CN107090238B - A kind of POSS crosslinking polyarylate ultraviolet light solidified protection coating and preparation method thereof - Google Patents
A kind of POSS crosslinking polyarylate ultraviolet light solidified protection coating and preparation method thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses a kind of POSS to be crosslinked polyarylate ultraviolet light solidified protection coating comprising following component and its mass content: alkene end group polyarylate oligomer: 70~99%；Eight vinyl-POSS:0.5~28%；Photoinitiator: 0.05~2%；Defoaming agent: 0.1~0.5%；Levelling agent: 0.1~0.5%.The invention also discloses the preparation methods of above-mentioned POSS crosslinking polyarylate ultraviolet light solidified protection coating.POSS crosslinking polyarylate coating of the present invention not only maintains the excellent chemical corrosion resistance of polyarylate material, weatherability, high and low temperature resistance and good flame retardant property and extremely low hygroscopicity, also because POSS there are due to there is high hardness and excellent anti-wear property, be highly suitable for the wear-and corrosion-resistant coating material of substrate under adverse circumstances.
Description
Technical field
The present invention relates to a kind of POSS crosslinking polyarylate ultraviolet light solidified protection coatings and preparation method thereof, belong to photocuring
Coating preparation field.
Background technique
Abrasion, fracture and corrosion are three big principal modes of material failure, thus develop the high-performance protective of anticorrosion antiwear
Coating material is of great significance to the service life for extending basis material.
Polyarylate refers to the polymer of ester group both ends connection aromatic ring, and industrially mostly finger bisphenol-A and terephthalic acid (TPA) is (or right
Phthalyl chloride) and M-phthalic acid (or m-phthaloyl chloride) be the obtained polyarylate resin of raw material polycondensation.Polyarylate due to
Contain a large amount of aromatic units in strand, and connect these aromatic rings is the stable ester bond of performance, thus has excellent
Chemical corrosion resistance, weatherability, good flame retardant property and extremely low hydroscopicity, and wider using temperature, can -70~+
It is used for a long time at 180 DEG C, the anti-corrosion for being highly suitable under adverse circumstances (high temperature, low temperature, chemical attack, humidity etc.) substrate applies
Layer material.However, application of the polyarylate in protective coating field at present is also less since polyarylate is insoluble in organic solvent.
Summary of the invention
It fills and is crosslinked poly- the present invention is intended to provide a kind of ultraviolet light solidifies polyhedral oligomeric silsesquioxane (POSS)
Aromatic ester protective coating and preparation method thereof.POSS nano particle in the ultraviolet curable coating has excellent dispersibility,
Prepared polyarylate coating has high hardness, chemical corrosion resistance outstanding and wearability, while also having excellent
High and low temperature resistance, weatherability and flame retardant property.The curing rate of prepared ultraviolet curable coating is fast, low energy consumption, operation
Simply, and film performance is excellent, has practical application value.
The purpose of the present invention is be achieved through the following technical solutions:
A kind of POSS crosslinking polyarylate ultraviolet light solidified protection coating comprising following component and its mass content:
Alkene end group polyarylate oligomer: 70~99%；
Eight vinyl-POSS:0.5~28%；
Photoinitiator: 0.05~2%；
Defoaming agent: 0.1~0.5%；
Levelling agent: 0.1~0.5%.
In a preferred embodiment of the invention, above-mentioned each component preferred mass content are as follows:
Alkene end group polyarylate oligomer: 90~98%；
Eight vinyl-POSS:1~8%；
Photoinitiator: 0.5~1%；
Defoaming agent: 0.1~0.5%；
Levelling agent: 0.1~0.5%.
Under the premise of POSS can be scattered, the content of POSS is higher, and the hardness of coating is higher.But excessive POSS is past
Good dispersion cannot be formed in polyarylate matrix toward will lead to its generation aggregation.Therefore, suitable alkene end group polyarylate
The mass content of oligomer and eight vinyl-POSS are most important to the performance of protective coating of the invention.
Preferably, the number-average molecular weight of the alkene end group polyarylate oligomer is 1000~6000g/mol.
The schematic arrangement of above-mentioned POSS crosslinking polyarylate ultraviolet light solidified protection coating is as shown in Figure 1.
