CN109293931A - Insoluble insoluble metal-modified dissaving polymer of one kind and preparation method thereof - Google Patents
Insoluble insoluble metal-modified dissaving polymer of one kind and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of insoluble insoluble metal-modified dissaving polymers and preparation method thereof, insoluble insoluble metal-modified dissaving polymer is made by the way that metal acetate salting liquid is added dropwise into the carboxylic dissaving polymer solution of end group, metal-modified dissaving polymer is the carboxylic dissaving polymer of end group and the network polymer that metal ion crosslinked is formed, it is with insoluble insoluble characteristic, most of organic solvents are not dissolved at 80 DEG C or less, it is not melted in room temperature to T range, T >=370 DEG C, crosslinking is to pass through ion key connection realization by acid ion Yu metal ion that coordination is keyed the carboxylic hyperbranched polymer molecule end of end group simultaneously with metal ion by the oxygen atom in the double bond inside the carboxylic hyperbranched polymer molecule of end group.The method of the present invention solves the problems, such as that blend machine-shaping is difficult when dissaving polymer blending, and metal-modified dissaving polymer is made has insoluble insoluble characteristic under general processing conditions.
Description
Technical field
The invention belongs to additive agent fields, are related to the insoluble insoluble metal-modified dissaving polymer of one kind and its preparation side
Method.
Background technique
Dissaving polymer such as hyper-branched polyester etc. has highly branched molecular structure, applies in polymer blended field
Extensively, such as hyper-branched polyester is blended with fire retardant, and dissaving polymer is often widely used in work as viscosity modifier
In the every field of industry production.
The synthetic method of dissaving polymer has very much, according to monomer type, can be mainly divided into two major classes: one kind is single
Body method (SMM) mainly utilizes ABnType or potential ABnType monomer is polymerize；Another kind of is dual MCU system method (DMM), this
Kind method is needed with two kinds of monomers or a pair of of monomer to polymerizeing, and common dual MCU system method mainly has A2+B3Type monomer is poly-
It closes.The synthetic method of metal coordinating polymer mainly includes that direct coordination method, monomer coordination method, crosslinking coordination method and polymer are anti-
Ying Fa.Wherein, crosslinking coordination method be by with can reactive functionality polymer and metal ion (as crosslinking agent) divided
Cross-linking reaction between subchain is to be made using metal complex coordinate bond as the method for the network polymer of crosslinking points.Metal coordination
Dissaving polymer be widely used as blend in the field of polymers.
However, researcher pass through the study found that with relative molecular weight increase, the viscosity of dissaving polymer can be by
It is cumulative to add, if but dissaving polymer compares with linear polymer, the increasing degree of the viscosity of dissaving polymer compares line
The increased amplitude of type polymer is much smaller.This is because dissaving polymer can form structure more closely in a solvent,
It is spherical in shape in a solvent and winds without chain.Although dissaving polymer can have Swelling in a solvent, before it is swollen
Volume change afterwards is smaller, and compared with the linear polymer that larger volume variation can occur in a solvent, dissaving polymer can
To regard " small molecule " in Special Significance as.Therefore, adding when functional dissaving polymer is as blend (or additive)
Dosage is also restricted, and excessively high additive amount can make the viscosity of polymer too low, brings difficulty to the processing and forming of polymer.
Solution common at present is to improve functional dissaving polymer under the premise of meeting the processing flowability of blend
The content of middle functional element, so as to meet corresponding functional requirements (such as fire-retardant for functionality dissaving polymer obtained
Or sterilization etc.).The content of functional element has reached 20wt% in functional dissaving polymer reported in recent years, and functionality is super
Further increasing for functional element content is restricted in branched polymer, and therefore, researcher needs to find new method
Solve the problems, such as that additive amount is restricted when dissaving polymer is blended with other polymers.
Patent application publication number is that the patent of CN101905172A proposes that a kind of functional hyperbranched polymer supported platinum is urged
Agent is to polymerize the platinum of+4 valences in platinum dioxide by the way that the obtained functionality of coordination key connection is hyperbranched with dissaving polymer
Object, but its purpose field is self assembly, and product obtained is equally soluble in organic solvent, can not solve dissaving polymer conduct
Additive brings difficult problem to machine-shaping.Cerrada P et al. proposes one in " Macromolecules " article
Kind Liquid Crystalline Metallomesogenic Polymers, first with dialdehyde monomer 1, bis- [(4- formoxyl -3- hydroxyphenyl) oxygen] decane of 10- and diamines
Liquid crystal poly methylene imine semi-flexible is made in monomer 2- methyl-1,4- phenylenediamine polycondensation, then will have the poly- first of main chain liquid crystal of hydroxyl
The fully dispersed suspension of imines in organic solvent, the liquid crystal metal being finally crosslinked after complexing using it with metallic ion coordination
Coordination polymer.But product made from this method also only has liquid crystal liquid crystal property, does not have and does not melt insoluble characteristic, equally can not
Additive amount height can bring difficulty to machine-shaping when solving the problems, such as dissaving polymer as additive.
