CN109762154B - Macromonomers containing lactam structures and their use for preparing polymer polyols - Google Patents
Macromonomers containing lactam structures and their use for preparing polymer polyols Download PDFInfo
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- CN109762154B CN109762154B CN201811559783.1A CN201811559783A CN109762154B CN 109762154 B CN109762154 B CN 109762154B CN 201811559783 A CN201811559783 A CN 201811559783A CN 109762154 B CN109762154 B CN 109762154B
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Abstract
The invention relates to a preparation method of a macromonomer containing a lactam structure, which comprises the following steps: 1) reacting aziridine with polyester polyol or polyether polyol at a molar ratio of 0.8: 1-1.2: 1 at 100-150 ℃; 2) reacting the compound in the formula (II) with the product in the step 1) at the temperature of 60-180 ℃ to prepare the macromonomer containing a lactam structure. The invention further relates to a macromonomer containing a lactam structure, having the following structure:
wherein R is a polyester segment or a polyether segment; r1And R2Independently selected from H or alkyl with 1-3 carbon atoms. The invention also relates to the use of macromers containing lactam structures for preparing polymer polyols. The macromonomer containing the lactam structure has the advantages of small viscosity and low using amount, is suitable for being used as a dispersion stabilizer of polymer polyol, and the obtained polymer polyol has low viscosity.
Description
Technical Field
The present invention relates to the preparation of polymer polyols. In particular to a macromonomer with a lactam structure, a preparation method thereof and a method for preparing polymer polyol by using the macromonomer.
Background
The vinyl polymer grafted polyether polyol is commonly called polymer polyol (POP) and is prepared by taking general polyether polyol as basic polyether and grafting a vinyl monomer into liquid polyether through free radical in-situ polymerization. The polymer polyol has a wide application range and is greatly demanded by the market.
Due to different synthesis methods, polymer polyol products have different properties. Synthetic methods can generally be divided into two categories: one is the conventional in situ polymerization method, in which the hydrogen atom of methine on the polyether main chain can be transferred to form chain free radical under the action of free radical, and vinyl monomer is initiated to polymerize to form graft polymer. The other method is a macromonomer method, and adopts a method of introducing polyether polyol with double bonds, wherein unsaturated double bonds are introduced into the structure of the polyether polyol, and then, vinyl monomers are used for graft copolymerization, so that the polymer polyol with high solid content and high styrene is obtained.
Although some progress has been made in reducing the viscosity of polymer polyols and increasing the solids content of polymer polyols, there is still a need for further improvements in high and low solids content and stability. Wherein the properties of the macromer stabilizer play a key role.
The content of the macromonomer in the polyether polyol matrix directly affects the particle size, viscosity and the like of the grafted polyether polyol, and the macromonomer method can be used for controlling the polymerization characteristics (such as selecting the type of the vinyl unsaturated bond) and controlling the relative molecular mass of the macromonomer. The research on the copolymerization kinetics of the vinyl monomer and the macromonomer shows that the particle size of the synthesized grafted polyether polyol is reduced, the viscosity of the system is increased and the reaction rate with the vinyl monomer is increased along with the increase of the dosage of the macromonomer.
To improve the stabilizer properties of polymer polyols, small amounts of unsaturation, i.e., reactive macromer stabilizers, are introduced into the polyol. As disclosed in US3652639, US3823201, which uses "stabilizer precursors" (macromers) having specific reactive unsaturation for the preparation of polymer polyols, the polymer polyols prepared have a relatively low solids content. Later patents US5196476 and EP0786480 disclose a method for preparing POP by a prepolymer method, in which first a radical polymerization initiator is reacted with a macromonomer and an ethylenically unsaturated monomer to prepare a prepolymer, and then the prepolymer is polymerized with the ethylenically unsaturated monomer in the presence of a polyether to prepare POP, which has the disadvantage that the amount of the macromonomer used is large (9 wt%), and the viscosity is high (in the examples, 8900cp is described at 39.5% solid content).
