CN105585652A - Preformed stabilizer preparation method and method for preparing polymer polyol by preformed stabilizer - Google Patents
Preformed stabilizer preparation method and method for preparing polymer polyol by preformed stabilizer Download PDFInfo
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Abstract
The invention relates to a preformed stabilizer preparation method and a method for preparing polymer polyol by the preformed stabilizer. The preformed stabilizer comprises about 5-30 parts of a vinyl polymer and about 40-80 parts of polyoxypropylene polyol, and is used for preparing the polymer polyol with high solid content. The polymer polyol contains 40-50 parts of the vinyl polymer and about 35-55 parts of polyoxyalkylene polyol. The particle size distribution of the polymer polyol is wide, particles with the particle size being 20 nm-100 nm account for about 1-20% of total amount of the total solid particles; and particles with the particle size being 700-4000 nm account for about 0.1-20% of total amount of the total solid particles. The viscosity of the high solid content polymer polyol is low with 3000 mPa.s-10000 mPa.s (25 DEG C), and the method preferably selects the product with viscosity being 3000 mPa.s-7000 mPa.s (25 DEG C).
Description
Technical field
The present invention relates to a kind of preparation method of preformed stabilizers and prepare the method for polymer polyatomic alcohol by it.
Background technology
Polymer polyatomic alcohol is large industrial products, can give the load-carrying properties that polyurethane product is good, and improves the opening of foam. It is mainly used in the production of the soft bubble of bulk of polyurethane, the soft bubble of high resilience, the soft bubble of molding. Polymer polyatomic alcohol is that one or more vinyl monomers form taking basic polyether polyalcohol as continuous phase in-situ polymerization. First the polymer polyatomic alcohol with business Practical significance is developed by American PaulStamberger, and starts to have applied for multinomial patent in nineteen sixties. Occurred again subsequently multiple synthetic method, for example polyvinyl is synthetic separately, then dilutes in polyalcohol, has prepared so-called " redispersibility graft polyol " with this kind of method. But producing the usual way that polymer polyatomic alcohol retains is so far in the polymerization of continuous phase basic polyether polyalcohol situ with one or more vinyl monomers. In the present invention, term " polymer " polyalcohol " refer to the polymer polyatomic alcohol that vinyl monomer is produced by home position polymerization reaction.
Since polymer polyatomic alcohol product comes out, its production and use have run into many problems. The vinyl monomer that synthetic polymer polyatomic alcohol adopts is the earliest acrylonitrile, product solid content is low, below 30%, viscosity is large, sometimes exceedes 10000mPa.s/25 DEG C, is unfavorable for the technological operation in course of conveying, stop up filter screen and the pump housing, can not meet the use of modernization large-scale precision equipment, color jaundice simultaneously, core is easily burnt in foamed product jaundice. This is to cause because annulation generation chromophore has occurred in single acrylonitrile monemer polymerization.
For addressing the above problem, people have carried out a large amount of research work, have occurred many new technologies. Problem, first-selected styrene and acrylonitrile monemer copolymerization with two or more vinyl monomer copolymerization solves the jaundice of polymer polyatomic alcohol color and foam burns core are proposed in US Patent No. 4208314. Polymer polyatomic alcohol product synthetic when styrene monomer is greater than acrylonitrile monemer in monomer ratio is white, and the burning core problem of foamed product is improved. The shortcoming of this kind of method is the increase along with styrene-content, and product viscosity increases, and conversion ratio reduces, the dispersion stabilization variation of system.
A kind of low-viscosity polymeric polyalcohol and its preparation method are disclosed in US Patent No. 20060025491. It,, by polymer controls agent (chain-transferring agent) amount is brought up on the level that is enough to produce most smooth particles, can reduce the viscosity of polymer polyatomic alcohol, and the polymer polyatomic alcohol of preparation keeps good filterability and high solids content more simultaneously. Therefore think, more the polymer controls agent of a large amount is more effective when high solids content at polymer polyatomic alcohol.
In EP0786480, disclose a kind of for preparing the method for preformed stabilizers under existing at radical initiator, under it exists by the coupling polyalcohol based on polyalcohol gross weight at least 30% (weight content), by one or more ethylenically unsaturated monomer polymerizations of 5～40% (weight contents), described coupling polyalcohol can contain the unsaturated bond of induction. These preformed stabilizers can be for the preparation of polymer polyatomic alcohol stable and that particle size distribution range is narrow. Coupling polyalcohol obtains in preformed stabilizers, the small particle diameter product that preferably wherein particle diameter is 100nm～700nm.
Summary of the invention
The present invention relates to a kind of preparation method of preformed stabilizers and prepare the method for polymer polyatomic alcohol by it. Technical scheme of the present invention is as follows:
The preparation of preformed stabilizers: adopt more lower boiling micromolecular compound as continuous phase, under the condition of 75 DEG C～85 DEG C, under radical initiator, unsaturated macromers exist, one or more vinyl monomers of in-situ polymerization, form a kind of translucent or opaque suspension, then in suspension, add polyoxyalkylene polyol, micromolecular compound is dispelled in distillation, obtain preformed stabilizers system, wherein comprise 5～30 parts of polyvinyls and 40～80 parts of polyoxyalkylene polyols.