Therefore, machine-shaping smoothly insoluble insoluble metal-modified dissaving polymer and its system when studying a kind of blending
Preparation Method has a very important significance.
Summary of the invention
When being blended present invention aim to address above-mentioned dissaving polymer existing in the prior art with other polymers
Difficult problem is caused to blend machine-shaping, machine-shaping is smoothly insoluble insoluble metal-modified when providing a kind of blending
Dissaving polymer and preparation method thereof.
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of insoluble insoluble metal-modified dissaving polymer is the carboxylic dissaving polymer of end group and metal from
The network polymer that son is cross-linked to form, metal-modified dissaving polymer has insoluble insoluble characteristic, insoluble at 80 DEG C or less
It in organic solvent I, is not melted in room temperature to T range, T >=370 DEG C, the fusing point of metal-modified dissaving polymer of the invention
It higher than the melting temperature of most polymer, will not be melted when being blended with polymer melting, because total without caused by
Mixed object machine-shaping is difficult；
The crosslinking is by the oxygen atom and metal in the double bond inside the carboxylic hyperbranched polymer molecule of end group
Ion is logical by the acid ion and metal ion of coordination key connection while the carboxylic hyperbranched polymer molecule end of end group
Cross what ion key connection was realized；
Metal ion may load on dissaving polymer in two forms:
A, dissaving polymer swelling after ,-the COOH of spherical surface and/orDissociation removes H+, with metal ion with
Ionic bond is linked, and is shown below:
Oxygen on b, carbonyl or phosphorus oxygen key is connected with metal ion with coordinate bond, is shown below:
Both the above mode exists, and usually, coordinate bond is bigger to insoluble contribution.
The organic solvent I is aromatic hydrocarbon solvent, fat hydrocarbon solvent, alicyclic hydrocarbon type solvent, halogenated hydrocarbon solvent, alcohol
Class solvent, esters solvent, ketones solvent, acetonitrile, pyridine, phenol, n,N-Dimethylformamide or n,N-dimethylacetamide, this
The metal-modified dissaving polymer of invention does not dissolve in most organic solvents, be only herein simply enumerate it is some commonly use it is molten
Agent.
As a preferred technical scheme:
A kind of insoluble insoluble metal-modified dissaving polymer as described above, the aromatic hydrocarbon solvent are benzene, first
Benzene, dimethylbenzene, styrene, butyl toluene or vinyltoluene；The fat hydrocarbon solvent is n-hexane, pentane, hexane or pungent
Alkane；The alicyclic hydrocarbon type solvent is hexamethylene, cyclohexanone or toluene cyclohexanone；The halogenated hydrocarbon solvent be chlorobenzene, dichloro-benzenes,
Methylene chloride, chloroform, carbon tetrachloride, trichloro ethylene, tetrachloro-ethylene, trichloropropane or dichloroethanes；The alcohols solvent is first
Alcohol, ethyl alcohol, isopropanol, n-butanol, cyclohexanol, benzyl alcohol, ethylene glycol or propylene glycol；The esters solvent is methyl acetate, vinegar
Acetoacetic ester or propyl acetate；The ketones solvent is acetone, espeleton, methylisobutylketone, cyclohexanone or toluene cyclohexanone.
A kind of insoluble insoluble metal-modified dissaving polymer as described above, the metal-modified dissaving polymer
Aerial initial decomposition temperature is 300~400 DEG C, the partial size of the metal-modified dissaving polymer is 150~
500nm。
A kind of insoluble insoluble metal-modified dissaving polymer as described above, the carboxylic hyperbranched poly of end group
The quantity for closing carboxyl in object accounts for the 25%~100% of end group total amount, and the content of carboxyl depends on the carboxylic hyperbranched poly of end group
The degree of branching of object is closed, the end group of the dissaving polymer is carboxyl, or also containing other groups such as hydroxyls；Carboxyl-content mistake
The low crosslinking points that will lead to the network polymer being cross-linked to form are very few, and spatial network is not sufficiently stable, and cannot be formed insoluble insoluble
Property；Contain ester group, the carboxylic hyperbranched polymerization of end group in the molecule of the carboxylic dissaving polymer of end group
The degree of branching of object is 30~100%, and the weight average molecular weight of the carboxylic dissaving polymer of end group is 1100~50000g/
mol.The degree of branching of the carboxylic dissaving polymer of end group is higher, the dissaving polymer of formation more level off to dendroid polymerization
Object, i.e., symmetry with higher, in subsequent reaction, the space structure of formation is more stable, while dissaving polymer
The degree of branching it is higher, molecular weight is bigger, and biggish molecular weight is meant to react with more metal ions.
