CN115232257A - Preparation method of low-viscosity polymer polyol, obtained polymer polyol and application - Google Patents
Preparation method of low-viscosity polymer polyol, obtained polymer polyol and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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Abstract
The invention discloses a preparation method of low-viscosity polymer polyol, the obtained polymer polyol and application thereof, wherein the preparation method comprises the following steps: adopting raw materials comprising basic polyether polyol, a stabilizer precursor, an unsaturated monomer, an initiator and a chain transfer agent to react to obtain the low-viscosity polymer polyol; wherein the molecular structure of the basic polyether polyol comprises a propylene oxide homopolymerized chain segment and a propylene oxide-ethylene oxide copolymerized chain segment. The invention adopts the base polyether polyol with a specific structure to synthesize the polymer polyol, thereby achieving the purpose of reducing viscosity.
Description
Technical Field
The invention belongs to the field of preparation of polymer polyols, and particularly relates to a preparation method of a low-viscosity polymer polyol, the obtained polymer polyol and application.
Background
Polymer polyols are a large number of industrial products, and are prepared by in situ polymerization of one or more vinyl monomers using a base polyether polyol as the continuous phase. Polymer polyols are used primarily in the production of polyurethane foams.
A problem generally encountered in the manufacture of polymer polyols, i.e. systems in which the polymer is stably dispersed in the base polyol, is to obtain a polymer polyol having both a relatively high solid polymer content and a sufficiently low viscosity for easy handling. Polymer polyols having this combination of properties are advantageous for the properties of any polyurethane foam produced from the polymer polyol. In order to stably disperse the polymer particles in the liquid polyol medium, a dispersion stabilizer precursor is generally required.
The polymeric polyol is made using a macromer which contains in the molecule at least one or more polymerizable double bonds which are copolymerizable with the ethylenically unsaturated monomer to form part of the polymer segment and one or more polyether polyol segments, the polymer extending polyol segment being compatible with the liquid polyol medium in which it is dispersed, thereby stabilizing the dispersion. The concept of synthesizing similar macromers is known, and references disclosing stabilizer precursors (or macromers) for polymer polyols include, for example, U.S. Pat. nos. 4,550,194, 4,652,589, and 4,997,857. The stabilizer precursors of U.S. Pat. No. 4,997,857 are characterized by these four features: (1) they are prepared from starting polyols having a functionality greater than 4; (2) at least 60% of them retain unsaturated bonds; (3) they have a viscosity greater than 2000 centipoise at 25 ℃; and (4) the starting polyol is capped with ethylene oxide and/or the adduct formed between the starting polyol and the reactive unsaturated compound is capped with ethylene oxide.
Disclosure of Invention
In order to solve the problem that the product viscosity of the polymer polyol product is greatly improved along with the improvement of the solid content of the polymer polyol product in the prior art, the invention adopts the basic polyether polyol with a specific structure to synthesize the polymer polyol, thereby achieving the purpose of reducing the viscosity.
An object of the present invention is to provide a method for preparing a low viscosity polymer polyol, comprising: adopting raw materials comprising basic polyether polyol, a stabilizer precursor, an unsaturated monomer, an initiator and a chain transfer agent to react to obtain the low-viscosity polymer polyol; wherein, the molecular structure of the basic polyether polyol comprises a propylene oxide homopolymerization chain segment and a propylene oxide-ethylene oxide copolymerization chain segment.
Wherein the low viscosity polymer polyol has a solids content of 40% or more and a viscosity of less than 4200 cps at 25 ℃.
In a preferred embodiment, the propylene oxide homo-segments are present in an amount of 10 to 70%, preferably 20 to 60%, based on 100% by weight of the total polyether polyol; the content of the propylene oxide/ethylene oxide copolymer segment is 30 to 90%, preferably 40 to 80%.
In a further preferred embodiment, the content of ethylene oxide structural units is from 2 to 25%, preferably from 5 to 16%, based on 100% by weight of the total base polyether polyol.
In a preferred embodiment, the propylene oxide-ethylene oxide copolymerized segment includes one copolymerized segment or a plurality of copolymerized segments.
