CN114085370B - Poly (carbonate-ether) polyol dispersant, high-stability polymer polyol and preparation method thereof - Google Patents
Poly (carbonate-ether) polyol dispersant, high-stability polymer polyol and preparation method thereof Download PDFInfo
- Publication number
- CN114085370B CN114085370B CN202111481221.1A CN202111481221A CN114085370B CN 114085370 B CN114085370 B CN 114085370B CN 202111481221 A CN202111481221 A CN 202111481221A CN 114085370 B CN114085370 B CN 114085370B
- Authority
- CN
- China
- Prior art keywords
- polyol
- ether
- carbonate
- poly
- dispersant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
-
- 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
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- 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
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0291—Aliphatic polycarbonates unsaturated
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a poly (carbonate-ether) polyol dispersant, which only contains one unsaturated bond in the molecular structure; the molecular structure of the poly (carbonate-ether) polyol dispersant contains carbonate ether linkages. According to the dispersing agent with the specific structure for preparing the polymer polyol, as the carboxylic acid with unsaturated double bonds is selected as the initiator, each macromolecule in the prepared macromolecular dispersing agent only contains one unsaturated bond, so that the possibility of crosslinking and gelling in the subsequent reaction is avoided, and the stability of the product is ensured; and because the macromolecular dispersant also contains carbonate ether bond, the macromolecular dispersant can be ensured to have good compatibility with the basic polyether polycarbonate ether polyol, thereby leading the prepared polymer polyol to have lower viscosity and higher storage stability.
Description
Technical Field
The invention belongs to the technical field of macromolecules, and relates to a poly (carbonate-ether) polyol dispersant, a high-stability polymer polyol and a preparation method thereof, in particular to a poly (carbonate-ether) polyol dispersant, a high-stability polymer polyol and a preparation method thereof.
Background
The polymer polyol (POP), also called grafted polyether polyol, is a modified polyether prepared by taking polyether polyol as a matrix and carrying out free radical graft copolymerization with unsaturated monomers such as styrene, acrylonitrile and the like, and is widely applied to the production of high-load-bearing soft foam and semi-hard foam polyurethane. The preparation method is used for preparing the cold curing high-resilience foam, can effectively increase the compressive strength of a foam product, improves the hardness and the bearing capacity of the foam product, and can increase the openness of the foam. The polyurethane product yield in China accounts for more than 40 percent of the whole world and reaches 1000 ten thousand tons, wherein the polyurethane soft foam represented by seats, simmons and sponges exceeds 20 percent. In addition to graft copolymerization, the polymer polyols contain olefin homopolymers and copolymers dispersed in polyether polyols, which are dispersions of vinyl-containing polymers in liquid mother liquor polyether polyols. The dispersion consists of a liquid surface blended emulsion. Belongs to a thermodynamically unstable system and does not follow certain rules of the existing surface chemistry. Since the reduction of the free energy of the liquid is advantageous for the stability of the product, it is necessary to control the addition of a dispersant during the polymerization reaction, thereby preventing and preventing the segregation and turbidity of the large molecular weight agglomerates in the mother liquor, and thus, the viscosity of the product can be greatly reduced.
Carbon dioxide is used as a raw material, and reacts with epoxide to prepare a high polymer material, which is one of the most promising approaches for efficiently utilizing carbon dioxide carbon resources at present and is paid much attention by researchers. Since the reaction of carbon dioxide and propylene oxide to prepare polymers reported by Mr. Miao Xiang Hem, 1969,130,210 in Japan, 1969, research in this field is endlessly repeated, double Metal Cyanide (DMC) reported in the last 60 th century can catalyze the homopolymerization of epoxy compounds with high efficiency, and the performance of the obtained polyether polyol is obviously superior to that of the polyether polyol prepared by the traditional KOH catalyst system. In 1985, the Kuyper group first used Zn 3 [Fe(CN) 6 ]2 catalyzing the copolymerization of carbon dioxide and epoxide, thus initiating a new set of research on the copolymerization of carbon dioxide and epoxide.
However, the polycarbonate ether polyol prepared by copolymerization of carbon dioxide and epoxide has large viscosity and different molecular structure from the general polyether polyol, is easy to delaminate in the mixing process with the general polyether polyol, is inconvenient to store and transport, and further causes poor dispersibility and poor storage stability of polymer polyol.
Therefore, how to obtain a polymer polyol with high stability has become one of the focuses of great attention of many prospective researchers in the field.
Disclosure of Invention
In view of this, the present invention provides a poly (carbonate-ether) polyol dispersant, a high stability polymer polyol and a method for preparing the same, and particularly a poly (carbonate-ether) polyol dispersant, which uses the poly (carbonate-ether) polyol having a specific structure as a macromolecular dispersant that can be well compatible with a polycarbonate ether polyol as a base polyether, thereby making the prepared polymer polyol have lower viscosity and storage stability.
The invention provides a poly (carbonate-ether) polyol dispersant, which only contains one unsaturated bond in the molecular structure;
the molecular structure of the poly (carbonate-ether) polyol dispersant contains carbonate ether linkages.
