CN112708122B - Polycarbonate polyol, preparation method and application thereof - Google Patents

Polycarbonate polyol, preparation method and application thereof Download PDF

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CN112708122B
CN112708122B CN202110046211.9A CN202110046211A CN112708122B CN 112708122 B CN112708122 B CN 112708122B CN 202110046211 A CN202110046211 A CN 202110046211A CN 112708122 B CN112708122 B CN 112708122B
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polycarbonate polyol
reaction
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temperature
pentanediol
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CN112708122A (en
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李旭峰
秦承群
黎源
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Wanhua Chemical Group Co Ltd
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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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/305—General preparatory processes using carbonates and alcohols
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G64/0208—Aliphatic polycarbonates saturated

Abstract

The invention disclosesThe polycarbonate polyol with the structural general formula shown in the formula (1) is prepared by introducing single type of dihydric alcohol, and performing vacuum polycondensation, catalyst inactivation, hydroxyl dehydration and double bond combination reaction, has the characteristics of low viscosity and high compatibility, is used for polyurethane elastomers, adhesives, coatings and foaming materials, and is favorable for reducing the operation cost and expanding the terminal application field. HO- (R-OCOO)n1‑(R＝R‑OCOO)n2-OH (formula I).

Description

Polycarbonate polyol, preparation method and application thereof
Technical Field
The invention belongs to the technical field of polycarbonate polyols, and particularly relates to a low-viscosity polycarbonate polyol with a novel structure, and a preparation method and application thereof.
Background
The polycarbonate polyol is a polyester polyol with excellent comprehensive performance, has the performance advantages of both the polyester polyol and the polyether polyol, is a high-end raw material for synthesizing polyurethane materials, and is widely applied to the fields of elastomers, adhesives, coatings and the like.
However, when preparing polyurethane materials, polycarbonate polyols have the disadvantages of high viscosity and poor compatibility with other reactants, and need to be heated to a higher temperature for use when in use, thereby increasing the preparation cost; meanwhile, due to the limitation of compatibility, the application of the product is limited because the available other monomers are less in types.
In order to solve such problems, a solution commonly used in the industry is to reduce the crystallinity and viscosity of polycarbonate polyols by selecting a way of copolymerizing different kinds of diols. The copolymerization of 1, 6-hexanediol and 1, 5-pentanediol is most commonly used, and the copolymer is liquid flowable at room temperature, but is too viscous to require heating to achieve a satisfactory flow rate, relative to the 1, 6-hexanediol homopolymer product which is a waxy solid at room temperature. While the improvement of the copolymer is more limited with respect to compatibility. And the price of the comonomer is expensive, and the development of downstream markets is not facilitated.
Therefore, there is a strong need to develop a polycarbonate polyol having low viscosity, high compatibility, and high cost performance.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a polycarbonate polyol with a novel structure, which has the characteristics of low viscosity and high compatibility.
Another object of the present invention is to provide a process for producing a polycarbonate polyol having such a novel structure.
It is a further object of the present invention to provide the use of polycarbonate polyols of this novel structure.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a polycarbonate polyol prepared from a single type of diol monomer having the structural formula HO-R-OH, and having the structure of (formula I):
HO-(R-OCOO)n1-(R＝R-OCOO)n2-OH (formula I)
Wherein R is C2-C10Linear or branched alkyl of (a); the dihydric alcohol HO-R-OH is selected from at least any one of 1, 10-decanediol, 1, 9-nonanediol, 1, 8-octanediol, 1, 7-heptanediol, 1, 6-hexanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-butanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, diethylene glycol or ethylene glycol; preferably, the dihydric alcohol is at least any one of 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-butanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol or diethylene glycol.
In a specific embodiment, the molecular weight of the polycarbonate polyol having the structure (formula I) is 500-4000, and accordingly n1 ranges from 1.6 to 44.8, n2 ranges from 0.01 to 22.4, while n1+ n2 ranges from 1.6 to 44.8, and n2/(n1+ n2) ranges from 0.1% to 50%.