A kind of insoluble insoluble metal-modified dissaving polymer as described above, the metal ion are Co2+、Ni2+、
Cu2+Or Zn2+, the metal ion provides by its corresponding mol ratio of metal acetate, metal in the metal-modified dissaving polymer
The content of ion is 5.5~12.5wt%.Metal ion content is too low to will lead to metal-modified dissaving polymer obtained
It is functional poor, and its insoluble insoluble characteristic can be impacted.
The present invention also provides the as described above a kind of preparation method of insoluble insoluble metal-modified dissaving polymer, to
Metal acetate salting liquid is added dropwise in the carboxylic dissaving polymer solution of end group and is made insoluble insoluble metal-modified hyperbranched
Polymer.Metal acetate salting liquid be added dropwise the carboxylic dissaving polymer solution of inlet side base in after, metal ion simultaneously by
Mol ratio of metal acetate ionizes the electrostatic attraction of the electrostatic attraction for the acetate ion to be formed and the carboxyl end group of dissaving polymer
Power, due to both electrostatic attractions approximation, metal ion will not rapidly by the carboxyl total overall reaction on dissaving polymer surface,
Metal ion is slow release in the whole process, can be deep into the inside of hyperbranched polymer molecule, with hyperbranched poly
The oxygen atom closed in the double bond inside object establishes more stable coordinate bond, the metal-modified dissaving polymer tool because prepared by
There is insoluble insoluble characteristic.
Method as described above, the specific steps are as follows:
(1) the carboxylic dissaving polymer of end group and mol ratio of metal acetate are dissolved in organic solvent II and deionization respectively
The carboxylic dissaving polymer solution of end group and metal ion solution are obtained in water；
(2) under the conditions of stirring and sonic oscillation, metal ion solution is added drop-wise to the carboxylic hyperbranched polymerization of end group
It is reacted in object solution；After metal ion solution is added dropwise in the carboxylic dissaving polymer solution of end group, can rapidly with
The end group of dissaving structure is reacted, and metal ion is only capable of reacting with end group in the case where no sonic oscillation, i.e., most
End form at metal-modified dissaving polymer only surface layer have a circle metal be coordinated insoluble not crucible zone, inside be not coordinated；
(3) mixed liquor after reaction is post-processed to obtain insoluble insoluble metal-modified dissaving polymer.
Method as described above, in step (1), the organic solvent II is chloroform, acetone or n,N-Dimethylformamide,
The concentration of the carboxylic dissaving polymer solution of end group is 0.7~1.25mol/L, the concentration of the metal ion solution
For 0.7~1.25mol/L；
In step (2), the stirring is mechanical stirring or magnetic agitation, and the rate of stirring is 200~500rpm, stirring speed
Degree determines the size for the metal-modified dissaving polymer to be formed；The power of sonic oscillation is 600~1200W, sonic oscillation
Power it is higher, obtained metal-modified hyperbranched polymer structure is more uniform, and too low power will lead to resulting metal and change
Property dissaving polymer only surface layer coordination of metal ion, inside is not coordinated；The speed of the dropwise addition is 0.5~2 drop/sec, every drop
Volume be 0.05~0.1mL, the carboxylic dissaving polymer of end group and metal ion in reaction system after completion of dropwise addition
Molar ratio is 1:0.64~46.69；The additive amount of metal ion is too low, which cannot to form enough coordination structures, will lead to be formed
The insoluble insoluble property of metal-modified dissaving polymer is impacted.
In step (3), the post-processing, which refers to, to be filtered, washed and dried, and the drying carries out under vacuum conditions,
Vacuum degree is -0.1MPa, and drying time is 8~12h, and drying temperature is 25 DEG C.
Method as described above, the carboxylic dissaving polymer of end group are to utilize A2+B3Made from synthetic method, A2
For containing two reactive groups and at least one of which is the monomer of carboxyl, B3For the list containing three reactive hydroxyl groups
Body.
Method as described above, the A2Title and its corresponding structural formula it is as follows:
Pyrazine -2,3- dicarboxylic acids 2- carboxyethyl phenyl phosphinic acid 5- tert-butyl -1,3- benzene dicarboxylic acid 2- carboxyethyl phosphoric acid
The B3Title and its corresponding structural formula it is as follows:
Invention mechanism:
After metal salt ionizes in aqueous solution, there is interactions for interionic, and cation is by anion around it
Electrostatic attraction, the anion also electrostatic attraction by surrounding cation.Ion by with xenogenesis charge from
It, will also be by the mutual expelling force of the ion with like charges while sub mutually attraction.Therefore, the behavior of ion in the solution is not
Be it is entirely free on his, metal ion solution concentration is bigger, and interionic interaction force is stronger.And end group is carboxylic hyperbranched
Polymer can be swollen in organic solvent II, when metal ion solution is slowly dropped to the carboxylic hyperbranched poly of end group
When in polymer solution, metal ion may be loaded in two forms on the carboxylic dissaving polymer of end group: (1) after being swollen
The carboxylic dissaving polymer surface of end group-COOH and/orH can be dissociated+,-COO-And/orWith
Metal ion is keyed by ion；(2) carbonyl and/or phosphorus oxygen double bond inside the carboxylic hyperbranched polymer structure of end group
On oxygen and metal ion by coordination key connection.