In a further preferred embodiment, when a segment of copolymerized segments is included, it is a random copolymerized segment or a gradient copolymerized segment, preferably, when a gradient copolymerized segment, in which the content of ethylene oxide is gradually increased (but the total EO content is still within the aforementioned range).
In a still further preferred embodiment, when the propylene oxide-ethylene oxide copolymerized segment includes a plurality of copolymerized segments, the ethylene oxide content in each copolymerized segment is different, preferably gradually increased, in the direction in which the molecular chain extends (but the total EO content is still within the aforementioned range).
Specifically, when the propylene oxide-ethylene oxide copolymerized segment comprises two copolymerized segments, the molecular structure of the base polyether polyol is as shown in formula (1):
R-(PO) n -[(PO x1 EO y1 )-(PO x2 EO y2 )]formula (1)
In the formula (I), (PO) x1 EO y1 ) Denotes a first-stage copolymerization segment，(PO x2 EO y2 ) Represents a second-stage copolymerized segment wherein x1>x2，y1<y2。
In a preferred embodiment, the molecular weight of the base polyether polyol is from 2000 to 8000, preferably from 3000 to 6000, more preferably from 3000 to 4000.
In a preferred embodiment, the base polyether polyol is obtained by: and (2) taking polyol as an initiator, adding propylene oxide in the presence of a catalyst I for reaction, and adding a mixture of propylene oxide and ethylene oxide after the reaction is finished to obtain the basic polyether polyol.
In a further preferred embodiment, the catalyst I is selected from at least one of phosphazene catalysts, alkali metal catalysts and bi/multimetallic catalysts.
Wherein the phosphazene catalyst, the alkali metal catalyst and the bi/polymetallic catalyst are disclosed in the prior art.
In a still further preferred embodiment, the polyol is selected from at least one of ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose.
Wherein, the preparation of the basic polyether polyol is carried out by adopting the temperature and the pressure disclosed in the prior art.
In a preferred embodiment, the stabilizer precursor is obtained by: the stabilizer precursor is prepared by reacting raw materials including polyether polyol, polyisocyanate, isocyanate containing unsaturated reaction bonds and a catalyst II.
In a further preferred embodiment, the viscosity of the stabilizer precursor is from 1500 to 8000mPa.s/25 ℃, preferably from 2000 to 6000mPa.s/25 ℃, more preferably from 2000 to 5000mPa.s/25 ℃.
For example, the viscosity of the stabilizer precursor may be 1500mPa.s/25 ℃, 2000mPa.s/25 ℃, 3000mPa.s/25 ℃, 4000mPa.s/25 ℃, 5000mPa.s/25 ℃, 6000mPa.s/25 ℃, 7000mPa.s/25 ℃ or 8000mPa.s/25 ℃.
In a preferred embodiment, the polyether polyol is a copolymer of propylene oxide and ethylene oxide (preferably a propylene oxide-ethylene oxide block copolymer) containing from 2 to 8 (preferably from 3 to 8, more preferably from 3 to 6) hydroxyl groups at the end.
In a further preferred embodiment, the polyether polyol has a molecular weight of 900 to 12000, preferably 9000 to 12000.
For example, the polyether polyol used to prepare the stabilizer precursor may have a molecular weight of 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, or 12000.
In a still further preferred embodiment, the polyether polyol has an ethylene oxide unit content of from 5 to 20% by weight, preferably from 8 to 16% by weight.
Specifically, the polyether polyol is obtained as follows: taking polyhydric alcohol as an initiator, and adding propylene oxide and ethylene oxide in the presence of a catalyst I (preferably sequentially) to react to obtain the product, wherein the polyhydric alcohol is at least one selected from ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose, and is preferably sorbitol; and/or the catalyst I is selected from at least one of a phosphazene catalyst, an alkali metal catalyst and a bi/multi-metal catalyst.
Wherein, the polyether polyol is prepared by adopting the temperature and the pressure disclosed in the prior art.
In a preferred embodiment, the isocyanate containing unsaturated reactive bond is at least one selected from 3-isopropyl-dimethylbenzyl isocyanate and ethyl isocyanate methacrylate.
In a preferred embodiment, the polyisocyanate is selected from compounds containing at least two isocyanate groups, such as diisocyanates.
