CN109232861A - Polymeric system and preparation method thereof - Google Patents
Polymeric system and preparation method thereof Download PDFInfo
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- CN109232861A CN109232861A CN201810709855.XA CN201810709855A CN109232861A CN 109232861 A CN109232861 A CN 109232861A CN 201810709855 A CN201810709855 A CN 201810709855A CN 109232861 A CN109232861 A CN 109232861A
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- polymeric system
- polyalcohol
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- borate crosslinker
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4078—Curing agents not provided for by the groups C08G59/42 - C08G59/66 boron containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
- C08K5/3465—Six-membered rings condensed with carbocyclic rings
Abstract
The invention belongs to technical field of polymer materials, and in particular to a kind of polymeric system and preparation method thereof.The polymeric system includes: polyalcohol, containing borate crosslinker and pH adjusting agent;Wherein, the polyalcohol contains at least two diol structure segments, and for a boron atom containing in borate crosslinker at most with a carbon atom Direct Bonding, the diol structure segment in the polyalcohol and the boron in the borate crosslinker form boric acid ester bond;The glass transition temperature of the polymeric system is higher than plasticization temperature.Because the glass transition temperature of Inventive polymers system can be adjusted in a big way by polyalcohol, to be suitable for the requirement of different occasions.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of polymeric system and preparation method thereof.
Background technique
High-molecular organic material is also known as polymer or high polymer, is one kind by one or more of molecules or micel (structure
Unit or monomer) with macromolecular of the covalently bonded synthesis with multiple repeated monomer units;It is such as fine that they can be natural products
Dimension, protein and natural rubber etc. are also possible to made from synthetic method, such as synthetic rubber, synthetic resin, synthetic fibers
Abiotic high polymer etc..
The plasticization temperature of polymer is the temperature that key exchange occurs for reversible key in polymer, and for the moulding of polymer, provide can
Row, the glass transition temperature of polymer is to realize that the shape of polymer is fixed, when being lower than this temperature, polymer conversion
For glassy state, key exchange process is slow, to make the fixed shape of polymer and obtain certain mechanical property.But existing synthesis is poly-
During closing object, being difficult to for the polymer for adjusting control, therefore obtaining often is difficult to the glass transition temperature of polymer
It is suitble to the requirement of different occasions.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, a kind of polymeric system and its preparation side are provided
Method, it is intended to which the glass transition temperature for solving existing polymer is difficult to, so that the technology that can not adapt to more occasion demands is asked
Topic.
For achieving the above object, The technical solution adopted by the invention is as follows:
One aspect of the present invention provides a kind of polymeric system, the polymeric system include: polyalcohol, containing borate crosslinker and
PH adjusting agent;Wherein,
The polyalcohol contains at least two diol structure segments, a boron atom containing in borate crosslinker at most with
One carbon atom Direct Bonding, the boron in diol structure segment and the borate crosslinker in the polyalcohol form borate
Key;
The glass transition temperature of the polymeric system is higher than plasticization temperature.
Another aspect of the present invention provides a kind of preparation method of above-mentioned polymeric system, includes the following steps:
There is provided the polyalcohol, containing borate crosslinker and pH adjusting agent;
It is mixed by the polyalcohol, containing borate crosslinker and pH adjusting agent, is heated to the glass of the polymeric system
More than glass transition temperature, deformation process is then carried out, obtains initial polymer material;
The initial polymer material is cooled to the glass transition temperature of the polymeric system hereinafter, obtaining described
Polymeric system.
In polymeric system provided by the invention, polyalcohol and borate crosslinker form boric acid ester bond, pass through boric acid ester bond structure
The whole network structure of polymeric system is built up, the key exchange temperature of the boric acid ester bond is lower, and pH adjusting agent can make the boric acid
Ester bond is more stable, by the selection to polyalcohol, can determine and regulate and control the commutative temperature of boric acid ester bond;Meanwhile polymeric acceptor
The glass transition temperature of system is provided by polyol moiety, is convenient to realize to vitrifying turn by different types of polyalcohol
The regulation of temperature, therefore, the glass transition temperature that polymeric system may finally be reached by the selection to polyalcohol are high
In plasticization temperature.When more than glass transition temperature, due to the exchange of boric acid ester bond, polymeric system can obtain lower
Viscosity is easy to moulding, and when below glass transition temperature, slowly due to the exchange of boric acid ester bond, polymeric system can be obtained
Preferable mechanical property;Because the glass transition temperature of Inventive polymers system can be adjusted in a big way by polyalcohol
Section, to be suitable for the requirement of different occasions.