After metal acetate salting liquid is added drop-wise to the carboxylic dissaving polymer solution of end group by the present invention, due to acetate
The electrostatic attraction of ion pair metal ion is approximate with carboxyl, therefore metal ion will not be carboxylic by the end group of swelling rapidly
The carboxyl total overall reaction on dissaving polymer surface, forming one " outer close interior thin ", (i.e. surface engagement is intensive, and internal engagement is dilute
Dredge) structure, under the conditions of sonic oscillation, a part of metal ion can be from the end being keyed with metal ion by ion
The gap on the carboxylic dissaving polymer surface of base enters the internal junction of the carboxylic dissaving polymer of end group after swelling
In structure, and with inside the carboxylic hyperbranched polymer structure of end group phosphorus oxygen double bond or carbonyl it is sufficiently coordination cross-linked, formed equal
Even cross-linked structure avoids general so that metal-modified dissaving polymer obtained has insoluble insoluble property
Electrification complex ion complex is soluble in the defect of organic solvent, solves functional dissaving polymer additive amount when being blended
It is excessively high that difficult problem can be brought to Polymer moulding.
The utility model has the advantages that
(1) the insoluble insoluble metal-modified dissaving polymer of one kind of the invention, has and is insoluble in common organic solvents
And the characteristics of not melting is heated, it approximate can be considered as inorganic particle when being blended and processing with other polymers, not lose its function
Property under the premise of, reduce the influence to blend rheological property, thus improve its be blended when additive amount, improve altogether
The content of functional element in mixed object, so that blended product obtained has more preferably effect；
(2) preparation method of the insoluble insoluble metal-modified dissaving polymer of one kind of the invention, simple and easy, cost
It is low, there is fabulous promotional value.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of insoluble insoluble metal-modified dissaving polymer, preparation step are as follows:
(1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2For pyrazine -2,3- dicarboxyl
Acid；B3For 1,1,1- tri- (methylol) propane；
Contain ester group in the carboxylic hyperbranched polymer molecule of obtained end group, the quantity of carboxyl accounts for end group total amount
25%, the degree of branching 60%, weight average molecular weight 2000g/mol；
(2) the carboxylic dissaving polymer of end group is dissolved in the end group that concentration is obtained in chloroform as 0.7mol/L containing carboxylic
It is molten to be obtained the metal ion that concentration is 0.8mol/L by the dissaving polymer solution of base in deionized water for cobalt acetate dissolution
Liquid；
(3) under the conditions of the sonic oscillation that mechanical stirring and power that rate is 200rpm are 600W, metal ion is molten
Drop, which is added in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 0.5 drop/sec, every drop
Volume be 0.05mL, after completion of dropwise addition in reaction system end group carboxylic dissaving polymer and metal ion molar ratio
For 1:30.5；
(4) mixed liquor after reaction is filtered, washed and is dried to obtain insoluble insoluble metal-modified over-expense
Fluidized polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 8h, and drying temperature is
25℃。
Insoluble insoluble metal-modified dissaving polymer is finally made, is the carboxylic hyperbranched polymer molecule of end group
In C=O double bond on oxygen atom and Co2+By in coordination the key connection simultaneously carboxylic hyperbranched polymer molecule of end group
- COO-Ion and Co2+It is keyed the network polymer to be formed by ion, there is insoluble insoluble characteristic, at 80 DEG C or less
Insoluble in benzene,toluene,xylene, styrene, butyl toluene, vinyltoluene, n-hexane, pentane, hexane, octane, hexamethylene,
Cyclohexanone, toluene cyclohexanone, chlorobenzene, dichloro-benzenes, methylene chloride, chloroform, carbon tetrachloride, trichloro ethylene, tetrachloro-ethylene, trichlorine third
Alkane, dichloroethanes, methanol, ethyl alcohol, isopropanol, n-butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, methyl acetate, acetic acid
Ethyl ester, propyl acetate, acetone, espeleton, methylisobutylketone, cyclohexanone, toluene cyclohexanone, acetonitrile, pyridine, phenol, N, N-
Dimethylformamide and n,N-dimethylacetamide, in room temperature to not melting within the scope of 370 DEG C；Metal-modified dissaving polymer
Partial size be 220~280nm, aerial initial decomposition temperature be 330 DEG C；Co in metal-modified dissaving polymer2+'s
Content is 8.3wt%.