The preparation of polymer polyatomic alcohol: under radical initiator, preformed stabilizers exist, under the condition of 110 DEG C～125 DEG C, in one or more vinyl monomers of polyoxyalkylene polyol situ polymerization, the stable dispersion of the decentralized photo that forms a kind of continuous phase that comprises polyoxyalkylene polyol and comprise polyvinyl solid, be polymer polyatomic alcohol, wherein comprise 40～50 parts of polyvinyls and 35～55 parts of polyoxyalkylene polyols.
Unsaturated macromers in the present invention is the preparation method who adopts macromonomer of the prior art. Can adopt any method preparation of US Patent No. P4462715, USP4390645, USP5093412, USP4342840. In the polyoxyalkylene polyol that is initiator at a kind of polyfunctionality compound, introduce derivable carbon-carbon double bond. Polyoxyalkylene polyol can be glycerin polyether, trimethylolpropane polyethers, sorbierite polyethers, castor-oil plant wet goods compound, introducing derivable carbon-carbon double bond can be by react a kind of polyether ester generating with maleic anhydride, or reacts and obtain with the double bond containing compound such as allyl glycidyl ether, acrylic or methacrylic acid isocyano Arrcostab. By weight percentage, macromonomer addition is 6%～40% of preformed stabilizers total amount.
Small molecule monomer in the present invention can be isopropyl alcohol, ethanol, benzene,toluene,xylene, halogenated hydrocarbons or water and their mixture, preferably isopropyl alcohol and (or) ethanol. By weight percentage, consumption is 40%～80% of preformed stabilizers total amount.
The radical initiator of selecting in polymerisation is generally peroxide, azo-compound etc. Preferred azo compound in the present invention, as azodiisobutyronitrile and (or) azo-bis-iso-dimethyl, available identical or different radical initiator in preformed stabilizers and polymer polyatomic alcohol. While wherein synthesizing preformed stabilizers, by weight percentage, consumption is 0.04%～0.3% of preformed stabilizers total amount to initator; When synthesis of polymer polyalcohol, by weight percentage, consumption is 0.2%～0.6% of reaction raw materials total amount to initator
The chain-transferring agent of selecting in polymerisation can be n-dodecyl mercaptan, isopropyl alcohol, benzene, toluene, halogenated hydrocarbons or water etc. and their mixture. In the present invention, preferred n-dodecyl mercaptan is as chain-transferring agent; Wherein chain-transferring agent consumption is 0.3%～0.6% of reaction raw materials total amount.
Be suitable for vinyl monomer of the present invention and comprise all vinyl monomers that are suitable for preparing polymer polyatomic alcohol that are generally accepted, as vinyl chloride and vinylidene chloride etc.; Acrylonitrile; The mixture of styrene, brominated styrene etc. and these compounds. Available identical or different vinyl monomer in preformed stabilizers and polymer polyatomic alcohol, preferably all adopts styrene and acrylonitrile in preformed stabilizers and polymer polyatomic alcohol. While wherein synthesizing preformed stabilizers, by weight percentage, monomer consumption is 5%～30% of preformed stabilizers total amount; When synthesis of polymer polyalcohol, by weight percentage, consumption is 40%～50% of reaction raw materials total amount.
The selection of polyoxyalkylene polyol is to be determined by the final use of produced polymer polyatomic alcohol, for example polymer polyatomic alcohol is for the production of the soft bubble of massive polyurethane, just select general soft polyurethane foam polyoxyalkylene polyol, be generally the polyoxyalkylene polyol of the three-functionality-degree of molecular weight 3000 left and right; For the production of high rebound foam, just select high rebound foam polyoxyalkylene polyol, be generally the polyoxyalkylene polyol of the highly active three-functionality-degree of molecular weight 5000 left and right. In the present invention, in preformed stabilizers and polymer polyatomic alcohol, select identical polyoxyalkylene polyol.
The present invention finds, different from US20060025491 and EP0786480 is, dispersion using the preformed stabilizers that comprises unsaturated macromers and a small amount of polyvinyl as synthesis of polymer polyalcohol, can obtain the wider polymer polyatomic alcohol product of solid particulate distributions, its particle diameter is about 20nm～about 4000nm, and the particle that wherein particle diameter is 20nm～100nm accounts for approximately 1%～20% of total solid particle total amount; Particle diameter be the particle of 700nm～4000nm account for total solid particle total amount approximately 0.1%～20%. Product solid particulate distributions is wider, and polymers with high solids content polyalcohol viscosity is lower, is 3000mPas～10000mPas (25 DEG C), preferably the product of 3000mPas～7000mPas (25 DEG C).