In a further preferred embodiment, the polyisocyanate is at least one selected from the group consisting of isophorone diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 1, 4-cyclohexane diisocyanate, norbornane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, and 4,4' -diphenylmethane diisocyanate.
In a preferred embodiment, the catalyst II is at least one selected from tin-based catalysts, amine-based catalysts, and other metal catalysts, preferably from tin-based catalysts.
In a further preferred embodiment, the catalyst II is selected from at least one of dibutyl tin dilaurate, stannous octoate, tetrabutyl titanate, triethylenediamine.
In a preferred embodiment, the amount of the polyisocyanate used in the preparation of the stabilizer precursor is 0.05 to 5 parts by weight, the amount of the isocyanate having an unsaturated reactive bond used is 0.05 to 5 parts by weight, and the amount of the catalyst II used is 10 to 1000ppm by weight, based on 100 parts by weight of the polyether polyol.
In a further preferred embodiment, the amount of the polyisocyanate used in the preparation of the stabilizer precursor is 0.1 to 2 parts by weight, the amount of the isocyanate having an unsaturated reactive bond is 0.1 to 2 parts by weight, and the amount of the catalyst II used is 50 to 500ppm by weight, based on 100 parts by weight of the polyether polyol.
For example, the polyisocyanate may be used in an amount of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.5, 1.8 or 2 parts by weight based on 100 parts by weight of the polyether polyol in preparing the stabilizer precursor; the isocyanate containing unsaturated reaction bonds is used in an amount of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.5, 1.8 or 2 parts by weight; the catalyst II is used in amounts of 50, 60, 70, 80, 90, 100, 120, 150, 200, 300, 400, 500ppm by weight.
In a preferred embodiment, the unsaturated monomer is selected from at least one of butadiene, isoprene styrene, alpha-methyl styrene, t-butyl styrene, chlorostyrene, cyanostyrene, bromostyrene, styrene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-dimethylacrylamide, N- (dimethylaminomethyl) acrylamide, vinyl ethers, vinyl ketones, vinylidene halides.
In a further preferred embodiment, the unsaturated monomer is selected from acrylonitrile and styrene, wherein the mass ratio of acrylonitrile to styrene is 1 (0.5-3), preferably 1 (1.5-2.5).
In a preferred embodiment, the chain transfer agent is selected from at least one of methanol, ethanol, butanol, isopropanol, mercaptans.
In a preferred embodiment, the initiator is selected from at least one of alkyl hydroperoxides, aryl hydroperoxides, persulfates, perborates, percarbonates, azo compounds.
In a further preferred embodiment, the initiator is selected from at least one of hydrogen peroxide, di (t-butyl) peroxide, t-butylperoxy diethyl acetate, t-butyl peroctoate, t-butyl peroxy isobutyrate, t-butyl peroxide, t-butyl peroxy pivalate, t-amyl peroxy pivalate, t-butyl peroxy-2-ethyl hexanoate, lauroyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, dimethyl azobisisobutyrate.
In a preferred embodiment, the method of making the polymer polyol comprises the steps of:
step 1, pre-reacting the stabilizer precursor with the unsaturated monomer in the presence of the initiator and the chain transfer agent to obtain a pre-reactant (PFS);
and 2, in the presence of the initiator, reacting the pre-reactant obtained in the step 1 with the base polyether polyol and the unsaturated monomer to obtain the polymer polyol.
In a preferred embodiment, in step 1, the amount of the initiator is 0.01 to 1%, the amount of the chain transfer agent is 20 to 80%, the amount of the stabilizer precursor is 10 to 50%, and the amount of the unsaturated monomer is 5 to 30%, based on 100% by weight of the total weight of the reaction raw materials in step 1.
In a further preferred embodiment, in step 1, the amount of the initiator is 0.05 to 0.5%, the amount of the chain transfer agent is 50 to 70%, the amount of the stabilizer precursor is 15 to 30%, and the amount of the unsaturated monomer is 10 to 20%, based on 100% by weight of the total reaction raw materials.
For example, in step 1, the initiator is used in an amount of 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.12%, 0.15%, 0.18%, 0.2%, 0.3%, 0.4%, or 0.5%, the chain transfer agent is used in an amount of 50%, 55%, 60%, 65%, or 70%, the stabilizer precursor is used in an amount of 15%, 20%, 25%, or 30%, and the unsaturated monomer is used in an amount of 10%, 12%, 15%, 18%, or 20%, based on 100% by weight of the total reaction raw materials.