As it can be seen that polyarylate oligomer is cross-linked into the network of an entirety as 3 D cross-linked dose by POSS, and POSS is also
It is used as inorganic filler simultaneously, and since it is reacted with polyarylate molecule, dispersibility of the POSS as inorganic filler
Very well.
In a preferred embodiment of the invention, the alkene end group polyarylate oligomer the preparation method is as follows:
(1) there-necked flask for filling condenser pipe and inert gas protection device is placed on magnetic stirring apparatus, is added into reaction flask
Enter reaction medium methylene chloride and a small amount of catalyst of triethylamine；By the paraphthaloyl chloride and hydroxy-ethyl acrylate of equimolar ratio
It is dissolved in methylene chloride, the concentration of paraphthaloyl chloride is 0.4~0.6mol/L, and the solution of above-mentioned preparation is transferred to constant pressure
Dropping funel is gradually added dropwise in reaction flask, and reaction temperature maintains 40~50 DEG C；After the completion of dropping liquid, under reflux temperature after
Continuous reaction stops heating when reaction system is released without hydrogen chloride gas, continues to be passed through nitrogen, until reaction system is cooled to room
Temperature obtains a kind of dichloromethane solution of alkene end group chlorobenzoyl chloride monomer；The chemical structural formula of the alkene end group chlorobenzoyl chloride monomer
Are as follows:
The preparation of the alkene end group chlorobenzoyl chloride monomer is proved to use with reference to an existing Master's thesis in the paper
Above-mentioned preparation method is successfully prepared alkene end group chlorobenzoyl chloride monomer；
It is added to aromatics diphenol monomer and quaternary ammonium salt phase transfer interfacial polycondensation catalyst in the aqueous solution of alkali, is formed
Monomer molar concentration is the aqueous solution of 0.4~1.0mol/L, and alkali is usually sodium hydroxide or potassium hydroxide；Aromatics diphenol monomer
Chemical structural formula is following one kind:
Aromatic diacid chlorides monomer adding into dichloromethane is dissolved to the organic phase solution to form acyl chlorides, it is dense to be made into monomer
Degree is 0.2~0.8mol/L；The chemical structural formula of the aromatic diacid chlorides monomer is following one kind:
Above-mentioned 3 kinds of raw materials prepare no sequencing；
(2) organic phase solution of aromatic diacid chlorides monomer is added gradually to aromatics diphenol list under Quick mechanical stirring
In the aqueous solution of the alkali of body and catalyst, the molar ratio of aromatics diphenol monomer and aromatic diacid chlorides is controlled 1.1~1.2, instead
Answering temperature is 10~50 DEG C, in reaction system there is no hydrogen chloride gas evolution, to reaction system a dropping step (1) preparation
The dichloromethane solution of alkene end group chlorobenzoyl chloride monomer carries out end capping reaction, and up to reaction system, there is no hydrogen chloride gas productions
It is raw, then stop that alkene end group chlorobenzoyl chloride monomer is added dropwise；After reaction, it is neutralized to neutrality with acid, stood, to reaction solution two-phase point
After layer, lower layer's organic phase is added drop-wise to precipitating in intensively stirred precipitating reagent, precipitating product is cleaned with ethyl alcohol and distilled water respectively,
Buchner funnel vacuum filter is finally placed in 60 DEG C of the dry 8~12h of vacuum drying oven, obtains alkene end group polyarylate oligomer.
The chemical structural formula of above-mentioned eight vinyl-POSS is as shown in Figure 2.
Above-mentioned photoinitiator is radical photoinitiator, can specifically be selected from 2,4,6- trimethylbenzoyls-hexichol
Base phosphine oxide, bis(benzoylphenyl) phosphine oxide, 2,2- dimethoxy-phenylf ethyl ketone, benzophenone, 2,4- dihydroxy hexichol first
One or more of ketone, thio propoxyl group thioxanthone and isopropyl thioxanthone.
The present invention also provides a kind of preparation methods of above-mentioned POSS crosslinking polyarylate ultraviolet light solidified protection coating, specifically
It is as follows:
Alkene end group polyarylate oligomer, eight vinyl-POSS, photoinitiator, defoaming agent and levelling agent are pressed into above-mentioned quality
Percent dissolution is made into the solution that mass fraction is 5~40% in organic solvent, after deploying uniformly at 30~50 DEG C, passes through
The mode of spraying, dip-coating or spin coating is coated in substrate surface, at room temperature surface drying, then irradiates 5~30 minutes, obtains under ultraviolet light
Polyarylate ultraviolet light solidified protection coating is crosslinked to POSS.
