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction and form solid (polymkeric substance) content, move liquid continuously to the polyether polyol groove by the side overflow at 42% polyether polyol;
(e) drying: with polyether polyol in the groove 110 ℃ of service temperatures and-the 95kPa working pressure through flash drum, steam tower and falling-film evaporator etc. and obtain dried polyether polyol.Dried polyether polyol performance sees Table 2.
Embodiment 8:
(a) activate still: respectively dispersion agent 1, input speed 218 Grams Per Hours; Ethylbenzene, input speed 60 Grams Per Hours; Polyether glycol 551C, input speed 200 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 2.1 Grams Per Hours enter in 80 milliliters of activation stills that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is 10 minutes at 112 ± 5 ℃, the mean residence time of material, dispersion agent is activated at a certain temperature and moves liquid continuously to the seeding polymerization reactor by the side overflow;
(b) seeding polymerization reactor: respectively vinylbenzene, input speed 135.3 Grams Per Hours; Vinyl cyanide, input speed 45.1 Grams Per Hours; Dodecyl mercaptan carbon, input speed 1.8 Grams Per Hours; Polyether glycol 551C, input speed 287.2 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 2.16 Grams Per Hours; With come the feed liquid in the self activation still to enter in 900 milliliters of seeding polymerization reactors that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 19.5%, the seed polymer polyether glycol of dispersed phase polymer particle diameter 0.1～0.5 μ, move liquid continuously to polymerization reaction kettle (1) by the side overflow;
(c) polymerization reaction kettle (1): respectively vinylbenzene, input speed 766.5 Grams Per Hours; Vinyl cyanide, input speed 255.6 Grams Per Hours; Dodecyl mercaptan carbon, input speed 10.2 Grams Per Hours; Polyether glycol 551C, input speed 1135.2 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 12.23 Grams Per Hours: and enter with given input speed from the feed liquid in the seeding polymerization reactor and to have temperature regulator, nitrogen protection, in 4800 milliliters of polymerization reaction kettles (1) of electric mixer and side overflow discharging, controlled temperature is at 115 ± 5 ℃, the mean residence time of material is about 120 minutes, under the initiator effect, carry out free radicals copolymerization reaction and form solid (polymkeric substance) content 30%, the polyether polyol of dispersed phase polymer particle diameter 0.15～0.65 μ moves liquid to the polyether polyol groove continuously by the side overflow;
(e) drying: with polyether polyol in the groove 110 ℃ of service temperatures and-the 95kPa working pressure through flash drum, steam tower and falling-film evaporator etc. and obtain dried polyether polyol.Dried polyether polyol performance sees Table 2.
Embodiment 9:
(a) activate still: respectively dispersion agent 1, input speed 145 Grams Per Hours; Ethylbenzene, input speed 40 Grams Per Hours; Polyether glycol 330N, input speed 200 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 2.8 Grams Per Hours enter in 75 milliliters of activation stills that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is 10 minutes at 112 ± 5 ℃, the mean residence time of material, dispersion agent is activated at a certain temperature and moves liquid continuously to the seeding polymerization reactor by the side overflow;
(b) seeding polymerization reactor: respectively vinylbenzene, input speed 79.2 Grams Per Hours; Vinyl cyanide, input speed 42.6 Grams Per Hours; Dodecyl mercaptan carbon, input speed 1.2 Grams Per Hours; Polyether glycol 330N, input speed 404.8 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 1.46 Grams Per Hours; With come the feed liquid in the self activation still to enter in 900 milliliters of seeding polymerization reactors that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 8.7%, the seed polymer polyether glycol of dispersed phase polymer particle diameter 0.1～0.5 μ, move liquid continuously to polymerization reaction kettle (1) by the side overflow;