In a preferred embodiment, in step 2, the amount of the initiator is 0.05 to 2%, the amount of the pre-reactant is 1 to 20%, the amount of the base polyether polyol is 20 to 80%, and the amount of the unsaturated monomer is 20 to 70%, based on 100% by weight of the total reaction raw materials in step 2.
In a further preferred embodiment, in step 2, the amount of the initiator is 0.1 to 1%, the amount of the pre-reactant is 5 to 15%, the amount of the base polyether polyol is 30 to 60%, and the amount of the unsaturated monomer is 30 to 60%, based on 100% by weight of the total weight of the reaction raw materials in step 2.
For example, in step 2, the initiator is used in an amount of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%, based on 100% by weight of the total reaction raw materials in step 2; the pre-reactant is used in an amount of 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, the base polyether polyol is used in an amount of 30%, 35%, 40%, 45%, 50%, 55% or 60%, and the unsaturated monomer is used in an amount of 30%, 35%, 40%, 45%, 50%, 55% or 60%.
In a preferred embodiment, in step 2, the weight ratio of the base polyether polyol to the unsaturated monomer is 1 (0.8-1.2), preferably 1 (0.9-1.1).
For example, the weight ratio of the base polyether polyol to the unsaturated monomer is 1.
In a preferred embodiment, in step 1, the pre-reaction is carried out at 80 to 150 ℃, preferably at 100 to 140 ℃.
In a preferred embodiment, in step 2, the reaction is carried out at 80 to 140 ℃, preferably at 100 to 130 ℃.
Another object of the present invention is to provide a low viscosity polymer polyol obtained by the production process described in the first object of the present invention.
Wherein the low viscosity polymer polyol has a solids content of 40% or more and a viscosity of less than 4200 cps at 25 ℃.
It is a further object of the present invention to provide the use of low viscosity polymer polyols obtained by the process according to one of the objects of the present invention in polyurethane foams.
The polyurethane foam synthesized by using the low-viscosity polymeric polyol has the characteristics of high resilience, high compression ratio, low permanent deformation and the like.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value and should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, the various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts the basic polyether polyol with a specific structure to synthesize the polymer polyol, thereby achieving the purpose of reducing viscosity;
(2) The polyurethane foam synthesized by adopting the polymeric polyol has the characteristics of high resilience, high compression ratio, low permanent deformation and the like.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
It is to be noted that the various features described in the following detailed description may be combined in any suitable manner without contradiction. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the idea of the present invention is not violated, and the technical solution formed thereby is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
The phosphazene catalyst was obtained using the procedure of example 3 in CN 111087599A.
[ example 1] base polyether polyol A1
Adding 28g of glycerol and 1g of phosphazene catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 254g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, controlling the internal pressure to be 2hr after the reaction is finished, continuously adding 230g of propylene oxide and 20g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, controlling the internal pressure to be 2hr after the reaction is finished, continuously adding 378g of propylene oxide and 90g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, transferring into a refining kettle after the internal pressure is finished for 2hr, dehydrating, and filtering to obtain the basic polyether polyol A1.
[ example 2 ] base polyether polyol A2
Adding 28g of glycerol and 1g of phosphazene catalyst into A2-liter closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 250g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2hr after the reaction is finished, continuing adding 608g of propylene oxide and 114g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2hr after the reaction is finished, transferring into a refining kettle, dehydrating and filtering to obtain the base polyether polyol A2.
[ example 3 ] base polyether polyol A3
Adding 28g of glycerol and 1g of phosphazene catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 404g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2hr after the reaction is finished, continuing adding 488g of propylene oxide and 80g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2hr after the reaction is finished, transferring into a refining kettle, dehydrating and filtering to obtain the basic polyether polyol A3.
[ example 4 ] basic polyether polyol A4
Adding 28g of glycerol and 1g of phosphazene catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 580g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2hr after the reaction is finished, continuously adding 232g of propylene oxide and 160g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2hr after the reaction is finished, transferring into a refining kettle, dehydrating and filtering to obtain the basic polyether polyol A4.