Preferably, the number average molecular weight of the poly (carbonate-ether) polyol dispersant is 1000 to 20000;
the mass content of carbon dioxide in the poly (carbonate-ether) polyol dispersant is 1-35%;
the poly (carbonate-ether) polyol dispersant is a macromolecular dispersant for the preparation of polymer polyols;
the poly (carbonate-ether) polyol dispersant accounts for 1-20% of the polymer polyol by mass.
The invention provides a preparation method of a poly (carbonate-ether) polyol dispersant, which comprises the following steps:
in the presence of a double metal cyanide catalyst and an unsaturated bond-containing carboxylic acid compound initiator, carbon dioxide and an epoxy compound are subjected to copolymerization reaction to obtain the poly (carbonate-ether) polyol dispersant.
Preferably, the double metal cyanide compound comprises Zn 3 [Co(CN) 6 ] 2 、Zn 3 [Ni(CN) 6 ] 2 And Zn 3 [Fe(CN) 6 ] 2 One or more of;
the epoxy compound comprises one or more of ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, epichlorohydrin and styrene oxide;
the mass ratio of the epoxy compound to the carboxylic acid compound initiator containing unsaturated bonds is (40-200): 1.
preferably, the mass ratio of the epoxy compound to the catalyst is (100 to 10000): 1;
the pressure of the carbon dioxide is 0.01-12 MPa;
the carboxylic acid compound initiator containing unsaturated bonds comprises one or more of maleic acid, fumaric acid, itaconic acid, ricinoleic acid, aconitic acid and trans-aconitic acid;
the temperature of the copolymerization reaction is 5-120 ℃;
the time of the copolymerization reaction is 1 to 48 hours.
The invention provides a polymer polyol, which is prepared from raw materials comprising a poly (carbonate-ether) polyol dispersant;
the poly (carbonate-ether) polyol dispersant comprises the poly (carbonate-ether) polyol dispersant according to any one of the above claims or the poly (carbonate-ether) polyol dispersant prepared by the preparation method according to any one of the above claims.
Preferably, the base polyether of the polymer polyol is a polycarbonate ether polyol;
the mass content of carbon dioxide in the poly (carbonate-ether) polyol dispersant is 1-35%;
the mass content of carbon dioxide in the polycarbonate ether polyol is 1-35%;
the mass content of carbon dioxide in the poly (carbonate-ether) polyol dispersant and the mass content of carbon dioxide in the polycarbonate ether polyol deviate within ± 5%;
the initiator for preparing the polycarbonate ether polyol comprises a C1-C10 polyol compound, a hydroxyl-containing polymer with the molecular weight of less than 2000g/mol, and one or more of aliphatic saturated carboxylic acid, alicyclic saturated carboxylic acid and aromatic carboxylic acid.
The invention provides a preparation method of polymer polyol, which comprises the following steps:
1) Mixing polycarbonate ether polyol base polyether, a compound containing unsaturated double bonds, a free radical initiator, a chain transfer agent and a macromolecular dispersant, and reacting to obtain polymer polyol;
the macromolecular dispersant comprises the poly (carbonate-ether) polyol dispersant described in any one of the above technical schemes or the poly (carbonate-ether) polyol dispersant prepared by the preparation method described in any one of the above technical schemes.
Preferably, the unsaturated double bond-containing compound comprises one or more of styrene, acrylonitrile, methacrylonitrile, alpha-methylstyrene, butylstyrene, methacrylic acid, butyl methacrylate, acrylate, maleate, hydroxyethyl methacrylate and acrylic acid;
the free radical initiator comprises one or more of azodiisobutyronitrile, dimethyl azodiisobutyrate, benzoyl peroxide, tert-butyl peroxy (2-ethylhexanoate) and tert-butyl peroxydiethylacetate;
the chain transfer agent comprises one or more of isopropanol, dodecyl mercaptan, 2-butanol, methanol, isobutanol and isopropanol.
Preferably, the macromolecular dispersant accounts for 1-20% of the mass of the polymer polyol raw material;
the reaction temperature is 110-145 ℃;
the reaction time is 1 to 10 hours;
the mixing in the step 1) comprises the following specific steps:
firstly, adding part of the polycarbonate ether polyol into a reaction device, and then dropwise adding a mixed solution formed by the rest of the polycarbonate ether polyol, a compound containing unsaturated double bonds, a free radical initiator, a chain transfer agent and a macromolecular dispersing agent.
The invention provides a poly (carbonate-ether) polyol dispersant, which only contains one unsaturated bond in the molecular structure; the molecular structure of the poly (carbonate-ether) polyol dispersant contains carbonate ether linkages. Compared with the prior art, the invention aims at solving the problems that the existing carbon dioxide-based polycarbonate ether polyol prepared by copolymerizing carbon dioxide and epoxide is easy to delaminate in the mixing process with the general polyether polyol and is inconvenient to store and transport due to large viscosity and difference of molecular structure with the general polyether polyol. According to the invention, researches show that in the prior art, the polymer polyol taking the polycarbonate ether polyol as the basic polyether is prepared by adopting the macromolecular dispersing agent prepared from the general polyether, so that the problems of poor dispersibility, poor storage stability and the like of the polymer polyol exist.
