CN115232257B - Preparation method of low-viscosity polymer polyol, polymer polyol obtained by preparation method and application of polymer polyol - Google Patents
Preparation method of low-viscosity polymer polyol, polymer polyol obtained by preparation method and application of polymer polyol Download PDFInfo
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- CN115232257B CN115232257B CN202110434167.9A CN202110434167A CN115232257B CN 115232257 B CN115232257 B CN 115232257B CN 202110434167 A CN202110434167 A CN 202110434167A CN 115232257 B CN115232257 B CN 115232257B
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- 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, wherein the preparation method comprises the following steps: the low-viscosity polymer polyol is obtained by adopting raw materials comprising basic polyether polyol, stabilizer precursor, unsaturated monomer, initiator and chain transfer agent to react; 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. The invention adopts the basic polyether polyol with a specific structure to synthesize the polymer polyol, thereby achieving the purpose of reducing the viscosity.
Description
Technical Field
The invention belongs to the field of polymer polyol preparation, and particularly relates to a preparation method of low-viscosity polymer polyol, the obtained polymer polyol and application.
Background
The polymer polyol is a large amount of industrial products, and is formed by in-situ polymerization of one or more vinyl monomers by taking a basic polyether polyol as a continuous phase. The polymer polyol is mainly used for preparing polyurethane foam plastics.
A problem commonly 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 such a 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 polyols are produced using macromers which contain in their molecule at least one or more polymerizable double bonds and one or more polyether polyol segments, the double bonds being copolymerizable with the ethylenically unsaturated monomers to form part of the polymer segments, the polymer extended polyol segments being compatible with the liquid polyol medium in which the polymer is dispersed to stabilize 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 a starting polyol having a functionality greater than 4; (2) they have at least 60% of unsaturated bonds remaining; (3) their viscosity at 25 ℃ is greater than 2000 centipoise; 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 viscosity of a 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.
It is an object of the present invention to provide a process for the preparation of a low viscosity polymer polyol comprising: the low-viscosity polymer polyol is obtained by adopting raw materials comprising basic polyether polyol, stabilizer precursor, unsaturated monomer, initiator and chain transfer agent to react; 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 solids content in the low viscosity polymer polyol is 40% or greater and the viscosity at 25 ℃ is less than 4200 centipoise.
In a preferred embodiment, the propylene oxide homo-segment is present in an amount of 10 to 70%, preferably 20 to 60%, based on 100% by weight of the total base polyether polyol; the content of the propylene oxide and ethylene oxide copolymer segments is 30 to 90%, preferably 40 to 80%.
In a further preferred embodiment, the content of ethylene oxide building blocks 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 copolymer segment comprises a single segment or multiple segments.
In a further preferred embodiment, when a segment is included, it is a random or gradient copolymer segment, preferably when a gradient copolymer segment, wherein the ethylene oxide content 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 copolymer segment comprises a plurality of copolymer segments, the ethylene oxide content of each copolymer segment varies, preferably gradually increases, in the direction of molecular chain extension (although the total EO content is still within the aforementioned range).
Specifically, when the propylene oxide-ethylene oxide copolymer segment includes a two-segment copolymer segment, 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 )](1)
In formula (I), (PO) x1 EO y1 ) Represents a first segment of a copolymer segment, (PO x2 EO y2 ) Represents a second segment of a copolymer, wherein x1>x2，y1<y2。
In a preferred embodiment, the molecular weight of the base polyether polyol is 2000 to 8000, preferably 3000 to 6000, more preferably 3000 to 4000.
In a preferred embodiment, the base polyether polyol is obtained as follows: 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 a phosphazene catalyst, an alkali metal catalyst and a bi/multi metal catalyst.
Wherein the phosphazene catalyst, the alkali metal catalyst and the bi/multi-metal catalyst are all 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 pressure disclosed in the prior art.
In a preferred embodiment, the stabilizer precursor is obtained as follows: the stabilizer precursor is obtained by reacting raw materials including polyether polyol, polyisocyanate, isocyanate containing unsaturated reaction bonds and catalyst II.
In a further preferred embodiment, the viscosity of the stabilizer precursor is 1500 to 5000mpa.s/25 ℃, preferably 2000 to 600 mpa.s/25 ℃, more preferably 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 ℃, 600 mpa.s/25 ℃, 700 mpa.s/25 ℃ or 800mpa.s/25 ℃.