(c) polymerization reaction kettle (1): respectively vinylbenzene, input speed 158.3 Grams Per Hours; Vinyl cyanide, input speed 85.3 Grams Per Hours; Dodecyl mercaptan carbon, input speed 2.43 Grams Per Hours; Polyether glycol 330N, input speed 604.4 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 2.92 Grams Per Hours; With enter in the 1700 milliliters of polymerization reaction kettles (1) that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed from the feed liquid in the seeding polymerization reactor, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 30%, the polyether polyol of dispersed phase polymer particle diameter 0.15～0.65 μ, move liquid continuously to polymerization reaction kettle (2) by the side overflow;
(d) polymerization reaction kettle (2): respectively vinylbenzene, input speed 286 Grams Per Hours; Vinyl cyanide, 154 gram/times of input speed; Dodecyl mercaptan carbon, 4.4 gram/times of input speed; Polyether glycol 330N, input speed 806 Grams Per Hours; The initiator Diisopropyl azodicarboxylate, input speed 5.28 Grams Per Hours; With come the feed liquid in the polymerization reaction kettle (1) to enter in the 3100 milliliters of polymerization reaction kettles (2) that have temperature regulator, nitrogen protection, electric mixer and side overflow discharging with given input speed, controlled temperature is about 120 minutes at 115 ± 5 ℃, the mean residence time of material, under the initiator effect, carry out free radicals copolymerization reaction form solid (polymkeric substance) content 28%, the polyether polyol of dispersed phase polymer particle diameter 0.3～0.85 μ, move liquid continuously to the polyether polyol groove by the side overflow;
(e) drying: with polyether polyol in the groove 110 ℃ of service temperatures and-the 95kPa working pressure through flash drum, steam tower and falling-film evaporator etc. and obtain dried polyether polyol.Dried polyether polyol performance sees Table 2.
Table 1
| Project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Solid content/% viscosity/mPa.s (25 ℃) particle diameter/μ residual monomer concentration/ppm [vinylbenzene] [vinyl cyanide] | ?42 ?3850 ?0.3～0.82 ?105 ?20 | ?42 ?3920 ?0.3～0.8 ?95 ?30 | ?42 ?3820 ?0.4～0.8 ?100 ?35 | ?42 ?3900 ?0.3～0.8 ?120 ?35 | ?42 ?4880 ?0.2～0.7 ?114 ?24 |
Table 2
| Project | Example 6 | Example 7 | Example 8 | Example 9 |
| Solid content/% viscosity/mPa.s (25 ℃) particle diameter/μ residual monomer concentration/ppm [vinylbenzene] [vinyl cyanide] | ?42 ?3890 ?0.4～0.85 ?110 ?21 | ?42 ?4400 ?0.3～0.68 ?100 ?28 | ?42 ?4300 ?0.35～0.71 ?110 ?25 | ?28 ?2500 ?0.3～0.7 ?100 ?23 |
Claims (12)
1. the continuous preparation method of a polyether polyol is characterized in that it is made up of following technology:
(a) activate still: enter in the activation still that has temperature regulator, nitrogen protection, electric mixer and side overflow discharging with certain input speed (quality) respectively to dispersion agent, solvent, polyether glycol, initiator; the mean residence time of controlled temperature and material is activated dispersion agent at a certain temperature and moves liquid continuously to the seeding polymerization reactor by the side overflow.
(b) seeding polymerization reactor: respectively vinyl monomer; solvent; polyether glycol; initiator enters with certain input speed (quality) with the feed liquid of coming the self activation still and has temperature regulator; nitrogen protection; in the seeding polymerization reactor of electric mixer and side overflow discharging; the mean residence time of controlled temperature and material; under the initiator effect, carry out free radicals copolymerization reaction and form solid (polymkeric substance) content 5～30%; the seed polymer polyether glycol of dispersed phase polymer particle diameter 0.1～0.5 μ moves liquid to polymerization reaction kettle (1) continuously by the side overflow.
(c) polymerization reaction kettle (1): respectively vinyl monomer; solvent; polyether glycol; initiator and enter with certain input speed (quality) from the seed polymer in the seeding polymerization reactor and to have temperature regulator; nitrogen protection; the polymerization reaction kettle (1) of electric mixer and side overflow discharging; the mean residence time of controlled temperature and material; at solvent; the particle diameter of disperse phase seed polymer increases under initiator and the monomeric effect; form solid (polymkeric substance) content 5～42%; the polyether polyol of dispersed phase polymer particle diameter 0.15～0.65 μ moves liquid to polymerization reaction kettle (2) continuously by the side overflow.