The ingredient of polymer material is first mixed and heated to poly- by the preparation method of above-mentioned polymeric system provided by the invention
On the glass transition temperature for closing objects system, deformation is carried out to predetermined shape, is then cooled to the vitrifying of polymeric system
The polymeric system is obtained below transition temperature.When being heated to glass transition temperature or more, since the plasticizing of system turns
Temperature is lower than glass transition temperature, and key exchange reaction can occur for boric acid ester bond, at this point, under external force, mixing material
The macroscopic deformation of generation can become permanent plastic deformation by the exchange reaction of boric acid ester bond;When temperature is down to glass transition
When below temperature, due to the sub-chain motion of glassy state limitation polymer, the exchange of boric acid ester bond is slow, the shape of polymeric system
It is fixed, mechanical property improves.The glass transition temperature of final polymeric system obtained can be adjusted in a big way,
To be suitable for the requirement of different occasions.
Detailed description of the invention
Fig. 1 is the DMA spectrogram of polymeric system prepared by the embodiment of the present invention 1;
Fig. 2 is the DMA spectrogram of polymeric system prepared by the embodiment of the present invention 2;
Fig. 3 is the DMA spectrogram of polymeric system prepared by the embodiment of the present invention 3.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
On the one hand, the embodiment of the invention provides a kind of polymeric system, the polymeric system includes: polyalcohol, contains
Borate crosslinker and pH adjusting agent;Wherein,
The polyalcohol contains at least two diol structure segments, a boron atom containing in borate crosslinker at most with
One carbon atom Direct Bonding, the boron in diol structure segment and the borate crosslinker in the polyalcohol form borate
Key;
The glass transition temperature of the polymeric system is higher than plasticization temperature.
Another aspect of the present invention provides a kind of preparation method of above-mentioned polymeric system, includes the following steps:
In polymeric system provided in an embodiment of the present invention, polyalcohol and borate crosslinker form boric acid ester bond, pass through boric acid
Ester bond is built into the whole network structure of polymeric system, and the key exchange temperature of the boric acid ester bond is lower, and pH adjusting agent can make
The boric acid ester bond is more stable, by the selection to polyalcohol, can determine and regulate and control the commutative temperature of boric acid ester bond, plasticization temperature
The temperature of key exchange occurs for the reversible key of borate as in polymeric system;Meanwhile the glass transition temperature of polymeric system
It is provided by polyol moiety, is convenient to realize the regulation to glass transition temperature by different types of organic matter, therefore,
The glass transition temperature that polymeric system may finally be reached by the selection to polyalcohol is higher than plasticization temperature.In vitrifying
When more than transition temperature, due to the exchange of boric acid ester bond, polymeric system can obtain lower viscosity, be easy to moulding, in glass
When below glass transition temperature, slowly due to the exchange of boric acid ester bond, polymeric system can obtain preferable mechanical property;Yin Ben
The glass transition temperature of invention polymeric system can be adjusted in a big way by polyalcohol, to be suitable for different occasions
Requirement.
Specifically, for polyalcohol, two or more diol structure segment (such as β-two are contained in molecular structure
Alcohol structure or γ-diol structure, such as in a specific example, by reacting for mercapto glycerol and polynary epoxy, to polyalcohol point
Multiple beta-diol structures are introduced in son), polyalcohol plays conclusive work to the boric acid ester bond softening temperature of entire polymeric system
With boric acid ester bond softening temperature being adjusted by adjusting the composition of the part.For containing borate crosslinker, energy is selected
Contain borate crosslinker in combination with multiple beta-diol structures or γ-diol structure: if containing boron atom in borate crosslinker it is not direct with
Carbon atom bonding (such as borax, borate ester), then single boron atom can be combined with two diol structures;If boracic is crosslinked
Boron atom is mutually bonded (such as to benzene hypoboric acid) with a carbon atom in agent, then single boron atom can be with a diol structure phase
In conjunction with;If being mutually bonded containing boron atom in borate crosslinker with multiple (at least two) carbon atoms, the boron-containing compound is not as containing
The range of choice of borate crosslinker, therefore, a boron atom containing in borate crosslinker at most with a carbon atom Direct Bonding,
Entire polymeric system is set to obtain certain mechanical strength containing borate crosslinker.For pH adjusting agent, selection can be with system phase
The middle highly basic held: boric acid ester bond is a kind of dynamic covalent bond influenced by pH, and pH adjusting agent is to provide certain alkali to system
Property environment, keeps boric acid ester bond more stable.