The invention creatively designs a dispersant for preparing polymer polyol, and the poly (carbonate-ether) polyol dispersant with a specific structure adopts carboxylic acid with unsaturated double bonds as an initiator, so that each macromolecule in the prepared macromolecular dispersant only contains one unsaturated bond, the possibility of cross-linking and gelation in the subsequent reaction is avoided, and the stability of the product is ensured; and because the macromolecular dispersant also contains carbonate ether bonds, the macromolecular dispersant can be ensured to have good compatibility with the basic polyether polycarbonate ether polyol, so that the prepared polymer polyol has lower viscosity and higher storage stability.
The invention also provides a high-stability polymer polyol and a preparation method thereof, firstly, the basic polyether of the polymer polyol is polycarbonate ether polyol, and secondly, the macromolecular dispersant used for preparing the polymer polyol is prepared by the copolymerization reaction of DMC double metal cyanide catalyst, epoxide and carbon dioxide at a certain temperature in the presence of carboxylic acid initiator containing unsaturated bonds. The polymer polyol has a lower viscosity and higher storage stability.
Experimental results show that the polymer polyol prepared by the macromolecular dispersant prepared by the invention has obviously better properties such as viscosity, particle size, appearance and the like than the polymer polyol prepared by the conventional synthesized macromolecular dispersant.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs a purity which is conventional in the field of analytical purification or polymer polyol preparation.
All noun expressions, acronyms and designations of the invention belong to the general noun expressions, acronyms and designations in the field, each noun expression, acronyms and designation is clear and definite in the relevant application field, and a person skilled in the art can clearly, exactly and uniquely understand the noun expression, acronyms and designations.
The invention provides a poly (carbonate-ether) polyol dispersant, which only contains one unsaturated bond in the molecular structure;
the molecular structure of the poly (carbonate-ether) polyol dispersant contains carbonate ether linkages.
In the present invention, the unsaturated bond is preferably an unsaturated double bond.
In the present invention, the number average molecular weight of the poly (carbonate-ether) polyol dispersant is preferably 1000 to 20000, more preferably 5000 to 16000, and more preferably 6000 to 12000.
In the present invention, the mass content of carbon dioxide in the poly (carbonate-ether) polyol dispersant is preferably 1% to 35%, more preferably 5% to 25%, and still more preferably 10% to 20%.
It is noted that this definition is a conventional definition well known to those skilled in the art, which is associated analogously to the definition of the carbonate group content.
In the present invention, the poly (carbonate-ether) polyol dispersant is preferably a macromolecular dispersant used for preparing polymer polyols. That is, the poly (carbonate-ether) polyol dispersant provided by the present invention may be an application of a poly (carbonate-ether) polyol compound in the field of dispersants. Specifically, the dispersant preferably includes a macromolecular dispersant, and more preferably a dispersant for preparing a polymer polyol.
In the present invention, the poly (carbonate-ether) polyol dispersant is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and still more preferably 5 to 12% by mass of the polymer polyol from which it is prepared.
The invention provides a preparation method of a poly (carbonate-ether) polyol dispersant, which comprises the following steps:
in the presence of a double metal cyanide catalyst and an unsaturated bond-containing carboxylic acid compound initiator, carbon dioxide and an epoxy compound are subjected to copolymerization reaction to obtain the poly (carbonate-ether) polyol dispersant.
In the present invention, the double metal cyanide preferably comprises Zn 3 [Co(CN) 6 ] 2 、Zn 3 [Ni(CN) 6 ] 2 And Zn 3 [Fe(CN) 6 ] 2 More preferably Zn 3 [Co(CN) 6 ] 2 、Zn 3 [Ni(CN) 6 ] 2 Or Zn 3 [Fe(CN) 6 ] 2 。
In the present invention, the epoxy compound preferably includes one or more of ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, epichlorohydrin and styrene oxide, and more preferably ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, epichlorohydrin or styrene oxide.
In the present invention, the mass ratio of the epoxy compound to the unsaturated bond-containing carboxylic acid compound initiator is preferably (40 to 200): 1, more preferably (50 to 180): 1, more preferably (80 to 150): 1.
in the present invention, the mass ratio of the epoxy compound to the catalyst is preferably (100 to 10000): 1, more preferably (500 to 8000): 1, more preferably (1000 to 5000): 1.
in the present invention, the carboxylic acid-based compound initiator containing an unsaturated bond preferably includes one or more of maleic acid, fumaric acid, itaconic acid, ricinoleic acid, aconitic acid and trans-aconitic acid, and more preferably maleic acid, fumaric acid, itaconic acid, ricinoleic acid, aconitic acid or trans-aconitic acid.
In the present invention, the pressure of the carbon dioxide, i.e., the pressure of the copolymerization reaction, is preferably 0.01 to 12MPa, more preferably 0.1 to 10MPa, and still more preferably 1 to 7MPa.
In the present invention, the temperature of the copolymerization reaction is preferably 5 to 120 ℃, more preferably 15 to 110 ℃, more preferably 25 to 100 ℃, and more preferably 50 to 90 ℃.
In the present invention, the time for the copolymerization reaction is preferably 1 to 48 hours, more preferably 2 to 36 hours, more preferably 3 to 24 hours, and more preferably 4 to 16 hours.
The invention provides a polymer polyol, which is prepared from raw materials including a poly (carbonate-ether) polyol dispersant.
In the present invention, the poly (carbonate-ether) polyol dispersant preferably includes the poly (carbonate-ether) polyol dispersant described in any one of the above embodiments or the poly (carbonate-ether) polyol dispersant prepared by the preparation method described in any one of the above embodiments.