In the preparation of macromonomers, all groups having an unsaturated double bond reactive with active hydrogen can be used to prepare macromonomers, including organic halides, acids, acid halides, anhydrides, epoxides, isocyanates, olefin-based monomers, and the like. During polymerization, the macromonomer is also grafted onto the copolymer chain to form a block copolymer comprising polyether and acrylonitrile-styrene copolymer, which acts as a phase dispersion stabilizer between the continuous and dispersed phases to avoid agglomeration of the grafted polyether particles. The amount of macromer used is generally from 1 to 15% by mass of the monomer, the macromer generally having a molecular weight of greater than 2000g/mol and containing a linear or branched polyol having at least one reactive ethylenically unsaturated end group. Ethylenically unsaturated groups can be introduced into existing polyols by reaction with anhydrides (maleic anhydride, fumaric anhydride), acrylic and methacrylic acid acetate derivatives and also isocyanatoethyl acetate.
In the prior art, the macromonomer is prepared by carrying out esterification reaction on polyether polyol and maleic anhydride and then capping with ethylene oxide. However, the prior art has the problems of high product viscosity, more product particles and larger polymer particles, and particularly, maleic anhydride or phthalic anhydride is frequently used in the preparation process of the stabilizer, so that the stabilizer is easy to sublimate to block a gas phase pipeline, the maintenance cost of the device is increased, and the device can be stopped in severe cases.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a novel macromonomer having a lactam structure, a method for preparing the same, and a method for preparing a polymer polyol using the macromonomer. The problems of large using amount or large viscosity of a macromonomer stabilizer for preparing polymer polyol in the prior art are solved, and the problems of large viscosity, poor stability, uneven appearance of polymer particles or incompatibility of the properties of the polymer polyol in the prior art are also solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a macromonomer containing a lactam structure, which comprises the following steps:
1) aziridines
Reacting with polyester polyol or polyether polyol at a molar ratio of 0.8: 1-1.2: 1 at a temperature of 100-150 ℃, preferably at a molar ratio of 0.9: 1-1: 1, preferably at a temperature of 110-130 ℃;
2) reacting a compound of formula (II) with the product obtained in the step 1) at a temperature of 60-180 ℃, preferably 80-100 ℃, to obtain the macromonomer containing a lactam structure, wherein the molar ratio of the compound of formula (II) to the aziridine added in the step 1) is 0.7: 1-1: 1, preferably 0.9: 1-1: 1, and the compound of formula (II) has the following structure:
For example, the flow chart of the preparation method of the macromonomer containing a lactam structure is as follows:
wherein R is a polyester segment or a polyether segment, R is1、R2As defined above.
In some preferred embodiments of the invention, the polyether polyol is a polyether diol, for example obtained by reacting a starter compound having two active hydrogen atoms with one or more epoxides; the starting compound with two active hydrogen atoms comprises one or more of water, ethylene glycol, propylene glycol, butanediol, pentanediol and the like; the epoxide comprises one or the combination of more than two of ethylene oxide, propylene oxide and butylene oxide. More preferably, the number average molecular weight of the polyether polyol is 50-10000, preferably 1000-4000, and more preferably 1500-3000. E.g. produced by Wanhua chemical group, Ltd
2020。
In some preferred embodiments of the present invention, the polyester polyol is preferably a polyester diol, for example selected from the group consisting of polycarbonate diol, polycaprolactone diol, polypentanolactone diol, adipic acid-based polyester diol, phthalic acid-based polyester diol, preferably polyethylene adipate diol or polybutylene adipate diol. Further preferably, the number average molecular weight of the polyester polyol is 50 to 10000, preferably 1000 to 4000, and further preferably 1500 to 3000.
In some preferred embodiments of the present invention, the reaction of aziridine with polyether polyol in step 1) is preferably carried out under solvent conditions, the solvent is not particularly limited, and organic solvents such as ethers, hydrocarbons, esters or amides which do not participate in the reaction are generally selected, and preferred solvents are inert organic alkanes such as toluene, benzene, cyclohexane and xylene. The reaction can also be carried out in a non-solvent, but the use of a solvent is preferred, depending on the viscosity of the reaction product. In the preparation method of the present invention, the amount of the solvent used is not particularly limited, and may be appropriately selected by those skilled in the art according to specific raw materials and conditions.
