CN111234177B - Macromonomer stabilizer and preparation method thereof - Google Patents
Macromonomer stabilizer and preparation method thereof Download PDFInfo
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- CN111234177B CN111234177B CN202010199685.2A CN202010199685A CN111234177B CN 111234177 B CN111234177 B CN 111234177B CN 202010199685 A CN202010199685 A CN 202010199685A CN 111234177 B CN111234177 B CN 111234177B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8125—Unsaturated isocyanates or isothiocyanates having two or more isocyanate or isothiocyanate groups
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
Abstract
The invention provides a preparation method of a novel macromonomer stabilizer, which is prepared by reacting polyalkyl substituted isocyanate containing an oxapyrimidone structure with a hydroxyl unsaturated compound and a stabilizer polyether polyol. The macromer stabilizer has excellent dispersing and filtering properties.
Description
Technical Field
The invention belongs to the field of polyurethane, and particularly relates to a novel macromonomer stabilizer and a preparation method thereof.
Background
Polyurethane foams are prepared by reacting polyisocyanates and polyols in the presence of blowing agents, and various modified polyol products have been developed for the purpose of improving load-bearing and other properties. Common types are dispersions of polymer particles in polyols, such as vinyl polymer particle polyols (styrene-acrylonitrile dispersions), polyurea particle dispersions (PHD polyols), polyisocyanate polyadducts (PIPA polyols, polyurethane-polyurea particle dispersions). The current commercialization is widespread of dispersions of styrene/acrylonitrile copolymers in polyols.
High solids and low viscosity are the direction of development for current styrene/acrylonitrile copolymer polyol dispersions (i.e., polymer polyols, POPs). To achieve this, methods of introducing macromer stabilizers have been proposed in the art. The macromer stabilizer is prepared by introducing polymerizable double bonds into stabilizer polyether polyol by various means so as to increase the dispersion stability of styrene/acrylonitrile copolymer solids. Typical processes such as US4550194, US 4998857 disclose a process for the preparation of stabilizers prepared by ring-opening a pentaerythritol or sorbitol initiated stabilizer polyether polyol with maleic anhydride in the presence of a catalyst followed by reaction with an alkylene oxide such as ethylene oxide or propylene oxide, the stabilizer prepared using a sorbitol initiated stabilizer polyether polyol also incorporating unsaturation via maleic anhydride. US5093412, US4390645 disclose a process for preparing macromer stabilizers by reacting unsaturated isocyanates, such as 3-propenyl phenyl isocyanate (TMI) or 2-isocyanatoethyl methacrylate, with stabilizer polyether polyols. Korean patent KR100657874 describes a process for synthesizing a stabilizer by coupling an unsaturated hydroxy ester and a polyether polyol using a diisocyanate. These current processes have various disadvantages, such as the relatively high viscosity of the polymer polyols produced by the stabilizers prepared with maleic anhydride; the unsaturated isocyanate and the stabilizer polyether polyol have poor compatibility and slow mass transfer reaction; the coupling method is difficult to control the reaction stage, and is easy to cause gel and caking.
Therefore, there is a need for a macromer stabilizer with excellent use properties for the synthesis of polymer polyols.
Disclosure of Invention
The invention aims to provide a preparation method of a novel macromonomer stabilizer. The macromolecular monomer stabilizer prepared by the method has good use performance and can be used for synthesizing polymer polyol.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a macromolecular monomer stabilizer is characterized in that a polyalkyl substituted isocyanate containing an oxapyrimidone structure reacts with a hydroxyl unsaturated compound and a stabilizer polyether polyol to prepare the macromolecular monomer stabilizer.
In the invention, the preparation method of the macromolecular monomer stabilizer comprises the following steps:
i) synthesizing polyalkyl substituted isocyanate A with an oxygen-containing heteropyrimidinone structure by using polyalkyl diisocyanate and carbon dioxide;
ii) A forms an adduct B with the hydroxy unsaturated compound;
iii) continuously reacting B with stabilizer polyether polyol to obtain the macromonomer stabilizer.