[ example 5 ] basic polyether polyol A5
Adding 28g of glycerol and 1g of phosphazene catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 254g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2hr after the reaction is finished, continuously adding 200g of propylene oxide and 15g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2hr after the reaction is finished, continuously adding 408g of propylene oxide and 95g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, moving into a refining kettle after the internal pressure is finished for 2hr, dehydrating, and filtering to obtain the basic polyether polyol A5.
[ COMPARATIVE EXAMPLE 1] BASE POLYETHER POLYOL B1
Adding 28g of glycerol and 1g of phosphazene catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 580g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2hr after the reaction is finished, continuously adding 392g of propylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2hr after the reaction is finished, transferring into a refining kettle, dehydrating and filtering to obtain the basic polyether polyol B1.
[ COMPARATIVE EXAMPLE 2 ] BASE POLYETHER POLYOL B2
Adding 28g of glycerol and 1g of phosphazene catalyst into a 2-liter closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 812g of propylene oxide and 160g of ethylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, controlling the internal pressure after the reaction is finished to be 2 hours, transferring into a refining kettle after the internal pressure is finished to be 2 hours, dehydrating, and filtering to obtain the base polyether polyol B2.
[ COMPARATIVE EXAMPLE 3 ] basic polyether polyol B3
Adding 28g of glycerol and 1g of phosphazene catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 812g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2hr after the reaction is finished, continuing adding 160g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2hr after the reaction is finished, transferring into a refining kettle, dehydrating and filtering to obtain the basic polyether polyol B3.
[ example 6 ] stabilizer precursor C1
Adding 7g of sorbitol and 1.8g of phosphazene catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 1521g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure after the reaction is finished for 2hr, continuously adding 288g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure after the reaction is finished for 2hr, transferring into a refining kettle, dehydrating, and filtering to obtain polyether polyol with the molecular weight of 12000.
The stabilizer precursor C1 was prepared by heating the polyether polyol (100 parts) prepared above, 3-isopropyl-dimethylbenzyl isocyanate TMI (0.5 part), diphenylmethane diisocyanate MDI (0.5 part), and 100ppm stannous octoate catalyst at 80 ℃ for 2 hours to obtain a stabilizer precursor C1 having a viscosity of 2300mpa.s/25 ℃.
[ example 7 ] stabilizer precursor C2
Prepared by heating the polyether polyol (100 parts) prepared in example 6, ethyl methacrylate (1 part), diphenylmethane diisocyanate MDI (1 part) and 200ppm of stannous octoate catalyst at 80 ℃ for 2 hours, the viscosity of the resulting stabilizer precursor C2 was 3800mpa.s/25 ℃.
[ example 8 ] stabilizer precursor C3
Prepared by heating the polyether polyol prepared in example 6 (100 parts), ethyl methacrylate isocyanate (2 parts), diphenylmethane diisocyanate MDI (2 parts) and 500ppm of stannous octoate catalyst at 80 ℃ for 2 hours, the viscosity of the resulting stabilizer precursor C3 was 4300mpa.s/25 ℃.
Preparation of Polymer polyols
(1) Preparation of the pre-reactant PFS:
the preparation of the pre-reactants was carried out using a two-stage reaction system comprising a continuous stirred tank reactor (first reactor) equipped with an impeller and a plug flow reactor (second reactor).
Stabilizer precursors (C1 to C3 prepared in examples 6 to 7, respectively), isopropanol, a mixture of Styrene (SM) and Acrylonitrile (AN) [ SM/AN (mol) =2 ], and AN initiator ABIN azobisisobutyronitrile were added to a feed tank, passed from the feed tank through a static mixer connected in series in a continuous pumping manner, and then sequentially fed into a first reactor (continuous stirred tank reactor) and a second reactor (plug flow reactor) connected in series through feed pipes to allow thorough mixing reaction of the components, wherein the mixing reaction temperature of the two reactors was 120 ± 1 ℃, and the residence time in the reactors of the two reactors was 60 minutes. The pre-reactant PFS from the second reactor is then passed through a cooler into a collection vessel to give the pre-reactants PFS1, PFS2 and PFS3 (C1, C2 and C3 respectively employed).