Embodiment 2
A kind of insoluble insoluble metal-modified dissaving polymer, preparation step are as follows:
(1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2Are as follows: 2- carboxyethyl phenyl
Phosphonic acids；B3Are as follows: three (2- carboxyethyl) chlorinated isocyanurates；
Contain ester group in the carboxylic hyperbranched polymer molecule of obtained end group, the quantity of carboxyl accounts for end group total amount
27%, the degree of branching 53%, weight average molecular weight 43000g/mol；
(2) the carboxylic dissaving polymer dissolution of end group the end group that concentration is 0.85mol/L is obtained in acetone to contain
Nickel acetate dissolution is obtained the metal ion that concentration is 0.95mol/L by the dissaving polymer solution of carboxyl in deionized water
Solution；
(3) under the conditions of the sonic oscillation that magnetic agitation and power that rate is 300rpm are 900W, metal ion is molten
Drop, which is added in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 1 drop/sec, every drop
Volume is 0.08mL, and the molar ratio of the carboxylic dissaving polymer of end group and metal ion is in reaction system after completion of dropwise addition
1:28.2；
(4) mixed liquor after reaction is filtered, washed and is dried to obtain insoluble insoluble metal-modified over-expense
Fluidized polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 9h, and drying temperature is
25℃。
Insoluble insoluble metal-modified dissaving polymer is finally made, is the carboxylic hyperbranched polymer molecule of end group
In C=O double bond and oxygen atom and Ni in P=O double bond2+Pass through the carboxylic hyperbranched polymerization of end group simultaneously of coordination key connection
- COO in object molecule-Ion andIon and Ni2+The network polymer to be formed is keyed by ion, have it is insoluble not
Molten characteristic does not dissolve in organic solvent I at 80 DEG C or less, and the specific type of organic solvent I and embodiment 1 are consistent, room temperature extremely
It is not melted within the scope of 375 DEG C；The partial size of metal-modified dissaving polymer is 150~300nm, and temperature is decomposed in aerial starting
Degree is 380 DEG C；Ni in metal-modified dissaving polymer2+Content be 10.3wt%.
Embodiment 3
A kind of insoluble insoluble metal-modified dissaving polymer, preparation step are as follows:
(1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2Are as follows: 5- tert-butyl -1,3-
Benzene dicarboxylic acid；B3Are as follows: 2,4,5- trihydroxybutyrophenone；
Contain ester group in the carboxylic hyperbranched polymer molecule of obtained end group, the quantity of carboxyl accounts for end group total amount
25%, the degree of branching 30%, weight average molecular weight 15000g/mol；
(2) the carboxylic dissaving polymer of end group is dissolved in N,N-dimethylformamide and obtains concentration and is
The carboxylic dissaving polymer solution of the end group of 0.9mol/L, copper acetate dissolution is obtained concentration in deionized water is
The metal ion solution of 1.0mol/L；
(3) under the conditions of the sonic oscillation that magnetic agitation and power that rate is 400rpm are 700W, metal ion is molten
Drop, which is added in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 1 drop/sec, every drop
Volume is 0.06mL, and the molar ratio of the carboxylic dissaving polymer of end group and metal ion is in reaction system after completion of dropwise addition
1:46.69；
(4) mixed liquor after reaction is filtered, washed and is dried to obtain insoluble insoluble metal-modified over-expense
Fluidized polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 12h, drying temperature
It is 25 DEG C.
Insoluble insoluble metal-modified dissaving polymer is finally made, is the carboxylic hyperbranched polymer molecule of end group
In C=O double bond in oxygen atom and Cu2+By in coordination the key connection simultaneously carboxylic hyperbranched polymer molecule of end group
- COO-Ion and Cu2+It is keyed the network polymer to be formed by ion, there is insoluble insoluble characteristic, at 80 DEG C or less
Insoluble in organic solvent I, the specific type of organic solvent I and embodiment 1 are consistent, in room temperature to not melting within the scope of 380 DEG C；Gold
The partial size for belonging to modified ultra-branching polymer is 230~300nm, and aerial initial decomposition temperature is 390 DEG C；It is metal-modified super
Cu in branched polymer2+Content be 7.5wt%.