In another aspect of the present invention, the preparation method of the polycarbonate polyol comprises the following steps:
1) normal pressure ester exchange reaction: heating a reactant A containing a carbonate bond, a dihydric alcohol reactant B and a catalyst C to a reaction temperature by a program to perform an ester exchange reaction, and simultaneously rectifying to remove the generated small molecular alcohol D;
2) and (3) vacuum polycondensation reaction: continuing the reaction of the reactant in the step 1) under vacuum to high vacuum for reaction, and simultaneously further rectifying to remove the generated small molecular alcohol to obtain a product polycarbonate polyol;
3) catalyst deactivation: introducing steam into the product obtained in the step 2) to hydrolyze the catalyst into titanium dioxide;
4) hydroxyl dehydration reaction: further reacting the product obtained in the step 3) at a specific reaction temperature under vacuum to dehydrate the terminal hydroxyl groups to form terminal alkenyl groups in a certain proportion;
5) double bond bonding reaction: and (3) reacting the product obtained in the step 4) under a specific reaction temperature and an ultraviolet lamp to prepare the polycarbonate polyol with the structure of the formula 1.
In a specific embodiment, in the step 1), the reactant a is selected from one or more of dimethyl carbonate, ethylene carbonate or diphenyl carbonate; the reactant B is selected from at least any one of 1, 10-decanediol, 1, 9-nonanediol, 1, 8-octanediol, 1, 7-heptanediol, 1, 6-hexanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-butanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, diethylene glycol or ethylene glycol; preferably, the reactant B is selected from at least any one of 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-butanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol or diethylene glycol; the catalyst C is selected from titanate esters, preferably tetrabutyl titanate or isopropyl titanate; further preferably, the molar ratio of the reactant A to the reactant B is from 0.83 to 1.31, preferably from 1.08 to 1.28, and the amount of catalyst C is from 5 to 200ppm, preferably from 10 to 100ppm, based on the theoretical yield of polycarbonate polyol.
In a particular embodiment, in said step 1), the starting temperature is comprised between 20 and 100 ℃, preferably between 40 and 60 ℃; the heating rate is 0.5-5 ℃/min, preferably 1-3 ℃/min; the end temperature is 160-220 ℃, preferably 180-200 ℃; the total reaction time is 4-12h, preferably 6-8 h.
In a specific embodiment, the reaction temperature in step 2) is 200-250 ℃, preferably 220-240 ℃; programmed depressurization time is 0.1-2h, preferably 0.5-1 h; the end pressure is from 0.01 to 10kPa, preferably from 0.1 to 5 kPa; the total reaction time is 6-100h, preferably 10-48 h.
In a specific embodiment, in the step 3), steam is introduced into the product obtained in the step 2) in a normal-pressure closed kettle, so that the system pressure reaches 10-20kPa gauge pressure, and the reaction is maintained at 110 ℃ for 10-120 s.
In a specific embodiment, in the step 4), the product obtained in the step 3) is heated to the temperature of 170-250 ℃, and is vacuumized for 1-5h to form a certain proportion of terminal alkenyl groups and remove water vapor, wherein the vacuum degree is 0.01-10kPa, and preferably 0.1-5 kPa.
In a specific embodiment, in the step 5), the product obtained in the step 4) is cooled to 30-100 ℃ to make the system viscosity reach 1000-. The detailed process is that oxygen is introduced at the reaction temperature, and the oxygen can rapidly react with residual free radicals to quench the residual free radicals without further treatment.
In a further aspect of the present invention, the polycarbonate polyol or the polycarbonate polyol prepared by the method is used in polyurethane elastomers, adhesives, coatings or foamed materials.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) the method adopts a single type of dihydric alcohol and a compound containing a carbonate bond to carry out ester exchange and polycondensation reaction, then carries out hydroxyl dehydration and photocatalytic double bond combination to form the polycarbonate polyol containing the structure of-R ═ R-double bond, so that regular crystalline polymer is difficult to form in the polycarbonate polyol, and the melting point and the viscosity of the polymer are reduced.