In another aspect, the present invention provides a macromonomer containing a lactam structure, having the following structure:
wherein R is a polyester segment or a polyether segment; r1And R2Independently selected from H or alkyl of 1-3 carbon atoms, preferably H and methyl.
In some preferred embodiments of the present invention, the polyether segments are preferably derived from polyether diols, for example from polyether polyols obtained by reacting a starter compound having two active hydrogen atoms with one or more epoxides; the starting compound with two active hydrogen atoms comprises one or more of water, ethylene glycol, propylene glycol, butanediol, pentanediol and the like; the epoxide comprises one or the combination of more than two of ethylene oxide, propylene oxide and butylene oxide. More preferably, the polyether chain segment is derived from polyether polyol with the number average molecular weight of 50-10000, preferably 1000-4000, and more preferably 1500-3000. E.g. produced by Wanhua chemical group, Ltd
2020。
In a particular embodiment of the present invention,
wherein n is 1-50 and m is 1-60.
In some preferred embodiments of the present invention, in the macromonomer of formula (I), the polyester segment is derived from a polyester diol, for example, from a polycarbonate diol, a polycaprolactone diol, a polyglutamic acid diol, an adipic acid-based polyester diol, a phthalic acid-based polyester diol, preferably a polyethylene adipate diol or a polybutylene adipate diol. Further preferably, the polyester chain segment is derived from polyester polyol with the number average molecular weight of 50-10000, preferably 1000-4000, and further preferably 1500-3000.
In a particular embodiment of the invention, the macromonomer containing a lactam structure is prepared according to the above-described preparation method.
In another aspect, the present invention provides a method for preparing polymer polyol, and the preparation of the polymer polyol according to the present invention can be performed by methods known to those skilled in the art, such as the method disclosed in CN 104045763A. Wherein the macromonomer used is the macromonomer containing a lactam structure described above or the macromonomer containing a lactam structure prepared according to the preparation method described above.
Preparing a polymer polyol by reacting raw materials comprising a macromonomer containing a lactam structure, a base polyether polyol and an ethylenically unsaturated monomer at 80-160 ℃; the reaction temperature is preferably 90 ℃ to 150 ℃, and more preferably 100 ℃ to 140 ℃; the amount of the macromonomer containing a lactam structure is from 0.1 to 3% by weight, preferably from 0.5 to 2% by weight, based on the weight of the polymer polyol; the amount of the base polyether polyol is 30-90 wt%, preferably 40-70 wt% of the weight of the polymer polyol; the amount of the ethylenically unsaturated monomer is 9 to 60 wt%, preferably 20 to 60 wt% of the weight of the polymer polyol;
in some preferred embodiments of the present invention, in the preparation method of the polymer polyol, the base polyether polyol is obtained by ring-opening polymerization of ethylene oxide and/or propylene oxide with one or more of polyols having a hydroxyl functionality of 2 to 6 as an initiator; preferably, the polyether polyol with the weight-average molecular weight of 500-12000, the hydroxyl functionality of 2-6 and the content of ethylene oxide of 2-20 wt% based on the weight of the polyether polyol is selected; further preferably, the polyether polyol has a weight average molecular weight of 1500 to 8000, a hydroxyl functionality of 3 to 5, and an ethylene oxide content of 5 to 15 wt% based on the weight of the polyether polyol. E.g. produced by Wanhua chemical group, Ltd
F3156 and/or
F3135。
In some preferred embodiments of the present invention, in the method for preparing the polymer polyol, the ethylenically unsaturated monomer includes: aliphatic conjugated dienes, monovinylidene aromatic monomers, α, β -ethylenically unsaturated carboxylic acids and esters thereof, α, β -ethylenically unsaturated nitriles and amides, vinyl esters, vinyl ethers, vinyl ketones, vinylidene halides, and the like, as well as mixtures of two or more of the foregoing monomers. The aliphatic conjugated diene is, for example, butadiene and isoprene; such as styrene, alpha-methylstyrene, tert-butylstyrene, chlorostyrene, cyanostyrene and bromostyrene; α, β -ethylenically unsaturated carboxylic acids and esters thereof are, for example, acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, 2-hydroxyethyl acrylate, butyl acrylate, itaconic acid, maleic anhydride; α, β -ethylenically unsaturated nitriles and amides, for example Acrylonitrile (AN), methacrylonitrile, acrylamide, methacrylamide, N-dimethylacrylamide, N- (dimethylaminomethyl) acrylamide; the vinyl ester is, for example, vinyl acetate. The ethylenically unsaturated monomers are preferably monovinylidene aromatic monomers and ethylenically unsaturated nitriles, more preferably a mixture of styrene (St) and Acrylonitrile (AN).