Brief description of the drawings
The particle diameter distribution map of Fig. 1: embodiment 1 preformed stabilizers A;
The particle diameter distribution map of Fig. 2: embodiment 2 preformed stabilizers B;
The particle diameter distribution map of Fig. 3: embodiment 3 preformed stabilizers C;
The particle diameter distribution map of Fig. 4: embodiment 4 preformed stabilizers D;
The particle diameter distribution map of Fig. 5: embodiment 5 preformed stabilizers E;
The particle diameter distribution map of Fig. 6: embodiment 6 preformed stabilizers F;
The particle diameter distribution map of Fig. 7: embodiment 7 preformed stabilizers G;
The particle diameter distribution map of Fig. 8: embodiment 8 preformed stabilizers H;
The particle diameter distribution map of Fig. 9: embodiment 9 preformed stabilizers I;
The particle diameter distribution map of Figure 10: embodiment 10 preformed stabilizers J;
The particle diameter distribution map of Figure 11: embodiment 11 preformed stabilizers K;
The particle diameter distribution map of Figure 12: embodiment 12 preformed stabilizers L;
The particle diameter distribution map of Figure 13: embodiment 13 preformed stabilizers I;
The particle diameter distribution map of Figure 14: embodiment 14 preformed stabilizers II;
The particle diameter distribution map of Figure 15: embodiment 15 preformed stabilizers III;
The particle diameter distribution map of Figure 16: embodiment 16 preformed stabilizers IV;
The particle diameter distribution map of Figure 17: embodiment 17 preformed stabilizers V;
The particle diameter distribution map of Figure 18: embodiment 18 preformed stabilizers VI;
The particle diameter distribution map of Figure 19: embodiment 19 preformed stabilizers VII;
The particle diameter distribution map of Figure 20: embodiment 20 preformed stabilizers VIII;
The particle diameter distribution map of Figure 21: embodiment 21 preformed stabilizers IX;
The particle diameter distribution map of Figure 22: embodiment 22 preformed stabilizers X;
The particle diameter distribution map of Figure 23: embodiment 23 preformed stabilizers XI;
The particle diameter distribution map of Figure 24: embodiment 24 preformed stabilizers XII.
Detailed description of the invention
The preparation of preformed stabilizers:
Embodiment 1:1000ml reactor, is equipped with agitator, heater, attemperating unit and feeder. In reactor, drop into 50g unsaturated macromers and 200g isopropyl alcohol, be warming up to 75 DEG C～85 DEG C, 0.5g azo-bis-iso-dimethyl, 25g styrene, 25g acrylonitrile, 199.5g isopropyl alcohol are mixed as liftout, liftout adds in bed material continuously, feed time is 2 hours, and after charging completes, insulation absorbs 2 hours, adds 399.5g polyoxyalkylene polyol, be warming up to 110 DEG C～130 DEG C decompression distillation and remove volatile materials and unreacted monomer, be preformed stabilizers A. In preformed stabilizers A, comprise 9.3 parts of polyvinyls and 80 parts of polyoxyalkylene polyols. Figure 1 shows that the particle diameter distribution map of preformed stabilizers A, its average grain diameter is 109.5nm.
2: two 250ml reactor series connection of embodiment, are equipped with agitator, heater, attemperating unit and feeder. In two reactors, drop into respectively about 150g product A as bed material, be warming up to 75 DEG C～85 DEG C, 300g unsaturated macromers, 2.25g azodiisobutyronitrile, 52.5g brominated styrene, 22.5g acrylonitrile, 1122.75g isopropyl alcohol are mixed, add continuously in bed material, feed time is 3 hours, collect overflow material, and by 1120g polyoxyalkylene polyol and overflow mixing of materials, under 110 DEG C～130 DEG C conditions, decompression distillation removes volatile materials and unreacted monomer, is preformed stabilizers B. In preformed stabilizers B, comprise 5 parts of polyvinyls and 74.3 parts of polyoxyalkylene polyols. Figure 2 shows that the particle diameter distribution map of preformed stabilizers B, its average grain diameter is 105.7nm.
Embodiment 3:1000ml reactor, is equipped with agitator, heater, attemperating unit and feeder. In reactor, drop into 150g unsaturated macromers and 100g isopropyl alcohol, be warming up to 75 DEG C～85 DEG C, 1g azodiisobutyronitrile, 21g vinyl chloride, 14g acrylonitrile, 214g isopropyl alcohol are mixed as liftout, liftout adds in bed material continuously, feed time is 2.5 hours, and after charging completes, insulation absorbs 1.5 hours, adds 314g polyoxyalkylene polyol, be warming up to 110 DEG C～130 DEG C decompression distillation and remove volatile materials and unreacted monomer, be preformed stabilizers C. In preformed stabilizers C, comprise 6.5 parts of polyvinyls and 63 parts of polyoxyalkylene polyols. Figure 3 shows that the particle diameter distribution map of preformed stabilizers C, its average grain diameter is 113.6nm.