Further, in polymeric system provided in an embodiment of the present invention, the polyalcohol be small molecule or oligomer,
Relative molecular weight is generally below 5000;Specifically, the polyalcohol is by multi-thiol monomer, polynary epoxy monomer, polynary third
At least one of olefin(e) acid esters monomer and 3- sulfydryl -1,2- propylene glycol, 3- amido-1,2-propanediol, 3- methylamino -1,2- third
At least one of glycol is condensed to yield.Wherein, the multi-thiol monomer is selected from the multi-thiol of 2-40 carbon atom;It is described
Polynary epoxy monomer is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy resin and 2-40 carbon atom
At least one of polynary epoxy;The multicomponent methacrylate class monomer is selected from tricyclic [5.2.1.02,6] decane dimethanol dipropyl
At least one of olefin(e) acid ester, trimethylolpropane trimethacrylate and pentaerythritol tetraacrylate.It is highly preferred that the 2-
The multi-thiol of 40 carbon atoms is selected from 2,2 '-(1,2- second diyl dioxygen generations) double ethyl mercaptans, four (3- mercaptopropionic acid) Ji Wusi
At least one of alcohol ester, trimethylolpropane tris (3-thiopropionate) and glycol dimercaptoacetate;It is highly preferred that institute
The polynary epoxy for stating 2-40 carbon atom is selected from bisphenol A diglycidyl ether, the glycidyl -4,4- diamino of N, N, N, N,-four
Diphenyl-methane, polypropylene glycol diepoxide for example methyl ether, polyethylene glycol diepoxide for example methyl ether, p- (the third oxygen of 2,3- epoxy
Base)-N, in (2,3- glycidyl) aniline of N- bis- and 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters at least
It is a kind of.Further, described to be selected from boric acid, borax, boron containing borate crosslinker in polymeric system provided in an embodiment of the present invention
Acid esters (such as trimethylborate), to benzene hypoboric acid, 4- vinylphenylboronic acid, 3- vinylphenylboronic acid and 3- acrylamido benzene boron
At least one of acid;The pH adjusting agent is selected from 1,8- diazabicyclo [5.4.0] 11 carbon -7- alkene and tri- azepine of 1,5,7-
At least one of two rings [4.4.0] certain herbaceous plants with big flowers -5- alkene.
Specifically, synthesize the segment containing diol structure polyalcohol when, the polynary preferable liquid form of epoxy monomer it is polynary
Epoxy monomer component, liquid are easier to mix with other components, such as: use bisphenol A diglycidyl ether, N, N, N, N ,-four
Glycidyl -4,4- diaminodiphenylmethane, p- (2,3- glycidoxy)-N, N- bis- (2,3- glycidyl) aniline, 3,4-
Epoxycyclohexyl-methyl 3, the system of 4- epoxycyclohexyl formic acid esters, softening temperature use two ring of polypropylene glycol at 80 DEG C or more
The system of oxidative ethane methyl ether, polyethylene glycol diepoxide for example methyl ether, softening temperature is in room temperature hereinafter, by two class epoxy monomers
It is used in mixed way, adjustable system in softening temperature a certain range can be obtained.Such as preferred multi-thiol monomer: multi-thiol can make ring
Oxygen molecule carries out chain extension, and to enhance the mechanical property of final system, preferred multi-thiol molecular weight and structure are suitable herein, right
The softening temperature of final polymeric system influences relatively small.By the selection to polyalcohol, the polymeric acceptor is finally obtained
The glass transition temperature of system may range from 40-100 DEG C, and softening temperature can be adjusted to tract below glass transition temperature.