2) The polycarbonate polyol has the characteristics of low viscosity and low melting point, has good fluidity at room temperature, is low in operation cost in the process of synthesizing polyurethane, has good compatibility with polyester polyol, polyether polyol, various organic solvents and auxiliaries participating in polyurethane synthesis, and can be widely applied to the fields of polyurethane elastomers, adhesives, coatings, foaming materials and the like.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
A preparation method of polycarbonate polyol shown in formula I comprises the following steps:
1) normal pressure ester exchange reaction: and (3) heating a reactant A containing a carbonate bond, a dihydric alcohol reactant B and a catalyst C to a reaction temperature by a program to perform an ester exchange reaction, and simultaneously rectifying to remove the generated small molecular alcohol D.
Wherein, the reactant A containing the carbonate bond is selected from one or more of dimethyl carbonate, ethylene carbonate or diphenyl carbonate, but is not limited to the above, and can also be other compounds containing the carbonate bond. Reactant B is a single kind of diol monomer with a structural formula of HO-R-OH, such as at least one selected from 1, 10-decanediol, 1, 9-nonanediol, 1, 8-octanediol, 1, 7-heptanediol, 1, 6-hexanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-butanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, diethylene glycol or ethylene glycol; preferably, for low melting point requirements, the diol is at least any one of 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-butanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, or diethylene glycol. Catalyst C is selected from titanates such as tetrabutyl titanate or isopropyl titanate, but is not limited thereto. The transesterification reaction generates a byproduct D, which is a small molecular alcohol, the category of the byproduct D depends on the selected reactant A, for example, the reactant A is dimethyl carbonate, the byproduct small molecular alcohol D is methanol, the reactant A is ethylene carbonate, the byproduct small molecular alcohol D is ethylene glycol, the reactant A is diphenyl carbonate, and the byproduct small molecular alcohol D is phenol.
Wherein the molecular weight of the target product determines the molar ratio of reactants a and B. The molecular weight of the low-melting-point and low-viscosity polycarbonate polyol (formula I) of the invention is 500-4000, correspondingly, the molar ratio of the reactant A to the reactant B is 0.83-1.31, preferably 1.08-1.28, and the amount of the catalyst C is 5-200ppm, preferably 10-100ppm of the theoretical yield of the target product polycarbonate polyol, wherein the theoretical yield of the target product polycarbonate polyol can be calculated according to the input amounts of the reactant A and the reactant B, and the like, which is well known to those skilled in the art. .
Wherein the initial temperature of the ester exchange reaction programmed temperature rise is 20-100 ℃, preferably 40-60 ℃; the heating rate is 0.5-5 ℃/min, preferably 1-3 ℃/min; the end temperature is 160-220 ℃, preferably 180-200 ℃; after the target temperature is reached, the reaction is continued while maintaining the temperature for a total reaction time of 4 to 12 hours, preferably 6 to 8 hours. The total reaction time includes the time for the temperature programming and the time for continuing the reaction after the target temperature is reached.
2) And (3) vacuum polycondensation reaction: and (2) continuously carrying out the reaction of the reactant in the step 1) under vacuum to high vacuum, and further rectifying to remove the generated small molecular alcohol to obtain the product polycarbonate polyol.
Wherein, the temperature of the reaction materials in the step 1) is continuously programmed to the reaction temperature of 200-; the programmed vacuum time is 0.1-2h, preferably 0.5-1h, and the pressure is linearly reduced in the pressure reduction process; the end pressure is from 0.01 to 10kPa, preferably from 0.1 to 5 kPa; the total reaction time is 6-100h, preferably 10-48h, namely the total reaction time from temperature programming, pressure reducing programming and polycondensation reaction, and the total reaction time is different according to the difference of the molecular weight of the product and is in the range of 6-100h, preferably in the range of 10-48 h. The higher the molecular weight of the product, the lower the end group concentration and the slower the reaction rate. When the molecular weight of the product is 500, the vacuum reaction time is about 6 hours to complete; when the molecular weight of the product is 4000, the vacuum reaction time needs about 100 hours to complete.