In the present invention, the polyalkyl diisocyanate in step i) is selected from isocyanates having 6 to 12 carbon alkyl substituent groups, preferably 2,2,3, 3-tetramethyl-1, 4-butanediisocyanate (TMBDI). As is well known in the art, isocyanates are obtained by phosgenating the corresponding diamine compounds or by thermal cleavage of the corresponding carbamates. The preparation process and source of the 2,2,3, 3-tetramethyl-1, 4-butanediisocyanate of the present invention are not limited thereto, and preferably, the azobisisobutyronitrile byproduct tetramethylbutanedinitrile is obtained by hydrogenation and phosgenation, as described in CN 107090064A.
In the invention, the molar ratio of the carbon dioxide to the polyalkyl diisocyanate in the step i) is 1 (0.5-5), preferably 1 (1.7-2.9).
In the invention, the structural formula of A in the step i) is shown as follows:
wherein M represents an alkyl substituent group containing 6 to 12 carbons, preferably a saturated aliphatic hydrocarbon segment, more preferably a tetramethylbutyl group, in which case the polyalkyl diisocyanate is TMSDI; n is an integer other than zero, preferably 1 or 2.
In the present invention, the reaction of step i) is carried out in the presence of a catalyst which is an alkyl-substituted organophosphorus, preferably one or more of triphenylphosphine, triethylphosphine and tributylphosphine.
In the invention, the reaction temperature of the step i) is 20-100 ℃, and preferably 40-80 ℃; the reaction can be carried out at normal pressure or higher pressure, and the preferable reaction pressure is the normal pressure of the added carbon dioxide; the reaction may be carried out in a solvent without using a solvent, and suitable solvents include aprotic solvents such as ethers, aliphatic hydrocarbons, aromatic hydrocarbons, esters, alkyl halides, and amides, and it is preferable to use no solvent.
In the present invention, the hydroxyl unsaturated compound in step ii) is a hydroxyl compound containing a polymerizable double bond, preferably a hydroxyl acrylate and/or a hydroxyl methacrylate, and more preferably hydroxyethyl methacrylate and/or hydroxyethyl acrylate. The isocyanate containing an oxapyrimidone structure may be reacted directly without treatment before the step ii) or may be reacted after purification. Conventional refining processes such as extraction, rectification, flash evaporation, falling film, short-path rectification and other unit operations. For safety reasons, the catalyst generally needs to be deactivated before purification, and methyl iodide, dimethyl sulfate, diazomethane and the like are added in a treatment mode.
In the present invention, the molar ratio of the hydroxyl group of the hydroxyl unsaturated compound to the NCO group of the isocyanate in the step ii) is (0.5 to 1.5):2, preferably (0.6 to 1.0): 2.
In the invention, the reaction temperature of the A and the hydroxyl unsaturated compound in the step ii) is-30-70 ℃, and preferably 5-35 ℃.
In the present invention, the reaction of step ii) is preferably carried out in the presence of a catalyst which is a substituted amine and/or substituted phosphine compound, preferably a tertiary substituted amine and/or tertiary substituted phosphine compound, such as triethylamine, tributylamine, triphenylphosphine, tri-n-butylphosphine.
In the present invention, in step ii), in order to prevent the unsaturated compound from polymerizing, it is preferable to add a polymerization inhibitor, such as hydroquinone monomethyl ether, in an amount of 10 to 1500 ppm.
As a preferred variant, the catalyst of step ii) is the same as the catalyst of step i), and if the isocyanate of the oxapyrimidone structure is not separated from the diisocyanate, step ii) can be carried out without further addition of catalyst.
For the sake of understanding, in the present invention, when the hydroxy unsaturated compound in step ii) is hydroxyethyl methacrylate and n ═ 1, the structural formula of the adduct B is as follows:
wherein M represents an alkyl substituent group having 6 to 12 carbon atoms, preferably a saturated aliphatic hydrocarbon segment, and more preferably a tetramethylbutyl group.
In the invention, the stabilizer polyether polyol in the step iii) is polyether prepared by ring-opening reaction of glycerin and/or trimethylolpropane initiator and propylene oxide and/or ethylene oxide; since the stabilizer polyether polyol can be prepared by any conventional method known in the art, the present invention will not be described in detail (for example, see encyclopedia of chemical industry (volume 9), first edition 1997, chemical industry Press P165-181). Preferably, the hydroxyl value of the stabilizer polyether polyol is 20-48 mgKOH/g, preferably 24-38 mgKOH/g; preferably, the ethylene oxide accounts for 3-20%, preferably 7-15% of the total mass of the epoxy compound.
