CN109370120A - A kind of antiultraviolet polymer composite - Google Patents
A kind of antiultraviolet polymer composite Download PDFInfo
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- CN109370120A CN109370120A CN201811219880.6A CN201811219880A CN109370120A CN 109370120 A CN109370120 A CN 109370120A CN 201811219880 A CN201811219880 A CN 201811219880A CN 109370120 A CN109370120 A CN 109370120A
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- Prior art keywords
- photochromic agent
- agent
- antiultraviolet
- photochromic
- polymer composite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The present invention relates to a kind of antiultraviolet polymer composites, it is formed by weight, and poly- fluoroolefins is 85 parts -120 parts；Polyetherimide is 3 parts -5 parts；The modified photochromic agent of polymethyl methacrylate is 10 parts -15 parts；Auxiliary agent is 1 part -5 parts；Photochromic agent includes inorganic photochromic agent and organic photochromic agent.In the technical program, by adding the modified photochromic agent of polymethyl methacrylate in poly- fluoroolefins, pass through the cladding of polymethyl methacrylate, realize distributing homogeneity of the photochromic material in poly- fluoroolefins, and being in the photochromic agent include inorganic ability of reverse photochromism agent also includes organic photochromic agent, it is realized with good ultraviolet light discoloration, improves composite material to the protective performance of ultraviolet light.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly relate to a kind of variation by light, the face of composite material
Color carries out the polymer composite of corresponding change, and the composite material has certain ultraviolet protection performance.
Background technique
The main application of poly- fluoroolefins is to be processed into film or coating, and specific gravity slightly overweights polyvinyl chloride film, has one
As fluorine resin characteristic, and its weather resistance is significant, and the film of preparation has certain transparency, and can be through can
Light-exposed and ultraviolet light absorbs infrared ray strongly, and the outdoor application time limit was up to 25 years or more under normal condition, and anti-flex performance
It is good, it is folding not easy to crack, meanwhile, also not by the erosion of grease, organic solvent, bases, acids and salt fog, electrical insulation capability
Well, also there is good cryogenic property, wearability and gas barrier.
But poly- fluoroolefins be restricted, and can be saturating because ultraviolet light can be penetrated in certain field use
Visible light is crossed, in the brightness for needing to reduce visible light, can not be changed.
Summary of the invention
The object of the present invention is to provide a kind of antiultraviolet polymer composites, not only remain the complete of poly- fluoroolefins
Portion's advantage, and and be able to solve in the prior art, poly- fluoroolefins do not have antiultraviolet function and cannot be to visible light
The problem of permeability is adjusted.
The present invention is achieved by the following technical solutions:
A kind of antiultraviolet polymer composite, by weight consisting of:
The photochromic agent includes inorganic photochromic agent and organic photochromic agent.
The inorganic photochromic agent is using CaHfO3 as the inorganic photochromic material of basis material, and expression formula is
M1-XHfO3: xR, xR, wherein M is one of alkali earth metal Ca, Sr, Ba；X is the doping of R, 0≤x≤0.03；R
To be doped to the rare earth element in basis material, selected from Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,
One of Lu or a variety of.
The mass ratio of the inorganic photochromic agent and the organic photochromic agent is 1:3.
In the modified photochromic agent of the polymethyl methacrylate, the photochromic agent accounts for the polymethylacrylic acid
The 0.1%-5% of the modified photochromic agent total weight of methyl esters.
The organic photochromic agent is that spiral shell adjoins and mutters and azobenzene.
The auxiliary agent includes one of oxidant, compatilizer, age resister, light stabilizer or multiple combinations.
The preparation method of the modified photochromic agent of the polymethyl methacrylate, comprising the following steps:
1) methyl methacrylate monomer and ethyl alcohol are added into reactor, makes the methacrylic acid after stirring
Methyl esters is dissolved completely in ethyl alcohol, and inorganic colour-changing agent and organic colour-changing agent is added, and continues to stir and be warming up to 60 DEG C -80 DEG C, then
Initiator B PO ethanol solution is added, stop heating and continues to be kept stirring 1-2 hours, is gradually cooled to solid；
2) above-mentioned solid abrasive is obtained into the modified photochromic agent of polymethyl methacrylate at powder.
The beneficial effects of the present invention are:
In the technical program, by adding the modified photochromic material of polymethyl methacrylate in poly- fluoroolefins,
By the cladding of polymethyl methacrylate, distributing homogeneity of the photochromic material in poly- fluoroolefins is realized, and should
Being in photochromic agent include inorganic ability of reverse photochromism agent also includes organic photochromic agent, is realized with good
Ultraviolet light discoloration improves composite material to the protective performance of ultraviolet light.
On the other hand, the technical program is by using organic photochromic agent, when on radiation of visible light to composite material,
The color change that will lead to the organic photochromic agent by design addition, changes the light transmission of visible light.
Specific embodiment
Carry out the technical solution that the present invention will be described in detail by the following examples, embodiment below is merely exemplary, only
It can be used to explanation and illustration technical solution of the present invention, and be not to be construed as the limitation to technical solution of the present invention.
In each embodiment of the application, wherein inorganic photochromic agent is according to Chinese Patent Application No. 201410622103.1
The inorganic ability of reverse photochromism agent of preparation, because can make fiber that different changes be presented wherein using different rare earth elements
Color effect can according to need in actual production and be changed rare earth element.
The application provides a kind of antiultraviolet polymer composite, by weight consisting of:
Photochromic agent includes inorganic photochromic agent and organic photochromic agent；Inorganic photochromic agent with it is organic photic
The mass ratio of colour-changing agent is 1:3.