In the present invention, the base polyether of the polymer polyol is preferably a polycarbonate ether polyol. It is noted that the polycarbonate ether polyol of the present invention is used as the base polyether (base polyol), while the poly (carbonate-ether) polyol dispersant is used as the macromolecular dispersant, and falls under two different concepts and definitions, and is also a compound of two different structures.
In the present invention, the mass content of carbon dioxide in the poly (carbonate-ether) polyol dispersant is preferably 1% to 35%, more preferably 5% to 25%, and still more preferably 10% to 20%.
In the present invention, the mass content of carbon dioxide in the polycarbonate ether polyol is preferably 1% to 35%, more preferably 5% to 25%, and still more preferably 10% to 20%.
In the present invention, the deviation of the mass content of carbon dioxide in the poly (carbonate-ether) polyol dispersant from the mass content of carbon dioxide in the polycarbonate ether polyol is preferably within ± 5%, more preferably within ± 4%, more preferably within ± 3%.
In the present invention, the initiator for preparing the polycarbonate ether polyol preferably comprises one or more of a C1-C10 polyol compound, a hydroxyl group-containing polymer having a molecular weight of less than 2000g/mol, an aliphatic saturated carboxylic acid, an alicyclic carboxylic acid and an aromatic carboxylic acid, more preferably a C1-C10 polyol compound, a hydroxyl group-containing polymer having a molecular weight of less than 2000g/mol, an aliphatic saturated carboxylic acid, an alicyclic saturated carboxylic acid or an aromatic carboxylic acid. Specifically, the starter of the polycarbonate ether polyol as the base polyether does not contain a carboxylic acid compound having an unsaturated double bond.
The invention provides a preparation method of polymer polyol, which comprises the following steps:
1) Mixing polycarbonate ether polyol basic polyether, a compound containing unsaturated double bonds, a free radical initiator, a chain transfer agent and a macromolecular dispersant, and reacting to obtain polymer polyol;
the macromolecular dispersant comprises the poly (carbonate-ether) polyol dispersant described in any one of the above technical schemes or the poly (carbonate-ether) polyol dispersant prepared by the preparation method described in any one of the above technical schemes.
In the present invention, the specific steps of mixing in step 1) are preferably:
firstly, adding part of the polycarbonate ether polyol into a reaction device, and then dropwise adding a mixed solution formed by the rest of the polycarbonate ether polyol, a compound containing unsaturated double bonds, a free radical initiator, a chain transfer agent and a macromolecular dispersing agent.
In the present invention, the unsaturated double bond-containing compound preferably includes one or more of styrene, acrylonitrile, methacrylonitrile, α -methylstyrene, butylstyrene, methacrylic acid, butyl methacrylate, acrylate, maleate, hydroxyethyl methacrylate and acrylic acid, and more preferably styrene, acrylonitrile, methacrylonitrile, α -methylstyrene, butylstyrene, methacrylic acid, butyl methacrylate, acrylate, maleate, hydroxyethyl methacrylate or acrylic acid.
In the present invention, the radical initiator preferably includes one or more of azobisisobutyronitrile, dimethyl azobisisobutyrate, benzoyl peroxide, t-butyl peroxy (2-ethylhexanoate) and t-butyl peroxydiethylacetate, and more preferably, azobisisobutyronitrile, dimethyl azobisisobutyrate, benzoyl peroxide, t-butyl peroxy (2-ethylhexanoate) or t-butyl peroxydiethylacetate.
In the present invention, the chain transfer agent preferably includes one or more of isopropyl alcohol, dodecyl mercaptan, 2-butanol, methanol, isobutyl alcohol and isopropyl alcohol, and more preferably isopropyl alcohol, dodecyl mercaptan, 2-butanol, methanol, isobutyl alcohol or isopropyl alcohol.
In the present invention, the mass percentage of the macromolecular dispersant in the polymer polyol raw material is preferably 1% to 20%, more preferably 3% to 15%, and still more preferably 5% to 10%.
In the present invention, the temperature of the reaction is preferably 110 to 145 ℃, more preferably 115 to 140 ℃, more preferably 120 to 135 ℃, and more preferably 125 to 130 ℃.
In the present invention, the reaction time is preferably 1 to 10 hours, more preferably 3 to 8 hours, and still more preferably 5 to 6 hours.
The invention is a complete and refined integral technical scheme, better ensures the dispersing performance of the poly (carbonate-ether) polyol dispersant, further improves the storage stability of the polymer polyol and reduces the viscosity of the polymer polyol, and the preparation method of the polymer polyol can specifically comprise the following steps:
the synthesis steps of the polymer polyol are as follows:
adding part of the polycarbonate ether polyol into a four-mouth bottle provided with a stirrer, a reflux condenser tube, an automatic sample injector and a thermometer, heating under the protection of nitrogen, controlling the reaction temperature to be 110-145 ℃, and dropwise adding the rest of the mixed solution of the polycarbonate ether polyol, styrene, acrylonitrile, isopropanol, AIBN and macromolecular dispersant at a constant speed under stirring (the dropwise adding time is 60 min). Aging and absorbing for 60min at 120 deg.C after charging, blowing nitrogen gas to remove unreacted monomer under vacuum, filtering with filter screen, and discharging to obtain POP (polymer polyol).