In the present invention, the molar ratio of the molar amount of NCO groups in the adduct B in step iii) to the hydroxyl groups of the stabilizer polyether polyol is (0.5-2): 1, preferably (0.9-1.22): 1.
In the present invention, said addition compound in step iii) is reacted with a stabilizer polyether polyol, and the stabilizer preparation process may be carried out by heating with or without a catalyst. The catalyst can be selected from catalysts capable of catalyzing isocyanate groups and hydroxyl groups, such as organic amine compounds, organic metal compounds, such as organic tin, organic bismuth and the like, and organic tin catalysts are preferably used. The dosage of the catalyst is 0.001-0.5% of the total mass of the isocyanate and the stabilizer polyether polyol.
In the present invention, the reaction of the adduct of step iii) with the stabilizer polyether polyol may be carried out with or without a solvent, and suitable solvents are aromatic, alkyl halide, aliphatic hydrocarbon, ester or ether solvents, preferably toluene and butyl acetate. The amount of the solvent may be 0.5 to 10 times (mass ratio) the amount of the adduct.
In the present invention, after the reaction between the polymer and the stabilizer polyether polyol in step iii) is finished, a part of the terminating agent is preferably added so as not to affect other subsequent reaction processes. Preferably an acid terminator, such as sulfuric acid, phosphoric acid or benzoyl chloride, and the addition amount of the acid terminator is 0.03-0.5% (mass percent) of the total charge amount.
Another object of the present invention is to provide a macromonomer stabiliser prepared by the above process.
A macromonomer stabilizer is prepared by the above method.
The invention also provides a method for preparing polymer polyol by using the macromonomer stabilizer.
In the present invention, the preparation process of the polymer polyol is as follows: in the presence of basic polyether polyol, styrene, acrylonitrile or other polymerizable double-bond compounds are mixed with a novel macromolecular monomer stabilizer, and after free radical polymerization, the polymer polyol with high solid content, low viscosity and good dispersion stability is obtained by demonomerization.
In the present invention, the base polyether polyol for preparing the polymer polyol is a polyaddition product of an epoxy compound (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) and a small molecule polyol (e.g., ethylene glycol, glycerin, trimethylolpropane, pentaerythritol) or an amine (e.g., ethanolamine, ethylenediamine, etc.).
In the method for preparing the polymer polyol according to the present invention, the polymerizable double bond compound includes one or more of styrene, methylstyrene, ethylstyrene, acrylonitrile, methacrylonitrile, ethacrylonitrile, methyl methacrylate, methyl acrylate, butyl acrylate, ethyl acrylate, and preferably a mixture of styrene and acrylonitrile. The amount of the polymerizable double bond compound added is about 19 to 61% by weight based on the total mass of the polymer polyol product, and a mixture of styrene and acrylonitrile is generally used, particularly in a mass ratio of styrene to acrylonitrile of 1:99 to 90: 10.
In the method for preparing the polymer polyol according to the present invention, the initiator is a compound capable of generating a radical, and as is well known in the art, an organic peroxide or an azo-based compound, preferably one or more of benzoyl peroxide, tert-amyl 2-ethylhexanoate peroxide, lauroyl peroxide, butyl octanoate peroxide, cyclohexyl di-tert-butyl peroxide, dimethyl azotetramethylsuccinate, Azobisisobutyronitrile (AIBN) and Azobismethylbutyronitrile (AMBN), may be used in an amount of 0.1 wt% to 1.1 wt% based on the total mass of the polymer polyol product.
In the present invention, in the process for preparing the polymer polyol, a chain transfer agent such as one or more of methanol, ethanol, isopropanol, butanol, ethanethiol, heptanethiol, octanethiol, dodecylmercaptan, toluene, ethylbenzene, xylene, preferably isopropanol and/or dodecylmercaptan, may be used to control the degree of polymerization. The chain transfer agent is used in an amount of 1.5 to 9.5 weight percent based on the weight of the polymer polyol product.
In the present invention, in the method for producing the polymer polyol, a continuous process may be employed, or a batch process may be employed.
In the method for preparing the polymer polyol, the free radical polymerization reaction is carried out at a temperature of 70 to 150 ℃, preferably 95 to 130 ℃.