Finally be preferably trimethylborate containing borate crosslinker: trimethylborate is liquid, good with reaction system compatibility, and
And for a boron atom in conjunction with two diol structures, additive amount is less in trimethylborate.For pH adjusting agent, preferred 1,1,
11 carbon -7- alkene of 8- diazabicyclo [5.4.0] and 1,5,7- tri- azabicyclic [4.4.0] certain herbaceous plants with big flowers -5- alkene are organic base, and are reacted
Miscibility is good, and alkalinity is suitable, and the catalyst that both alkali are reacted as sulfydryl in reaction system and epoxy group,
Excellent catalytic effect.
Further, in polymeric system provided in an embodiment of the present invention, the boron atom containing in borate crosslinker with
The molar ratio of diol structure segment in the polyalcohol is 1:(1-2);Containing borate crosslinker as crosslinking agent, by in monomer
Beta-diol structure or γ-diol structure, which combine, forms polymeric system, and theoretical stoichiometric is as follows than calculation method: for boron
The not direct borate crosslinker that contains with carbon atom bonding of atom, foundation is containing beta-diol structure in boron atom in borate crosslinker and monomer
And/or γ-diol structure molar ratio is 1:2, calculates the additive amount containing borate crosslinker;For boron atom and a carbon atom
Bonding contains borate crosslinker, according to containing beta-diol structure and/or γ-diol structure mole in boron atom in borate crosslinker and monomer
Ratio is 1:1, calculates the additive amount containing borate crosslinker.Further, the pH adjusting agent and the quality containing borate crosslinker
Than for (05-2): 1, such as 1,8- diazabicyclo [5.4.0] 11 carbon -7- alkene or 1,11 carbon of 8- diazabicyclo [5.4.0] -
The mass ratio of 7- alkene and trimethylborate is 1:1.
In short, above-mentioned bond together to form polymer network by boric acid ester bond containing borate crosslinker and polyalcohol, boric acid ester bond exists
Reversible key exchange more than certain temperature can occur, and form more stable covalent bond compared to common cross-linking agent, be material
Material system provides plasticity;The key exchange temperature of boric acid ester bond is lower compared to other reversible key (such as carboxylic acid ester bond) temperature,
Can meet should be not higher than this requirement of the glass transition temperature of monomeric polyol.
On the other hand, the embodiment of the invention also provides a kind of preparation method of above-mentioned polymeric system,
S01: the polyalcohol is provided, containing borate crosslinker and pH adjusting agent;
S02: mixing by the polyalcohol, containing borate crosslinker and pH adjusting agent, is heated to the polymeric system
Glass transition temperature more than, then carry out deformation process, obtain initial polymer material;
S03: the initial polymer material is cooled to the glass transition temperature of the polymeric system hereinafter, obtaining
The polymeric system.
The ingredient of polymer material is first mixed and is added by the preparation method of above-mentioned polymeric system provided in an embodiment of the present invention
On heat to the glass transition temperature of polymeric system, deformation is carried out to predetermined shape, is then cooled to polymeric system
The polymeric system is obtained below glass transition temperature.When being heated to glass transition temperature or more, due to system
It is plasticized transition temperature and is lower than glass transition temperature, key exchange reaction can occur for boric acid ester bond, at this point, under external force, mixing
The macroscopic deformation that condensation material occurs can become permanent plastic deformation by the exchange reaction of boric acid ester bond;When temperature is down to glass
When changing transition temperature or less, due to the sub-chain motion of glassy state limitation polymer, the exchange of boric acid ester bond is slow, polymeric system
Shape fixed, mechanical property improve.The glass transition temperature of final polymeric system obtained can be in larger range
Interior adjusting, to be suitable for the requirement of different occasions.And the preparation method of the polymeric system is easy to operate, is suitable for work
Industry mass production.
Finally, the glass transition temperature of polymeric system is 20-80 DEG C.The glass transition temperature of the polymeric system
It can be adjusted by the design of polyol molecule structure.In above-mentioned steps S01, polyalcohol is adjusted containing borate crosslinker and pH
It has illustrated above the selection of agent, has no longer illustrated here.
In above-mentioned steps S02: glass transition temperature or more is heated to, and under external force, by the polymer
The mixing of system ingredient is invisible to fade to predetermined shape;After being heated to glass transition temperature or more, boric acid ester bond can in system
Reversible key exchange occurs in the temperature, internal stress caused by external force is dissipated, and obtained shape is permanent shape, and external force is removed
Original-shape will not be returned back to after going.External force is removed, then cools the temperature to the glass transition temperature of system hereinafter, being had
There is the polymer material of designated shape and good mechanical properties.