The invention provides a high-stability polymer polyol and a preparation method thereof, firstly, the basic polyether of the polymer polyol is polycarbonate ether polyol, and secondly, the macromolecular dispersant used for preparing the polymer polyol is prepared by the copolymerization reaction of DMC double metal cyanide catalyst, epoxide and carbon dioxide at a certain temperature in the presence of carboxylic acid initiator containing unsaturated bonds.
Wherein, the process for preparing the polymer polyol also comprises a compound containing unsaturated double bonds, particularly preferably at least one selected from styrene, acrylonitrile, methacrylonitrile, alpha-methylstyrene, butylstyrene, methacrylic acid, butyl methacrylate, acrylate, maleate, hydroxyethyl methacrylate and acrylic acid, and a free radical initiator, particularly preferably at least one selected from azobisisobutyronitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxy (2-ethylhexanoate) or tert-butyl peroxydiethylacetate.
Specifically, the epoxide is one or more of ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, epichlorohydrin and styrene oxide.
Specifically, the carboxylic acid compounds containing unsaturated bonds mainly comprise: one or more of maleic acid, fumaric acid, itaconic acid, ricinoleic acid, aconitic acid, and trans-aconitic acid.
Specifically, the mass ratio of the alkylene oxide to the initiator is 40.
Specifically, the content of carbon dioxide in the prepared macromolecular dispersant is close to the content of carbon dioxide in the basic polyether, and is the most ideal, generally 1-35%, preferably 5-25%, and most preferably 10-20%.
Specifically, the proportion of the macromolecular dispersant in the total polymer polyol is 1-20%; preferably 3% to 15%.
Specifically, the DMC double metal cyanide catalyst of the present invention is not particularly limited in its source, and may be prepared by referring to the preparation method of chinese patent No. CN102617844, for example, according to the following method:
wherein the DMC catalyst is prepared by the following steps:
step a), mixing and dissolving tert-butyl alcohol, deionized water and a zinc salt compound to obtain a solution a;
step b) dissolving soluble potassium salt in deionized water to obtain a solution b;
step c) continuously adding the solution b into the solution a, stirring fully, then centrifuging or filtering for separation, and drying to obtain the Zn-based material 3 [Co(CN) 6 ] 2 Double metal cyanide catalysts of (2).
Preferably, the zinc salt compound is ZnCl 2 、ZnBr 2 、Zn(CH 3 COO) 2 、Zn(ClCH 2 COO) 2 、Zn(Cl 2 CHCOO) 2 、Zn(Cl 3 CHCOO) 2 、ZnSO 4 And Zn (NO) 3 ) 2 One or more of them.
Preferably, the soluble potassium salt is K 3 [Co(CN) 6 ]、K 3 [Fe(CN) 6 ]、K 3 [Ni(CN) 6 ]One or more of them.
Preferably, the step c further comprises controlling the reaction temperature to be 20-100 ℃, and the separated crude product further comprises: and sequentially carrying out slurrying washing on the crude product by using a mixed solution obtained by mixing the water and the tert-butyl alcohol in different proportions, and then carrying out centrifugation or filtration separation to obtain a product, and carrying out slurrying washing again until the product meets the requirement.
In particular, the base polyether of the synthetic polymer polyol is preferably a polycarbonate ether polyol, which is also prepared by a DMC double metal cyanide catalyst, but is prepared by copolymerizing an epoxide and carbon dioxide in the presence of a starter containing an active H (which does not contain unsaturated double bonds) at a temperature.
The preparation process of the polycarbonate ether polyol can be as follows:
in the presence of double metal cyanide catalyst and initiator, carbon dioxide and epoxy compound are copolymerized at certain temperature and time.
The initiator is one or more of H-containing compounds, preferably C1-C10 polyalcohol compounds, hydroxyl-containing polymers with molecular weight less than 2000g/mol, saturated aliphatic carboxylic acids, saturated alicyclic carboxylic acids and aromatic carboxylic acids.
Preferably, the C1-C10 alcohol compound is preferably selected from one or more of C1-C10 polyol compounds such as ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, decanediol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, neopentyl glycol, 1, 2-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, starch, and cellulose.
Preferably, the carboxylic acid compounds include C1 to C10 polycarboxylic acid compounds, such as one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1, 3-acetonic acid, malic acid, citric acid, gamma-hydroxybutyric acid, gamma-aminobutyric acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, and pyromellitic acid.
Specifically, the copolymerization reaction temperature is preferably 5 to 120 ℃, and more preferably 50 to 90 ℃;
specifically, the copolymerization reaction time is preferably 1 to 48 hours, more preferably 4 to 16 hours;
specifically, the copolymerization reaction pressure is preferably 0 to 12MPa, more preferably 1 to 7MPa.
The invention relates to a poly (carbonic ester-ether) polyol dispersant, a high-stability polymer polyol and a preparation method thereof. The dispersant for preparing the polymer polyol is a poly (carbonate-ether) polyol dispersant with a specific structure, and because carboxylic acid with unsaturated double bonds is selected as an initiator, each macromolecule in the prepared macromolecular dispersant only contains one unsaturated bond, so that the possibility of cross-linking and gelation in subsequent reaction is avoided, and the stability of a product is ensured; and because the macromolecular dispersant also contains carbonate ether bond, the macromolecular dispersant can be ensured to have good compatibility with the basic polyether polycarbonate ether polyol, thereby leading the prepared polymer polyol to have lower viscosity and higher storage stability.