4: two 500ml reactor series connection of embodiment, are equipped with agitator, heater, attemperating unit and feeder. In two reactors, drop into respectively about 400g products C as bed material, be warming up to 75 DEG C～85 DEG C, 6g azodiisobutyronitrile, 40g styrene, 50g brominated styrene, 90g acrylonitrile, 800g unsaturated macromers, 1014g ethanol are mixed as liftout, liftout adds in bed material continuously, feed time is 2 hours, collect overflow material, and by 1014g polyoxyalkylene polyol and overflow mixing of materials, under 110 DEG C～130 DEG C conditions, decompression distillation removes volatile materials and unreacted monomer, is preformed stabilizers D. In preformed stabilizers D, comprise 8.1 parts of polyvinyls and 50.5 parts of polyoxyalkylene polyols. Figure 4 shows that the particle diameter distribution map of preformed stabilizers D, its average grain diameter is 121.6nm.
Embodiment 5: with two 250ml reactor series connection, agitator, heater, attemperating unit and feeder are housed. First in two reactors, add respectively about 150g product D as bed material, be warming up to 75 DEG C～85 DEG C, 0.4g azo-bis-iso-dimethyl, 130g styrene, 70g acrylonitrile, 60g unsaturated macromers, 739.6g isopropyl alcohol are mixed and added continuously in bed material, feed time is approximately 4.5 hours, collect whole overflow materials, after completing, charging adds 739.6g polyoxyalkylene polyol in overflow material, under 110 DEG C～130 DEG C conditions, decompression distillation removes volatile materials and unreacted monomer, is preformed stabilizers E. In preformed stabilizers E, comprise 18.2 parts of polyvinyls and 73.9 parts of polyoxyalkylene polyols. Figure 5 shows that the particle diameter distribution map of preformed stabilizers E, its average grain diameter is 106.1nm.
Embodiment 6:2000ml reactor, is equipped with agitator, heater, attemperating unit and feeder. In reactor, drop into 150g unsaturated macromers and 250g isopropyl alcohol, be warming up to 75 DEG C～85 DEG C, 1g azodiisobutyronitrile, 50g styrene, 50g acrylonitrile, 170g unsaturated macromers, 329g isopropyl alcohol are mixed as liftout, liftout adds in bed material continuously, feed time is 3 hours, after charging completes, insulation absorbs 1.5 hours, adds 579g polyoxyalkylene polyol. After charging completes, the decompression distillation under 110 DEG C～130 DEG C conditions of overflow material is removed to volatile materials and unreacted monomer, be preformed stabilizers F. In preformed stabilizers F, comprise 9.1 parts of polyvinyls and 57.9 parts of polyoxyalkylene polyols. Figure 6 shows that the particle diameter distribution map of preformed stabilizers F, its average grain diameter is 110.4nm.
7: two 500ml reactor series connection of embodiment, are equipped with agitator, heater, attemperating unit and feeder. In two reactors, drop into respectively about 400g product F as bed material, be warming up to 75 DEG C～85 DEG C, 8g azodiisobutyronitrile, 400g styrene, 200g acrylonitrile, 1000g unsaturated macromers, 2392g isopropyl alcohol are mixed as liftout, liftout adds in bed material continuously, feed time is 5.5 hours, collect overflow material, 2392g polyoxyalkylene polyol is mixed with overflow material, under 110 DEG C～130 DEG C conditions, decompression distillation removes volatile materials and unreacted monomer, is preformed stabilizers G. In preformed stabilizers G, comprise 13.5 parts of polyvinyls and 59.5 parts of polyoxyalkylene polyols. Figure 7 shows that the particle diameter distribution map of preformed stabilizers G, its average grain diameter is 151.6nm.
Embodiment 8:2000ml reactor, is equipped with agitator, heater, attemperating unit and feeder. In reactor, drop into 200g unsaturated macromers and 200g ethanol, be warming up to 75 DEG C～85 DEG C, 3g azodiisobutyronitrile, 60g brominated styrene, 60g acrylonitrile, 200g unsaturated macromers, 277g ethanol are mixed as liftout, liftout adds in bed material continuously, feed time is 2.5 hours, after charging completes, insulation absorbs 2 hours, adds 477g polyoxyalkylene polyol. After charging completes, the decompression distillation under 110 DEG C～130 DEG C conditions of overflow material is removed to volatile materials and unreacted monomer, be preformed stabilizers H. In preformed stabilizers H, comprise 10.5 parts of polyvinyls and 48 parts of polyoxyalkylene polyols. Figure 8 shows that the particle diameter distribution map of preformed stabilizers H, its average grain diameter is 181.8nm.