In some preferred embodiments of the present invention, in the preparation method of the polymer polyol, the ethylenically unsaturated monomer is a mixture of styrene and acrylonitrile in a molar ratio of 50: 50 to 99: 1, and more preferably a mixture of styrene and acrylonitrile in a molar ratio of 55: 45 to 80: 20.
In some preferred embodiments of the present invention, in the preparation method of the polymer polyol, the preparation method is performed by initiating a polymerization initiator, and the initiator is used in an amount of 0.01 to 5 wt%, preferably 0.1 to 0.6 wt%, based on the weight of the polymer polyol; the polymerization initiator is a peroxide, preferably one or a combination of two or more of alkyl hydroperoxide, aryl hydroperoxide, peroxyester, persulfate, perborate, or percarbonate, such as tert-butyl peroxy-2-ethylhexanoate (TBPEH), and/or an azo compound.
In some preferred embodiments of the present invention, in the method for preparing the polymer polyol, the preparation of the polymer polyol is performed in the presence of a chain transfer agent, and the amount of the chain transfer agent is 0.1 to 10 wt%, preferably 0.2 to 5 wt%, based on the weight of the polymer polyol; the chain transfer agent is preferably 1-butanol, 2-butanol, isopropanol, ethanol, methanol, water, cyclohexane or mercaptan.
In some preferred embodiments of the present invention, in the preparation method of the polymer polyol, a prepolymer is prepared by using the macromonomer containing a lactam structure and a part of the ethylenically unsaturated monomer in the presence of the chain transfer agent, and then the prepolymer is reacted with the base polyether polyol and the remaining ethylenically unsaturated monomer to obtain the polymer polyol.
Compared with the prior art, the invention has the following beneficial effects:
1) in the preparation method of the macromonomer containing the lactam structure, the process of preparing the macromonomer is double bond polymerization reaction, the conversion rate is high, no post-treatment is needed, the process is simple, the operation is simple, the requirement is low, and the control is facilitated;
2) the macromonomer of the invention has the advantages of small viscosity and low usage amount, and is suitable for being used as a dispersion stabilizer of polymer polyol;
3) the polymeric polyol prepared by using the macromonomer has the advantages of low viscosity, good stability, uniform appearance of polymer particles and the like; the preparation process has no blocky polymer, can maintain long-time operation without cleaning the reaction device, and reduces the production and operation cost.
Drawings
FIG. 1 shows nuclear magnetic spectra of macromers containing lactam structure in examples 1 and 4;
FIG. 2 nuclear magnetic spectrum of the macromonomer containing lactam structure in examples 2 and 3.
Detailed Description
The process provided by the present invention is described in further detail below, but the present invention is not limited thereto.
Raw materials
All materials referred to in the examples were obtained from the reagent avastin unless otherwise specified and were analytically pure unless otherwise specified.
Test method
The residual bill analysis is carried out by GC-MS: gas phase instrument model: agilent 7890-5975C insert XL-MSD with Triple-Axis Detector; a chromatographic column: DB-5MS (30m 0.25mm 0.25 μm); MS parameters: a vacuum pump: turbo pump, ion source: EI, scanning mode: SIM, ion source temperature: at 250 ℃ to obtain a mixture.