In another aspect of the present invention, there is provided a process for preparing a polyurethane foam, which comprises reacting a polymer polyol with an isocyanate in the presence of a polyurethane catalyst, a blowing agent and a crosslinking agent, using the above polymer polyol. The specific procedures are well known in the art.
In the preparation process of the polyurethane foam, the polymer polyol accounts for 9-120 wt% of the isocyanate; the amount of the polyurethane catalyst is 0.005-4 wt% relative to the amount of the polymer polyol; the amount of the foaming agent is 0.1-25 wt% relative to the polymer polyol; the amount of the cross-linking agent is 0.01 wt% to 5 wt% relative to the polymer polyol.
Polyurethane catalysts are known in the art and include organometallic catalysts such as stannous octoate, stannous oleate, dibutyltin dilaurate, dibutyltin diacetate, and amine catalysts such as one or more of trimethylamine, triethylamine, Triethylenediamine (TEDA), dimethylethanolamine, and bis (2, 2-dimethylamino) -ethyl ether. If a cross-linking agent is used, glycerol and/or diethanolamine may be included. Suitable blowing agents include water, acetone, carbon dioxide, halogenated hydrocarbons, aliphatic alkanes and cycloalkanes. As further additives, flame retardants, surfactants, fillers, dyes or pigments may also be used.
In the invention, the vacuum pressure is absolute pressure.
The novel macromonomer stabilizer prepared by the invention has the following positive effects: the polymerizable double bond block in the stabilizer is in the middle of the novel macromolecular monomer stabilizer, so that the polymer polyol prepared from the stabilizer has better dispersion stability (the particle size is less than 300nm) and excellent filtering performance (the passing rate of a 200-mesh filter screen is more than 98%).
Detailed Description
The present invention will be described in detail by way of specific embodiment examples. The scope of the invention is not limited by the specific embodiments.
The compounds and main equipment used in the present invention are described below:
polyether polyol a: stabilizer polyether polyol, high resilience soft foam polyether polyol prepared by the reaction of glycerol, propylene oxide and ethylene oxide, Wanhua chemical group Limited company, hydroxyl value of 28.0 +/-1.5 mgKOH/g and brand number of
Polyether polyol B: basic polyether polyol, common soft foam polyether polyol prepared by the reaction of glycerin, propylene oxide and ethylene oxide, Wanhua chemical group Limited company, hydroxyl value 56.0 +/-1.5
mgKOH/g, brand number of
TMBDI: 2,2,3, 3-tetramethyl-1, 4-butanediisocyanate with the purity of 99.2 percent is self-made;
MEHQ: hydroquinone monomethyl ether, purity > 95%, an avastin reagent;
t-9: stannous octoate with purity higher than 95 percent, and an alatin reagent;
comparative stabilizer a: polyether polyol A was reacted with maleic anhydride and capped with EO at a viscosity of 4100cp @25 ℃.
13C-NMR: bruker AVANCEIII NMR spectrometer, 400MHz, deuterated chloroform solvent, pulse sequence zgig30, d12s, ns 4096, and the number of sampling points 64 k.
Viscometer: brooks technologies, Inc., DV-I + prime viscometer, 4# spindle.
A reaction kettle: the tobacco pipe is controlled by the medical science, the volume is 1 liter, the pressure resistance is 5MPa, and the use temperature is 0-300 ℃.
Short-range rectification device: VKL70-5FDRR full-heating full-gear pump molecular distillation device, reida ltd, germany (VTA GMBH & co. kg), processing conditions (if not stated, all short-range operations in this patent are the conditions): the temperature of an inner cooler is-5 ℃, the temperature of a main evaporator is 150 ℃, the discharge of heavy components is kept at 60 ℃, the operating pressure is 7.5Pa, the cooling medium of a cold trap before a pump is liquid nitrogen, the feeding frequency of a gear pump is 25Hz, and the rotating speed of a rotor is 400 r/min.
And (3) particle size testing: malvern ZS90, preparing polymer polyol ethanol solution, wherein the mass ratio of the polymer polyol to the absolute ethanol is 1:10,000, and the quartz measuring cell is 1cm x 1 cm.
And (3) testing the filtration performance: 200g of polymer polyol was taken, filtered at room temperature (25 ℃) using 200 mesh stainless steel, and after a certain period of time, the ratio of the mass of the filtrate to the total amount of polymer polyol was measured.
