CN110951064B - Phthalocyanine metal salt modified polyurethane elastomer and preparation method thereof - Google Patents
Phthalocyanine metal salt modified polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN110951064B CN110951064B CN201911263319.2A CN201911263319A CN110951064B CN 110951064 B CN110951064 B CN 110951064B CN 201911263319 A CN201911263319 A CN 201911263319A CN 110951064 B CN110951064 B CN 110951064B
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- C08G18/40—High-molecular-weight compounds
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G65/32—Polymers modified by chemical after-treatment
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- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
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- C08G65/32—Polymers modified by chemical after-treatment
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Abstract
The application relates to a method for preparing phthalocyanine metal salt modified polyurethane elastomer, which comprises the following steps: (1) under the protection of inert atmosphere and at a first reaction temperature which is enough to melt the raw materials, reacting phthalocyanine metal salt modified polyol with isocyanate for a first preset time period to obtain a polyurethane prepolymer; (2) mixing the polyurethane prepolymer and the chain extender at a second reaction temperature for a second predetermined time period to obtain a reaction mixture; (3) and curing the reaction mixture at a third reaction temperature for a third predetermined period of time to obtain the phthalocyanine metal salt modified polyurethane elastomer. The present application also relates to phthalocyanine metal salt-modified polyurethane elastomers prepared using the method as described above. The phthalocyanine metal salt modified polyurethane elastomer has higher heat resistance and equivalent mechanical strength, and can be applied to the field needing heat resistance.
Description
Technical Field
The application relates to the technical field of polyols, in particular to a phthalocyanine metal salt modified polyurethane elastomer and a preparation method thereof.
Background
The polyols may include small molecule polyols, polyether polyols, polyester polyols, and the like. The polyester polyols may include conventional polyester polyols, polycaprolactone polyols, and polycarbonate diols, which contain ester groups (COO) or carbonate groups (OCOO). The conventional polyester polyol is generally a polyester polyol obtained by polycondensation of a dicarboxylic acid, a diol and the like. Conventional polyester polyols can be classified into aliphatic polyester polyols and aromatic polyester polyols according to whether the polyester polyol structure contains a benzene ring. Common aliphatic polyester polyols include adipic polyester diols and common aromatic polyester polyols include polyphthalate polyester polyols. Polyester polyols are widely used in the preparation of polyurethane elastomers, polyurethane foams, polyurethane adhesives and polyurethane coatings.
Polyurethane elastomer is an important polyurethane material and a special synthetic rubber variety, and the modulus of the polyurethane elastomer is between that of common rubber and plastic. The polyurethane elastomer has excellent comprehensive properties such as good wear resistance, good low temperature resistance, high strength and high elongation, large load supporting capacity, excellent oil resistance and the like, and has good adhesion, strong shock absorption capability and larger adjustable range of hardness. However, the polyurethane elastomer has poor heat resistance, and its physical dimensions and mechanical properties change at high use temperatures. When the existing polyester polyol is used for preparing the polyurethane elastomer, the long-term service temperature of the obtained polyurethane elastomer cannot exceed 120 ℃, and the short-term service temperature of the obtained polyurethane elastomer cannot exceed 150 ℃, so that the application of the polyurethane elastomer in a high-temperature environment is greatly limited.
Various methods have been proposed to improve the heat resistance of polyurethane elastomers, and the most common method is to increase the ratio of polar groups to rigid groups in the molecular structure of polyurethane elastomers. For example, chinese patent application publication No. CN107266658A discloses a method for preparing a polyurethane elastomer with ferrocene in the main chain, which comprises mixing oligomer diol with diisocyanate to obtain an isocyanate-terminated polyurethane prepolymer; and adding ferrocene-containing diol to obtain the polyurethane elastomer with the main chain containing ferrocene. The initial thermal decomposition temperature of the polyurethane elastomer provided by the patent document can reach 342 ℃ at most, the tensile strength and the elongation at break at room temperature respectively reach 42.6MPa and 1018 percent, and the polyurethane elastomer can still be stretched by 400 percent at 100 ℃. The method for improving the heat resistance of the polyurethane elastomer can also comprise the steps of modifying the polyurethane prepolymer by using an inorganic material, blending other high polymer materials such as long-chain nylon and the like with the thermoplastic polyurethane elastomer, and the like.
The phthalocyanine metal salt is a macrocyclic aromatic compound with 18 pi electrons, and has very good heat resistance and light resistance stability. However, in the prior art of polyurethane elastomer production, phthalocyanine metal salts are generally used only as pigments.
For this reason, there is a continuing need in the art to develop a highly heat-resistant polyurethane elastomer and a method for preparing the same.
Disclosure of Invention
The present application aims to provide a method for preparing a phthalocyanine metal salt-modified polyurethane elastomer having high heat resistance by using a phthalocyanine metal salt-modified polyol.
It is also an object of the present invention to provide a high heat-resistant phthalocyanine metal salt-modified polyurethane elastomer prepared by the method as described above.