And (3) viscosity measurement: measured using a Brookfield DV-II + Pro viscometer, using a spindle RV 6. The shear viscosity torque was measured to be 50.
Examples
Example 1
Step 1)
In a reactor having a capacity of 1 liter and equipped with a stirrer, a heater, a thermocouple, a condensation device with a water separator, an inlet device and an outlet device, under nitrogen protection: 8.4g of aziridine and 416.4g (0.2082mol) of polyether polyol
2020 (Functionality 2, hydroxyl number 56, number average molecular weight 2000, Van Waals chemical Co., Ltd.) and 200g of toluene were mixed uniformly, reacted at 110 ℃ for 4 hours, and then cooled to room temperature.
Step 2)
Adding 16.8g of 3, 4-dimethylfuran-2, 5-dione into the reaction solution in the step 1), heating to 80 ℃ under stirring, reacting for 2 hours, and cooling to obtain a 1# macromonomer solution containing a lactam structure.
As can be seen from FIG. 1, the macromonomer prepared in example 1 gives the desired lactam structure.
Example 2
Step 1)
In a reactor having a capacity of 1 liter and equipped with a stirrer, a heater, a thermocouple, a condensation device with a water separator, an inlet device and an outlet device, under nitrogen protection: 8.9g of aziridine and 416.4g (0.2082mol) of polyether polyol
2020 (Functionality 2, hydroxyl number 56, number average molecular weight 2000, Van Waals chemical Co., Ltd.) and 200g of toluene were mixed uniformly, reacted at 120 ℃ for 4 hours, and then cooled to room temperature.
Step 2)
Adding 17.73g of maleic anhydride into the reaction liquid in the step 1), heating to 90 ℃ under stirring, reacting for 2 hours, and cooling to obtain a No. 2 macromonomer solution containing a lactam structure.
As can be seen from FIG. 2, the macromonomer prepared in example 2 gives the desired lactam structure.
Example 3
Step 1)
In a reactor having a capacity of 1 liter and equipped with a stirrer, a heater, a thermocouple, a condensation device with a water separator, an inlet device and an outlet device, under nitrogen protection: 9.4g of aziridine and 416.4g (0.2082mol) of polyether polyol
2020 (Van Hua chemical group Co., Ltd., functionality 2, hydroxyl value 56, number averageMolecular weight 2000) and 200g of toluene, uniformly mixing, maintaining the temperature of 130 ℃ for reaction for 4 hours, and then cooling to room temperature.
Step 2)
Adding 18.67g of maleic anhydride into the reaction liquid in the step 1), heating to 100 ℃ under stirring, reacting for 2 hours, and cooling to obtain a 3# macromonomer solution containing a lactam structure.
As can be seen from FIG. 2, the macromonomer prepared in example 3 gives the desired lactam structure.
Example 4
Step 1)
In a reactor having a capacity of 1 liter and equipped with a stirrer, a heater, a thermocouple, a condensation device with a water separator, an inlet device and an outlet device, under nitrogen protection: 8.4g of aziridine and 416.4g (0.2082mol)
2020 (Functionality 2, hydroxyl number 56, number average molecular weight 2000, Van. Waals chemical Co., Ltd.) and 200g of toluene were mixed uniformly, reacted at 130 ℃ for 4 hours, and then cooled to room temperature.
Step 2)
Adding 24.2g of 3, 4-dimethylfuran-2, 5-dione into the reaction solution in the step 1), heating to 90 ℃ under stirring, reacting for 2 hours, and cooling to obtain a 4# macromonomer solution containing a lactam structure.
As can be seen from FIG. 1, the macromonomer prepared in example 4 gives the desired lactam structure.
Comparative example 1
Using polyether polyols
F3135 (Vanhua chemical group Co., Ltd., functionality 3, hydroxyl number 35, weight average molecular weight 5000)120g was reacted with maleic anhydride 3.2g at 115 deg.CThis was done for 5h, followed by capping with 8g of ethylene oxide and reaction at 120 ℃ for 5h to give # 5 macromonomer.