Embodiment 9:2000ml reactor, is equipped with agitator, heater, attemperating unit and feeder. In reactor, drop into 60g unsaturated macromers and 340g ethanol, be warming up to 75 DEG C～85 DEG C, 1g azo-bis-iso-dimethyl, 100g styrene, 150g acrylonitrile, 349g isopropyl alcohol are mixed as liftout, liftout adds in bed material continuously, feed time is 3 hours, after charging completes, insulation absorbs 1 hour, adds 689g polyoxyalkylene polyol. After charging completes, the decompression distillation under 110 DEG C～130 DEG C conditions of overflow material is removed to volatile materials and unreacted monomer, be preformed stabilizers I. In preformed stabilizers I, comprise 22.5 parts of polyvinyls and 68.8 parts of polyoxyalkylene polyols. Figure 9 shows that the particle diameter distribution map of preformed stabilizers I, its average grain diameter is 198.7nm.
10: two 500ml reactor series connection of embodiment, are equipped with agitator, heater, attemperating unit and feeder. In two reactors, drop into respectively about 400g product I as bed material, be warming up to 75 DEG C～85 DEG C, 6g azodiisobutyronitrile, 500g styrene, 100g brominated styrene, 600g acrylonitrile, 480g unsaturated macromers, 2314g ethanol are mixed as liftout, liftout adds in bed material continuously, feed time is 6 hours, collect overflow material, 2314g polyoxyalkylene polyol is added in overflow material, under 110 DEG C～130 DEG C conditions, decompression distillation removes volatile materials and unreacted monomer, is preformed stabilizers J. In preformed stabilizers J, comprise 27.1 parts of polyvinyls and 57.8 parts of polyoxyalkylene polyols. Figure 10 shows that the particle diameter distribution map of preformed stabilizers J, its average grain diameter is 205.6nm.
11: two 2000ml reactor series connection of embodiment, are equipped with agitator, heater, attemperating unit and feeder. In two reactors, drop into respectively about 1600g product J as bed material, be warming up to 75 DEG C～85 DEG C, 16g azodiisobutyronitrile, 1600g styrene, 800g acrylonitrile, 1120g unsaturated macromers, 3902g isopropyl alcohol, 562g ethanol are mixed as liftout, liftout adds in bed material continuously, feed time is 5 hours, collect overflow material, 4452g polyoxyalkylene polyol is added in overflow material, after charging completes, the decompression distillation under 110 DEG C～130 DEG C conditions of overflow material is removed to volatile materials and unreacted monomer, be preformed stabilizers K. In preformed stabilizers K, comprise 30 parts of polyvinyls and 55.6 parts of polyoxyalkylene polyols. Figure 11 shows that the particle diameter distribution map of preformed stabilizers K, its average grain diameter is 217.6nm.
Embodiment 12:2000ml reactor, is equipped with agitator, heater, attemperating unit and feeder. In reactor, drop into 200g unsaturated macromers and 200g ethanol, be warming up to 75 DEG C～85 DEG C, 3g azodiisobutyronitrile, 180g vinyl chloride, 120g acrylonitrile, 97g unsaturated macromers, 200g ethanol are mixed as liftout, liftout adds in bed material continuously, feed time is 3 hours, after charging completes, insulation absorbs 2 hours, adds 400g polyoxyalkylene polyol. After charging completes, the decompression distillation under 110 DEG C～130 DEG C conditions of overflow material is removed to volatile materials and unreacted monomer, be preformed stabilizers L. In preformed stabilizers L, comprise 28.1 parts of polyvinyls and 40 parts of polyoxyalkylene polyols. Figure 12 shows that the particle diameter distribution map of preformed stabilizers L, its average grain diameter is 191.8nm.
The preparation of polymer polyatomic alcohol:
Embodiment 13: add 320g polyoxyalkylene polyol and 24g product A to stir in 1000mL reactor and be heated to 110 DEG C. By 1.6g azo-bis-iso-dimethyl, 128g acrylonitrile, 232g styrene, 3.2g n-dodecyl mercaptan and 91.2g polyoxyalkylene polyol mix, and under the condition of 110 DEG C, drip continuously in reactor time for adding 2～3 hours. Reacted rear insulation and absorbed 1～2 hour, after vacuumize and remove volatile materials and unreacted monomer, be polymer polyatomic alcohol I. In polymer polyatomic alcohol I, comprise 44.8 parts of polyvinyls and 51.5 parts of polyoxyalkylene polyols. Figure 13 shows that the particle diameter distribution map of polymer polyatomic alcohol I, its particle size range as shown in table 1 is 48.83～861.10nm. The particle size range of table 1 polymer polyatomic alcohol I
Embodiment 14: with two 500ml reactor series connection, agitator, heater, attemperating unit and feeder are all housed. First in two reactors, add respectively 200g product I as bed material, be heated to 125 DEG C, 1062g polyoxyalkylene polyol, 480g styrene, 320g acrylonitrile, 12g n-dodecyl mercaptan, 120g product B, 6g azo-bis-iso-dimethyl are mixed to rear adding continuously in bed material, and reaction temperature is controlled at 125 DEG C. Feed time is 5 hours, collects overflow material. After charging completes, overflow material is vacuumized and removes volatile materials and unreacted monomer, after vacuumizing, be polymer polyatomic alcohol II. In polymer polyatomic alcohol II, comprise 40 parts of polyvinyls and 53.1 parts of polyoxyalkylene polyols. Figure 14 shows that the particle diameter distribution map of polymer polyatomic alcohol II, its particle size range as shown in table 2 is 28.02～2384.08nm.