(d) polymerization reaction kettle (2): respectively vinyl monomer; solvent; polyether glycol; initiator and enter with certain input speed (quality) from the material in the polymerization reaction kettle (1) and to have temperature regulator; nitrogen protection; in the polymerization reaction kettle (2) of electric mixer and side overflow discharging; the mean residence time of controlled temperature and material; at solvent; the particle diameter of dispersed phase polymer further increases under initiator and the monomeric effect; form solid (polymkeric substance) content 20～42%; the polymkeric substance of dispersed phase polymer particle diameter 0.3～0.85 μ moves liquid to the polyether polyol groove continuously by the side overflow.
(e) drying: polyether polyol in the groove is obtained the exsiccant polyether polyol at certain service temperature and certain working pressure through flash drum, after steaming dryings such as tower and falling-film evaporator.
2. according to the continuous preparation method of the described polyether polyol of claim 1, it is characterized in that said polyether glycol is propylene oxide ring-opening polymerization or propylene oxide and oxyethane polyether glycol that ring-opening copolymerization forms, the functionality of its polyether glycol is between 2～4, hydroxyl value is between 26mgKOH/g～70mgKOH/g, proportion of primary OH groups is between 5%～98%, and polyether glycol is at (a), (b), (c), the ratio of the input speed (d) (quality) is (a): (b): (c): (d)=0～25: 10～25: 10～70: between 0～50;
3. according to the continuous preparation method of the described polyether polyol of claim 1, it is characterized in that said vinyl monomer can be two or more the monomer in vinylbenzene, alpha-methyl styrene, methyl acrylate, ethyl propenoate, butyl methacrylate, vinyl cyanide, vinyl acetate, vinyl acetate between to for plastic, the acrylamide, be preferably vinylbenzene, vinyl cyanide, two kinds of monomeric ratios (quality) are vinylbenzene: vinyl cyanide=50: 50～90: 10.
4. according to the continuous preparation method of the described polyether polyol of claim 1, it is characterized in that said vinyl monomer total input speed (quality) in (b), (c), (d) accounts for total polyether glycol input speed (quality) and 25%～42% of total vinyl monomer input speed (quality) sum, the ratio of the input speed (quality) of vinyl monomer in (b), (c), (d) is (b): (c): (d)=5～25: 10～85: 0～60.
5. according to the continuous preparation method of the described polyether polyol of claim 1, it is characterized in that said dispersion agent is the polyether glycol of vinyl modification, molecular weight is between 3000～7000, its input speed (quality) is 6%～30% of a total vinyl monomer input speed (quality), preferably 8%～25%.
6. according to the continuous preparation method of the described polyether polyol of claim 1, it is characterized in that said solvent can be ethylbenzene, toluene, Virahol, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dodecyl mercaptan carbon, tert-dodecyl mercaptan and C
5-C
11The mixture of one or more in the mercaptan, its input speed (quality) they are 0.4%～20% of vinyl monomer input speed (quality), preferably 0.4～15%.
7. according to the continuous preparation method of the described polyether polyol of claim 1, it is characterized in that said initiator is a Diisopropyl azodicarboxylate.
8. according to the continuous preparation method of the described polyether polyol of claim 1, it is characterized in that said temperature of reaction more than 90 ℃, preferably 115 ± 1 ℃.
9. according to the continuous preparation method of the described polyether polyol of claim 1, it is characterized in that the mean residence time of said (a) step material is 5～30 minutes, preferably 10 minutes;
10. according to the continuous preparation method of the described polyether polyol of claim 1, it is characterized in that the mean residence time in said (b), (c), (d) step material is 50～150 minutes, preferably 50～130 minutes;
11. continuous preparation method according to the described polyether polyol of claim 1, the service temperature that it is characterized in that said (e) step should be not less than 70 ℃, preferably is not less than 95 ℃, is not higher than 140 ℃, working pressure should not be higher than-70kPa, preferably is not higher than-90kPa;
12., it is characterized in that being connected by overflow between said (a) and (b), (c), (d) step material according to the continuous preparation method of the described polyether polyol of claim 1.
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- 2001-02-27 CN CNB011078502A patent/CN1161392C/en not_active Expired - Fee Related
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