Wherein the weight percentages of stabilizer precursor, isopropanol, a mixture of Styrene (SM) and Acrylonitrile (AN), and initiator are listed in Table 1.
Table 1:
| PFS1 | PFS2 | PFS3 | |
| isopropyl alcohol | 60wt％ | 50wt％ | 70wt％ |
| Stabiliser precursors C1 | 24wt％ | ||
| Stabiliser precursors C2 | ---- | 20wt％ | ---- |
| Stabiliser precursor C3 | ---- | ---- | 30wt％ |
| SM+AN | 16wt％ | 12wt％ | 20wt％ |
| Initiator | 0.1wt％ | 0.08wt％ | 0.2wt％ |
The weight amounts of each of the raw materials in table 1 are based on 100wt% of the total weight of the reaction raw materials in preparing the pre-reactants.
(2) Preparation of Polymer polyol:
the preparation of polymeric polyol was carried out using a two-stage reaction system comprising a continuous stirred tank reactor equipped with an impeller (first reactor) and a plug flow reactor (second reactor).
Adding a pre-reactant, a base polyether polyol, a mixture of Styrene (SM) and Acrylonitrile (AN) and AN initiator AIBN azobisisobutyronitrile into a feed tank, continuously pumping the mixture from the feed tank through a series of static mixers, then sequentially entering a first reactor (a continuous stirred tank reactor) and a second reactor (a plug flow reactor) in series through feed pipes to fully mix and react the components, wherein the mixing reaction temperature of the two reactors is 115 +/-1 ℃, the residence time of the two reactors in the reactors is 60 minutes, and passing a product polymer polyol from the second reactor through a cooler to enter a collection container. The crude product was vacuum stripped to remove volatiles. The total weight% of polymer in the product was calculated by the monomer concentration measured in the vapor lead crude polymer polyol.
Wherein the percentages of the pre-reactants, the base polyether polyol, the mixture of Styrene (SM) and Acrylonitrile (AN), and the initiator are listed in table 2.
Table 2:
the amounts of the respective raw materials in Table 2 were 100wt% based on the total weight of the raw materials for the reaction in step 2.
[ example 14 ] A method for producing a polycarbonate
The procedure of example 9 was repeated except that: the initiator is used in an amount of 0.1wt%, the base polyether polyol A1 accounts for 44wt% of the total weight, the monomer is 47wt%, and the pre-reactant adopts PFS2 and accounts for 7wt% of the total weight.
This example 14 also gives a low viscosity polymer polyol.
[ example 15 ] A method for producing a polycarbonate
The procedure of example 10 was repeated except that: the initiator is used in an amount of 1wt%, the base polyether polyol A2 accounts for 46wt% of the total weight, the monomer is used in an amount of 45wt%, and the pre-reactant is PFS2 and accounts for 10wt% of the total weight.
This example 15 also gives a low-viscosity polymer polyol.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the embodiments and implementations of the invention without departing from the spirit and scope of the invention, and are within the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (14)
1. A method of preparing a low viscosity polymer polyol, comprising: adopting raw materials comprising basic polyether polyol, a stabilizer precursor, an unsaturated monomer, an initiator and a chain transfer agent to carry out reaction to obtain the low-viscosity polymer polyol; wherein, the molecular structure of the basic polyether polyol comprises a propylene oxide homopolymerization chain segment and a propylene oxide-ethylene oxide copolymerization chain segment.
2. The production method according to claim 1,
the content of the propylene oxide homopolymerized chain segment is 10-70 percent, preferably 20-60 percent, based on 100 percent of the total weight of the basic polyether polyol; the content of the propylene oxide and ethylene oxide copolymerized segment is 30-90%, preferably 40-80%; and/or the presence of a gas in the gas,
the content of ethylene oxide structural units is 2 to 25%, preferably 5 to 16%, based on 100% by weight of the total base polyether polyol.
3. The method according to claim 1, wherein the propylene oxide-ethylene oxide copolymerized segment comprises a single copolymerized segment or a plurality of copolymerized segments.
4. The production method according to claim 3,
when a segment of copolymer segment is included, it is a random copolymer segment or a gradient copolymer segment, preferably, when it is a gradient copolymer segment, the content of ethylene oxide therein is gradually increased; and/or the presence of a gas in the atmosphere,
when the propylene oxide-ethylene oxide copolymer segment includes a plurality of copolymer segments, the ethylene oxide content in each copolymer segment is different, preferably gradually increased, in the direction in which the molecular chain extends.