The particle size range of table 2 polymer polyatomic alcohol II
Embodiment 15: with two 1000ml reactor series connection, agitator, heater, attemperating unit and feeder are all housed. First in two reactors, add respectively 400g product II as bed material, be heated to approximately 115 DEG C of left and right, 1860g polyoxyalkylene polyol, 1000g styrene, 204g brominated styrene, 516g acrylonitrile, 12g n-dodecyl mercaptan, 360g products C, 24g azodiisobutyronitrile are mixed to rear adding continuously in bed material, reaction temperature is controlled at 115 DEG C ± 5 DEG C, feed time is 4.5 hours, collects overflow material. After charging completes, overflow material is vacuumized and removes volatile materials and unreacted monomer, after vacuumizing, be polymer polyatomic alcohol III. In polymer polyatomic alcohol III, comprise 43.2 parts of polyvinyls and 46.7 parts of polyoxyalkylene polyols. Figure 15 shows that the particle diameter distribution map of polymer polyatomic alcohol III, its particle size range as shown in table 3 is 25.54～1500.68nm.
The particle size range of table 3 polymer polyatomic alcohol III
Embodiment 16: with two 1000ml reactor series connection, agitator, heater, attemperating unit and feeder are all housed. First in two reactors, add respectively 400g product III as bed material, be heated to approximately 115 DEG C of left and right, 1684g polyoxyalkylene polyol, 1092g styrene, 588g acrylonitrile, 20g n-dodecyl mercaptan, 600g product D, 16g azodiisobutyronitrile are mixed to rear adding continuously in bed material, reaction temperature is controlled at 115 DEG C ± 5 DEG C, feed time is 4 hours, collects overflow material. After charging completes, overflow material is vacuumized and removes volatile materials and unreacted monomer, after vacuumizing, be polymer polyatomic alcohol IV. In polymer polyatomic alcohol IV, comprise 42.1 parts of polyvinyls and 43 parts of polyoxyalkylene polyols. Figure 16 shows that the particle diameter distribution map of polymer polyatomic alcohol IV, its particle size range as shown in table 4 is 21.22～1646.25nm.
The particle size range of table 4 polymer polyatomic alcohol IV
Embodiment 17: with two 1000ml reactor series connection, agitator, heater, attemperating unit and feeder are all housed. First in two reactors, add respectively 400g product IV as bed material, be heated to approximately 115 DEG C of left and right, 1480g polyoxyalkylene polyol, 1056g vinylidene chloride, 704g acrylonitrile, 16g n-dodecyl mercaptan, 720g product E, 24g azodiisobutyronitrile are mixed to rear adding continuously in bed material, reaction temperature is controlled at 115 DEG C ± 5 DEG C, feed time is 4.5 hours, collects overflow material. After charging completes, overflow material is vacuumized and removes volatile materials and unreacted monomer, after vacuumizing, be polymer polyatomic alcohol V. In polymer polyatomic alcohol V, comprise 45 parts of polyvinyls and 37 parts of polyoxyalkylene polyols. Figure 17 shows that the particle diameter distribution map of polymer polyatomic alcohol V, its particle size range as shown in table 5 is 30.73～1247.03nm.
The particle size range of table 5 polymer polyatomic alcohol V
Embodiment 18: with two 1000ml reactor series connection, agitator, heater, attemperating unit and feeder are all housed. First in two reactors, add respectively 400g product V as bed material, be heated to approximately 125 DEG C, 1922g polyoxyalkylene polyol, 1148g styrene, 492g acrylonitrile, 18g n-dodecyl mercaptan, 400g product F, 20g azodiisobutyronitrile are mixed to rear adding continuously in bed material, reaction temperature is controlled at 125 DEG C, feed time is 4.5 hours, collects overflow material. After charging completes, overflow material is vacuumized and removes volatile materials and unreacted monomer, after vacuumizing, be polymer polyatomic alcohol VI. In polymer polyatomic alcohol VI, comprise 40.5 parts of polyvinyls and 48 parts of polyoxyalkylene polyols. Figure 18 shows that the particle diameter distribution map of polymer polyatomic alcohol VI, its particle size range as shown in table 6 is 25.54～1247.03nm.