3) Catalyst deactivation: introducing steam into the product of the step 2) to hydrolyze the catalyst into titanium dioxide.
Introducing steam into the product obtained in the step 2) in a normal-pressure closed kettle, enabling the system pressure to reach 10-20kPa gauge pressure, and keeping the reaction at 110 ℃ for 10-120s to hydrolyze the catalyst C into titanium dioxide.
4) Hydroxyl dehydration reaction: further reacting the product of the step 3) at a specific reaction temperature under vacuum to dehydrate the terminal hydroxyl groups to form a terminal alkenyl group with a certain proportion.
Wherein, the product of the step 3) is heated to the range of 170-250 ℃, and is vacuumized to further react for 1-5h to form a certain proportion of terminal alkenyl and remove water vapor, and the vacuum degree is in the range of 0.01-10kPa, preferably in the range of 0.1-5 kPa.
Researches show that the proportion of terminal alkenyl in the product is increased along with the increase of the reaction temperature; and the reaction time can be correspondingly shortened along with the increase of the using amount of the catalyst. Therefore, the effects of controlling the reaction time and the ratio of the terminal alkenyl groups of the product can be achieved by controlling the reaction temperature and the dosage of the catalyst.
5) Double bond bonding reaction: the product of step 4) is reacted under an ultraviolet lamp at a specific reaction temperature.
Wherein, the product of the step 4) is cooled to 30-100 ℃ to ensure that the viscosity of the system is in the range of 1000-5000cP, the reaction is carried out under the ultraviolet irradiation (under the light wavelength of 300-400 nm), and the retention time is in the range of 10s-5 h. And introducing oxygen to quench residual free radicals after the reaction is finished, thereby preparing the polycarbonate polyol with the structure of the formula 1.
HO-(R-OCOO)n1-(R＝R-OCOO)n2-OH (formula I)
The polycarbonate polyol is characterized in that the used alcohol monomer is single alcohol of HO-R-OH.
Wherein R is C2-C10Linear or branched alkyl groups of (a); specifically, the dihydric alcohol HO-R-OH is selected from any one or more of 1, 10-decanediol, 1, 9-nonanediol, 1, 8-octanediol, 1, 7-heptanediol, 1, 6-hexanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-butanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, diethylene glycol or ethylene glycol; for low melting point requirements, the diol is preferably any one or more of 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-butanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, or diethylene glycol.
The molecular weight of the polycarbonate polyol is 500-4000, and the molecular weights of n1 and n2 are different according to the molecular weight of a monomer HO-R-OH and have different value ranges; specifically, n1 ranges from 1.6 to 44.8, n2 ranges from 0.01 to 22.4, n1+ n2 ranges from 1.6 to 44.8, and n2/(n1+ n2) ranges from 0.1 to 50%.
In particular, the structure of formula I-R ═ R-is obtained by the monomer HO-R-OH. The inventors of the present invention found out in a large number of experimentsPolycarbonate polyol with the structure of HO- (R-OCOO) n-OH in TiO2Under catalysis, controllable intramolecular dehydration of terminal hydroxyl to form CH can be realized by controlling reaction temperature2CH-terminal group. Further, it has been found that by controlling the reaction temperature so that the reactants are at a specific viscosity range, at a suitable residence time, CH is formed2The reaction between the CH-end groups under uv light can form the structure-R-without further chain extension to form higher molecular weight polymers.
The polycarbonate polyols of formula I are those in which a comonomer of the structure HO-R ═ R-OH is incorporated by forming a structure of-R ═ R-. Due to the structural difference between HO-R ═ R-OH and HO-R-OH, regular crystalline polymers are difficult to form in polycarbonate polyol, and the melting point and the viscosity of the polymers are reduced. The presence of double bonds in-R-results in a less regular structure of the polycarbonate polyol, and a lower melting point and viscosity of the polymer, compared to the-R-structure.
The process of the present invention is further illustrated, but not limited, by the following more specific examples.