Example 1
i) Synthesis of polyalkyl substituted isocyanate with oxapyrimidone structure:
392g of TMBDI is added into a reaction kettle, the reaction kettle is sealed, 1.71g of tributylphosphine is added after nitrogen replacement, 30g of dry carbon dioxide is added after uniform stirring, the temperature is slowly raised to 65 ℃, the reaction is kept for 90 minutes, after the temperature is reduced, 3.6g of 10 percent diethyl ether solution of diazomethane is added under stirring, after 10 minutes of stirring at room temperature, after 30 minutes of air extraction, heavy components are collected by a short-range rectifying device, 98g of yellow oily liquid is measured, the NCO content is measured to be 19.8 percent (the theoretical value is 20.6 percent), and the measurement is carried out by13The purity was confirmed to be 99.0% by area normalization by C-NMR.
ii) adduct preparation:
50g of the product of step i) above are weighed andputting 0.05g of MEHQ in a four-neck flask, adding 0.1g of triethylamine and 15.1g of hydroxyethyl methacrylate at room temperature within 30min, heating to 48 ℃ under strong stirring, connecting a vacuum pipeline when gas is discharged, keeping vacuum at 20Pa, keeping vacuum at 5Pa after no gas is discharged, degassing for 3h, cooling and discharging. The NCO content was determined to be 7.88%. By passing13The purity was confirmed to be 1.2% (mass ratio) of the residual amount of oxapyrimidone isocyanate by C-NMR area normalization.
iii) stabilizer synthesis:
adding 500g of polyether polyol polyA into a three-necked bottle, adding 41.3g of the adduct and 30mg of T-9 catalyst, reacting for 2 hours, heating to 80 ℃, reacting for 1 hour, adding 1g of acetyl chloride for inactivation, vacuum degassing for 30 minutes, and cooling to obtain the stabilizer 1 with the viscosity of 6500cp @25 ℃.
Example 2
i) Synthesis of polyalkyl substituted isocyanate with oxapyrimidone structure:
392g of TMBDI is added into a reaction kettle, the reaction kettle is sealed, 1.71g of tributylphosphine is added after nitrogen replacement, 30g of dry carbon dioxide is added after uniform stirring, the temperature is slowly raised to 65 ℃, the reaction is kept for 90 minutes, vacuum degassing is carried out for 30 minutes, light yellow viscous liquid is obtained after temperature reduction, the NCO content is measured to be 35.05 percent (the theoretical value is 36.06 percent), and the reaction is carried out by13The oxapyrimidone isocyanate content was confirmed to be 48.5% by area normalization by C-NMR.
ii) adduct preparation:
weighing 50g of the product obtained in the step i) and 0.05g of MEHQ, placing the product and the MEHQ into a four-neck flask, adding 0.1g of triethylamine and 24.9g of hydroxyethyl acrylate at room temperature within 30min, heating to 48 ℃ under strong stirring, connecting a vacuum pipeline when gas is discharged, keeping vacuum at 20Pa, keeping vacuum at less than 5Pa, degassing for 3h when no gas is discharged, cooling and discharging. NCO content was determined to be 8.5%. By passing13The purity was confirmed to be 0.9% (mass ratio) of the residual amount of the oxapyrimidone-containing isocyanate by C-NMR area normalization.
iii) stabilizer synthesis:
adding 500g of polyether polyol polyA into a three-necked bottle, adding 44.90g of the adduct and 30mg of T-9 catalyst, reacting for 2h, heating to 80 ℃, reacting for 1h, adding 1g of acetyl chloride for inactivation, vacuum degassing for 30min, and cooling to obtain the stabilizer 2 with the viscosity of 5720cp @25 ℃.