Embodiment 4
A kind of insoluble insoluble metal-modified dissaving polymer, preparation step are as follows:
(1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2Are as follows: 2- carboxyethyl phosphoric acid；
B3Are as follows: 2,4,5- trihydroxybutyrophenone；
Contain ester group in the carboxylic hyperbranched polymer molecule of obtained end group, the quantity of carboxyl accounts for end group total amount
100%, the degree of branching 64%, weight average molecular weight 50000g/mol；
(2) the carboxylic dissaving polymer of end group is dissolved in obtained in chloroform concentration be 1.05mol/L end group contain
It is molten to be obtained the metal ion that concentration is 0.7mol/L by the dissaving polymer solution of carboxyl in deionized water for zinc acetate dissolution
Liquid；
(3) under the conditions of the sonic oscillation that mechanical stirring and power that rate is 500rpm are 1200W, metal ion is molten
Drop, which is added in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 0.5 drop/sec, every drop
Volume be 0.09mL, after completion of dropwise addition in reaction system end group carboxylic dissaving polymer and metal ion molar ratio
For 1:5.77；
(4) mixed liquor after reaction is filtered, washed and is dried to obtain insoluble insoluble metal-modified over-expense
Fluidized polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 8h, and drying temperature is
25℃。
Insoluble insoluble metal-modified dissaving polymer is finally made, is the carboxylic hyperbranched polymer molecule of end group
In C=O double bond and oxygen atom and Zn in P=O double bond2+Pass through the carboxylic hyperbranched polymerization of end group simultaneously of coordination key connection
- COO in object molecule-Ion andIon and Zn2+The network polymer to be formed is keyed by ion, have it is insoluble not
Molten characteristic does not dissolve in organic solvent I at 80 DEG C or less, and the specific type of organic solvent I and embodiment 1 are consistent, room temperature extremely
It is not melted within the scope of 380 DEG C；The partial size of metal-modified dissaving polymer is 330~500nm, and temperature is decomposed in aerial starting
Degree is 300 DEG C；Zn in metal-modified dissaving polymer2+Content be 9.3wt%.
Embodiment 5
A kind of insoluble insoluble metal-modified dissaving polymer, preparation step are as follows:
(1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2Are as follows: pyrazine -2,3- dicarboxyl
Acid；B3: three (2- carboxyethyl) chlorinated isocyanurates；
Contain ester group in the carboxylic hyperbranched polymer molecule of obtained end group, the quantity of carboxyl accounts for end group total amount
44%, the degree of branching 84%, weight average molecular weight 6000g/mol；
(2) the carboxylic dissaving polymer dissolution of end group is obtained into the end group that concentration is 1.0mol/L in acetone and contains carboxylic
It is molten to be obtained the metal ion that concentration is 1.25mol/L by the dissaving polymer solution of base in deionized water for cobalt acetate dissolution
Liquid；
(3) under the conditions of the sonic oscillation that mechanical stirring and power that rate is 500rpm are 1100W, metal ion is molten
Drop, which is added in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 2 drops/sec, every drop
Volume is 0.1mL, and the molar ratio of the carboxylic dissaving polymer of end group and metal ion is in reaction system after completion of dropwise addition
1:0.64；
(4) mixed liquor after reaction is filtered, washed and is dried to obtain insoluble insoluble metal-modified over-expense
Fluidized polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 11h, drying temperature
It is 25 DEG C.
Insoluble insoluble metal-modified dissaving polymer is finally made, is the carboxylic hyperbranched polymer molecule of end group
In C=O double bond in oxygen atom and Co2+By in coordination the key connection simultaneously carboxylic hyperbranched polymer molecule of end group
- COO-Ion and Co2+It is keyed the network polymer to be formed by ion, there is insoluble insoluble characteristic, at 80 DEG C or less
Insoluble in organic solvent I, the specific type of organic solvent I and embodiment 1 are consistent, in room temperature to not melting within the scope of 370 DEG C；Gold
The partial size for belonging to modified ultra-branching polymer is 260~350nm, and aerial initial decomposition temperature is 375 DEG C；It is metal-modified super
Co in branched polymer2+Content be 6.3wt%.
Embodiment 6
A kind of insoluble insoluble metal-modified dissaving polymer, preparation step are as follows:
(1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2Are as follows: 2- carboxyethyl phenyl
Phosphonic acids；B3Are as follows: 2,4,5- trihydroxybutyrophenone；
Contain ester group in the carboxylic hyperbranched polymer molecule of obtained end group, the quantity of carboxyl accounts for end group total amount
45%, the degree of branching 74%, weight average molecular weight 6000g/mol；
(2) the carboxylic dissaving polymer of end group is dissolved in the end group that concentration is obtained in chloroform as 1.1mol/L containing carboxylic
Cobalt acetate is dissolved and obtains the metal ion solution that concentration is 1.15mol/L in deionized water by the dissaving polymer solution of base；
(3) under the conditions of the sonic oscillation that magnetic agitation and power that rate is 300rpm are 1000W, metal ion is molten
Drop, which is added in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 2 drops/sec, every drop
Volume is 0.1mL, and the molar ratio of the carboxylic dissaving polymer of end group and metal ion is in reaction system after completion of dropwise addition
1:33.45；
(4) mixed liquor after reaction is filtered, washed and is dried to obtain insoluble insoluble metal-modified over-expense
Fluidized polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 10h, drying temperature
It is 25 DEG C.