In above-mentioned steps S03, turn in the vitrifying that the initial polymer material is cooled to the polymeric system
After step below temperature, further include the steps that being dried, it is small that 0.5-1 is such as dried in vacuo under the conditions of 100-120 DEG C
When.
The present invention successively carried out test of many times, and it is further detailed as reference pair invention progress now to lift A partial experiment result
Thin description, is described in detail combined with specific embodiments below.
Embodiment 1
A kind of polymeric system, raw material are as follows:
A) p- (2,3- glycidoxy)-N, N- bis- (2,3- glycidyl) aniline, Sigma-Aldrich company;Structure
Formula is as follows:
B) 3- sulfydryl -1,2-PD, TCI company;Structural formula is as follows:
C) trimethylborate, TCI company;Structure is as follows:
D) 11 carbon -7- alkene of 1,8- diazabicyclo [5.4.0]: TCI company;Structural formula is as follows:
Preparation method:
3- sulfydryl -1,2-PD and 5.41mmol trimethylborate of 10.82mmol is weighed, stirring is equal to mixing
It is even.Under water-bath cooling, 1,8- diazabicyclo [5.4.0], the 11 carbon -7- alkene of 3.69mmol is added, stirs evenly.It is added
P- (2,3- glycidoxy)-N, N- bis- (2,3- glycidyl) aniline of 3.61mmol, it is close by magnetic agitation at 50 DEG C
Envelope reaction 1 hour.It pours into aluminium dish and is reacted 8 hours in 80 DEG C of baking oven, it is 0.5 hour dry in 120 DEG C of vacuum drying ovens
Obtain product.
DMA (dynamic thermomechanical analysis) spectrogram of the polymeric system is as shown in Figure 1, as can be seen from Figure 1: the polymeric system
Glass transition temperature about between 50-60 DEG C, softening temperature be lower than the temperature.
Embodiment 2
A kind of polymeric system, raw material are as follows:
A) p- (2,3- glycidoxy)-N, N- bis- (2,3- glycidyl) aniline, Sigma-Aldrich company;
B) bisphenol A diglycidyl ether, Sigma-Aldrich company;Structural formula is as follows:
C) 3- sulfydryl -1,2-PD, TCI company;
D) trimethylborate, TCI company;
E) 11 carbon -7- alkene of 1,8- diazabicyclo [5.4.0], TCI company;
Preparation method:
3- sulfydryl -1,2-PD and 3.72mmol trimethylborate of 7.45mmol is weighed, is stirred to uniformly mixed.
Under water-bath cooling, 1,8- diazabicyclo [5.4.0], the 11 carbon -7- alkene of 2.54mmol is added, stirs evenly.It is added
P- (2,3- glycidoxy)-N, N- bis- (2,3- glycidyl) aniline of 1.19mmol and the bisphenol-A two of 1.94mmol shrink
Glycerin ether passes through magnetic agitation, sealing reaction 1 hour at 50 DEG C.It pours into aluminium dish and is reacted 8 hours in 80 DEG C of baking oven,
It is 0.5 hour dry in 120 DEG C of vacuum drying ovens, product can be obtained.
The DMA spectrogram of the polymeric system is as shown in Fig. 2, as can be seen from Figure 2: the glass transition temperature of the polymeric system
About between 60-70 DEG C, softening temperature is lower than the temperature.
Embodiment 3
A kind of polymeric system, raw material are as follows:
A) bisphenol A diglycidyl ether, Sigma-Aldrich company;
B) 2,2 '-(1,2- second diyl dioxygen generation) double ethyl mercaptans, Sigma-Aldrich company;Structural formula is as follows:
C) 3- sulfydryl -1,2-PD, TCI company;
D) trimethylborate, TCI company;
E) 1,8- diazabicyclo [5.4.0], 11 carbon -7- alkene, TCI company;
Preparation method:
3- sulfydryl -1,2-PD and 0.98mmol trimethylborate of 1.96mmol is weighed, is stirred to uniformly mixed.