In a preferred embodiment, the polyether polyol is a copolymer of propylene oxide and ethylene oxide (preferably a block copolymer of propylene oxide-ethylene oxide) having 2 to 8 (preferably 3 to 8, more preferably 3 to 6) hydroxyl groups at the terminal end.
In a further preferred embodiment, the polyether polyol has a molecular weight of 900 to 12000, preferably 9000 to 12000.
For example, the molecular weight of the polyether polyol used to prepare the stabilizer precursor may be 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, or 12000.
In a still further preferred embodiment, the polyether polyol has a weight content of ethylene oxide units of from 5 to 20%, preferably from 8 to 16%.
Specifically, the polyether polyol is obtained as follows: taking polyalcohol as an initiator, and adding propylene oxide and ethylene oxide in the presence of a catalyst I (preferably sequentially) to react, wherein the polyalcohol is at least one selected from ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose, and preferably sorbitol; and/or the catalyst I is at least one selected from phosphazene catalyst, alkali metal catalyst and double/multi-metal catalyst.
Wherein the polyether polyol is prepared by adopting the temperature and pressure disclosed in the prior art.
In a preferred embodiment, the isocyanate containing an unsaturated reactive bond is selected from at least one of 3-isopropyl-dimethylbenzyl isocyanate, ethyl 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 selected from at least one of isophorone diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 1, 4-cyclohexane diisocyanate, norbornane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -diphenylmethane diisocyanate.
In a preferred embodiment, the catalyst II is selected from at least one of tin-based catalysts, amine-based catalysts, 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 polyisocyanate is used in an amount of 0.05 to 5 parts by weight, the isocyanate containing unsaturated reactive bonds 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 at the time of preparing the stabilizer precursor.
In a further preferred embodiment, the amount of the polyisocyanate 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 is 50 to 500ppm by weight based on 100 parts by weight of the polyether polyol at the time of preparing the stabilizer precursor.
For example, in preparing the stabilizer precursor, the polyisocyanate 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 based on 100 parts by weight of the polyether polyol; the amount of the isocyanate containing unsaturated reaction bonds is 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 an amount 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 ether, vinyl ketone, 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, and 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-butyl diethyl acetate, t-butyl peroctoate, t-butyl peroxyisobutyrate, t-butyl peroxy, t-butyl peroxypivalate, t-amyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, lauroyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, dimethyl azobisisobutyrate.
In a preferred embodiment, the method of preparing 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, reacting the pre-reactant obtained in the step 1 with the basic polyether polyol and the unsaturated monomer in the presence of the initiator to obtain the polymer polyol.
In a preferred embodiment, in step 1, the initiator is used in an amount of 0.01 to 1%, the chain transfer agent is used in an amount of 20 to 80%, the stabilizer precursor is used in an amount of 10 to 50%, and the unsaturated monomer is used in an amount of 5 to 30% based on 100% of the total weight of the reaction raw materials in step 1.
In a further preferred embodiment, in step 1, the initiator is used in an amount of 0.05 to 0.5%, the chain transfer agent is used in an amount of 50 to 70%, the stabilizer precursor is used in an amount of 15 to 30%, and the unsaturated monomer is used in an amount of 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% of the total weight of the reaction materials.
In a preferred embodiment, in step 2, the initiator is used in an amount of 0.05 to 2%, the pre-reactant is used in an amount of 1 to 20%, the base polyether polyol is used in an amount of 20 to 80%, and the unsaturated monomer is used in an amount of 20 to 70% based on 100% of the total weight of the reaction materials in step 2.
In a further preferred embodiment, in step 2, the initiator is used in an amount of 0.1 to 1%, the pre-reactant is used in an amount of 5 to 15%, the base polyether polyol is used in an amount of 30 to 60% and the unsaturated monomer is used in an amount of 30 to 60% based on 100% of the total weight of the reaction 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 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 to 1.2), preferably 1 (0.9 to 1.1).
For example, the weight ratio of the base polyether polyol to the unsaturated monomer is 1:0.8, 1:0.85, 1:0.9, 1:0.92, 1:0.94, 1:0.96, 1:0.98, 1:1, 1:1.02, 1:1.05, 1:1.08, 1:1.1, 1:1.12, 1:1.15, 1:1.18, 1:1.2.