Example 3
i) Synthesis of polyalkyl substituted isocyanate with oxapyrimidone structure:
392g of TMBDI is added into a reaction kettle, the reaction kettle is sealed, 1.71g of tributylphosphine is added after nitrogen replacement, 41.2g of dry carbon dioxide is added after even stirring, the temperature is slowly raised to 65 ℃, the reaction is kept for 90 minutes, vacuum degassing is carried out for 30 minutes, light yellow viscous liquid is obtained after temperature reduction, the NCO content is measured to be 27.6 percent (the theoretical value is 26.89 percent), and the reaction is carried out by13The oxapyrimidone isocyanate content was confirmed to be 56.6% by area normalization by C-NMR.
ii) adduct preparation:
weighing 50g of the product obtained in the step i) and 0.05g of MEHQ, placing the product and the MEHQ into a four-neck flask, adding 0.1g of triethylamine and 12.7g of hydroxyethyl methacrylate at room temperature within 30min, heating to 48 ℃ under strong stirring, connecting a vacuum pipeline when gas is discharged, keeping vacuum at 20Pa, keeping vacuum at less than 5Pa after no gas is discharged, degassing for 3h, cooling and discharging. NCO content was determined to be 8.6%. By passing13The purity was confirmed to be 0.8% (mass ratio) of the residual amount of the oxapyrimidone-containing isocyanate by C-NMR area normalization.
iii) stabilizer synthesis:
adding 500g of polyether polyol polyA into a three-necked bottle, adding 41.3g of the adduct and 30mg of T-9 catalyst, reacting for 2 hours, heating to 80 ℃, reacting for 1 hour, adding 1g of acetyl chloride for inactivation, vacuum degassing for 30 minutes, and cooling to obtain the stabilizer 3 with the viscosity of 6304cp @25 ℃.
Example 4
Preparation of Polymer polyol 1:
a500 ml four-mouth bottle is provided with a stirrer, a heating device, a temperature control device and a feeder as a reactor. 56.4g (Wanhua) of base polyether is added into a reactor
) 4.6g of stabilizer 1, after nitrogen replacement, stirred and slowly heated to 110 ℃, and the tops (10.47g of isopropanol, 85.71g of base polyether) were continuously added
A mixture of 46.55g of acrylonitrile, 69.83g of styrene and 1.21g of azobisisobutyronitrile), and the temperature was controlled at 115 ℃. And (3) finishing the dropwise adding within 100min, finishing the feeding, carrying out an aging reaction for 1 hour, continuously carrying out vacuum demonomerization for 2 hours to obtain a product, and measuring the product index. Hydroxyl value of 29.0mgKOH/g, solid content of 44.5%, viscosity of 4105cp @25 ℃, particle size of 254nm, 50min passing rate of 200-mesh filter screen of 99.9%.
Example 5
Polymer polyol 2 preparation:
a500 ml four-mouth bottle is provided with a stirrer, a heating device, a temperature control device and a feeder as a reactor. 56.0g (Wanhua) of base polyether is added into a reactor
) 5.0g of stabilizer 2, after nitrogen displacement, stirred and slowly heated to 110 ℃, and the tops (10.47g of isopropanol, 85.71g of base polyether) are continuously added
A mixture of 46.55g of acrylonitrile, 69.83g of styrene and 1.21g of azobisisobutyronitrile), and the temperature was controlled at 120 ℃. And (3) finishing the dropwise adding within 100min, finishing the feeding, carrying out an aging reaction for 1 hour, continuously carrying out vacuum demonomerization for 2 hours to obtain a product, and measuring the product index. Hydroxyl value of 30.0mgKOH/g, solid content of 44.3%, viscosity of 4200cp @25 ℃, particle size of 265nm and 50min passing rate of a 200-mesh filter screen of 99.8 percent.
Example 6
Polymer polyol 3 preparation:
a500 ml four-mouth bottle is provided with a stirrer, a heating device, a temperature control device and a feeder as a reactor. 56.0g (Wanhua) of base polyether is added into a reactor
) 5.0g of stabilizer 3, after nitrogen substitution, slowly raising the temperature to 110 ℃ with stirring, and continuously adding the top material (10.47g of isopropanol, 85.71g of base polyether)
A mixed solution of 46.55g of acrylonitrile, 69.83g of styrene and 1.21g of azobisisobutyronitrile), and the temperature was controlled at 115 ℃ to 120 ℃. And (3) finishing the dropwise adding within 100min, finishing the feeding, carrying out an aging reaction for 1 hour, continuously carrying out vacuum demonomerization for 2 hours to obtain a product, and measuring the product index. Hydroxyl value of 30.1mgKOH/g, solid content of 44.4 percent, viscosity of 4275cp @25 ℃, particle size of 245nm and 50min passing rate of a 200-mesh filter screen of 99.9 percent.
Comparative example 1
The synthesis process is referred to CN 106519148A.