The phthalocyanine metal salt modified polyols disclosed herein are prepared by: firstly, 4-nitrophthalonitrile reacts with polyhydric alcohol to obtain phthalonitrile terminated polyhydric alcohol, and then the phthalonitrile terminated polyhydric alcohol, phthalonitrile and metal salt react to obtain phthalocyanine metal salt modified polyhydric alcohol. The preparation method of the phthalocyanine metal salt modified polyol has simple process and can be suitable for various types of polyols. The obtained phthalocyanine metal salt modified polyol contains 18 pi electronic structures, and can be used as a chain extender or a polyol component to prepare a high-heat-resistant polyurethane elastomer.
In order to solve the above technical problems, the present application provides the following technical solutions.
In a first aspect, the present application provides a method for preparing a phthalocyanine metal salt-modified polyurethane elastomer, characterized in that the method comprises the steps of:
(1) under the protection of inert atmosphere and at a first reaction temperature which is enough to melt the raw materials, reacting phthalocyanine metal salt modified polyol with isocyanate for a first preset time period to obtain a polyurethane prepolymer;
(2) mixing the polyurethane prepolymer and the chain extender at a second reaction temperature for a second predetermined time period to obtain a reaction mixture;
(3) curing the reaction mixture at a third reaction temperature for a third predetermined time period to obtain the phthalocyanine metal salt modified polyurethane elastomer;
wherein the phthalocyanine metal salt-modified polyol has a structure represented by the following general formula (1):
wherein the phthalocyanine metal salt modified polyol is obtained by reacting 4-nitrophthalonitrile, phthalonitrile, metal salt and initial polyol, and the structural general formula of the metal salt is MX2Wherein M represents a divalent metal cation, X represents a monovalent non-metal anion, and the structural general formula of the starting polyol is HO-R1-OH，R1Represents a carbon chain structure between two terminal hydroxyl groups in the starting polyol with the carbon number more than 2.
In one embodiment of the first aspect, the isocyanate is one or more of the following: diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethylm-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyldiphenylmethane diisocyanate, lysine diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, 2-methylpentane diisocyanate, 2, 4-dimethyloctane-1, 8-diisocyanate, 3 ' -dimethoxybiphenyl-4, 4 ' -diisocyanate, 4 ' -diphenyl ether diisocyanate, 4-methyldiphenylmethane-3, 4-diisocyanate, 2,4 ' -diphenyl sulfide diisocyanate, diethylbenzene diisocyanate and 4,4 ' -diphenylethane diisocyanate.
In one embodiment of the first aspect, the chain extender is the phthalocyanine metal salt modified polyol, an amine chain extender, a carboxylic acid chain extender, or an alcohol chain extender.
In one embodiment of the first aspect, the chain extender is selected from one or more of the following: ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, methylpropanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butylethylpropylene glycol, diethylpentanediol, 3-methyl-1, 5-pentanediol, trimethylpentanediol, ethylhexanediol, dodecanediol, 1, 4-dimethylolcyclohexane, cyclohexanediol, dodecanediol, trimethylolpropane, trimethylolethane, glycerol, 1,2, 6-hexanetriol, pentaerythritol, xylitol, sorbitol, mannitol; triethanolamine, diethanolamine, triisopropanolamine, methyldiethanolamine, dihydroxyisopropylaniline, dihydroxyisopropyl-p-toluidine, dihydroxyethyl aniline, dihydroxyethyl-p-aniline, dihydroxyethyl-m-phenylenediamine; dihydroxypropionic acid, dihydroxybutyric acid, adipic acid, sebacic acid, terephthalic acid, dimethyl terephthalate, isophthalic acid, phthalic anhydride, succinic acid, glutaric acid, azelaic acid, dodecanedioic acid, 1, 4-cyclohexanedicarboxylic acid, methyl 1, 4-cyclohexanedicarboxylate, and maleic anhydride.
In one embodiment of the first aspect, the first reaction temperature is from 60 ℃ to 90 ℃;
the second reaction temperature is 80-100 ℃;
the third reaction temperature is 100-120 ℃.
In one embodiment of the first aspect, the first predetermined period of time, the second predetermined period of time and the third predetermined period of time are each independently 2 hours to 48 hours, preferably 3 hours to 24 hours.
In one embodiment of the first aspect, the metal salt is selected fromOne or more of the following: ZnCl2、 ZnBr2、Zn(NO3)2、CuCl2、CuBr2、Cu(NO3)2、CoCl2、CoBr2、Co(NO3)2。
In one embodiment of the first aspect, the starting polyol is a small molecule polyol having 2-12 carbon atoms, a polyether polyol having a number average molecular weight of 200-.
In one embodiment of the first aspect, the starting polyol is selected from one or more of the following: ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, methylpropanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butylethylpropylene glycol, diethylpentanediol, 3-methyl-1, 5-pentanediol, trimethylpentanediol, ethylhexanediol, dodecanediol, 1, 4-dimethylolcyclohexane, cyclohexanediol, dodecanediol, trimethylolpropane, trimethylolethane, glycerol, 1,2, 6-hexanetriol, pentaerythritol, xylitol, sorbitol, mannitol, polyoxypropylene polyol, polyoxyethylene polyol, polytrimethylene ether glycol, aromatic polyether glycol, polytetrahydrofuran ether polyol, polyhexamethylene glycol polyol, pentaerythritol, xylitol, sorbitol, mannitol, polyoxypropylene polyol, polyoxyethylene polyol, polytrimethylene ether glycol, polytetramethylene ether glycol, polytetrahydrofuran ether polyol, and polyhexamethylene glycol, Polycaprolactone polyols, or polycarbonate polyols.
In a second aspect, the present application provides a phthalocyanine metal salt-modified polyurethane elastomer prepared by the method as described in the first aspect.
Compared with the prior art, the invention has the advantages that the use temperature of the phthalocyanine modified polyurethane elastomer is obviously improved compared with that of an unmodified product, and the phthalocyanine modified polyurethane elastomer has equivalent mechanical strength, so that the phthalocyanine modified polyurethane elastomer can be applied to the field needing high heat resistance.
Drawings
FIG. 1 is an FTIR plot of a zinc phthalocyanine-modified polycaprolactone polyol according to example 1.
FIG. 2 is an FTIR plot of butanediol grafted zinc phthalocyanine according to example 2.
FIG. 3 is a thermogravimetric analysis of polyurethane elastomers according to examples 5, 6 and comparative example 1.
FIG. 4 is a thermogravimetric analysis chart of the polyurethane elastomers according to examples 7, 8 and comparative example 2.
FIG. 5 is a differential scanning calorimetry plot of polyurethane elastomers according to examples 5, 6 and comparative example 1.
FIG. 6 is a differential scanning calorimetry plot of polyurethane elastomers according to examples 7, 8 and comparative example 2.
FIG. 7 is a dynamic mechanical thermogram of polyurethane elastomers according to examples 5, 6 and comparative example 1.
FIG. 8 is a dynamic mechanical thermogram of polyurethane elastomers according to examples 7, 8 and comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
When a conventional polyol is used to prepare a polyurethane elastomer, the heat resistance of the prepared polyurethane elastomer is not good enough, and it is difficult to use the polyurethane elastomer in a high-temperature environment at a temperature exceeding 150 ℃. The purpose of the present application is to provide a phthalocyanine metal salt modified polyol, wherein compared with the existing polyurethane elastomer, the high-temperature storage modulus retention rate and the storage modulus inflection point of the polyurethane elastomer prepared by using the phthalocyanine metal salt modified polyol described herein are significantly improved, which indicates that the obtained polyurethane elastomer has excellent heat resistance.
In a first aspect, the present application provides a method for preparing a phthalocyanine metal salt-modified polyurethane elastomer, characterized in that the method comprises the steps of:
(1) under the protection of inert atmosphere and at a first reaction temperature which is enough to melt the raw materials, reacting phthalocyanine metal salt modified polyol with isocyanate for a first preset time period to obtain a polyurethane prepolymer;
(2) mixing the polyurethane prepolymer and the chain extender at a second reaction temperature for a second predetermined time period to obtain a reaction mixture;
(3) curing the reaction mixture at a third reaction temperature for a third predetermined time period to obtain the phthalocyanine metal salt modified polyurethane elastomer;
wherein the phthalocyanine metal salt-modified polyol has a structure represented by the following general formula (1):
wherein the phthalocyanine metal salt modified polyol is obtained by reacting 4-nitrophthalonitrile, phthalonitrile, metal salt and initial polyol, and the structural general formula of the metal salt is MX2Wherein M represents a divalent metal cation, X represents a monovalent non-metal anion, and the structural general formula of the starting polyol is HO-R1-OH，R1Represents a carbon chain structure between two terminal hydroxyl groups in the starting polyol with the carbon number more than 2.
In one embodiment, the process for preparing a phthalocyanine metal salt modified polyol described herein comprises reacting K with a polyol2CO3The 4-nitrophthalonitrile and the initial polyol are uniformly mixed, and then heated to 60 ℃ under the protection of nitrogen for reaction for 24 hours to obtain the phthalonitrile terminated polyol. After the reaction is finished, phthalonitrile and ZnCl are added into a reaction system containing phthalonitrile-terminated polyol2Heating the obtained mixture to 150 ℃ under the protection of nitrogen, continuing to react for 8 hours, cooling, extracting and purifying to obtain the zinc phthalocyanine modified polyol.
In one embodiment, the process synthetic route of the phthalocyanine metal salt modified polyol and the phthalocyanine metal salt modified polyurethane elastomer related to the present application is as follows:
in the above scheme, OCN-R2-NCO stands for isocyanate. HO-R3-OH represents a chain extender. m represents the degree of polymerization and can be a positive integer greater than 2. In one embodiment, the isocyanate is selected from diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate or 1, 6-hexamethylene diisocyanate. In one embodiment, the chain extender is selected from 1, 4-butanediol, 1, 6-hexanediol, hydroquinone bis hydroxyethyl ether or phthalocyanine metal salt modified polyols.
In another embodiment, the isocyanate is one or more of the following: diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethylm-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyldiphenylmethane diisocyanate, lysine diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, 2-methylpentane diisocyanate, 2, 4-dimethyloctane-1, 8-diisocyanate, 3 ' -dimethoxybiphenyl-4, 4 ' -diisocyanate, 4 ' -diphenyl ether diisocyanate, 4-methyldiphenylmethane-3, 4-diisocyanate, 2,4 ' -diphenyl sulfide diisocyanate, diethylbenzene diisocyanate and 4,4 ' -diphenylethane diisocyanate.
In another embodiment, the chain extender is the phthalocyanine metal salt modified polyol, an amine chain extender, a carboxylic acid chain extender, or an alcohol chain extender.
In another embodiment, the chain extender is selected from one or more of the following: ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, methylpropanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butylethylpropylene glycol, diethylpentanediol, 3-methyl-1, 5-pentanediol, trimethylpentanediol, ethylhexanediol, dodecanediol, 1, 4-dimethylolcyclohexane, cyclohexanediol, dodecanediol, trimethylolpropane, trimethylolethane, glycerol, 1,2, 6-hexanetriol, pentaerythritol, xylitol, sorbitol, mannitol; triethanolamine, diethanolamine, triisopropanolamine, methyldiethanolamine, dihydroxyisopropylaniline, dihydroxyisopropyl-p-toluidine, dihydroxyethyl aniline, dihydroxyethyl-p-aniline, dihydroxyethyl-m-phenylenediamine; dihydroxypropionic acid, dihydroxybutyric acid, adipic acid, sebacic acid, terephthalic acid, dimethyl terephthalate, isophthalic acid, phthalic anhydride, succinic acid, glutaric acid, azelaic acid, dodecanedioic acid, 1, 4-cyclohexanedicarboxylic acid, methyl 1, 4-cyclohexanedicarboxylate, and maleic anhydride.
In one embodiment, the first reaction temperature is 60 ℃ to 90 ℃, preferably 60 ℃, 62 ℃, 65 ℃, 67 ℃, 70 ℃, 75 ℃, 77 ℃, 80 ℃, 90 ℃ or a range or sub-range between any two values therein.
In one embodiment, the second reaction temperature is 80 ℃ to 100 ℃, preferably 80 ℃, 85 ℃, 90 ℃, 97 ℃, 100 ℃ or a range or sub-range between any two values therein.
In one embodiment, the third reaction temperature is from 100 ℃ to 120 ℃, preferably 100 ℃, 108 ℃, 110 ℃, 115 ℃, 120 ℃ or a range or sub-range between any two values therein.
In one embodiment, the first, second and third predetermined time periods are each independently from 2 hours to 48 hours, preferably from 3 hours to 24 hours. The first, second, and third predetermined time periods are each independently 3 hours, 12 hours, 18 hours, 24 hours, 32 hours, or 48 hours.
4-Nitrophthalonitrile and phthalonitrile
The inventors of the present application have found through repeated experiments that only when 4-nitrophthalonitrile and phthalonitrile are used as raw materials, they can react with the starting polyol and finally introduce a phthalocyanine structure into the polyol.
In one embodiment, the mass ratio of the starting polyol and 4-nitrophthalonitrile is from 1:1 to 10:1, preferably from 1:2 to 1: 4.
In one embodiment, the mass ratio of the phthalonitrile and the phthalonitrile-capped polyol is 1: 1.
Metal salt
In the present application, the metal salt is mainly used as a cation introduced into the phthalocyanine metal salt. The metal salt used is not particularly limited in this application as long as it can react with the phthalonitrile-terminated polyol. The metal salt has a general structural formula of MX2Wherein M represents a divalent metal cation and X represents a monovalent non-metal anion. In one embodiment, the metal salt may be selected from one or more of the following: ZnCl2、ZnBr2、Zn(NO3) 2、CuCl2、CuBr2、Cu(NO3)2、CoCl2、CoBr2And Co (NO)3)2。
Starting polyol
In the present application, the starting polyol is the main raw material for preparing the phthalocyanine metal salt-modified polyol. The starting polyols described herein have the general structural formula HO-R1-OH，R1Represents a carbon chain structure between two terminal hydroxyl groups in the starting polyol with the carbon number more than 2.
The starter polyol described herein may include a small molecule polyol, a polyether polyol, or a polyester polyol. In one embodiment, the starting polyol is a small molecule polyol having 2-12 carbon atoms, a polyether polyol having a number average molecular weight of 200-.
In one embodiment, the starting polyol is selected from one or more of the following: ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, methylpropanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butylethylpropylene glycol, diethylpentanediol, 3-methyl-1, 5-pentanediol, trimethylpentanediol, ethylhexanediol, dodecanediol, 1, 4-dimethylolcyclohexane, cyclohexanediol, dodecanediol, trimethylolpropane, trimethylolethane, glycerol, 1,2, 6-hexanetriol, pentaerythritol, xylitol, sorbitol, mannitol, polyoxypropylene polyol, polyoxyethylene polyol, polytrimethylene ether glycol, aromatic polyether glycol, polytetrahydrofuran ether polyol, polyhexamethylene glycol polyol, pentaerythritol, xylitol, sorbitol, mannitol, polyoxypropylene polyol, polyoxyethylene polyol, polytrimethylene ether glycol, polytetramethylene ether glycol, polytetrahydrofuran ether polyol, and polyhexamethylene glycol, Polycaprolactone polyols, or polycarbonate polyols.
Basic catalyst
The basic catalyst used is not particularly limited in this application. In one embodiment, the first basic catalyst and the second basic catalyst are each independently selected from the group consisting of: sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium carbonate, potassium carbonate, and 1, 8-diazabicycloundecen-7-ene.
In one embodiment, the ratio of the amount of the first basic catalyst to the amount of the starting polyol material is 2: 1.
In a second aspect, the present application provides a phthalocyanine metal salt-modified polyurethane elastomer prepared by the method as described in the first aspect.
Examples
The technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application. The reagents and raw materials used are commercially available unless otherwise specified. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The starting materials used in the following examples correspond to the following:
4-nitrophthalonitrile: reagent grade (national medicine reagent);
PCL 205U: polycaprolactone diol with molecular weight of 530, hydroxyl value of 211.7gKOH/g (xylonite);
PCL 220N: polycaprolactone diol with molecular weight of 2000, hydroxyl value of 55.8gKOH/g (xylonite);
PTMG 650: polytetrahydrofuran ether glycol having a molecular weight of 650, a hydroxyl number of 176.8g KOH/g (BASF);
PTMG 2000: polytetrahydrofuran ether glycol of molecular weight 2000, hydroxyl number 57.1g KOH/g (BASF);
K2CO3: potassium carbonate (national reagent);
phthalonitrile, reagent grade (national reagent);
ZnCl2: zinc chloride, reagent grade (national medicine reagent);
CuCl2: copper chloride, reagent grade (national reagent);
DBU: 1, 8-diazabicycloundec-7-ene, reagent grade (national reagent);
MDI: 4, 4' -diphenylmethane diisocyanate (petitsein);
BDO: 1, 4-butanediol (national reagent);
solvents DMF (N, N-dimethylformamide), ethyl acetate, ethanol and cyclohexane are all reagent grade (Chinese medicine reagent).
Example 1:
will K2CO3(82.8g, 0.6mol), 4-nitrophthalonitrile (51.9g, 0.3mol) and PCL205U (633.6g, 1.2mol) were added to a reaction flask, heated to 60 ℃ under nitrogen protection, and the reaction was stirred for 24 hours. After the reaction was complete, phthalonitrile (38.4g, 0.3mol) and ZnCl were added2(40.8g, 0.3mol), DBU (300ml) and DMF (800ml) and the mixture was heated to 150 ℃ under nitrogen for 8 hours. After the reaction is finished, cooling to room temperature, firstly adding water for precipitation, and washing the filtered solid to be neutral by water. The solid was redissolved with ethyl acetate, the insoluble material was filtered off, then ethanol was added for precipitation, and the filtered solid was dried in a vacuum oven to obtain zinc phthalocyanine-modified polycaprolactone polyol (342.0g), with a hydroxyl value of 58.2 mgKOH/g.
Example 2:
will K2CO3(82.8g, 0.6mol), 4-Nitrophthalonitrile (51.9g, 0.3mol) and BDO (108.1g, 1.2mol) were dissolved in DMF (800ml), heated to 60 ℃ under nitrogen protection, stirred and reacted for 24 hours, after the reaction was complete, phthalonitrile (38.4g, 0.3mol), ZnCl were added2(40.8g, 0.3mol), DBU (300ml) and the mixture was heated to 150 ℃ under nitrogen for 8 hours. After the reaction is finished, cooling to room temperature, firstly adding water for precipitation, and washing the filtered solid to be neutral by water. The solid was redissolved with DMF and then precipitated by addition of ethanol, and the filtered solid was dried in a vacuum oven to give butanediol-grafted zinc phthalocyanine (153.4g) having a hydroxyl value of 152.1 mgKOH/g.
Example 3:
will K2CO3(82.8g, 0.6mol), 4-nitrophthalonitrile (51.9g, 0.3mol) and PTMG650(761.2g, 1.2mol) were charged into a reaction flask, heated to 60 ℃ under nitrogen and reacted for 24 hours with stirring. After the reaction was complete, phthalonitrile (38.4g, 0.3mol) and ZnCl were added2(40.8g, 0.3mol), DBU (300ml) and DMF (800ml) and the mixture was heated to 150 ℃ under nitrogen for 8 hours. After the reaction is finished, cooling to room temperature, firstly adding water for precipitation, and washing the filtered solid to be neutral by water. The solid was redissolved with ethyl acetate, insoluble material was filtered off, cyclohexane was then added for precipitation, and the filtered solid was dried in a vacuum oven to give zinc phthalocyanine-modified polytetrahydrofuran ether polyol (336.0g) having a hydroxyl value of 57.7 mgKOH/g.
Example 4:
will K2CO3(82.8g, 0.6mol), 4-nitrophthalonitrile (51.9g, 0.3mol) and PTMG650(761.2g, 1.2mol) were charged into a reaction flask, heated to 60 ℃ under nitrogen and reacted for 24 hours with stirring. After the reaction was complete, phthalonitrile (38.4g, 0.3mol) and CuCl were added2(40.4g, 0.3mol), DBU (300ml) and DMF (800ml) and the mixture was heated to 150 ℃ under nitrogen for 8 hours. After the reaction is finished, cooling to room temperature, firstly adding water for precipitation, and washing the filtered solid to be neutral by water. Dissolving the solid with ethyl acetate again, filtering off insoluble substances, adding cyclohexane for precipitation, and filtering to obtain solidAnd drying in a vacuum oven to obtain copper phthalocyanine modified polytetrahydrofuran ether polyol (334.8g), wherein the measured hydroxyl value is 56.2 mgKOH/g.
Example 5:
the zinc phthalocyanine-modified polycaprolactone polyol obtained in example 1 was melted at 80 ℃ for use. MDI (72.0g) is put into a dry reaction bottle, heated to 60 ℃ under the protection of nitrogen, added with zinc phthalocyanine modified polycaprolactone polyol (154.2g) for three times after being completely melted, heated to 80 ℃ and reacted for 3 hours at constant temperature to obtain the polyurethane prepolymer. NCO content was found to be 7.6%.
And (3) uniformly mixing the prepared polyurethane prepolymer (100g) and BDO (7.7g) at 90 ℃, pouring the mixture into a mold at 110 ℃ after vacuum defoaming, and demolding after vulcanizing for 24 hours to obtain the phthalocyanine modified polycaprolactone type polyurethane elastomer.
Example 6:
PCL220N was melted at 80 ℃ for use, and the butanediol-grafted zinc phthalocyanine obtained in example 2 was melted at 120 ℃ for use. MDI (64.2g) is put into a dry reaction bottle, heated to 60 ℃ under the protection of nitrogen, added with PCL220N (160.8g) in three times after being completely melted, heated to 80 ℃ and reacted for 3 hours at constant temperature to obtain the polyurethane prepolymer. NCO content was found to be 6.5%.
The polyurethane prepolymer (100g) prepared above and the butanediol-grafted zinc phthalocyanine (45.5g) obtained in example 2 were mixed uniformly at 90 ℃, vacuum defoamed, poured into a mold at 110 ℃, vulcanized for 24 hours, and then released from the mold, to obtain the polyurethane elastomer according to example 6.
Example 7:
the zinc phthalocyanine-modified polytetrahydrofuran ether polyol obtained in example 3 was melted at 80 ℃ for use. MDI (72.0g) is put into a drying reaction bottle, heated to 60 ℃ under the protection of nitrogen, added with zinc phthalocyanine modified polytetrahydrofuran ether polyol (155.6g) for three times after being completely melted, heated to 80 ℃ and reacted for 3 hours at constant temperature to obtain the polyurethane prepolymer. NCO content was found to be 7.6%.
And (3) uniformly mixing the prepared polyurethane prepolymer (100g) and BDO (7.7g) at 90 ℃, pouring the mixture into a mold at 110 ℃ after vacuum defoaming, and demolding after vulcanizing for 24 hours to obtain the zinc phthalocyanine modified polytetrahydrofuran type polyurethane elastomer.
Example 8:
the copper phthalocyanine-modified polytetrahydrofuran ether polyol obtained in example 4 was melted at 80 ℃ for use. MDI (72.0g) is put into a drying reaction bottle, heated to 60 ℃ under the protection of nitrogen, added with copper phthalocyanine modified polytetrahydrofuran ether polyol (159.7g) for three times after being completely melted, heated to 80 ℃ and reacted for 3 hours at constant temperature to obtain the polyurethane prepolymer. NCO content was found to be 7.5%.
And (3) uniformly mixing the prepared polyurethane prepolymer (100g) and BDO (7.6g) at 90 ℃, pouring the mixture into a mold at 110 ℃ after vacuum defoaming, vulcanizing for 24h, and then demolding to obtain the copper phthalocyanine modified polytetrahydrofuran type polyurethane elastomer.
Comparative example 1:
PCL220N was melted at 80 ℃ for use. MDI (72.0g) is put into a dry reaction bottle, heated to 60 ℃ under the protection of nitrogen, added with PCL220N (160.8g) in three times after being completely melted, heated to 80 ℃ and reacted for 3 hours at constant temperature to obtain the polyurethane prepolymer. NCO content was found to be 7.6%.
And (3) uniformly mixing the prepared polyurethane prepolymer (100g) and BDO (7.7g) at 90 ℃, pouring the mixture into a mold at 110 ℃ after vacuum defoaming, vulcanizing for 24 hours, and then demolding to obtain the polyurethane elastomer.
Comparative example 2:
the PTMG2000 was melted at 80 ℃ for further use. MDI (72.0g) is put into a dry reaction bottle, heated to 60 ℃ under the protection of nitrogen, PTMG2000(157.2g) is put into the dry reaction bottle for three times after the MDI is completely melted, and then heated to 80 ℃ for constant temperature reaction for 3 hours to obtain the polyurethane prepolymer. NCO content was found to be 7.6%.
And (3) uniformly mixing the prepared polyurethane prepolymer (100g) and BDO (7.7g) at 90 ℃, pouring the mixture into a mold at 110 ℃ after vacuum defoaming, vulcanizing for 24 hours, and then demolding to obtain the polyurethane elastomer.
The polyurethane elastomers were tested and characterized according to the following method:
hardness: according to GB/T531.1-2008;
tensile property: according to GB/T528-2009;
tear strength: according to GB/T529 and 2008;
heat resistance: DMA (dynamic thermal mechanical analyzer) is adopted, the stretching mode is adopted, the frequency is 10Hz, the heating rate is 3 ℃/min, the change curve of the storage modulus of a test sample along with the temperature is tested, and the heat resistance of the elastomer is measured through the retention rate of the storage modulus at high temperature and the temperature of the inflection point of the storage modulus.
Both the temperature rise rates of TGA (thermogravimetric analysis) and DSC (Charpy scanning calorimetry analysis) were 10 deg.C/min.
The results of the performance tests of the polyurethane elastomers obtained in examples 5 to 8 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1 Properties of polyurethane Elastomers
| Item | Example 5 | Example 6 | Example 7 | Example 8 | Comparative example 1 | Comparative example 2 |
| Hardness (Shao A) | 85 | 85 | 85 | 85 | 85 | 85 |
| Tensile Strength (MPa) | 40.3 | 35.6 | 35.6 | 33.6 | 35.8 | 28.2 |
| Elongation in exercise (%) | 432 | 551 | 532 | 493 | 472 | 503 |
| Storage modulus at 40 ℃ (MPa) | 21.5 | 24.6 | 21.2 | 27.8 | 20.3 | 23.5 |
| Storage modulus at 80 ℃ (MPa) | 18.4 | 22 | 16.6 | 22.2 | 15.6 | 18.7 |
| Storage modulus retention at 80 ℃ (%) | 86 | 89 | 78 | 80 | 77 | 80 |
| Storage modulus at 120 ℃ (MPa) | 17.8 | 21.3 | 15 | 19.1 | 14.7 | 16.3 |
| Storage modulus retention at 120 ℃ (%) | 83 | 87 | 71 | 69 | 72 | 69 |
| Inflection point of storage modulus (. degree. C.) | 157.4 | 156.4 | 146.1 | 135.4 | 135.9 | 134.7 |
| Temperature (. degree.C.) of 5% weight loss by heat | 311.2 | 316.7 | 305.9 | 304.2 | 305.7 | 304.1 |
| DSC high temperature onset melting temperature (. degree. C.) | 117.9 | 124.7 | 120.2 | 121.2 | 100.8 | 90.1 |
As can be seen from table 1, by comparing examples 5 and 6 with comparative example 1 and comparative examples 7 and 8 with comparative example 2, the high temperature performance is significantly improved by introducing phthalocyanine groups into the polyurethane elastomer under the condition that the material compositions are substantially the same.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (9)
1. A method for producing a phthalocyanine metal salt-modified polyurethane elastomer, characterized by comprising the steps of:
(1) under the protection of inert atmosphere and at a first reaction temperature which is enough to melt the raw materials, reacting phthalocyanine metal salt modified polyol with isocyanate for a first preset time period to obtain a polyurethane prepolymer;
(2) mixing the polyurethane prepolymer and the chain extender at a second reaction temperature for a second predetermined time period to obtain a reaction mixture;
(3) curing the reaction mixture at a third reaction temperature for a third predetermined time period to obtain the phthalocyanine metal salt modified polyurethane elastomer;
wherein the phthalocyanine metal salt-modified polyol has a structure represented by the following general formula (1):
wherein the phthalocyanine metal salt modified polyol is obtained by reacting 4-nitrophthalonitrile, phthalonitrile, metal salt and initial polyol, and the structural general formula of the metal salt is MX2Wherein M represents a divalent metal cation, X represents a monovalent non-metal anion, and the structural general formula of the starting polyol is HO-R1-OH，R1Represents a carbon chain structure between two terminal hydroxyl groups in the starting polyol with the carbon number more than 2;
wherein the first reaction temperature is 60-90 ℃;
the second reaction temperature is 80-100 ℃;
the third reaction temperature is 100-120 ℃;
wherein the initial polyol is a micromolecular polyol with 2-12 carbon atoms, a polyether polyol with the number average molecular weight of 200-2000 or a polyester polyol with the number average molecular weight of 200-2000.
2. The method for preparing a phthalocyanine metal salt-modified polyurethane elastomer according to claim 1, wherein the isocyanate is one or more of the following: diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethylm-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyldiphenylmethane diisocyanate, lysine diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, 2-methylpentane diisocyanate, 2, 4-dimethyloctane-1, 8-diisocyanate, 3 ' -dimethoxybiphenyl-4, 4 ' -diisocyanate, 4 ' -diphenyl ether diisocyanate, 4-methyldiphenylmethane-3, 4-diisocyanate, 2,4 ' -diphenyl sulfide diisocyanate, diethylbenzene diisocyanate and 4,4 ' -diphenylethane diisocyanate.
3. The method for preparing the phthalocyanine metal salt modified polyurethane elastomer as claimed in claim 1, wherein the chain extender is the phthalocyanine metal salt modified polyol, an amine chain extender, a carboxylic acid chain extender or an alcohol chain extender.
4. The method for preparing the phthalocyanine metal salt-modified polyurethane elastomer as claimed in claim 1, wherein the chain extender is one or more selected from the group consisting of: ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, methylpropanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butylethylpropylene glycol, diethylpentanediol, 3-methyl-1, 5-pentanediol, trimethylpentanediol, ethylhexanediol, dodecanediol, 1, 4-dimethylolcyclohexane, cyclohexanediol, dodecanediol, trimethylolpropane, trimethylolethane, glycerol, 1,2, 6-hexanetriol, pentaerythritol, xylitol, sorbitol, mannitol; triethanolamine, diethanolamine, triisopropanolamine, methyldiethanolamine, dihydroxyisopropylaniline, dihydroxyisopropyl-p-toluidine, dihydroxyethyl-o-aniline, dihydroxyethyl-p-aniline, dihydroxyethyl-m-phenylenediamine; dihydroxypropionic acid, dihydroxybutyric acid, adipic acid, sebacic acid, terephthalic acid, dimethyl terephthalate, isophthalic acid, phthalic anhydride, succinic acid, glutaric acid, azelaic acid, dodecanedioic acid, 1, 4-cyclohexanedicarboxylic acid, methyl 1, 4-cyclohexanedicarboxylate, and maleic anhydride.
5. The method for producing the phthalocyanine metal salt-modified polyurethane elastomer as claimed in any one of claims 1 to 4, wherein the first predetermined period of time, the second predetermined period of time, and the third predetermined period of time are each independently 2 hours to 48 hours.
6. The method for producing a phthalocyanine metal salt-modified polyurethane elastomer as claimed in claim 5, wherein the first predetermined period of time, the second predetermined period of time, and the third predetermined period of time are each independently 3 hours to 24 hours.
7. The method for preparing the phthalocyanine metal salt-modified polyurethane elastomer as claimed in claim 1, wherein the metal salt is selected from one or more of the following: ZnCl2、ZnBr2、Zn(NO3)2、CuCl2、CuBr2、Cu(NO3)2、CoCl2、CoBr2、Co(NO3)2。
8. The method for preparing a phthalocyanine metal salt-modified polyurethane elastomer as claimed in claim 1, wherein the starting polyol is one or more selected from the group consisting of: ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, methylpropanediol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butylethylpropylene glycol, diethylpentanediol, 3-methyl-1, 5-pentanediol, trimethylpentanediol, ethylhexanediol, dodecanediol, 1, 4-dimethylolcyclohexane, cyclohexanediol, dodecanediol, trimethylolpropane, trimethylolethane, glycerol, 1,2, 6-hexanetriol, pentaerythritol, xylitol, sorbitol, mannitol, polyoxypropylene polyol, polyoxyethylene polyol, polytrimethylene ether glycol, aromatic polyether glycol, polytetrahydrofuran ether polyol, polyhexamethylene glycol polyol, pentaerythritol, xylitol, sorbitol, mannitol, polyoxypropylene polyol, polyoxyethylene polyol, polytrimethylene ether glycol, polytetramethylene ether glycol, polytetrahydrofuran ether polyol, and polyhexamethylene glycol, Polycaprolactone polyols, or polycarbonate polyols.
9. A phthalocyanine metal salt-modified polyurethane elastomer prepared by the method as set forth in any one of claims 1 to 8.
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