Comparative example 2
Step 1)
In a reactor having a capacity of 1 liter and equipped with a stirrer, a heater, a thermocouple, a condensation device with a water separator, an inlet device and an outlet device, under nitrogen protection: 44.54g of methacrylic acid, 186g of a copolymerized glycol of polyethylene oxide and propylene oxide having a number average molecular weight of about 350 (EO/PO 5/2, molar ratio), 186g of a copolymerized glycol of polyethylene oxide and propylene oxide having a weight average molecular weight of about 400 (EO/PO 2/5, molar ratio), 480g of toluene, 1.6g of hydroquinone, and 1.2g of t-butyl titanate were uniformly mixed, reacted at 110 ℃ for 4 hours, and then cooled to room temperature.
Step 2)
Adding 25.6g of initiator Benzoyl Peroxide (BPO) into the reaction liquid in the step 1), heating to 80 ℃ with stirring, and reacting for 2 h. And cooling to obtain the 6# macromonomer solution.
Example 5 preparation of prepolymer:
example 5-1
The prepolymer was prepared using a two-stage reactor system consisting of a Continuous Stirred Tank Reactor (CSTR) (first stage) and a plug flow reactor (second stage). The residence time in each reactor was about 60 minutes. Reactants (isopropanol, 1# macromonomer solution containing a lactam structure, an ethylenically unsaturated monomer and an initiator) are fully mixed by a static mixer from a feeding tank, and then continuously enter a reactor through a feeding pipe, the temperature of a reaction mixture is controlled at 100 +/-5 ℃, the pressure of the whole reaction process is controlled by a pressure regulator of a second-stage reactor, the pressure is controlled at 0.7 +/-0.05 Mpa, and finally, the prepolymer is cooled by a cooler and enters a storage tank. A7 # prepolymer was prepared from the raw materials and in parts by weight as shown in Table 1.
Examples 5 and 2
The formulation is shown in Table 1, and the prepolymers of No. 8 to No. 10 were obtained by using the macromonomer solutions having a lactam structure of No. 2 to No. 4 in accordance with the method of example 5-1.
Comparative example 3: the formulations are shown in Table 1, and # 11 and # 12 prepolymers were obtained by the methods of reference example 5-1 using # 5 and # 6 macromonomer solutions, respectively.
TABLE 1 prepolymer formulation (wt%)
Example 6 polymer polyol preparation:
example 6-1
Polymer polyols are prepared using a two-stage reactor system consisting of a Continuous Stirred Tank Reactor (CSTR) (first stage) and a plug flow reactor (second stage). The residence time in each reactor was about 60 minutes. Reactants (7# prepolymer, basic polyether polyol, ethylenically unsaturated monomer, isopropanol and initiator Azobisisobutyronitrile (AIBN)) are fully mixed by a static mixer from a feeding tank, and continuously enter a reactor through a feeding pipe, the temperature of a reaction mixture is controlled to be 115 +/-5 ℃, the pressure of the whole reaction process is controlled by a pressure regulator of a second-stage reactor, the pressure is controlled to be 0.6 +/-0.05 Mpa, and finally, the product is cooled by a cooler and enters a product tank after two-stage vacuum demonomerization. According to the raw materials and parts by weight shown in Table 2, 13# polymer polyol was prepared.
Example 6 to 2
The formulations are shown in Table 2, and 14# to 16# polymer polyols were obtained by using 8# to 10# prepolymers, respectively, according to the method of example 6-1.
Comparative example 4: the formulations are shown in Table 2, and 17# and 18# polymer polyols were obtained by the methods described in reference to example 6-1 using # 11 and # 12 prepolymers, respectively.