The invention also provides a high-stability polymer polyol and a preparation method thereof, firstly, the basic polyether of the polymer polyol is polycarbonate ether polyol, and secondly, the macromolecular dispersant used for preparing the polymer polyol is prepared by the copolymerization reaction of DMC double metal cyanide catalyst, epoxide and carbon dioxide at a certain temperature in the presence of carboxylic acid initiator containing unsaturated bonds. The polymer polyol has a lower viscosity and higher storage stability.
Experimental results show that the polymer polyol prepared by the macromolecular dispersant prepared by the invention has obviously better properties such as viscosity, particle size, appearance and the like than the polymer polyol prepared by the conventional synthesized macromolecular dispersant.
To further illustrate the present invention, a poly (carbonate-ether) polyol dispersant, a high stability polymer polyol and a method for preparing the same, which are provided by the present invention, are described in detail below with reference to examples, but it should be understood that the examples are carried out on the premise of the technical scheme of the present invention, and that detailed embodiments and specific procedures are given only for further illustrating the features and advantages of the present invention, not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Examples 1 to 4
Synthesizing a macromolecular dispersant:
0.3g of the DMC double metal cyanide catalyst prepared above and 7.5g of fumaric acid starter were each charged into a 500ml reaction vessel, which was evacuated at 80 ℃ and charged with CO 2 Treating for 2h (aerating for 6 times), cooling to room temperature, adding 300g of propylene oxide into the reaction kettle, stirring at the rotating speed of 500rpm, introducing carbon dioxide into the reaction kettle through a carbon dioxide pressure regulator, and placing the reaction kettle into a constant-temperature bath for polymerization reaction. The pressure of the polymerized carbon dioxide is 2.0-5.0 Mpa, the polymerization reaction temperature is 75-90 ℃, and the reaction time is 8h. After the reaction is finished, the reaction kettle is cooled to room temperature by a cold water bath at the temperature of 25 ℃, unreacted propylene oxide is evaporated, and the remainder is dried in a vacuum oven at the temperature of 40 ℃ to constant weight, so that the macromolecular dispersant is obtained.
The macromolecular dispersants prepared in examples 1 to 4 were analyzed by GPC and nuclear magnetism.
Referring to Table 1, table 1 shows the parameters of the macromolecular dispersants prepared in examples 1 to 4 of the present invention.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Initiator | Fumaric acid | Ricinoleic acid | Itaconic acid | Itaconic acid |
| Carbon dioxide content (%) | 20 | 27 | 14 | 14 |
| Number average molecular weight (g/mol) | 7200 | 6500 | 4300 | 6500 |
| Reaction temperature (. Degree.C.) | 75 | 80 | 90 | 90 |
| Carbon dioxide pressure (MPa) | 4.0 | 5.0 | 2.0 | 2.0 |
Examples 5 to 8
Synthesis of Polymer polyol (POP) Using the Poly (carbonate-ether) polyol prepared in examples 1 to 4 above as a macromolecular dispersant
Adding part of the polycarbonate ether polyol into a four-mouth bottle provided with a stirrer, a reflux condenser tube, an automatic sample injector and a thermometer, heating under the protection of nitrogen, controlling the reaction temperature to be 110-145 ℃, and dropwise adding the rest of the mixed solution of the polycarbonate ether polyol, styrene, acrylonitrile, isopropanol, AIBN and macromolecular dispersant at a constant speed under stirring (dropwise adding for 1 hour). After the charging, aging and absorbing for 1.5 hours at 120 ℃, and blowing nitrogen gas to remove unreacted monomers in vacuum to obtain POP.
Referring to table 2, table 2 shows the synthesis formulations of polymer polyols (POPs) prepared in examples 5 to 8 of the present invention.
TABLE 2
The molecular weight of the base polyether (polycarbonate ether polyol) used in examples 5 to 6 was 4500g/mol, the carbon dioxide content was 17%; examples 7-8 used a base polyether (polycarbonate ether polyol) having a molecular weight of 5500g/mol and a carbon dioxide content of 10%, and examples 5-8 used a macromolecular dispersant derived from examples 1-4, respectively.
Comparative examples 1 to 3
The conventional method is used for synthesizing the macromolecular dispersant:
the MA and the PPO react at 110 ℃ according to equimolar amount to a theoretical acid value, excessive PO is added into a constant-pressure dropping funnel in a backflow and dropwise mode to carry out end-capping reaction until the acid value is smaller than 0.4mg KOH/g, unreacted PO is removed under reduced pressure, the temperature is reduced to 80 ℃ for carrying out isomerization reaction, and the yellowish, transparent and viscous macromolecular dispersing agent is obtained and used for next-step synthesis reaction.