Examples and comparative examples the main raw material sources (common commercial raw materials unless otherwise specified):
dimethyl carbonate: purchased from alatin, purity 99.9%;
1, 6-hexanediol: purchased from alatin, purity 99.9%;
1, 5-pentanediol: purchased from alatin, purity 98.5%;
1, 3-propanediol: purchased from alatin, purity 99.9%;
diethylene glycol, purchased from alatin, with a purity of 99.9%;
n-butyl titanate: purchased from alatin, purity 95%;
isopropyl titanate: purchased from aladine, 95% pure.
The analysis and detection method comprises the following steps:
model of nuclear magnetic instrument: bruker AVANCE III 400M nmr spectrometer;
viscosity test method: reference standard GB/T22235-;
the method for testing the ratio of terminal alkenyl comprises the following steps: the terminal alkenyl ratio was calculated by 1H-NMR using the peak area S1 representing the double bond at chemical shift 5.0ppm and the peak area S2 representing the terminal hydroxyl group at chemical shift 3.6ppm, which was S1/(S1+ S2) × 100%;
polycarbonate polyol hydroxyl value: tested with reference to standard GB/T12008.3-2009.
Example 1
1) Ester exchange reaction under normal pressure
1171g (13mol) of dimethyl carbonate, 1182g (10mol) of 1, 6-hexanediol and 0.17g of tetrabutyl titanate are added into a tank reactor with a rectifying tower at the temperature of 60 ℃, the temperature is increased to 180 ℃ according to the speed of 2 ℃/min under the protection of nitrogen, the temperature is kept for reaction for 3 hours, and methanol and dimethyl carbonate generated in the reaction process are removed through the rectifying tower.
2) Vacuum polycondensation reaction
The pressure of the normal pressure reactant is reduced to 1kPa within 1h, and simultaneously the temperature is increased to 220 ℃, and the pressure and the temperature are maintained to continue the reaction for 38 h.
3) Catalyst deactivation
Introducing steam into a normal-pressure closed kettle containing the product obtained in the step 2), enabling the system pressure to reach 10kPa gauge pressure, and keeping the reaction at 110 ℃ for 30 s.
4) Dehydration reaction of hydroxyl group
Heating the product obtained in the step 3) to 170 ℃, and reacting for 3 hours under the vacuum of 1kPa to obtain a product with the terminal alkenyl ratio of 1.5%.
5) Double bond bonding reaction
Cooling the product obtained in the step 4) to 60 ℃ (viscosity 4235cP), and carrying out ultraviolet irradiation at 300nm for 10 min. And finally introducing oxygen to quench residual free radicals.
1248g of the product polycarbonate polyol are obtained. The product had a hydroxyl number of 113.5mgKOH/g, was flowable at room temperature, and had a viscosity of 64587cP at 25 ℃.
Product structure analysis nuclear magnetic data were as follows: 1H NMR (400MHz, CDCl)3): 5.50(s, 4H), 4.13(s, 2H), 3.64(s, 2H), 1.61(s, 8H). The chemical shift of 5.50ppm peak indicates that the product contains double bondsThe peak with chemical shift of 4.13ppm indicates that the product contains a carbonate bond, the peak with chemical shift of 3.64ppm indicates that the product contains a terminal hydroxyl group, the peak with chemical shift of 1.61ppm indicates that the product contains an aliphatic carbon chain, and the result indicates that the product is the polycarbonate polyol containing a double-bond structure.
Example 2
1) Ester exchange reaction under normal pressure
1171g (13mol) of dimethyl carbonate, 761g (10mol) of 1, 3-propylene glycol and 0.008g of isopropyl titanate are added into a tank reactor with a rectifying tower at the temperature of 20 ℃, the temperature is increased to 160 ℃ according to the speed of 0.5 ℃/min under the protection of nitrogen, the reaction is kept at the temperature for continuous reaction for 7 hours, and methanol and dimethyl carbonate generated in the reaction process are removed through the rectifying tower.