The particle size range of table 6 polymer polyatomic alcohol VI
Embodiment 19: with two 1000ml reactor series connection, agitator, heater, attemperating unit and feeder are all housed. First in two reactors, add respectively 400g product VI as bed material, be heated to approximately 110 DEG C of left and right, 1820g polyoxyalkylene polyol, 1092g styrene, 728g acrylonitrile, 24g n-dodecyl mercaptan, 320g product G, 16g azodiisobutyronitrile are mixed to rear adding continuously in bed material, reaction temperature is controlled at 110 DEG C, feed time is 5 hours, collects overflow material. After charging completes, overflow material is vacuumized and removes volatile materials and unreacted monomer, after vacuumizing, be polymer polyatomic alcohol VII. In polymer polyatomic alcohol VII, comprise 46 parts of polyvinyls and 45.5 parts of polyoxyalkylene polyols. Figure 19 shows that the particle diameter distribution map of polymer polyatomic alcohol VII, its particle size range as shown in table 7 is 19.35～1500.68nm. The particle size range of table 7 polymer polyatomic alcohol VII
Embodiment 20: with two 500ml reactor series connection, agitator, heater, attemperating unit and feeder are all housed. First in two reactors, add respectively 300g product VII as bed material, be heated to approximately 120 DEG C of left and right, 700g polyoxyalkylene polyol, 577g styrene, 343g acrylonitrile, 9g n-dodecyl mercaptan, 366g product H, 5g azo-bis-iso-dimethyl are mixed to rear adding continuously in bed material, reaction temperature is controlled at 120 DEG C ± 5 DEG C, feed time is 4.5 hours, collects overflow material. After charging completes, overflow material is vacuumized and removes volatile materials and unreacted monomer, after vacuumizing, be polymer polyatomic alcohol VIII. In polymer polyatomic alcohol VIII, comprise 47 parts of polyvinyls and 35 parts of polyoxyalkylene polyols. Figure 20 shows that the particle diameter distribution map of polymer polyatomic alcohol VIII, its particle size range as shown in table 8 is 28.02～1247.03nm.
The particle size range of table 8 polymer polyatomic alcohol VIII
Embodiment 21: with two 500ml reactor series connection, agitator, heater, attemperating unit and feeder are all housed. First in two reactors, add respectively 300g product VIII as bed material, be heated to approximately 115 DEG C of left and right, 898g polyoxyalkylene polyol, 200g vinylidene chloride, 411g styrene, 329g acrylonitrile, 11g n-dodecyl mercaptan, 140g product I, 11g azo-bis-iso-dimethyl are mixed to rear adding continuously in bed material, reaction temperature is controlled at 115 DEG C ± 5 DEG C, feed time is 4 hours, collects overflow material. After charging completes, overflow material is vacuumized and removes volatile materials and unreacted monomer, after vacuumizing, be polymer polyatomic alcohol IX. In polymer polyatomic alcohol IX, comprise 49 parts of polyvinyls and 45 parts of polyoxyalkylene polyols. Figure 21 is depicted as the particle diameter distribution map of polymer polyatomic alcohol IX, and its particle size range as shown in table 9 is 19.35～1805.93nm.
The particle size range of table 9 polymer polyatomic alcohol IX
Embodiment 22: with two 1000ml reactor series connection, agitator, heater, attemperating unit and feeder are all housed. First in two reactors, add respectively 400g product IX as bed material, be heated to approximately 115 DEG C of left and right, 1600g polyoxyalkylene polyol, 1140g styrene, 768g acrylonitrile, 12g n-dodecyl mercaptan, 460g product J, 20g azodiisobutyronitrile are mixed to rear adding continuously in bed material, reaction temperature is controlled at 115 DEG C ± 5 DEG C, feed time is 4.5 hours, collects overflow material. After charging completes, overflow material is vacuumized and removes volatile materials and unreacted monomer, after vacuumizing, be polymer polyatomic alcohol X. In polymer polyatomic alcohol X, comprise 48.1 parts of polyvinyls and 40 parts of polyoxyalkylene polyols. Figure 22 is depicted as the particle diameter distribution map of polymer polyatomic alcohol X, and its particle size range as shown in table 10 is 30.73～2384.08nm.
The particle size range of table 10 polymer polyatomic alcohol X
Embodiment 23: with two 1000ml reactor series connection, agitator, heater, attemperating unit and feeder are all housed. First in two reactors, add respectively 500g product X as bed material, be heated to approximately 115 DEG C of left and right, 1692g polyoxyalkylene polyol, 1196g styrene, 644g acrylonitrile, 14g n-dodecyl mercaptan, 440g product K, 14g azodiisobutyronitrile are mixed to rear adding continuously in bed material, reaction temperature is controlled at 115 DEG C ± 5 DEG C, feed time is 5 hours, collects overflow material. After charging completes, overflow material is vacuumized and removes volatile materials and unreacted monomer, after vacuumizing, be polymer polyatomic alcohol XI. In polymer polyatomic alcohol XI, comprise 46.9 parts of polyvinyls and 42.3 parts of polyoxyalkylene polyols. Figure 23 is depicted as the particle diameter distribution map of polymer polyatomic alcohol XI, and its particle size range as shown in table 11 is 21.22～1247.03nm.