Conventional synthetic polymer polyol (POP):
adding part of the polycarbonate ether polyol into a four-mouth bottle provided with a stirrer, a reflux condenser tube, an automatic sample injector and a thermometer, heating under the protection of nitrogen, controlling the reaction temperature to be 110-145 ℃, and dropwise adding the rest of the mixed solution of the polycarbonate ether polyol, styrene, acrylonitrile, isopropanol, AIBN and macromolecular dispersant at a constant speed under stirring (dropwise adding for 1 hour). After the charging, aging and absorbing for 1.5 hours at 120 ℃, and blowing nitrogen gas to remove unreacted monomers in vacuum to obtain POP.
Referring to Table 3, table 3 shows the synthesis formulations of polymer polyols (POPs) prepared in comparative examples 1 to 3 of the present invention.
TABLE 3
Comparative examples 1-2 the base polyether (polycarbonate ether polyol) used had a molecular weight of 4500g/mol, and a carbon dioxide content of 17%; comparative example 3 the base polyether (polycarbonate ether polyol) used had a molecular weight of 5500g/mol and a carbon dioxide content of 10%.
The polymer polyols (POPs) prepared in examples 5 to 7 of the present invention and comparative examples 1 to 3 were subjected to a performance test.
Referring to Table 4, table 4 shows the results of the performance test of the polymer polyols (POPs) prepared in examples 5 to 7 according to the present invention and comparative examples 1 to 3.
TABLE 4
While the present invention has been described in detail with respect to a poly (carbonate-ether) polyol dispersant, a high stability polymer polyol, and methods of making the same, the principles and embodiments of the present invention are described herein using specific examples, which are intended to facilitate an understanding of the process of the present invention and its core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. Use of a poly (carbonate-ether) polyol as a dispersant for the preparation of a polymer polyol;
the poly (carbonate-ether) polyol has a molecular structure containing only one unsaturated bond;
the poly (carbonate-ether) polyol contains a carbonate ether linkage in the molecular structure;
the dispersant is a macromolecular dispersant;
the base polyether of the polymer polyol is a polycarbonate ether polyol.
2. Use according to claim 1, wherein the poly (carbonate-ether) polyol has a number average molecular weight of 1000 to 20000;
the mass content of carbon dioxide in the poly (carbonate-ether) polyol is 1% -35%;
the mass ratio of the poly (carbonate-ether) polyol to the polymer polyol is 1-20%.
3. A process for the preparation of a poly (carbonate-ether) polyol for use according to any one of claims 1 to 2, comprising the steps of:
in the presence of a double metal cyanide catalyst and an unsaturated bond-containing carboxylic acid compound initiator, carbon dioxide and an epoxy compound are subjected to copolymerization reaction to obtain the poly (carbonate-ether) polyol.
4. The method as claimed in claim 3, wherein said double metal cyanide compound comprises Zn 3 ［Co(CN) 6 ］ 2 、Zn 3 ［Ni(CN) 6 ］ 2 And Zn 3 ［Fe(CN) 6 ］ 2 One or more of;
the epoxy compound comprises one or more of ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, epichlorohydrin and styrene oxide;
the mass ratio of the epoxy compound to the carboxylic acid compound initiator containing an unsaturated bond is (40 to 200): 1.
5. the production method according to claim 3, wherein the mass ratio of the epoxy compound to the catalyst is (100 to 10000): 1;
the pressure of the carbon dioxide is 0.01 to 12MPa;
the carboxylic acid compound initiator containing unsaturated bonds comprises one or more of maleic acid, fumaric acid, itaconic acid, ricinoleic acid, aconitic acid and trans-aconitic acid;
the temperature of the copolymerization reaction is 5 to 120 ℃;
the time of the copolymerization reaction is 1 to 48 hours.
6. A polymer polyol, characterized in that the polymer polyol is prepared from a raw material comprising a poly (carbonate-ether) polyol as a dispersant;
the poly (carbonate-ether) polyol is a poly (carbonate-ether) polyol in the application of any one of claims 1 to 2 or a poly (carbonate-ether) polyol prepared by the preparation method of any one of claims 3 to 5.
7. The polymer polyol of claim 6, wherein the poly (carbonate-ether) polyol has a carbon dioxide content of 1% to 35% by mass;
the mass content of carbon dioxide in the polycarbonate ether polyol is 1% -35%;
the mass content of carbon dioxide in the poly (carbonate-ether) polyol and the mass content of carbon dioxide in the polycarbonate ether polyol deviate within ± 5%;
the initiator for preparing the polycarbonate ether polyol comprises a C1-C10 polyol compound, a hydroxyl-containing polymer with the molecular weight of less than 2000g/mol, and one or more of aliphatic saturated carboxylic acid, alicyclic saturated carboxylic acid and aromatic carboxylic acid.
8. A method of making a polymer polyol, comprising the steps of:
1) Mixing polycarbonate ether polyol basic polyether, a compound containing unsaturated double bonds, a free radical initiator, a chain transfer agent and a macromolecular dispersant, and reacting to obtain polymer polyol;
the macromolecular dispersant is poly (carbonate-ether) polyol in the application of any one of claims 1 to 2 or poly (carbonate-ether) polyol prepared by the preparation method of any one of claims 3 to 5.
9. The method according to claim 8, wherein the unsaturated double bond-containing compound comprises one or more of styrene, acrylonitrile, methacrylonitrile, α -methylstyrene, butylstyrene, methacrylic acid, acrylic ester, maleic ester, and acrylic acid;
the free radical initiator comprises one or more of azodiisobutyronitrile, dimethyl azodiisobutyrate, benzoyl peroxide, tert-butyl peroxy (2-ethylhexanoate) and tert-butyl peroxy diethylacetate;
the chain transfer agent comprises one or more of dodecyl mercaptan, 2-butanol, methanol, isobutanol and isopropanol.