In a preferred embodiment, in step 1, the pre-reaction is carried out at 80-150 ℃, preferably at 100-140 ℃.
In a preferred embodiment, in step 2, the reaction is carried out at 80-140 ℃, preferably at 100-130 ℃.
It is a second object of the present invention to provide a low viscosity polymer polyol obtained by the production process according to one of the objects of the present invention.
Wherein the solids content in the low viscosity polymer polyol is 40% or greater and the viscosity at 25 ℃ is less than 4200 centipoise.
It is a further object of the present invention to provide the use of the 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 polymer polyol has the characteristics of high rebound, high collapse ratio, low permanent deformation and the like.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give 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 the viscosity;
(2) The polyurethane foam synthesized by the polymer polyol has the characteristics of high rebound, high compression set ratio, low permanent deformation and the like.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are 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, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
The phosphazene catalyst was obtained using the procedure of example 3 in CN111087599 a.
Example 1 base polyether polyol A1
Adding 28g of glycerol and 1g of phosphazene catalyst into a 2-liter sealed 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 2 hours 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 ℃, keeping the internal pressure for 2 hours 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 the refining kettle for dehydration after the internal pressure is finished for 2 hours, 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 sealed 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 ℃, internally pressing for 2 hours after the reaction is finished, continuously adding 608g of propylene oxide and 114g of ethylene oxide after the internal pressing is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, moving into a refining kettle for dehydration after the internal pressing for 2 hours after the reaction is finished, and filtering to obtain the basic polyether polyol A2.
Example 3 base polyether polyol A3
Adding 28g of glycerol and 1g of phosphazene catalyst into a 2-liter sealed 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 ℃, controlling the internal pressure to be 2hr after the reaction is finished, continuously 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 ℃, controlling the internal pressure to be 2hr after the reaction is finished, transferring into a refining kettle, dehydrating, and filtering to obtain the basic polyether polyol A3.
Example 4 base polyether polyol A4
Adding 28g of glycerol and 1g of phosphazene catalyst into a 2-liter sealed 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 ℃, internally pressing for 2 hours after the reaction is finished, continuously adding 232g of propylene oxide and 160g of ethylene oxide after the internal pressing is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, moving into a refining kettle for dehydration after the internal pressing is finished for 2 hours, and filtering to obtain the basic polyether polyol A4.
Example 5 base polyether polyol A5
Adding 28g of glycerol and 1g of phosphazene catalyst into a 2-liter sealed 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 2 hours 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 2 hours 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 ℃, transferring into the refining kettle for dehydration after the internal pressure is finished for 2 hours, 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 2-liter sealed 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 ℃, internally pressing for 2 hours after the reaction is finished, continuously adding 392g of propylene oxide after the internal pressing is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃ for 2 hours after the internal pressing 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 ℃, internally pressing for 2 hours after the reaction is finished, transferring into a refining kettle for dehydration after the internal pressure is 2 hours after the reaction is finished, and filtering to obtain the basic polyether polyol B2.
[ comparative example 3 ] base polyether polyol B3
Adding 28g of glycerol and 1g of phosphazene catalyst into a 2-liter sealed 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 ℃, internally pressing for 2 hours after the reaction is finished, continuously adding 160g of ethylene oxide after the internal pressing is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃ for 2 hours after the internal pressing 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 2-liter 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 for 2 hours after the reaction is finished, 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 ℃, transferring into a refining kettle for dehydration after the internal pressure is finished for 2 hours, 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 parts), diphenylmethane diisocyanate MDI (0.5 parts) and 100ppm stannous octoate catalyst at 80℃for 2 hours, and the resulting viscosity was found to be 2300mPa.s/25 ℃.
[ example 7 ] stabilizer precursor C2
Prepared by heating the polyether polyol prepared in example 6 (100 parts), ethyl methacrylate (1 part), diphenylmethane diisocyanate MDI (1 part) and 200ppm stannous octoate catalyst at 80 ℃ for 2 hours, the resulting stabilizer precursor C2 had a viscosity of 3800mpa.s/25 ℃.
[ example 8 ] stabilizer precursor C3
Prepared by heating the polyether polyol prepared in example 6 (100 parts), ethyl methacrylate (2 parts), diphenylmethane diisocyanate MDI (2 parts) and 500ppm stannous octoate catalyst at 80 ℃ for 2 hours, the resulting stabilizer precursor C3 had a viscosity of 4300mpa.s/25 ℃.