5. The method of claim 1, wherein the stabilizer precursor is obtained by: the stabilizer precursor is prepared by reacting raw materials including polyether polyol, polyisocyanate, isocyanate containing unsaturated reaction bonds and a catalyst II.
6. The method according to claim 5,
the polyether polyol is a copolymer of propylene oxide and ethylene oxide, and the tail end of the polyether polyol contains 2-8 hydroxyl groups; and/or the presence of a gas in the gas,
the molecular weight of the polyether polyol is 900-12000; and/or the presence of a gas in the gas,
the weight content of the ethylene oxide unit in the polyether polyol is 5-20%.
7. The production method according to claim 5,
the polyisocyanate is selected from compounds containing at least two isocyanate groups, preferably at least one of isophorone diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 1, 4-cyclohexane diisocyanate, norbornane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate and 4,4' -diphenylmethane diisocyanate; and/or the presence of a gas in the gas,
the catalyst II is at least one selected from tin catalysts, amine catalysts and other metal catalysts, preferably at least one selected from dibutyl tin dilaurate, stannous octoate, tetrabutyl titanate and triethylene diamine; and/or the presence of a gas in the atmosphere,
the isocyanate containing unsaturated reaction bonds is selected from at least one of 3-isopropyl-dimethyl benzyl isocyanate and ethyl isocyanate methacrylate.
8. The process according to claim 5, wherein the polyisocyanate is used in an amount of 0.05 to 5 parts by weight, the isocyanate having an unsaturated reactive bond is used in an amount of 0.05 to 5 parts by weight, and the catalyst II is used in an amount of 10 to 1000ppm by weight, based on 100 parts by weight of the polyether polyol.
9. The method according to claim 1,
the unsaturated monomer is selected from at least one of butadiene, isoprene styrene, alpha-methyl styrene, tert-butyl styrene, chlorostyrene, cyanostyrene, bromostyrene, styrene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-dimethylacrylamide, N- (dimethylaminomethyl) acrylamide, vinyl ether, vinyl ketone and vinylidene halide; and/or the presence of a gas in the atmosphere,
the chain transfer agent is selected from at least one of methanol, ethanol, butanol, isopropanol and mercaptan; and/or the presence of a gas in the atmosphere,
the initiator is selected from at least one of alkyl hydroperoxide, aryl hydroperoxide, persulfate, perborate, percarbonate and azo compound.
10. The method according to any one of claims 1 to 9, wherein the method for producing the polymer polyol comprises the steps of:
step 1, in the presence of the initiator and the chain transfer agent, pre-reacting the stabilizer precursor with the unsaturated monomer to obtain a pre-reactant;
and 2, in the presence of the initiator, reacting the pre-reactant obtained in the step 1 with the base polyether polyol and the unsaturated monomer to obtain the polymer polyol.
11. The production method according to claim 10,
in the step 1, based on 100 percent of the total weight of the raw materials for reaction in the step 1, the dosage of the initiator is 0.01 to 1 percent, the dosage of the chain transfer agent is 20 to 80 percent, the dosage of the stabilizer precursor is 10 to 50 percent, and the dosage of the unsaturated monomer is 5 to 30 percent; and/or the presence of a gas in the atmosphere,
in the step 2, based on 100 percent of the total weight of the raw materials in the step 2, the amount of the initiator is 0.05 to 2 percent, the amount of the pre-reactant is 1 to 20 percent, the amount of the base polyether polyol is 20 to 80 percent, and the amount of the unsaturated monomer is 20 to 70 percent.
12. The production method according to claim 10,
in step 1, the pre-reaction is carried out at 80-150 ℃, preferably at 100-140 ℃; and/or the presence of a gas in the gas,
in step 2, the reaction is carried out at 80 to 140 ℃, preferably at 100 to 130 ℃.
13. A low viscosity polymer polyol obtained by the production process as claimed in any one of claims 1 to 12.
14. Use of a low viscosity polymer polyol obtainable by the process according to any of claims 1 to 12 in polyurethane foams.
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