2) Vacuum polycondensation
The pressure of the normal pressure reactant is reduced to 10kPa within 2h, and simultaneously the temperature is increased to 200 ℃, and the pressure and the temperature are maintained to continue the reaction for 96 h.
3) Catalyst deactivation
Introducing steam into a normal-pressure closed kettle containing the product obtained in the step 2), enabling the system pressure to reach a gauge pressure of 15kPa, and keeping the reaction at 110 ℃ for 120 s.
4) Dehydration reaction of hydroxyl group
Heating the product obtained in the step 3) to 250 ℃, and reacting for 5h under the vacuum of 0.01kPa to obtain the product with the terminal alkenyl proportion of 48.3%.
5) Double bond bonding reaction
Cooling the product obtained in the step 4) to 95 ℃ (viscosity of 2876cP), and carrying out ultraviolet irradiation at 300nm for 5 h. And finally introducing oxygen to quench residual free radicals.
1014g of the product polycarbonate polyol are obtained. The product had a hydroxyl number of 29.3mgKOH/g, was flowable at room temperature, and had a viscosity of 88926cP at 25 ℃.
Example 3
1) Ester exchange reaction under normal pressure
934g (10.4mol) of dimethyl carbonate, 1042g (10mol) of 1, 5-pentanediol and 0.24g of tetrabutyl titanate are added into a tank reactor with a rectifying tower at 100 ℃, the temperature is increased to 220 ℃ at the speed of 3 ℃/min under the protection of nitrogen, the reaction is kept at the temperature for continuous reaction for 7 hours, and methanol and dimethyl carbonate generated in the reaction process are removed through the rectifying tower.
2) Vacuum polycondensation
The pressure of the normal pressure reactant is reduced to 0.01kPa within 0.1h, and simultaneously the temperature is increased to 250 ℃, and the pressure and the temperature are maintained for continuous reaction for 6 h.
3) Catalyst deactivation
Introducing steam into a normal-pressure closed kettle containing the product obtained in the step 2), enabling the system pressure to reach a gauge pressure of 20kPa, and keeping the reaction at 110 ℃ for 10 s.
4) Dehydration reaction of hydroxyl group
Heating the product obtained in the step 3) to 190 ℃, and reacting for 1h under the vacuum of 10kPa to obtain the product with the terminal alkenyl proportion of 14.3%.
5) Double bond bonding reaction
Cooling the product of the step 4) to 35 ℃ (viscosity 3498cP), and irradiating by ultraviolet light at 300nm for 12 s. And finally introducing oxygen to quench residual free radicals.
1243g of the product polycarbonate polyol are obtained. The product had a hydroxyl value of 201.3mgKOH/g, was flowable at room temperature, and had a viscosity of 23752cP at 25 ℃.
Example 4
1) Ester exchange reaction under normal pressure
1122g (12.5mol) of dimethyl carbonate, 1061g (10mol) of diethylene glycol and 0.07g of tetrabutyl titanate are added into a tank reactor with a rectifying tower at the temperature of 45 ℃, the temperature is increased to 205 ℃ according to the speed of 5 ℃/min under the protection of nitrogen, the reaction is kept at the temperature for continuous reaction for 6 hours, and methanol and dimethyl carbonate generated in the reaction process are removed through the rectifying tower.
2) Vacuum polycondensation
The pressure was reduced to 4kPa over 0.5h for the atmospheric reactants while the temperature was increased to 235 ℃ and the reaction was continued for 57h while maintaining the pressure and temperature.
3) Catalyst deactivation
Introducing steam into a normal-pressure closed kettle containing the product obtained in the step 2), enabling the system pressure to reach 18kPa gauge pressure, and keeping the reaction at 110 ℃ for 95 s.
4) Dehydration reaction of hydroxyl group
Heating the product obtained in the step 3) to 240 ℃, and reacting for 3 hours under the vacuum of 5kPa, wherein the terminal alkenyl proportion of the product is measured to be 38.9%.
5) Double bond bonding reaction
Cooling the product of the step 4) to 75 ℃ (viscosity of 1257cP), and carrying out ultraviolet irradiation at 300nm for 2 h. And finally introducing oxygen to quench residual free radicals.