The preparation of above-mentioned POSS crosslinking polyarylate ultraviolet light solidified protection coating, solvent for use are methylene chloride, three chloromethanes
One of alkane, tetrachloromethane, tetrahydrofuran and acetone.
The invention proposes a kind of POSS crosslinking polyarylate ultraviolet light solidified protection coatings and preparation method thereof.The coating is
It is main component by the polyarylate oligomer of alkenyl of end group using octavinyl-POSS as crosslinking agent, by ultraviolet light-initiated poly-
Close the method preparation of object crosslinking curing.Polyarylate body is introduced into using organic-inorganic materials POSS as crosslinking agent
In system, not only make the coating material remain the excellent chemical corrosion resistance of polyarylate itself, weatherability, high temperature resistance,
Resistance to low temperature, dimensional stability and good flame retardant property and extremely low hygroscopicity, but also it is high to assign the coating
Hardness and wear-resisting persistence.Prepared POSS crosslinking polyarylate coating be highly suitable under harsh environment (high temperature, low temperature,
Humidity, chemical attack etc.) substrate coating protection material.Prepared ultraviolet curable coating curing rate is fast, low energy consumption, behaviour
Make simply, and film performance is excellent, there is practical application value.
Compared with prior art, the invention has the following advantages:
(1) it is introduced into POSS as crosslinking agent in polyarylate coating material, due to there is chemistry between POSS and polymer
Key, it is well dispersed in polyarylate matrix, it is not easy to reunite；
(2) POSS is crosslinked polyarylate coating and not only maintains the excellent chemical corrosion resistance of polyarylate material, weatherability, resistance to
High temperature performance and good flame retardant property and extremely low hygroscopicity, also because POSS there are due to there is high hardness and excellent
Different anti-wear property is highly suitable for the wear-and corrosion-resistant coating material of substrate under adverse circumstances；
(3) the ultraviolet curable coating curing rate prepared by the present invention is fast, low energy consumption, easy to operate, and applies film property
Can be excellent, there is practical application value.
Certainly, it implements any of the products of the present invention and does not necessarily require achieving all the advantages described above at the same time.
Detailed description of the invention
Fig. 1 is the schematic arrangement that POSS of the invention is crosslinked polyarylate ultraviolet light solidified protection coating；
Fig. 2 is the chemical structural formula of eight vinyl-POSS of the invention.
Specific embodiment
Herein, the range indicated by " numerical value to another numerical value ", is that one kind avoids enumerating in the description
The summary representation of all numerical value in the range.Therefore, the record of a certain special value range, covers the numberical range
Interior any number and the relatively fractional value range defined by any number in the numberical range, as bright in the description
Text writes out any number as should be compared with fractional value range.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit the scope of protection of the present invention.The improvement and tune that technical staff makes according to the present invention in practical applications
It is whole, still fall within protection scope of the present invention.Defoaming agent and levelling agent in following embodiment are commercial product.