Under water-bath cooling, 1,8- diazabicyclo [5.4.0], the 11 carbon -7- alkene of 0.67mmol is added, stirs evenly.It is added
The 2 of 1.96mmol, the bisphenol A diglycidyl ether of 2 '-(1,2- second diyl dioxygen generation) double ethyl mercaptans and 2.94mmol, at 50 DEG C
Pass through magnetic agitation, sealing reaction 1 hour down.It pours into aluminium dish and is reacted 8 hours in 80 DEG C of baking oven, 120 DEG C of vacuum drying ovens
Middle drying 0.5 hour, can be obtained product.
The DMA map of the polymeric system is as shown in figure 3, as can be seen from Figure 3: the glass transition temperature of the polymeric system
About between 40-50 DEG C, softening temperature is lower than the temperature.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of polymeric system, which is characterized in that the polymeric system includes: polyalcohol, containing borate crosslinker and pH adjusting
Agent;Wherein,
The polyalcohol contains at least two diol structure segments, a boron atom containing in borate crosslinker at most with one
Carbon atom Direct Bonding, the boron in diol structure segment and the borate crosslinker in the polyalcohol form boric acid ester bond;
The glass transition temperature of the polymeric system is higher than plasticization temperature.
2. polymeric system as described in claim 1, which is characterized in that the boron atom containing in borate crosslinker and described more
The molar ratio of diol structure segment in first alcohol is 1:(1-2);And/or
The pH adjusting agent and the mass ratio containing borate crosslinker are (05-2): 1.
3. polymerization system as described in claim 1, which is characterized in that the polyalcohol is by multi-thiol monomer, polynary epoxy
At least one of monomer, multicomponent methacrylate class monomer and 3- sulfydryl -1,2- propylene glycol, 3- amido-1,2-propanediol, 3- first
At least one of amido-1,2-propanediol is condensed to yield.
4. polymeric system as claimed in claim 3, which is characterized in that the multi-thiol monomer is selected from 2-40 carbon atom
Multi-thiol;And/or
The polynary epoxy monomer is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac epoxy resin and 2-40
At least one of polynary epoxy of carbon atom;And/or
The multicomponent methacrylate class monomer is selected from tricyclic [5.2.1.02,6] decane dimethanol diacrylate, trihydroxy methyl third
At least one of alkane triacrylate and pentaerythritol tetraacrylate.
5. polymeric system as claimed in claim 4, which is characterized in that the multi-thiol of the 2-40 carbon atom is selected from 2,
2 '-(1,2- second diyl dioxygen generations) double ethyl mercaptans, four (3- mercaptopropionic acid) pentaerythritol esters, trimethylolpropane tris (3- sulfydryl
At least one of propionic ester) and glycol dimercaptoacetate.
6. polymeric system as claimed in claim 4, which is characterized in that the polynary epoxy of the 2-40 carbon atom is selected from double
Phenol A diglycidyl ether, the glycidyl -4,4- of N, N, N, N,-four diaminodiphenylmethane, polypropylene glycol diepoxide for example methyl
Ether, polyethylene glycol diepoxide for example methyl ether, p- (2,3- glycidoxy)-N, N- bis- (2,3- glycidyl) aniline and 3,4-
At least one of epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters.
7. polymerization system as claimed in any one of claims 1 to 6, which is characterized in that described to be selected from boric acid, boron containing borate crosslinker
Sand, borate, in benzene hypoboric acid, 4- vinylphenylboronic acid, 3- vinylphenylboronic acid and 3- acrylamido phenyl boric acid extremely
Few one kind;And/or
The pH adjusting agent is selected from 1,8- diazabicyclo [5.4.0] 11 carbon -7- alkene and tri- azabicyclic of 1,5,7- [4.4.0]
At least one of certain herbaceous plants with big flowers -5- alkene.
8. such as the preparation method of the described in any item polymeric systems of claim 1-7, which comprises the steps of:
There is provided the polyalcohol, containing borate crosslinker and pH adjusting agent;
It is mixed by the polyalcohol, containing borate crosslinker and pH adjusting agent, is heated to the vitrifying of the polymeric system
More than transition temperature, deformation process is then carried out, obtains initial polymer material;
The initial polymer material is cooled to the glass transition temperature of the polymeric system hereinafter, obtaining the polymerization
Objects system.
9. preparation method as claimed in claim 8, which is characterized in that the glass transition temperature of the polymeric system is
40-100℃。
10. preparation method as claimed in claim 8, which is characterized in that described the initial polymer material to be cooled to
After step below the glass transition temperature of polymeric system, further include the steps that being dried.
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