1304g of the product polycarbonate polyol are obtained. The product had a hydroxyl value of 57.3mgKOH/g, was flowable at room temperature, and had a viscosity of 37256cP at 25 ℃.
Example 5
1) Ester exchange reaction under normal pressure
1070g (11.9mol) of dimethyl carbonate, 591g (5mol) of 1, 6-hexanediol, 521g (5mol) of 1, 5-pentanediol and 0.10g of isopropyl titanate are added into a tank reactor with a rectifying tower at 80 ℃, the temperature is increased to 200 ℃ at the speed of 1 ℃/min under the protection of nitrogen, the reaction is kept at the temperature for continuous reaction for 8 hours, and methanol and dimethyl carbonate generated in the reaction process are removed through the rectifying tower.
2) Vacuum polycondensation
The pressure was reduced to 0.2kPa over 1.5h for the atmospheric reactants while the temperature was increased to 240 ℃ and the reaction was continued for 20h while maintaining this pressure and temperature.
3) Catalyst deactivation
Introducing steam into a normal-pressure closed kettle containing the product obtained in the step 2), enabling the system pressure to reach 12kPa gauge pressure, and keeping the reaction at 110 ℃ for 50 s.
4) Dehydration reaction of hydroxyl group
Heating the product obtained in the step 3) to 180 ℃, and reacting for 1.5 hours under the vacuum of 8kPa, wherein the terminal alkenyl proportion of the product is 9.8 percent.
5) Double bond bonding reaction
Cooling the product of step 4) to 50 ℃ (viscosity 1872cP) and ultraviolet irradiation at 300nm for 30 s. And finally introducing oxygen to quench residual free radicals.
1348g of the product polycarbonate polyol are obtained. The product had a hydroxyl number of 74.2mgKOH/g, was flowable at room temperature, and had a viscosity of 19783cP at 25 ℃.
Comparative example 1
1) Ester exchange reaction under normal pressure
1171g (13mol) of dimethyl carbonate, 1182g (10mol) of 1, 6-hexanediol and 0.17g of n-butyl titanate are added into a tank reactor with a rectifying tower at the temperature of 60 ℃, the temperature is increased to 180 ℃ according to the speed of 2 ℃/min under the protection of nitrogen, the temperature is kept for reaction for 2 hours, and methanol and dimethyl carbonate generated in the reaction process are removed through the rectifying tower.
2) Vacuum polycondensation
The pressure of the normal pressure reactant is reduced to 1kPa within 1h, simultaneously the temperature is increased to 220 ℃, and the pressure and the temperature are maintained for continuous reaction for 38h, thereby obtaining 1148g of the product polycarbonate polyol. The product had a hydroxyl value of 109.4mgKOH/g and was solid and non-flowable at room temperature.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. 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 (15)

1. A polycarbonate polyol, which is prepared from a diol monomer having the structural formula HO-R-OH, and has the following structure (formula I):
HO-(R-OCOO)n1-(R＝R-OCOO)n2-OH (formula I)
Wherein R is C2-C10Linear or branched alkyl of (a); the dihydric alcohol HO-R-OH is selected from at least any one of 1, 10-decanediol, 1, 9-nonanediol, 1, 8-octanediol, 1, 7-heptanediol, 1, 6-hexanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-butanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, diethylene glycol or ethylene glycol;
the molecular weight of the polycarbonate polyol with the structure (formula I) is 500-4000, correspondingly, n1 ranges from 1.6 to 44.8, n2 ranges from 0.01 to 22.4, and n1+ n2 ranges from 1.6 to 44.8, and n2/(n1+ n2) ranges from 0.1% to 50%.
2. The polycarbonate polyol according to claim 1, wherein the diol is at least one of 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-butanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, or diethylene glycol.