Embodiment 1
A kind of POSS crosslinking polyarylate ultraviolet light solidified protection coating provided in this embodiment is prepared by the following method:
The first step prepares alkene end group polyarylate oligomer:
(1) there-necked flask for filling condenser pipe and inert gas protection device is placed on magnetic stirring apparatus, is added into reaction flask
Enter reaction medium methylene chloride and a small amount of catalyst of triethylamine；By the paraphthaloyl chloride and hydroxy-ethyl acrylate of equimolar ratio
It is dissolved in methylene chloride, the concentration of paraphthaloyl chloride is 0.4mol/L, and is transferred to constant pressure funnel, is gradually added dropwise to
In reaction flask, reaction temperature maintains 40~50 DEG C；After the completion of dropping liquid, the reaction was continued under reflux temperature, to reaction system without
Stop heating when hydrogen chloride gas is released, continue to be passed through nitrogen, until reaction system is cooled to room temperature, obtains a kind of alkene end group benzene
The dichloromethane solution of formyl chloride monomer；The chemical structural formula of the alkene end group chlorobenzoyl chloride monomer are as follows:
By aromatics diphenol monomer and quaternary ammonium salt phase transfer interfacial polycondensation catalyst cetyl trimethylammonium bromide, it is added
Into the aqueous solution of sodium hydroxide, the aqueous solution that monomer molar concentration is 0.4mol/L is formed；The chemistry knot of aromatics diphenol monomer
Structure formula are as follows:
Aromatic diacid chlorides monomer adding into dichloromethane is dissolved to the organic phase solution to form acyl chlorides, it is dense to be made into monomer
Degree is 0.2mol/L；The chemical structural formula of the aromatic diacid chlorides monomer are as follows:
Above-mentioned 3 kinds of raw materials prepare no sequencing；
(2) organic phase solution of aromatic diacid chlorides monomer is added gradually to aromatics diphenol list under Quick mechanical stirring
In the sodium hydrate aqueous solution of body and catalyst, the molar ratio control of aromatics diphenol monomer and aromatic diacid chlorides is reacted 1.1
Temperature is 10~20 DEG C, is prepared to, there is no hydrogen chloride gas evolution, continue in reaction system to reaction system a dropping step (1)
Alkene end group chlorobenzoyl chloride monomer dichloromethane solution, carry out end capping reaction, up to reaction system, there is no hydrogen chloride gas
It generates；After reaction, it is neutralized to neutrality with acid, stands, after reaction solution two phase stratification, lower layer's organic phase is added drop-wise to strongly
Precipitating in the precipitating reagent of stirring, precipitating product are cleaned with ethyl alcohol and distilled water respectively, and Buchner funnel vacuum filter is finally placed in 60
DEG C the dry 8h of vacuum drying oven, obtain alkene end group polyarylate oligomer.After tested, the number of the alkene end group polyarylate oligomer is equal
Molecular weight is 6000g/mol.
Second step, preparation POSS are crosslinked polyarylate ultraviolet light solidified protection coating:
According to following weight percent, by alkene end group polyarylate oligomer, eight vinyl-POSS, photoinitiator, defoaming agent
Be dissolved in levelling agent be made into methylene chloride mass fraction be 10% solution, at 30~40 DEG C deploy uniformly after, pass through
The mode of spraying, dip-coating or spin coating is coated in substrate surface, at room temperature surface drying, then irradiates 5 minutes, obtains under ultraviolet light
POSS is crosslinked polyarylate ultraviolet light solidified protection coating:
Alkene end group polyarylate oligomer: 90%；
Eight vinyl-POSS:7%；
Photoinitiator 2,4,6- trimethylbenzoy-dipheny phosphine oxide: 2%；
Defoaming agent: 0.5%；
Levelling agent: 0.5%.
Embodiment 2
A kind of POSS crosslinking polyarylate ultraviolet light solidified protection coating provided in this embodiment is prepared by the following method:
The first step prepares alkene end group polyarylate oligomer:
(1) there-necked flask for filling condenser pipe and inert gas protection device is placed on magnetic stirring apparatus, is added into reaction flask
Enter reaction medium methylene chloride and a small amount of catalyst of triethylamine；By the paraphthaloyl chloride and hydroxy-ethyl acrylate of equimolar ratio
It is dissolved in methylene chloride, the concentration of paraphthaloyl chloride is 0.6mol/L, and is transferred to constant pressure funnel, is gradually added dropwise to
In reaction flask, reaction temperature maintains 40~50 DEG C；After the completion of dropping liquid, the reaction was continued under reflux temperature, to reaction system without
Stop heating when hydrogen chloride gas is released, continue to be passed through nitrogen, until reaction system is cooled to room temperature, obtains a kind of alkene end group benzene
The dichloromethane solution of formyl chloride monomer；The chemical structural formula of the alkene end group chlorobenzoyl chloride monomer are as follows:
By aromatics diphenol monomer and quaternary ammonium salt phase transfer interfacial polycondensation catalyst benzyltrimethylammonium chloride, it is added to hydrogen
In the aqueous solution of sodium oxide molybdena, the aqueous solution that monomer molar concentration is 1.0mol/L is formed；The chemical structural formula of aromatics diphenol monomer
Are as follows:
Aromatic diacid chlorides monomer adding into dichloromethane is dissolved to the organic phase solution to form acyl chlorides, it is dense to be made into monomer
Degree is 0.8mol/L；The chemical structural formula of the aromatic diacid chlorides monomer are as follows:
Above-mentioned 3 kinds of raw materials prepare no sequencing；
(2) organic phase solution of aromatic diacid chlorides monomer is added gradually to aromatics diphenol list under Quick mechanical stirring
In the sodium hydrate aqueous solution of body and catalyst, the molar ratio control of aromatics diphenol monomer and aromatic diacid chlorides is reacted 1.2
Temperature is 40~50 DEG C, is prepared to, there is no hydrogen chloride gas evolution, continue in reaction system to reaction system a dropping step (1)
Alkene end group chlorobenzoyl chloride monomer dichloromethane solution, carry out end capping reaction, up to reaction system, there is no hydrogen chloride gas
It generates；After reaction, it is neutralized to neutrality with acid, stands, after reaction solution two phase stratification, lower layer's organic phase is added drop-wise to strongly
Precipitating in the precipitating reagent of stirring, precipitating product are cleaned with ethyl alcohol and distilled water respectively, and Buchner funnel vacuum filter is finally placed in 60
DEG C the dry 12h of vacuum drying oven, obtain alkene end group polyarylate oligomer.After tested, the number of the alkene end group polyarylate oligomer
Average molecular weight is 1000g/mol.