Insoluble insoluble metal-modified dissaving polymer is finally made, is the carboxylic hyperbranched polymer molecule of end group
In C=O double bond and oxygen atom and Co in P=O double bond2+Pass through the carboxylic hyperbranched polymerization of end group simultaneously of coordination key connection
- COO in object molecule-Ion andIon and Co2+The network polymer to be formed is keyed by ion, have it is insoluble not
Molten characteristic does not dissolve in organic solvent I at 80 DEG C or less, and the specific type of organic solvent I and embodiment 1 are consistent, room temperature extremely
It is not melted within the scope of 370 DEG C；The partial size of metal-modified dissaving polymer is 180~260nm, and temperature is decomposed in aerial starting
Degree is 375 DEG C；Co in metal-modified dissaving polymer2+Content be 5.6wt%.
Embodiment 7
A kind of insoluble insoluble metal-modified dissaving polymer, preparation step are as follows:
(1) A is utilized2+B3The carboxylic dissaving polymer of end group: wherein A is made in synthetic method2Are as follows: 5- tert-butyl -1,3-
Benzene dicarboxylic acid；B3Are as follows: 2,3,4- trihydroxy-acetophenone；
Contain ester group in the carboxylic hyperbranched polymer molecule of obtained end group, the quantity of carboxyl accounts for end group total amount
37%, the degree of branching 85%, weight average molecular weight 37000g/mol；
(2) the carboxylic dissaving polymer of end group is dissolved in N,N-dimethylformamide and obtains concentration and is
The carboxylic dissaving polymer solution of the end group of 1.25mol/L, copper acetate dissolution is obtained concentration in deionized water is
The metal ion solution of 1.2mol/L；
(3) under the conditions of the sonic oscillation that mechanical stirring and power that rate is 200rpm are 600W, metal ion is molten
Drop, which is added in the carboxylic dissaving polymer solution of end group, to be reacted, wherein the speed being added dropwise is 2 drops/sec, every drop
Volume is 0.05mL, and the molar ratio of the carboxylic dissaving polymer of end group and metal ion is in reaction system after completion of dropwise addition
1:9.1；
(4) mixed liquor after reaction is filtered, washed and is dried to obtain insoluble insoluble metal-modified over-expense
Fluidized polymer, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 12h, drying temperature
It is 25 DEG C.
Insoluble insoluble metal-modified dissaving polymer is finally made, is the carboxylic hyperbranched polymer molecule of end group
In C=O double bond in oxygen atom and Cu2+By in coordination the key connection simultaneously carboxylic hyperbranched polymer molecule of end group
- COO-Ion and Cu2+It is keyed the network polymer to be formed by ion, there is insoluble insoluble characteristic, at 80 DEG C or less
Insoluble in organic solvent I, the specific type of organic solvent I and embodiment 1 are consistent, in room temperature to not melting within the scope of 370 DEG C；Gold
The partial size for belonging to modified ultra-branching polymer is 310~480nm, and aerial initial decomposition temperature is 360 DEG C；It is metal-modified super
Cu in branched polymer2+Content be 12.3wt%.
Embodiment 8~20
A kind of insoluble insoluble metal-modified dissaving polymer, preparation step and embodiment 1 are almost the same, unlike
A2And B3Type, final obtained insoluble insoluble metal-modified dissaving polymer not melt temperature scope, starting thermal decomposition
The content of temperature, partial size and metal ion is different, is specifically shown in Table 1:
Table 1
The carboxylic hyperbranched polymerization of end group in the insoluble insoluble metal-modified dissaving polymer of one kind made from final
Object molecule and metal ion crosslinked situation are as shown in table 2:
Table 2
Claims (10)
1. a kind of insoluble insoluble metal-modified dissaving polymer, it is characterized in that: being the carboxylic dissaving polymer of end group
The network polymer formed with metal ion crosslinked, metal-modified dissaving polymer has insoluble insoluble characteristic, at 80 DEG C
Organic solvent I is not dissolved in below, is not melted in room temperature to T range, T >=370 DEG C；
The crosslinking is by the oxygen atom and metal ion in the double bond inside the carboxylic hyperbranched polymer molecule of end group
By coordination key connection simultaneously the carboxylic hyperbranched polymer molecule end of end group acid ion and metal ion by from
Sub-key connection is realized；
The organic solvent I is that aromatic hydrocarbon solvent, fat hydrocarbon solvent, alicyclic hydrocarbon type solvent, halogenated hydrocarbon solvent, alcohols are molten
Agent, esters solvent, ketones solvent, acetonitrile, pyridine, phenol, N,N-dimethylformamide or DMAC N,N' dimethyl acetamide.