The particle size range of table 11 polymer polyatomic alcohol XI
Embodiment 24: with two 1000ml reactor series connection, agitator, heater, attemperating unit and feeder are all housed. First in two reactors, add respectively 600g product XI as bed material, be heated to approximately 115 DEG C of left and right, 1762g polyoxyalkylene polyol, 1000g styrene, 400g brominated styrene, 600g acrylonitrile, 20g n-dodecyl mercaptan, 200g product I, 18g azodiisobutyronitrile are mixed to rear adding continuously in bed material, reaction temperature is controlled at 115 DEG C ± 5 DEG C, feed time is 4 hours, collects overflow material. After charging completes, overflow material is vacuumized and removes volatile materials and unreacted monomer, after vacuumizing, be polymer polyatomic alcohol XII. In polymer polyatomic alcohol X, comprise 50 parts of polyvinyls and 44 parts of polyoxyalkylene polyols. Figure 24 is depicted as the particle diameter distribution map of polymer polyatomic alcohol XII, and its particle size range as shown in table 12 is 48.83～4154.87nm.
The particle size range of table 12 polymer polyatomic alcohol XII
Table 13 embodiment the physical property of product
| Preformed stabilizers | Viscosity (mPas/25 DEG C) | Average grain diameter (nm) | 150 eye mesh screen filterabilityes |
| A | 1100 | 109.5 | 100 parts |
| B | 1300 | 105.7 | 100 parts |
| C | 2300 | 113.6 | 100 parts |
| D | 3000 | 121.6 | 100 parts |
| E | 1000 | 106.1 | 100 parts |
| F | 2500 | 110.4 | 100 parts |
| G | 2200 | 151.6 | 100 parts |
| H | 2600 | 181.8 | 100 parts |
| I | 1800 | 198.7 | 100 parts |
| J | 2600 | 205.6 | 100 parts |
| K | 2400 | 217.6 | 100 parts |
| L | 2650 | 191.8 | 100 parts |
Table 14 embodiment the physical property of product
Claims (9)
1. preformed stabilizers system for the preparation of polymer polyatomic alcohol and preparation method thereof, is characterized in that adopting 25 DEG C of < to boilThe compound of 130 DEG C of < of point, 10≤molecular weight≤150 is as continuous phase, at radical initiator, unsaturated large moleculeUnder monomer exists, under the condition of 75 DEG C～85 DEG C, one or more vinyl monomers of in-situ polymerization, form a kind of semi-transparentBright or opaque suspension then adds polyoxyalkylene polyol in this suspension, and little molecule chemical combination is dispelled in distillationThing, obtains preformed stabilizers, wherein comprises 5～30 parts of polyvinyls and 40～80 parts of polyoxyalkylene polyols.
2. preformed stabilizers according to claim 1, is characterized in that, wherein radical initiator is azo compound,Comprise azodiisobutyronitrile, azo-bis-iso-dimethyl.
3. preformed stabilizers according to claim 1, is characterized in that, wherein vinyl monomer be vinyl chloride, vinylidene chloride,One or more in acrylonitrile, styrene, brominated styrene etc.
4. preformed stabilizers according to claim 1, is characterized in that, wherein unsaturated macromers is by maleic anhydrideReact with polyfunctionality polyoxyalkylene polyol the polyether ester forming, molecular weight is 5000～10000.
5. preformed stabilizers according to claim 1, is characterized in that, wherein micromolecular compound is that normal temperature is liquid changeCompound, comprises isopropyl alcohol, ethanol, benzene, toluene, halogenated hydrocarbons or water and their mixture.
6. the method for a polymer polyatomic alcohol of being prepared by the preformed stabilizers of claim 1: it is characterized in that causing at free radicalUnder agent, preformed stabilizers exist, under the condition of 110 DEG C～125 DEG C, in polyoxyalkylene polyol situ polymerization oneOr several vinyl monomers, form a kind of continuous phase that comprises polyoxyalkylene polyol and comprise polyvinyl solidThe stable dispersion of decentralized photo, comprise 40～50 parts of polyvinyls and 35～55 parts of polyoxyalkylene polyols,In this polymer polyatomic alcohol, solid grain size scope is about 20nm～4000nm.
7. polymer polyatomic alcohol according to claim 6, is characterized in that, wherein radical initiator is azo compound,Comprise azodiisobutyronitrile, azo-bis-iso-dimethyl.
8. polymer polyatomic alcohol according to claim 6, is characterized in that, wherein vinyl monomer is vinyl chloride, inclined to one side chloroetheneOne or more in alkene, acrylonitrile, styrene, brominated styrene.
9. polymer polyatomic alcohol according to claim 6, is characterized in that, wherein chain-transferring agent be n-dodecyl mercaptan,Isopropyl alcohol, benzene, toluene, halogenated hydrocarbons or water and their mixture.
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