Second step, preparation POSS are crosslinked polyarylate ultraviolet light solidified protection coating:
According to following weight percent, by alkene end group polyarylate oligomer, eight vinyl-POSS, photoinitiator, defoaming agent
It is dissolved in levelling agent and is made into the solution that mass fraction is 40% in acetone, after being deployed uniformly at 40~50 DEG C, by spraying,
The mode of dip-coating or spin coating is coated in substrate surface, at room temperature surface drying, then irradiates 30 minutes under ultraviolet light, obtains POSS friendship
Join polyarylate ultraviolet light solidified protection coating:
Alkene end group polyarylate oligomer: 98%；
Eight vinyl-POSS:1.3%；
Photoinitiator isopropyl thioxanthone: 0.5%；
Defoaming agent: 0.1%；
Levelling agent: 0.1%.
Embodiment 3
A kind of POSS crosslinking polyarylate ultraviolet light solidified protection coating provided in this embodiment is prepared by the following method:
The first step prepares alkene end group polyarylate oligomer:
(1) there-necked flask for filling condenser pipe and inert gas protection device is placed on magnetic stirring apparatus, is added into reaction flask
Enter reaction medium methylene chloride and a small amount of catalyst of triethylamine；By the paraphthaloyl chloride and hydroxy-ethyl acrylate of equimolar ratio
It is dissolved in methylene chloride, the concentration of paraphthaloyl chloride is 0.5mol/L, and is transferred to constant pressure funnel, is gradually added dropwise to
In reaction flask, reaction temperature maintains 40~50 DEG C；After the completion of dropping liquid, the reaction was continued under reflux temperature, to reaction system without
Stop heating when hydrogen chloride gas is released, continue to be passed through nitrogen, until reaction system is cooled to room temperature, obtains a kind of alkene end group benzene
The dichloromethane solution of formyl chloride monomer；The chemical structural formula of the alkene end group chlorobenzoyl chloride monomer are as follows:
By aromatics diphenol monomer and quaternary ammonium salt phase transfer interfacial polycondensation catalyst phenyl trimethicone ammonium chloride, it is added to hydrogen
In the aqueous solution of sodium oxide molybdena, the aqueous solution that monomer molar concentration is 0.6mol/L is formed；The chemical structural formula of aromatics diphenol monomer
Are as follows:
Aromatic diacid chlorides monomer adding into dichloromethane is dissolved to the organic phase solution to form acyl chlorides, it is dense to be made into monomer
Degree is 0.4mol/L；The chemical structural formula of the aromatic diacid chlorides monomer are as follows:
Above-mentioned 3 kinds of raw materials prepare no sequencing；
(2) organic phase solution of aromatic diacid chlorides monomer is added gradually to aromatics diphenol list under Quick mechanical stirring
In the sodium hydrate aqueous solution of body and catalyst, the molar ratio of aromatics diphenol monomer and aromatic diacid chlorides is controlled 1.15, instead
Answering temperature is 20~30 DEG C, is made to, there is no hydrogen chloride gas evolution, continue in reaction system to reaction system a dropping step (1)
The dichloromethane solution of standby alkene end group chlorobenzoyl chloride monomer carries out end capping reaction, and up to reaction system, there is no hydrogen chloride gas
Body generates；After reaction, it is neutralized to neutrality with acid, stands, after reaction solution two phase stratification, lower layer's organic phase is added drop-wise to by force
Precipitating in the precipitating reagent of strong stirring, precipitating product are cleaned with ethyl alcohol and distilled water respectively, and Buchner funnel vacuum filter is finally placed in
The dry 10h of 60 DEG C of vacuum drying oven, obtains alkene end group polyarylate oligomer.After tested, the alkene end group polyarylate oligomer
Number-average molecular weight is 3000g/mol.
Second step, preparation POSS are crosslinked polyarylate ultraviolet light solidified protection coating:
According to following weight percent, by alkene end group polyarylate oligomer, eight vinyl-POSS, photoinitiator, defoaming agent
Be dissolved in levelling agent be made into tetrahydrofuran mass fraction be 5% solution, at 30~40 DEG C deploy uniformly after, pass through spray
The mode of painting, dip-coating or spin coating is coated in substrate surface, at room temperature surface drying, then irradiates 15 minutes, obtains under ultraviolet light
POSS is crosslinked polyarylate ultraviolet light solidified protection coating:
Alkene end group polyarylate oligomer: 70%；
Eight vinyl-POSS:28%；
Photoinitiator 2,2- dimethoxy-phenylf ethyl ketone: 1.4%；
Defoaming agent: 0.3%；
Levelling agent: 0.3%.
The schematic arrangement of POSS crosslinking polyarylate ultraviolet light solidified protection coating of the invention is as shown in Figure 1.
As it can be seen that POSS as 3 D cross-linked dose by different polyarylate molecule cross-links at the network of an entirety, and
POSS is also used as inorganic filler simultaneously, and since it is reacted with polyarylate molecule, POSS is as inorganic filler
The hardness and wearability of the dispersed POSS crosslinking polyarylate protective coating very well, obtained greatly improve.
The obtained protective coating of embodiment 1-3 is tested for the property:
The micro- of coating is carried out using microhardness testers (71 types, the first optical instrument factory of Shanghai apply load 0.0981N)
Hardness test.It was found that poly- virtue of the vickers microhardness of the polyarylate coating containing POSS in embodiment 1-3 than being free of POSS
Coating is higher by 34~52%.
Using paint film wear resistant instrument (Shanghai Modern Environmental Engineering Technology Co., Ltd.'s manufacture), referring to GB1768-79 pairs of national standard
Coating carries out wearability test, and (load 1000g, elastic grinding wheel diameter is 50mm, with a thickness of 13mm, rotary speed 10.99m/
s).Test result shows that the wearability of the polyarylate coating of embodiment 1-3 improves 10%-70% after POSS is added.
Under the teaching of the present invention and the above embodiments, those skilled in the art are easy to it is envisioned that cited by the present invention
Or each raw material enumerated or its equivalent alterations, each processing method or its equivalent alterations can realize the present invention and each original
The parameter bound value of material and processing method, interval value can realize the present invention, embodiment numerous to list herein.