10. The preparation method according to claim 8, wherein the macromolecular dispersant accounts for 1-20% of the polymer polyol raw material by mass;
the reaction temperature is 110 to 145 ℃;
the reaction time is 1 to 10 hours;
the mixing in the step 1) comprises the following specific steps:
firstly, adding part of the polycarbonate ether polyol into a reaction device, and then dropwise adding a mixed solution formed by the rest of the polycarbonate ether polyol, a compound containing unsaturated double bonds, a free radical initiator, a chain transfer agent and a macromolecular dispersing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111481221.1A CN114085370B (en) | 2021-12-06 | 2021-12-06 | Poly (carbonate-ether) polyol dispersant, high-stability polymer polyol and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111481221.1A CN114085370B (en) | 2021-12-06 | 2021-12-06 | Poly (carbonate-ether) polyol dispersant, high-stability polymer polyol and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114085370A CN114085370A (en) | 2022-02-25 |
| CN114085370B true CN114085370B (en) | 2023-04-07 |
Family
ID=80306723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111481221.1A Active CN114085370B (en) | 2021-12-06 | 2021-12-06 | Poly (carbonate-ether) polyol dispersant, high-stability polymer polyol and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114085370B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232258A (en) * | 2022-07-19 | 2022-10-25 | 南京金栖化工集团有限公司 | Polyester ether-based polymer polyol and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398577C (en) * | 2004-12-29 | 2008-07-02 | 中国石化集团天津石油化工公司 | Method for preparing polyalcohol of polymer |
| CN102617844B (en) * | 2012-03-28 | 2013-03-06 | 中国科学院长春应用化学研究所 | Preparing method of poly (carbonic ester-ether) polyalcohol |
| CN105061746B (en) * | 2015-08-04 | 2016-11-30 | 中国科学院长春应用化学研究所 | A kind of preparation method of poly(carbonate-ether) polyol |
| CN110577636A (en) * | 2019-09-25 | 2019-12-17 | 淮安巴德聚氨酯科技有限公司 | Dispersing agent for polymer polyol and preparation method of polymer polyol |
| CN113278143B (en) * | 2021-05-27 | 2022-12-20 | 中国科学院长春应用化学研究所 | Efficient unsaturated carbon dioxide-based polyol and preparation method thereof |
-
2021
- 2021-12-06 CN CN202111481221.1A patent/CN114085370B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114085370A (en) | 2022-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102617844B (en) | Preparing method of poly (carbonic ester-ether) polyalcohol | |
| CN1035188C (en) | Process for preparing polymer polyols, and polymer polyol so made | |
| CN114085370B (en) | Poly (carbonate-ether) polyol dispersant, high-stability polymer polyol and preparation method thereof | |
| EP3249000B1 (en) | Method for circularly preparing polyether polyol by using dmc catalyst | |
| JP2002508417A (en) | Polymer polyol and stabilizer system | |
| EP1401912A1 (en) | Process for the production of polyol blends | |
| WO2017020470A1 (en) | Preparation method for poly(carbonate-ether)polyol | |
| CN110023374B (en) | High molecular weight polyether carbonate polyols | |
| CN108070082B (en) | Method for preparing low-viscosity high-molecular-weight polyether polyol | |
| CN107602751A (en) | A kind of low molecule amount hydroxyl chlorinated polyether resin and preparation method thereof | |
| CN110591010B (en) | Water-resistant styrene-free artificial stone resin and preparation method thereof | |
| CN105566618B (en) | A kind of modified butanediol ester poly succinic acid and preparation method thereof | |
| HU212247B (en) | Process for synthesis of stable, low viscosity polimer poliols and for preparation polyurethane products | |
| CN112625231B (en) | Catalyst for preparing polyol, preparation method and application thereof | |
| CN106432706A (en) | Novel self-emulsifying water-based polyester emulsion and preparation method thereof | |
| CN111484605B (en) | Full-bio-based unsaturated polyester prepolymer for dynamically vulcanizing polylactic acid and preparation method thereof | |
| CN109021218A (en) | A kind of high barrier degradable copolyester material and preparation method thereof | |
| CN116333279B (en) | Polycarbonate toughening resin | |
| TWI278483B (en) | Styrene resin composition and process for producing the same | |
| CN109293907B (en) | High molecular weight polyester based on biomass as monomer, preparation method and application | |
| CN114479045B (en) | Carbon dioxide-based elastomer and preparation method thereof | |
| CN108559033A (en) | The preparation method of macromolecular stabilizer agent performed polymer | |
| EP1493767B1 (en) | Process to produce unsaturated polyester polyols | |
| CN1109058C (en) | Composite catalyst bimetal cyanide and its preparing process and application | |
| US6696521B2 (en) | High performance ortho UPR |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Qiao Lijun Inventor after: Miao Yuyang Inventor after: Li Zhifeng Inventor after: Wang Xianhong Inventor before: Qiao Lijun Inventor before: Miao Yuyang Inventor before: Li Zhifeng Inventor before: Wang Xianhong |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |