CN114672023B - Preparation method of flexible hyperbranched water-soluble polyimide resin - Google Patents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention relates to a water-soluble polyimide resin solution (IPC class number: C08G 18/80), in particular to a preparation method of a flexible hyperbranched water-soluble polyimide resin solution. The flexible hyperbranched water-soluble polyimide resin is prepared by reacting diamine containing siloxane functional groups, diamine containing double hydroxyl groups, diamine containing double bonds and tetracarboxylic dianhydride, has the advantages of being green, environment-friendly, simple and efficient, enriches the structure of the existing polyimide, and expands the performance and application fields of polyimide.
Description
Technical Field
The invention relates to a water-soluble polyimide resin (IPC class number: C08G 18/80), in particular to a preparation method of a flexible hyperbranched water-soluble polyimide resin.
Background
Polyimide resin is a high molecular polymer with imide ring in the main chain, and has excellent high temperature resistance, mechanical property, insulating property and electric property. Polyimide has been paid attention to in the electronics industry, but polyimide has to be used in a liquid state in the field of microelectronics industry, but polyimide resins studied so far are basically insoluble in water and can only be used in organic solvent type polyimide resin solutions formed by dissolving in organic solvents such as dimethylacetamide and dimethylformamide. In addition, the organic solvent type polyimide resin still has a great viscosity under the condition of low solid content, and a great amount of organic solvent is needed to dilute the polyimide resin during use. However, organic solvents pose serious environmental problems and health risks.
Patent application CN104761898A discloses a water-soluble polyimide resin solution and a preparation method thereof, and the patent prepares a transparent, uniform and stable water-soluble polyimide resin solution by controlling the dosage of the anionic surfactant, mixing the anionic surfactant with the organic solvent type polyimide resin solution to form a mixed solution, and gradually adding water into the mixed solution. However, this patent does not disclose the selection of dianhydride and diamine of the organic solvent type polyimide resin, and in addition, a large amount of water is required to dissolve the organic solvent type polyimide resin in water, which is not fundamentally solved by the water solubility problem of polyimide.
Therefore, the flexible hyperbranched water-soluble polyimide resin prepared by the invention has the advantages of green, environment-friendly, simplicity and high efficiency, enriches the structure of the existing polyimide, and expands the performance and application fields of polyimide.
Disclosure of Invention
In order to solve the above problems, the present invention provides a flexible hyperbranched water-soluble polyimide resin synthesized from diamine and dianhydride.
As a preferred embodiment, the diamine and dianhydride have at least one compound containing a dihydroxy group.
As a preferred embodiment, the diamine and dianhydride have at least one tetracarboxylic group-containing compound.
As a preferred embodiment, the dianhydride contains a tetracarboxylic functional group.
The invention relates to a preparation method of flexible hyperbranched water-soluble polyimide resin, which mainly comprises the following steps:
(1) Under the protection of nitrogen, diamine is added into ionic liquid according to a certain proportion, dry dianhydride monomer is added in batches, and stirring is carried out for 2-6 hours at 15-25 ℃ to obtain polyamic acid solution;
(2) Adding a chain extender into the polyamic acid solution, and stirring at room temperature for reaction to obtain a polyimide prepolymer solution;
(3) And (3) passing the polyimide prepolymer solution through thermal imine to obtain hyperbranched water-soluble polyimide.
As a preferred embodiment, the dianhydride is
One or more of them. />
As a preferred embodiment, the dianhydride is
(CAS number: 89-32-7).
As a preferred embodiment, the diamine is a mixture of diamines containing siloxane functions, diamines containing dihydroxy groups and diamines containing double bonds.
As a preferred embodiment, the molar ratio of the diamine containing siloxane functions and the diamine containing dihydroxy groups, the diamine containing double bonds is 100: (10-20): (20-30).
The applicant found that when using a diamine containing a dihydroxy group and a diamine containing a double bond, the hyperbranched water-soluble polyimide prepared was flocculated by polymerization in water to form a flocculent when dissolved in water, and found through a number of inventive experiments that when the diamine containing a siloxane functional group and the diamine containing a dihydroxy group, the molar ratio of the diamine containing a double bond was 100: (10-20): in the case of (20-30), the solubility of the polyimide is improved, so that the polyimide can be uniformly and stably distributed in water. The applicant speculates that: when the diamine containing siloxane functional groups and the diamine containing double hydroxyl groups react with the tetracarboxylic dianhydride, under the action of hydrophilic groups in the polyimide polymer, the acting force between the internal macromolecules and water molecules is larger than the attractive force between the internal macromolecules, and the water molecules can invade between the macromolecules, so that the molecular gaps of the polymer become larger and looser, and finally, the molecular chains of the polyimide can be uniformly dispersed in the water due to the thermal movement of the molecular chains, so that a uniform and stable polyimide aqueous solution is formed.
As a preferred embodiment, the preparation method of the diamine containing siloxane functional groups mainly comprises the following steps:
(1) Adding a silicon-containing compound into a reactor, stirring and introducing nitrogen;
(2) Then hydroxyl-terminated silicone oil is dripped, and the reaction is carried out for 2 to 4 hours at the temperature of 45 to 60 ℃ after the dripping is finished;
(3) Excess monomer is distilled off under reduced pressure to give diamines containing siloxane functions.
As a preferred scheme, the molar ratio of the silicon-containing compound to the hydroxyl-terminated silicone oil is 1: (3-3.5).
As a preferred embodiment, the silicon-containing compound is one or more of (2-aminoethoxy) (t-butyl) dimethylsilane (CAS number: 101711-55-1), trimethylsilyl 1-aminocyclopentane carboxylate (CAS number: 124900-79-4), (4-amino-3, 3-dimethylbutyl) (methyl) dimethoxysilane (CAS number: 156849-43-3).
As a preferred embodiment, the silicon-containing compound is (2-aminoethoxy) (t-butyl) dimethylsilane.
As a preferred scheme, the preparation method of the hydroxyl-terminated silicone oil comprises the following steps: heating cyclosiloxane to 110-120 ℃ under the protection of nitrogen, adding 1, 2-propylene diamine and deionized water, stirring for 1-3 h, cooling, extracting, and distilling under reduced pressure to obtain hydroxyl-terminated silicone oil.
As a preferred embodiment, the cyclosiloxane is acetoxyheptamethyl cyclotetrasiloxane (CAS number 14697-86-0).
As a preferable scheme, the molar ratio of the cyclosiloxane to the 1, 2-propylene diamine is (2-3): 1.
the applicant found through a number of inventive experiments that when the molar ratio of cyclosiloxane, 1, 2-propanediamine is (2-3): 1, hydroxyl-terminated silicone oil with a relative molecular mass of 800-1000 g/mol can be obtained, and meanwhile, the storage stability is excellent, so that the flexibility of polyimide is improved, and meanwhile, the stability of polyimide in water is also improved. The applicant speculates that: under the action of 1, 2-propylene diamine, the cyclosiloxane is degraded in a macromolecular short chain, and meanwhile, when the molar ratio of the 1, 2-propylene diamine is (2-3): 1, the molecular weight distribution of the end group silicone oil reaches an equilibrium state, thereby preparing the end hydroxyl silicone oil with the storage stability and the relative molecular mass of 800-1000 g/mol. Furthermore, the applicant found in experiments that when the molar ratio of cyclosiloxane, 1, 2-propanediamine is (2-3): when 1 is too small, the yield of the hydroxyl-terminated silicone oil is improved, but the hydroxyl content of the hydroxyl-terminated silicone oil is reduced, the relative molecular weight is increased, the subsequent formation of diamine containing siloxane functional groups is not facilitated, but the consumption of 1, 2-propanediamine is small, the whole ring-opening polymerization of cyclosiloxanes cannot be realized, and more raw materials remain.
As a preferred embodiment, the diamine containing dihydroxy groups is
One or more of (a) and (b).
As a preferred embodiment, the diamine containing dihydroxy groups is
As a preferred embodiment, the diamine containing double bonds is one or more of N-acetylethylenediamine, N-acetylethylenediamine (CAS number 106675-70-1), N- ((tert-butoxy) carbonyl) -N, N' -dimethylethylenediamine (CAS number 112257-19-9).
As a preferred embodiment, the diamine containing a double bond is N- ((tert-butoxy) carbonyl) -N, N' -dimethylethylenediamine.
As a preferable scheme, the ionic liquid is imidazole ionic liquid.
As a preferable scheme, the imidazole ionic liquid is a mixture of imidazole tetrafluoroborates and 1-butyl-3-methylimidazole hexafluorophosphate.
As a preferable scheme, the mass ratio of the imidazole tetrafluoroborate salt to the 1-butyl-3-methylimidazole hexafluorophosphate is 1: (1-1.1).
The applicant found that when imidazole-based ionic liquids participate in the reaction, it is advantageous to separate the residual moisture in diamine and dianhydride monomers from byproducts produced during the polyimide synthesis process, thereby facilitating the formation of polyamic acid, and hyperbranched water-soluble polyimide having high storage stability is easily obtained even when heated at low temperature and in a short time, and the applicant speculates that: because the imidazole ionic liquid possibly plays a role of a certain activator in the polyimide synthesis process, the induction of a molecular chain in a system is improved, and the method is favorable for separating residual moisture and polyimide in a monomer and has a good catalytic effect, so that hyperbranched water-soluble polyimide with high storage stability can be easily obtained through low-temperature and short-time heating.
As a preferred scheme, the molar ratio of the diamine to the ionic liquid is 1: (1.5-2.3).
As a preferred embodiment, the molar ratio of the diamine to dianhydride monomers is 1: (1-1.05).
As a preferred embodiment, the chain extender does not contain a benzene ring.
As a preferred embodiment, the chain extender contains both thiol and hydroxyl groups.
As a preferred embodiment, the chain extender is one or more of (R) -2, 4-dihydroxy-N- [3- [ (2-mercaptoethyl) amino ] -3-oxopropyl ] -3, 3-dimethylbutyramide (CAS number: 496-65-1), 2- [5- (2-hydroxyethyl-mercapto) pentylmercapto ] ethanol (CAS number: 5400-84-0), 3- ((2-mercapto-1-methylpropyl) thio) -2-butanol (CAS number: 54957-02-7).
As a preferred embodiment, the chain extender is 3- ((2-mercapto-1-methylpropyl) thio) -2-butanol.
As a preferable scheme, the addition amount of the chain extender is 3-5 times of the mole ratio of free amino groups and aldehyde groups in the polyamic acid solution.
The applicant finds that in the experimental process, 3- ((2-mercapto-1-methylpropyl) sulfur) -2-butanol containing mercapto and hydroxy is added, so that polyimide has more active substances and meanwhile, the flexibility of the polyimide is improved, and the hyperbranched water-soluble polyimide has proper rigidity and flexibility. The applicant speculates that: this is probably because 3- ((2-mercapto-1-methylpropyl) thio) -2-butanol containing mercapto and hydroxy is connected to the polyimide molecular structure through click chemistry, so that the polyimide molecular structure contains ether bond, alkyl, thioether and other flexible groups, the rigid structure of the molecular chain is destroyed, the flexibility and conformation of chain segments are increased, the interaction between the molecular chains is effectively reduced, the crystallinity of the polyimide is reduced, the polyimide has more active substances, and meanwhile, the flexibility of the polyimide is improved, so that the hyperbranched water-soluble polyimide has proper rigidity and flexibility.
The beneficial effects are that:
1. the invention is defined by the definition that when the diamine containing siloxane functions and the diamine containing dihydroxy groups, the molar ratio of diamine containing double bonds is 100: (10-20): in the case of (20-30), the solubility of the polyimide is improved, so that the polyimide can be uniformly and stably distributed in water.
2. The invention is characterized in that the molar ratio of the cyclosiloxane to the 1, 2-propylene diamine is (2-3): 1, hydroxyl-terminated silicone oil with a relative molecular mass of 800-1000 g/mol can be obtained, and meanwhile, the polyimide has excellent storage stability and improves the flexibility of polyimide.
3. The invention uses imidazole ionic liquid (imidazole tetrafluoroborate and 1-butyl-3-methylimidazole hexafluorophosphate) to participate in the reaction, which is favorable for separating residual moisture in diamine and dianhydride monomers and byproducts produced in the polyimide synthesis process, thereby improving the generation of polyamide acid, and even though the polyimide is heated at low temperature and in a short time, hyperbranched water-soluble polyimide with high storage stability can be easily obtained.
4. According to the invention, 3- ((2-mercapto-1-methylpropyl) sulfur) -2-butanol containing mercapto and hydroxy is added, so that polyimide has more active substances and meanwhile, the flexibility of polyimide is improved, and therefore, hyperbranched water-soluble polyimide has proper rigidity and flexibility.
5. The flexible hyperbranched water-soluble polyimide resin solution prepared by the method is uniform and stable, improves the safety in the transportation and use processes, and meets the current environmental protection requirements.
Detailed Description
Examples
Example 1
The embodiment 1 provides a preparation method of flexible hyperbranched water-soluble polyimide resin, which comprises the following steps:
(1) Under the protection of nitrogen, diamine is added into ionic liquid according to a certain proportion, dry dianhydride monomer is added in batches, and stirring is carried out for 4 hours at 20 ℃ to obtain polyamic acid solution;
(2) Adding a chain extender into the polyamic acid solution, and stirring at room temperature for reaction to obtain a polyimide prepolymer solution;
(3) And (3) passing the polyimide prepolymer solution through thermal imine to obtain hyperbranched water-soluble polyimide.
The dianhydride isIs that
(CAS number: 89-32-7).
The diamine is a mixture of diamine containing siloxane functional groups, diamine containing double hydroxyl groups and diamine containing double bonds.
The mass of the diamine in this example was 100g.
The molar ratio of the diamine containing siloxane functional groups to the diamine containing double hydroxyl groups is 100:15:25.
the preparation method of the diamine containing siloxane functional groups comprises the following steps:
(1) Adding a silicon-containing compound into a reactor, stirring and introducing nitrogen;
(2) Then hydroxyl-terminated silicone oil is dripped, and the reaction is carried out for 3 hours at 50 ℃ after the dripping is finished;
(3) Excess monomer is distilled off under reduced pressure to give diamines containing siloxane functions.
The molar ratio of the silicon-containing compound to the hydroxyl-terminated silicone oil is 1:3.2.
the silicon-containing compound is (2-aminoethoxy) (tert-butyl) dimethylsilane (CAS number: 101711-55-1).
The preparation method of the hydroxyl-terminated silicone oil comprises the following steps: heating cyclosiloxane to 115 ℃ under the protection of nitrogen, adding 1, 2-propylene diamine and deionized water, stirring for 2 hours, cooling, extracting, and distilling under reduced pressure to obtain hydroxyl-terminated silicone oil. The cyclosiloxane is acetoxy heptamethyl cyclotetrasiloxane (CAS number 14697-86-0). The molar ratio of the cyclosiloxane to the 1, 2-propylene diamine is 2.5:1.
the diamine containing double hydroxyl is
The diamine containing double bonds is N- ((tert-butoxy) carbonyl) -N, N' -dimethylethylenediamine (CAS number 112257-19-9).
The ionic liquid is imidazole ionic liquid. The imidazole ionic liquid is a mixture of imidazole tetrafluoroborates and 1-butyl-3-methylimidazole hexafluorophosphate. The mass ratio of the imidazole tetrafluoroborate to the 1-butyl-3-methylimidazole hexafluorophosphate is 1:1.
the imidazole tetrafluoroborates were purchased from 1-vinyl-3-ethylimidazole tetrafluoroborate ionic liquids of the marsuporov biotechnology company.
The 1-butyl-3-methylimidazolium phosphate was purchased from wuhan's biosciences, inc.
The molar ratio of the diamine to the ionic liquid is 1:2.
the molar ratio of the diamine to the dianhydride monomer is 1:1.
the chain extender is 3- ((2-mercapto-1-methylpropyl) thio) -2-butanol. The addition amount of the chain extender is 4 times of the mole ratio of free amino groups and aldehyde groups in the polyamic acid solution.
Example 2
The embodiment 2 provides a preparation method of flexible hyperbranched water-soluble polyimide resin, which comprises the following steps:
(1) Under the protection of nitrogen, diamine is added into ionic liquid according to a certain proportion, dry dianhydride monomer is added in batches, and stirring is carried out for 4 hours at 20 ℃ to obtain polyamic acid solution;
(2) Adding a chain extender into the polyamic acid solution, and stirring at room temperature for reaction to obtain a polyimide prepolymer solution;
(3) And (3) passing the polyimide prepolymer solution through thermal imine to obtain hyperbranched water-soluble polyimide.
The dianhydride is
(CAS number: 89-32-7).
The diamine is a mixture of diamine containing siloxane functional groups, diamine containing double hydroxyl groups and diamine containing double bonds.
The mass of the diamine in this example was 100g.
The molar ratio of the diamine containing siloxane functional groups to the diamine containing double hydroxyl groups is 100:20:30.
the preparation method of the diamine containing siloxane functional groups comprises the following steps:
(1) Adding a silicon-containing compound into a reactor, stirring and introducing nitrogen;
(2) Then hydroxyl-terminated silicone oil is dripped, and the reaction is carried out for 3 hours at 50 ℃ after the dripping is finished;
(3) Vacuum distillation to obtain diamine containing siloxane functional group.
The molar ratio of the silicon-containing compound to the hydroxyl-terminated silicone oil is 1:3.2.
the silicon-containing compound is (2-aminoethoxy) (tert-butyl) dimethylsilane (CAS number: 101711-55-1).
The preparation method of the hydroxyl-terminated silicone oil comprises the following steps: heating cyclosiloxane to 115 ℃ under the protection of nitrogen, adding 1, 2-propylene diamine and deionized water, stirring for 2 hours, cooling, extracting, and distilling under reduced pressure to obtain hydroxyl-terminated silicone oil. The cyclosiloxane is acetoxy heptamethyl cyclotetrasiloxane (CAS number 14697-86-0). The molar ratio of the cyclosiloxane to the 1, 2-propylene diamine is 2.5:1.
the diamine containing double hydroxyl is
The diamine containing double bonds is N- ((tert-butoxy) carbonyl) -N, N' -dimethylethylenediamine (CAS number 112257-19-9).
The ionic liquid is imidazole ionic liquid; the imidazole ionic liquid is a mixture of imidazole tetrafluoroborates and 1-butyl-3-methylimidazole hexafluorophosphate. The mass ratio of the imidazole tetrafluoroborate to the 1-butyl-3-methylimidazole hexafluorophosphate is 1:1.
the imidazole tetrafluoroborates were purchased from 1-vinyl-3-ethylimidazole tetrafluoroborate ionic liquids of the marsuporov biotechnology company.
The 1-butyl-3-methylimidazolium phosphate was purchased from wuhan's biosciences, inc.
The molar ratio of the diamine to the ionic liquid is 1:2.
the molar ratio of the diamine to the dianhydride monomer is 1:1.
the chain extender is 3- ((2-mercapto-1-methylpropyl) thio) -2-butanol. The addition amount of the chain extender is 4 times of the mole ratio of free amino groups and aldehyde groups in the polyamic acid solution.
Comparative example 1
The embodiment of comparative example 1 is the same as example 1; in contrast, comparative example 1 provides a method for preparing a flexible hyperbranched water-soluble polyimide resin, comprising the steps of:
(1) Under the protection of nitrogen, diamine is added into an aprotic solvent according to a certain proportion, dry dianhydride monomer is added in batches, and stirring is carried out for 4 hours at 20 ℃ to obtain polyamic acid solution;
(2) Adding a chain extender into the polyamic acid solution, and stirring at room temperature for reaction to obtain a polyimide prepolymer solution;
(3) And (3) passing the polyimide prepolymer solution through thermal imine to obtain hyperbranched water-soluble polyimide.
The aprotic solvent is N-methylpyrrolidone.
Comparative example 2
The embodiment of comparative example 2 is the same as example 1; the difference is that the diamine in comparative example 2 is a mixture of diamines containing dihydroxy groups and diamines containing double bonds, the weight ratio of the diamines containing dihydroxy groups to the diamines containing double bonds being 15:25.
performance test:
(1) Solubility: 500g of the hyperbranched water-soluble polyimide prepared in examples 1 to 2 and comparative examples 1 to 2 was added with water to prepare an aqueous solution having a weight percent of 10%, and then stirred at 50℃for 3 hours, and if the occurrence of a precipitate or gel phenomenon was observed, it was judged to be unacceptable.
(2) Storage stability: hyperbranched water-soluble polyimide (solid content 10 wt%) was left at room temperature for 12 hours and the viscosity was measured, and if the decrease in the initial viscosity was more than 10% or the generation of precipitate or gel was observed, it was not acceptable.
Performance test results:
table 1 shows the results of performance tests of the water-soluble polyimide resin solutions prepared in examples 1 to 2 and comparative examples 1 to 2.
TABLE 1
| Solubility of | Storage stability | |
| Example 1 | Qualified product | Qualified product |
| Example 2 | Qualified product | Qualified product |
| Comparative example 1 | Qualified product | Failure to pass |
| Comparative example 2 | Failure to pass | Failure to pass |
Claims (8)
1. A preparation method of flexible hyperbranched water-soluble polyimide resin is characterized by comprising the following steps:
(1) Under the protection of nitrogen, diamine is added into ionic liquid according to a certain proportion, dry dianhydride monomer is added in batches, and stirring is carried out for 2-6 hours at 15-25 ℃ to obtain polyamic acid solution;
(2) Adding a chain extender into the polyamic acid solution, and stirring at room temperature for reaction to obtain a polyimide prepolymer solution;
(3) The polyimide prepolymer solution is subjected to thermal imine to obtain hyperbranched water-soluble polyimide;
the diamine is diamine containing siloxane functional groups, and a mixture of diamine containing double hydroxyl groups and diamine containing double bonds; the molar ratio of the diamine containing siloxane functional groups to the diamine containing double hydroxyl groups is 100: (10-20): (20-30);
the chain extender contains mercapto and hydroxy.
2. The method for producing a flexible hyperbranched water-soluble polyimide resin according to claim 1, wherein the dianhydride contains a dihydroxy group.
3. The method for producing a flexible hyperbranched water-soluble polyimide resin according to claim 1, wherein the dianhydride is
，/>
，/>
，/>
One or more of (a) and (b).
4. The method for producing a flexible hyperbranched water-soluble polyimide resin according to claim 1, characterized in that the method for producing a diamine containing siloxane functional groups comprises the steps of:
(1) Adding a silicon-containing compound into a reactor, stirring and introducing nitrogen;
(2) Then hydroxyl-terminated silicone oil is dripped, and the reaction is carried out for 2 to 4 hours at the temperature of 45 to 60 ℃ after the dripping is finished;
(3) Vacuum distillation to obtain diamine containing siloxane functional group.
5. The method for producing a flexible hyperbranched water-soluble polyimide resin according to claim 4, wherein the silicon-containing compound is one or more of (2-aminoethoxy) (tert-butyl) dimethylsilane, trimethylsilyl 1-aminocyclopentane carboxylate, and (4-amino-3, 3-dimethylbutyl) (methyl) dimethoxysilane.
6. The method for producing a flexible hyperbranched water-soluble polyimide resin according to claim 1, wherein the diamine containing dihydroxy groups is
，/>
One or more of (a) and (b).
7. The method for producing a flexible hyperbranched water-soluble polyimide resin according to claim 4, wherein the diamine containing double bonds is one or more of N-acetylethylenediamine, N- ((tert-butoxy) carbonyl) -N, N' -dimethylethylenediamine.
8. The method for preparing a flexible hyperbranched water-soluble polyimide resin according to claim 1, wherein the ionic liquid is an imidazole ionic liquid.
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