3. A method for producing the polycarbonate polyol of claim 1 or 2, comprising the steps of:
1) normal pressure ester exchange reaction: heating a reactant A containing a carbonate bond, a glycol reactant B and a catalyst C to a reaction temperature by a program to perform an ester exchange reaction, and simultaneously rectifying to remove a generated micromolecular alcohol D;
2) and (3) vacuum polycondensation reaction: continuing the reaction product obtained in the step 1) to perform reaction under vacuum to high vacuum, and simultaneously further rectifying to remove the generated small molecular alcohol to obtain a product polycarbonate polyol;
3) catalyst deactivation: introducing steam into the product obtained in the step 2) to hydrolyze the catalyst into titanium dioxide;
4) hydroxyl dehydration reaction: heating the product obtained in the step 3) to the temperature of 170-250 ℃, vacuumizing for 1-5h to form a terminal alkenyl group with a certain proportion, and removing water vapor;
5) double bond bonding reaction: cooling the product obtained in the step 4) to 30-100 ℃ to enable the viscosity of the system to reach 1000-5000cP, reacting under the irradiation of ultraviolet light for 10s-5h, and introducing oxygen to quench residual free radicals after the reaction is finished to obtain the polycarbonate polyol with the structure of the formula 1.
4. The method for preparing polycarbonate polyol according to claim 3, wherein in step 1), the reactant A is selected from one or more of dimethyl carbonate, ethylene carbonate or diphenyl carbonate; the reactant B is at least one selected from 1, 10-decanediol, 1, 9-nonanediol, 1, 8-octanediol, 1, 7-heptanediol, 1, 6-hexanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-butanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, diethylene glycol or ethylene glycol; the catalyst C is selected from titanate esters.
5. The method for producing a polycarbonate polyol as claimed in claim 4, wherein in step 1), the reactant B is at least one selected from the group consisting of 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-butanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol and diethylene glycol; the catalyst C is tetrabutyl titanate or isopropyl titanate.
6. The process for producing polycarbonate polyol according to any one of claims 3 to 5, wherein the molar ratio of the reactant A to the reactant B is 0.83 to 1.31, and the amount of the catalyst C is 5 to 200ppm based on the theoretical yield of the polycarbonate polyol.
7. The method for producing a polycarbonate polyol according to claim 6, wherein the molar ratio of the reactant A to the reactant B is 1.08 to 1.28, and the amount of the catalyst C is 10 to 100ppm based on the theoretical yield of the polycarbonate polyol.
8. The method for producing a polycarbonate polyol according to claim 4, wherein the starting temperature in step 1) is 20 to 100 ℃; the heating rate is 0.5-5 ℃/min; the end temperature is 160-220 ℃; the total reaction time is 4-12 h.
9. The method for producing a polycarbonate polyol according to claim 8, wherein in step 1), the initial temperature is 40 to 60 ℃; the heating rate is 1-3 ℃/min; the end temperature is 180-200 ℃; the total reaction time is 6-8 h.
10. The method for producing a polycarbonate polyol as claimed in claim 3, wherein the reaction temperature in step 2) is 200-250 ℃; programmed depressurization time is 0.1-2 h; the final pressure is 0.01-10 kPa; the total reaction time is 6-100 h.
11. The method for preparing polycarbonate polyol as claimed in claim 10, wherein the reaction temperature in step 2) is 220-240 ℃; programmed depressurization time is 0.5-1 h; the final pressure is 0.1-5 kPa; the total reaction time is 10-48 h.
12. The method for producing a polycarbonate polyol as claimed in claim 3, wherein in the step 3), steam is introduced into the product obtained in the step 2) in a closed vessel having an atmospheric pressure, so that the system pressure is 10 to 20kPa gauge, and the reaction is maintained at 110 ℃ for 10 to 120 seconds.
13. The method for producing a polycarbonate polyol according to claim 3, wherein the degree of vacuum in step 4) is 0.01 to 10 kPa.
14. The method for producing a polycarbonate polyol according to claim 3, wherein the degree of vacuum in step 4) is 0.1 to 5 kPa.
15. Use of the polycarbonate polyol according to claim 1 or 2 or prepared by the process according to any one of claims 3 to 14 in polyurethane elastomers, adhesives, coatings or foams.
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