TABLE 2 formulation (wt%) and Properties of Polymer polyols
In comparative example 4, agglomeration and particles occurred during the preparation of No. 18 polymer polyol, and the agglomeration occurred on the stirring paddle, and the reaction could not be completed. And the viscosity of the 17# polymer polyol is obviously higher than that of the 13# to 16# polymer polyol. This shows that the polymeric polyol prepared by using the macromonomer of the present invention has the advantages of low viscosity, good stability, uniform appearance of polymer particles, etc.; the preparation process has no blocky polymer, can maintain long-time operation without cleaning the reaction device, and reduces the production and operation cost.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (30)
1. A method for preparing a macromonomer containing a lactam structure comprises the following steps:
1) reacting aziridine with polyester polyol or polyether polyol at a molar ratio of 0.8: 1-1.2: 1 at 100-150 ℃;
2) reacting a compound of a formula (II) with a product obtained in the step 1) at a temperature of 60-180 ℃ to obtain the macromonomer containing a lactam structure, wherein the mole ratio of the compound of the formula (II) to aziridine added in the step 1) is 0.7: 1-1: 1, and the compound of the formula (II) has the following structure:
2. The production method according to claim 1,
in the step 1), the molar ratio is 0.9: 1-1: 1; the temperature is 110-130 ℃;
in the step 2), the temperature is 80-100 ℃; the molar ratio is 0.9: 1-1: 1; r1And R2Independently selected from H and methyl.
3. The process according to claim 1, wherein the polyether polyol is obtained by reacting a starting compound having two active hydrogen atoms with one or more epoxides; the starting compound with two active hydrogen atoms comprises one or the combination of more than two of water, ethylene glycol, propylene glycol, butanediol and pentanediol; the epoxide comprises one or the combination of more than two of ethylene oxide, propylene oxide and butylene oxide.
4. The method according to claim 3, wherein the polyether polyol has a number average molecular weight of 50 to 10000.
5. The method according to claim 4, wherein the polyether polyol has a number average molecular weight of 1000 to 4000.
6. The production method according to claim 4, wherein the polyether polyol has a number average molecular weight of 1500 to 3000.
7. The method according to claim 1, wherein the polyester polyol is one or a combination of two or more selected from the group consisting of polycarbonate diol, polycaprolactone diol, polypentanolactone diol, adipic acid-based polyester diol, and phthalic acid-based polyester diol.
8. The method according to claim 7, wherein the polyester polyol is a polyethylene adipate diol or a polybutylene adipate diol.
9. The method according to claim 7, wherein the polyester polyol has a number average molecular weight of 50 to 10000.
10. The method according to claim 9, wherein the polyester polyol has a number average molecular weight of 1000 to 4000.
11. The method according to claim 9, wherein the polyester polyol has a number average molecular weight of 1500 to 3000.
12. The method according to claim 1, wherein the step 1) is carried out in a solvent which is one or a combination of two or more of ethers, hydrocarbons, esters, and amides that do not participate in the reaction.
13. The method according to claim 12, wherein the solvent is one or a combination of two or more of toluene, benzene, cyclohexane, and xylene.
14. A macromonomer comprising a lactam structure having the structure:
wherein R is a polyester segment or a polyether segment; r1And R2Independently selected from H or alkyl with 1-3 carbon atoms.
15. A macromonomer containing a lactam structure according to claim 14 wherein R is1And R2Independently selected from H and methyl.
16. A macromonomer containing a lactam structure according to claim 14 wherein said macromonomer containing a lactam structure is produced by the production process according to any one of claims 1 to 13.
17. A macromonomer comprising a lactam structure according to claim 14 wherein said polyether segment is derived from a polyether polyol obtained by reacting a starting compound having two active hydrogen atoms with one or more epoxides; the starting compound with two active hydrogen atoms comprises one or the combination of more than two of water, ethylene glycol, propylene glycol, butanediol and pentanediol; the epoxide comprises one or the combination of more than two of ethylene oxide, propylene oxide and butylene oxide.
18. The macromonomer containing a lactam structure according to claim 17, wherein the polyether segment is derived from a polyether polyol having a number average molecular weight of 50 to 10000.
19. The macromonomer containing a lactam structure of claim 18, wherein the polyether segment is derived from a polyether polyol having a number average molecular weight of 1000 to 4000.
20. The macromonomer containing a lactam structure of claim 18, wherein the polyether segment is derived from a polyether polyol having a number average molecular weight of 1500 to 3000.