Claims (6)
1. a kind of POSS is crosslinked polyarylate ultraviolet light solidified protection coating, which is characterized in that including following component and its quality
Content:
Alkene end group polyarylate oligomer: 70~99%；
Eight vinyl-POSS:0.5~28%；
Photoinitiator: 0.05~2%；
Defoaming agent: 0.1~0.5%；
Levelling agent: 0.1~0.5%；
Wherein,
The alkene end group polyarylate oligomer the preparation method is as follows:
(1) it prepares alkene end group chlorobenzoyl chloride monomer: under agitation, reaction medium methylene chloride being added into reaction flask and lacks
The catalyst of triethylamine of amount；The paraphthaloyl chloride of equimolar ratio and hydroxy-ethyl acrylate are dissolved in methylene chloride, and by
It is gradually added dropwise in reaction flask, reaction temperature maintains 40~50 DEG C；After the completion of dropping liquid, the reaction was continued under reflux temperature, to anti-
Stop heating when system being answered to release without hydrogen chloride gas, continue to be passed through nitrogen, until reaction system is cooled to room temperature, obtains one kind
The dichloromethane solution of alkene end group chlorobenzoyl chloride monomer；The chemical structural formula of the alkene end group chlorobenzoyl chloride monomer are as follows:
It is added to aromatics diphenol monomer and quaternary ammonium salt phase transfer interfacial polycondensation catalyst in the aqueous solution of alkali, forms monomer
Molar concentration is the aqueous solution of 0.4~1.0mol/L；The chemical structural formula of the aromatics diphenol monomer is following one kind:
Dissolve aromatic diacid chlorides monomer adding into dichloromethane to form organic phase solution, be made into monomer concentration be 0.2~
0.8mol/L；The aromatic diacid chlorides monomer is following one kind:
(2) by the organic phase solution of aromatic diacid chlorides monomer Quick mechanical stirring under be added gradually to aromatics diphenol monomer and
In the aqueous solution of the alkali of catalyst, the control of the molar ratios of aromatics diphenol and aromatic diacid chlorides is in 1.1~1.2, reaction temperature
10~50 DEG C, the alkene end group benzene to, there is no hydrogen chloride gas evolution, be prepared to reaction system a dropping step (1) in reaction system
The dichloromethane solution of formyl chloride monomer carries out end capping reaction, until reaction system there is no hydrogen chloride gas generation, then stops
Alkene end group chlorobenzoyl chloride monomer is added dropwise；After reaction, it is neutralized, precipitating, cleaning, filtering, drying, obtains the poly- virtue of alkene end group
Ester oligomer.
2. POSS as described in claim 1 is crosslinked polyarylate ultraviolet light solidified protection coating, which is characterized in that each component
Mass content are as follows:
Alkene end group polyarylate oligomer: 90~98%；
Eight vinyl-POSS:1~8%；
Photoinitiator: 0.5~1%；
Defoaming agent: 0.1~0.5%；
Levelling agent: 0.1~0.5%.
3. POSS as claimed in claim 1 or 2 is crosslinked polyarylate ultraviolet light solidified protection coating, which is characterized in that the alkene
The number-average molecular weight of end group polyarylate oligomer is 1000~6000g/mol.
4. POSS as claimed in claim 1 or 2 is crosslinked polyarylate ultraviolet light solidified protection coating, which is characterized in that the light
Initiator is radical photoinitiator, is selected from 2,4,6- trimethylbenzoy-dipheny phosphine oxides, double benzoylphenyls
Phosphine oxide, 2,2- dimethoxy-phenylf ethyl ketone, benzophenone, 2,4 dihydroxyl benzophenone, thio propoxyl group thioxanthone and
One or more of isopropyl thioxanthone.
5. the preparation method of any POSS crosslinking polyarylate ultraviolet light solidified protection coating in a kind of claim 1-4,
It is characterized in that, alkene end group polyarylate oligomer, eight vinyl-POSS, photoinitiator, defoaming agent and levelling agent are pressed above-mentioned matter
Amount percent dissolution is made into the solution that mass fraction is 5~40% in organic solvent, after deploying uniformly at 30~50 DEG C, leads to
The mode for crossing spraying, dip-coating or spin coating is coated in substrate surface, at room temperature surface drying, then irradiates 5~30 minutes under ultraviolet light,
Obtain POSS crosslinking polyarylate ultraviolet light solidified protection coating.
6. the preparation method of POSS crosslinking polyarylate ultraviolet light solidified protection coating as claimed in claim 5, which is characterized in that
Organic solvent used is one of methylene chloride, chloroform, tetrachloromethane, tetrahydrofuran or acetone.
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| CN107938169B (en) * | 2017-12-22 | 2019-05-31 | 中科院广州化学有限公司 | A kind of POSS modified nano fiber film and its preparation method and application |
| CN109554107A (en) * | 2018-11-27 | 2019-04-02 | 深圳市高域化学材料有限公司 | A kind of UV light-cured type elasticity self-healing coatings |
| CN110628250A (en) * | 2019-10-17 | 2019-12-31 | 温州市澳南标牌有限公司 | Anti-doodling paint |
| CN111454648B (en) * | 2020-03-27 | 2021-07-30 | 顺德职业技术学院 | High-strength flexible transparent wear-resistant hardened coating on surface of folding screen and preparation method thereof |
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