Preparation of Polymer polyol
(1) Preparation of the pre-reactant PFS:
the preparation of the pre-reactants was carried out using a two-stage reaction system comprising a continuously stirred tank reactor (first reactor) equipped with impellers 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) =2:1 ] and the initiator ABIN azobisisobutyronitrile were fed into a feed tank, passed from the feed tank through a static mixer 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) in series through a feed pipe to allow the components to undergo a sufficient mixing reaction, wherein the mixing reaction temperature of the two reactors was 120±1 ℃, and the residence time of the two reactors in the reactors was 60 minutes. The pre-reactants PFS from the second reactor were then passed through a cooler and into a collection vessel to obtain said pre-reactants PFS1, PFS2 and PFS3 (C1, C2 and C3 respectively).
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％ |
| Stabilizer precursor C1 | 24wt％ | ||
| Stabilizer precursor C2 | ---- | 20wt％ | ---- |
| Stabilizer precursor C3 | ---- | ---- | 30wt％ |
| SM+AN | 16wt％ | 12wt％ | 20wt％ |
| Initiator(s) | 0.1wt％ | 0.08wt％ | 0.2wt％ |
The weight amounts of the various materials in Table 1 are based on 100wt% of the total weight of the reaction materials in the preparation of the pre-reactants.
(2) Preparation of Polymer polyol:
the preparation of the polymeric polyol was carried out using a two-stage reaction system comprising a continuous stirred tank reactor (first reactor) equipped with impellers and a plug flow reactor (second reactor).
The pre-reactants, the base polyether polyol, the mixture of Styrene (SM) and Acrylonitrile (AN) and the initiator AIBN azobisisobutyronitrile were fed into a feed tank, continuously pumped from the feed tank through a series of static mixers, and then sequentially fed through a feed pipe into a first reactor (continuous stirred tank reactor) and a second reactor (plug flow reactor) in series to allow the components to undergo a well-mixed reaction, wherein the mixing reaction temperature of the two reactors was 115.+ -. 1 ℃ and the residence time of the two reactors in the reactor was 60 minutes, and the product polymer polyol from the second reactor was passed through a cooler into a collection vessel. The crude product was vacuum stripped to remove volatiles. The total weight% of polymer in the product is calculated from the measured monomer concentration in the 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 various materials used in Table 2 are based on 100wt% of the total weight of the reaction materials in step 2.
[ example 14 ]
The procedure of example 9 was repeated, except that: the initiator was used in an amount of 0.1wt% based on the total weight of 44wt% based on the total weight of the polyether polyol A1, 47wt% based on the total weight of the monomers, and the pre-reactant was PFS2 and was 7wt% based on the total weight.
This example 14 also gives a low viscosity polymer polyol.
[ example 15 ]
The procedure of example 10 was repeated, except that: the initiator was used in an amount of 1wt% based on the total weight of 46wt% based on the total weight of the polyether polyol A2 and 45wt% based on the total weight of the monomers, and the pre-reactant was PFS2 and was 10wt% based on the total weight.
This example 15 also gives a low viscosity polymer polyol.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (17)
1. A method of preparing a low viscosity polymer polyol comprising: the low-viscosity polymer polyol is obtained by adopting raw materials comprising basic polyether polyol, stabilizer precursor, unsaturated monomer, initiator and chain transfer agent to react; 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; based on 100% of the total weight of the basic polyether polyol, the content of the propylene oxide homopolymerization chain segments is 10-70%, and the content of the propylene oxide and ethylene oxide copolymerization chain segments is 30-90%.
2. The method according to claim 1, wherein,
the content of the propylene oxide homopolymerization chain segments is 20-60% based on 100% of the total weight of the basic polyether polyol; the content of the propylene oxide and ethylene oxide copolymer chain segments is 40-80%; and/or the number of the groups of groups,
the content of the ethylene oxide structural unit is 2-25% based on 100% of the total weight of the basic polyether polyol.
3. The method according to claim 2, wherein the ethylene oxide structural unit is contained in an amount of 5 to 16% based on 100% by weight of the total base polyether polyol.