A500 ml four-mouth bottle is provided with a stirrer, a heating device, a temperature control device and a feeder as a reactor. 55.4g of base polyether and 4.7g of comparative stabilizer A were added to the reactor, the mixture was stirred and slowly heated to 110 ℃ after nitrogen substitution, and the top material (a mixture of 10.47g of isopropyl alcohol, 85.71g of base polyether, 46.55g of acrylonitrile, 69.83g of styrene and 1.21g of azobisisobutyronitrile) was continuously added thereto at a controlled temperature of 115 ℃. And (3) finishing the dropwise adding within 100min, finishing the feeding, carrying out an aging reaction for 1 hour, continuously carrying out vacuum demonomerization for 2 hours to obtain a product, and measuring the product index. Hydroxyl value of 30.81mgKOH/g, solid content of 44.32%, viscosity of 4815cp @25 ℃, particle size of 650nm, 50min passing rate of a 200-mesh filter screen of 97.2%.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (13)
1. A preparation method of a macromonomer stabilizer is characterized by comprising the following steps:
i) synthesizing polyalkyl substituted isocyanate A with an oxygen-containing heteropyrimidinone structure by using polyalkyl diisocyanate and carbon dioxide;
ii) A forms an adduct B with the hydroxy unsaturated compound;
iii) continuously reacting the B with stabilizer polyether polyol to obtain a macromonomer stabilizer;
wherein the structural formula of the polyalkyl substituted isocyanate containing the oxapyrimidone structure is as follows:
m represents an alkyl substituent group having 6 to 12 carbon atoms; n is 1;
wherein the hydroxyl unsaturated compound is hydroxyethyl methacrylate;
wherein the structural formula of the reaction product of the polyalkyl-substituted isocyanate containing the oxapyrimidone structure and the hydroxyl unsaturated compound is as follows:
m represents an alkyl substituent group having 6 to 12 carbon atoms.
2. The process according to claim 1, wherein M in the formula of the polyalkyl-substituted isocyanate is tetramethylbutyl, and in this case the polyalkyl diisocyanate is TMSDI;
m in the reaction product of the polyalkyl-substituted isocyanate and the hydroxy unsaturated compound is tetramethylbutyl, in which case the polyalkyl diisocyanate is TMSDI.
3. The process according to claim 1, wherein the polyalkyl diisocyanate in step i) is 2,2,3, 3-tetramethyl-1, 4-butanediisocyanate (TMBDI);
and/or the molar ratio of the carbon dioxide to the polyalkyl diisocyanate is 1 (0.5-5).
4. The preparation method of claim 3, wherein the molar ratio of the carbon dioxide to the polyalkyl diisocyanate in the step i) is 1 (1.7-2.9).
5. The process of claim 1 wherein the reaction of step i) is in the presence of a catalyst which is an alkyl substituted organophosphorus.
6. The method according to claim 5, wherein the catalyst of step i) is one or more of triphenylphosphine, triethylphosphine, and tributylphosphine.
7. The method according to claim 1, wherein the molar ratio of the hydroxyl group of the hydroxyl unsaturated compound to the NCO group of the isocyanate in the step ii) is (0.5-1.5): 2.
8. The method according to claim 7, wherein the molar ratio of the hydroxyl group of the hydroxyl unsaturated compound to the NCO group of the isocyanate in the step ii) is (0.6-1.0): 2.
9. The method according to claim 1, wherein the stabilizer polyether polyol in step iii) is a polyether prepared by ring-opening reaction of glycerin and/or trimethylolpropane initiator and propylene oxide and/or ethylene oxide.
10. The method as claimed in claim 9, wherein the hydroxyl value of the polyether polyol used as the stabilizer in step iii) is 20 to 48 mgKOH/g.
11. The method as claimed in claim 10, wherein the hydroxyl value of the polyether polyol used as the stabilizer in step iii) is 24 to 38 mgKOH/g.
12. The preparation method according to claim 1, wherein the molar ratio of the molar amount of NCO groups in the adduct B in step iii) to the hydroxyl groups of the stabilizer polyether polyol is (0.5-2): 1.
13. The method of claim 12, wherein the molar ratio of the molar amount of NCO groups in the adduct B of step iii) to the hydroxyl groups of the stabilizer polyether polyol is (0.9-1.22): 1.
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