2. the insoluble insoluble metal-modified dissaving polymer of one kind according to claim 1, which is characterized in that the virtue
Fragrant hydrocarbon solvent is benzene,toluene,xylene, styrene, butyl toluene or vinyltoluene；The fat hydrocarbon solvent is positive oneself
Alkane, pentane, hexane or octane；The alicyclic hydrocarbon type solvent is hexamethylene, cyclohexanone or toluene cyclohexanone；The halogenated hydrocarbon is molten
Agent is chlorobenzene, dichloro-benzenes, methylene chloride, chloroform, carbon tetrachloride, trichloro ethylene, tetrachloro-ethylene, trichloropropane or dichloroethanes；
The alcohols solvent is methanol, ethyl alcohol, isopropanol, n-butanol, cyclohexanol, benzyl alcohol, ethylene glycol or propylene glycol；The esters are molten
Agent is methyl acetate, ethyl acetate or propyl acetate；The ketones solvent is acetone, espeleton, methylisobutylketone, cyclohexanone
Or toluene cyclohexanone.
3. the insoluble insoluble metal-modified dissaving polymer of one kind according to claim 1 or 2, which is characterized in that institute
Stating the aerial initial decomposition temperature of metal-modified dissaving polymer is 300~400 DEG C, the metal-modified hyperbranched poly
The partial size for closing object is 150~500nm.
4. the insoluble insoluble metal-modified dissaving polymer of one kind according to claim 3, which is characterized in that the end
The quantity of carboxyl accounts for the 25%~100% of end group total amount in the carboxylic dissaving polymer of base, and the end group is carboxylic super
Contain ester group in the molecule of branched polymer, the degree of branching of the carboxylic dissaving polymer of end group is 30~100%, institute
The weight average molecular weight for stating the carboxylic dissaving polymer of end group is 1100~50000g/mol.
5. the insoluble insoluble metal-modified dissaving polymer of one kind according to claim 4, which is characterized in that the gold
Category ion is Co2+、Ni2+、Cu2+Or Zn2+, the metal ion is provided by its corresponding mol ratio of metal acetate, described metal-modified super
The content of metal ion is 5.5~12.5wt% in branched polymer.
6. the method for preparing the insoluble insoluble metal-modified dissaving polymer of one kind as claimed in any one of claims 1 to 5,
It is characterized in that: metal acetate salting liquid is added dropwise into the carboxylic dissaving polymer solution of end group is made insoluble insoluble metal
Modified ultra-branching polymer.
7. according to the method described in claim 6, it is characterized in that, specific step is as follows:
(1) the carboxylic dissaving polymer of end group and mol ratio of metal acetate are dissolved in organic solvent II and deionized water respectively
Obtain the carboxylic dissaving polymer solution of end group and metal ion solution；
(2) under the conditions of stirring and sonic oscillation, it is molten that metal ion solution is added drop-wise to the carboxylic dissaving polymer of end group
It is reacted in liquid；
(3) mixed liquor after reaction is post-processed to obtain insoluble insoluble metal-modified dissaving polymer.
8. the method according to the description of claim 7 is characterized in that the organic solvent II is chloroform, acetone in step (1)
Or n,N-Dimethylformamide, the concentration of the carboxylic dissaving polymer solution of end group are 0.7~1.25mol/L, institute
The concentration for stating metal ion solution is 0.7~1.25mol/L；
In step (2), the stirring is mechanical stirring or magnetic agitation, and the rate of stirring is 200~500rpm, the ultrasound vibration
The power swung is 600~1200W, and the speed of the dropwise addition is 0.5~2 drop/sec, and the volume of every drop is 0.05~0.1mL, is added dropwise
After in reaction system the molar ratio of the carboxylic dissaving polymer of end group and metal ion be 1:0.64~46.69；
In step (3), the post-processing, which refers to, to be filtered, washed and dried, and the drying carries out under vacuum conditions, vacuum
Degree is -0.1MPa, and drying time is 8~12h, and drying temperature is 25 DEG C.
9. according to the method described in claim 8, it is characterized in that, the carboxylic dissaving polymer of the end group is to utilize A2+
B3Made from synthetic method, A2For containing two reactive groups and at least one of which is the monomer of carboxyl, B3For can be anti-containing three
The monomer for the hydroxyl group answered.
10. according to the method described in claim 9, it is characterized in that, the A2For pyrazine -2,3- dicarboxylic acids, 2- carboxyethyl phenyl
Phosphinic acids, 5- tert-butyl -1,3- benzene dicarboxylic acid or 2- carboxyethyl phosphoric acid, the B3For 1,1,1- tri- (methylol) propane, three (2-
Ethoxy) chlorinated isocyanurates, 2,4,5- trihydroxybutyrophenone, 2,3,4- trihydroxy-acetophenone or 1,2,4- trihydroxy benzene.
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