4. The method of claim 1, wherein the propylene oxide-ethylene oxide copolymer segment comprises a single segment or multiple segments;
when included, it is a random copolymer segment or a gradient copolymer segment; and/or the number of the groups of groups,
when the propylene oxide-ethylene oxide copolymer segment includes a plurality of copolymer segments, the ethylene oxide content of each copolymer segment is different in the direction in which the molecular chain extends.
5. The method according to claim 4, wherein,
when a segment of the copolymer segment is included, it is a gradient copolymer segment in which the content of ethylene oxide gradually increases; and/or the number of the groups of groups,
when the propylene oxide-ethylene oxide copolymer segment includes a plurality of copolymer segments, the ethylene oxide content of each copolymer segment gradually increases in the direction in which the molecular chain extends.
6. The method of preparation according to claim 1, characterized in that the stabilizer precursor is obtained as follows: the stabilizer precursor is obtained by reacting raw materials including polyether polyol, polyisocyanate, isocyanate containing unsaturated reaction bonds and catalyst II.
7. The method according to claim 6, wherein,
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 number of the groups of groups,
the molecular weight of the polyether polyol is 900-12000; and/or the number of the groups of groups,
the weight content of the ethylene oxide units in the polyether polyol is 5-20%.
8. The method according to claim 6, wherein,
the polyisocyanate is selected from compounds containing at least two isocyanate groups; and/or the number of the groups of groups,
the catalyst II is at least one selected from tin catalysts, amine catalysts and other metal catalysts; and/or the number of the groups of groups,
the isocyanate containing unsaturated reaction bonds is at least one selected from 3-isopropyl-dimethylbenzyl isocyanate and ethyl methacrylate.
9. The method according to claim 8, wherein,
the polyisocyanate is at least one selected from 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 number of the groups of groups,
the catalyst II is at least one selected from dibutyl tin dilaurate, stannous octoate, tetrabutyl titanate and triethylenediamine.
10. The method according to claim 6, wherein the amount of the polyisocyanate is 0.05 to 5 parts by weight, the amount of the unsaturated bond-containing isocyanate is 0.05 to 5 parts by weight, and the amount of the catalyst II is 10 to 1000ppm by weight based on 100 parts by weight of the polyether polyol.
11. The method according to claim 1, wherein,
the unsaturated monomer is at least one selected from butadiene, isoprene, styrene, alpha-methylstyrene, tertiary butyl styrene, chlorostyrene, cyanostyrene, bromostyrene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-dimethylacrylamide, N- (dimethylaminomethyl) acrylamide, vinyl ether, vinyl ketone and vinylidene halide; and/or the number of the groups of groups,
the chain transfer agent is at least one selected from methanol, ethanol, butanol, isopropanol and mercaptan; and/or the number of the groups of groups,
the initiator is at least one selected from alkyl hydroperoxides, aryl hydroperoxides, persulfates, perborates, percarbonates, azo compounds.
12. The preparation method according to one of claims 1 to 11, characterized in that the preparation method of 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;
and 2, reacting the pre-reactant obtained in the step 1 with the basic polyether polyol and the unsaturated monomer in the presence of the initiator to obtain the polymer polyol.
13. The method according to claim 12, wherein,
in the step 1, the amount of the initiator is 0.01-1%, the amount of the chain transfer agent is 20-80%, the amount of the stabilizer precursor is 10-50% and the amount of the unsaturated monomer is 5-30% based on 100% of the total weight of the reaction raw materials in the step 1; and/or the number of the groups of groups,
in the step 2, the amount of the initiator is 0.05-2%, the amount of the pre-reactant is 1-20%, the amount of the base polyether polyol is 20-80%, and the amount of the unsaturated monomer is 20-70% based on 100% of the total weight of the reaction raw materials in the step 2.
14. The method according to claim 12, wherein,
in step 1, the pre-reaction is carried out at 80-150 ℃; and/or the number of the groups of groups,
in step 2, the reaction is carried out at 80-140 ℃.
15. The method of claim 14, wherein the process comprises,
in step 1, the pre-reaction is carried out at 100-140 ℃; and/or the number of the groups of groups,
in step 2, the reaction is carried out at 100-130 ℃.
16. A low viscosity polymer polyol obtained by the production method according to any one of claims 1 to 15.
17. Use of the low viscosity polymer polyol according to any one of claims 1 to 15 in polyurethane foam.
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