21. The macromonomer containing a lactam structure according to claim 14, wherein the polyester segment is derived from one or a combination of two or more of polycarbonate diol, polycaprolactone diol, polypentanolactone diol, adipic acid-based polyester diol, and phthalic acid-based polyester diol.
22. A macromonomer comprising a lactam structure according to claim 21 wherein said polyester segment is derived from a polyethylene adipate diol or a polybutylene adipate diol.
23. The macromonomer containing a lactam structure according to claim 21, wherein the polyester segment is derived from a polyester polyol having a number average molecular weight of 50 to 10000.
24. The macromonomer containing a lactam structure of claim 23, wherein the polyester segment is derived from a polyester polyol having a number average molecular weight of 1000 to 4000.
25. The macromonomer containing a lactam structure of claim 23, wherein the polyester segment is derived from a polyester polyol having a number average molecular weight of 1500 to 3000.
26. A preparation method of polymer polyol is characterized by reacting raw materials comprising a macromonomer containing a lactam structure, a basic polyether polyol and an ethylenically unsaturated monomer at a temperature of 80-160 ℃; and/or
The amount of said macromer containing lactam structure is from 0.1 to 3% by weight, based on the weight of said polymer polyol; the using amount of the basic polyether polyol is 30-90 wt%; the amount of the ethylenically unsaturated monomer is 9-60 wt%;
wherein the macromonomer containing a lactam structure is the macromonomer containing a lactam structure according to any one of claims 14 to 25 or the macromonomer containing a lactam structure produced by the production method according to any one of claims 1 to 13.
27. The method of claim 26, wherein the reaction temperature is 90 ℃ to 150 ℃.
28. The method of claim 26, wherein the reaction temperature is 100 ℃ to 140 ℃.
29. The method according to claim 26, wherein the amount of the macromonomer having a lactam structure used is 0.5 to 2% by weight based on the weight of the polymer polyol; the using amount of the basic polyether polyol is 40-70 wt%; the amount of the ethylenically unsaturated monomer is 20-60 wt%.
30. The method according to claim 26, wherein the polymer polyol is obtained by preparing a prepolymer from the lactam structure-containing macromonomer and the ethylenically unsaturated monomer in a total amount of 20 to 50 wt% in the presence of a chain transfer agent, and then reacting the prepolymer with the base polyether polyol and the remaining ethylenically unsaturated monomer.
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| US3262991A (en) * | 1963-03-20 | 1966-07-26 | Dow Chemical Co | Cross-linked reaction product of aziridinyl polyester resins with cyclic anhydrides |
| CN104045763A (en) * | 2013-03-11 | 2014-09-17 | 中国石油化工集团公司 | Method for continuously producing pre-polymer of polymer polyol |
| CN106519148A (en) * | 2016-11-03 | 2017-03-22 | 万华化学集团股份有限公司 | Combtype macro monomer and preparation method thereof, polymer polyol and polyurethane foam |
| CN107090064A (en) * | 2017-05-24 | 2017-08-25 | 万华化学集团股份有限公司 | A kind of macromonomer with many alkyl structures, preparation method and the method that polymer polyatomic alcohol is prepared using it |
| CN108003297A (en) * | 2017-12-12 | 2018-05-08 | 万华化学集团股份有限公司 | A kind of preparation method of polymer polyatomic alcohol and its polymer polyatomic alcohol of preparation |
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| US3262991A (en) * | 1963-03-20 | 1966-07-26 | Dow Chemical Co | Cross-linked reaction product of aziridinyl polyester resins with cyclic anhydrides |
| CN104045763A (en) * | 2013-03-11 | 2014-09-17 | 中国石油化工集团公司 | Method for continuously producing pre-polymer of polymer polyol |
| CN106519148A (en) * | 2016-11-03 | 2017-03-22 | 万华化学集团股份有限公司 | Combtype macro monomer and preparation method thereof, polymer polyol and polyurethane foam |
| CN107090064A (en) * | 2017-05-24 | 2017-08-25 | 万华化学集团股份有限公司 | A kind of macromonomer with many alkyl structures, preparation method and the method that polymer polyatomic alcohol is prepared using it |
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