Inorganic photochromic agent is the expression formula M using CaHfO3 as the inorganic photochromic material of basis material1- XHfO3: xR, xR, wherein M is one of alkali earth metal Ca, Sr, Ba；X is the doping of R, 0≤x≤0.03；R is to mix
The miscellaneous rare earth element into basis material, in Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
It is one or more.
In the other embodiments of the application, the color that rare earth element can according to need change is changed, because dilute
The type of earth elements is more, in the following embodiment of the application, with CaHfO3:La2O3For be illustrated, but never
It can think that the inorganic photochromic agent of the application is only applicable to CaHfO3:La2O3, but can be adapted for other elements of rare earth,
For example, CaHfO3:Sc2O3, CaHfO3:Y2O3, CaHfO3:CeO2, CaHfO3:Pr2O3, CaHfO3:Nd2O3, CaHfO3:Sm2O3、
CaHfO3:Eu2O3, CaHfO3:Gd2O3, CaHfO3:Tb2O3, CaHfO3:Dy2O3, CaHfO3:Ho2O3, CaHfO3:Er2O3、
CaHfO3:Tm2O3, CaHfO3:Yb2O3, CaHfO3:Lu2O3It is only the length problem because of application documents, without arranging one by one
Out.
In the modified photochromic agent of the polymethyl methacrylate, the photochromic agent accounts for the polymethylacrylic acid
The 0.1%-5% of the modified photochromic agent total weight of methyl esters.
Organic photochromic agent is that spiral shell adjoins and mutters and azobenzene；The following example of the application, which is only listed spiral shell and adjoined, mutters and azobenzene
It is in mass ratio a kind of combination of 1:1, other combinations are in the description without explanation.
Auxiliary agent includes one of oxidant, compatilizer, age resister, light stabilizer or multiple combinations.In this application,
Auxiliary agent is the prior art, and the use of auxiliary agent is not in the improved technology scheme of the application, and therefore, the application is not to auxiliary agent
Concrete component is illustrated, and the institute's auxiliary agent that can be used in the application can be applicable in.
In this application, by using polyetherimide, it can guarantee the modified photochromic agent of polymethyl methacrylate
The aggregation being evenly distributed and prevent the modified photochromic agent of polymethyl methacrylate in the composite, while polyetherimide
The use of amine can be improved mechanical performance, wear-resisting property and the flame retardant property of composite material.
The preparation method of the modified photochromic agent of the polymethyl methacrylate, comprising the following steps:
1) methyl methacrylate monomer and ethyl alcohol are added into reactor, makes the methacrylic acid after stirring
Methyl esters is dissolved completely in ethyl alcohol, and inorganic photochromic agent and organic photochromic agent is added, continue to stir and be warming up to 60 DEG C-
80 DEG C, initiator B PO ethanol solution is added, stops heating and continues to be kept stirring 1-2 hours, be gradually cooled to solid；
2) above-mentioned solid abrasive is obtained into the modified photochromic agent of polymethyl methacrylate at powder.
Polymethyl methacrylate is modified photochromic agent, to coat polymethyl methacrylate by core of photochromic agent
The core-shell structure of shell, the core-shell structure can guarantee the stable bond between high molecular material and be evenly distributed.
Embodiment 1
A kind of antiultraviolet polymer composite, by weight consisting of:
Photochromic agent inorganic photochromic agent therein is CaHfO3:La2O3。
In the modified photochromic agent of the polymethyl methacrylate, the photochromic agent accounts for the polymethylacrylic acid
The 0.1% of the modified photochromic agent total weight of methyl esters.
Organic photochromic agent is that spiral shell adjoins the composition muttered with azobenzene, and wherein spiral shell adjoins the mass ratio 1:1 to mutter with azobenzene.
Auxiliary agent includes one of oxidant, compatilizer, age resister, light stabilizer or multiple combinations.
The preparation method of the modified photochromic agent of the polymethyl methacrylate, comprising the following steps:
1) methyl methacrylate monomer and ethyl alcohol are added into reactor, makes the methacrylic acid after stirring
Methyl esters is dissolved completely in ethyl alcohol, and inorganic colour-changing agent and organic colour-changing agent is added, and continues to stir and be warming up to 60 DEG C -80 DEG C, then
Initiator B PO ethanol solution is added, stop heating and continues to be kept stirring 1-2 hours, is gradually cooled to solid；
2) above-mentioned solid abrasive is obtained into the modified photochromic agent of polymethyl methacrylate at powder.
In following embodiment of the invention, the preparation method of the modified photochromic agent of polymethyl methacrylate is homogeneous
Together, below in an example, without illustrating one by one.
Embodiment 2
A kind of antiultraviolet polymer composite, by weight consisting of:
Photochromic agent inorganic photochromic agent therein is CaHfO3:La2O3。
In the modified photochromic agent of the polymethyl methacrylate, the photochromic agent accounts for the polymethylacrylic acid
The 5% of the modified photochromic agent total weight of methyl esters.
Organic photochromic agent is that spiral shell adjoins the composition muttered with azobenzene, and wherein spiral shell adjoins the mass ratio 1:1 to mutter with azobenzene.
Auxiliary agent includes one of oxidant, compatilizer, age resister, light stabilizer or multiple combinations.
Embodiment 3
A kind of antiultraviolet polymer composite, by weight consisting of:
Photochromic agent inorganic photochromic agent therein is CaHfO3:La2O3。
In the modified photochromic agent of the polymethyl methacrylate, the photochromic agent accounts for the polymethylacrylic acid
The 0.5% of the modified photochromic agent total weight of methyl esters.
Organic photochromic agent is that spiral shell adjoins the composition muttered with azobenzene, and wherein spiral shell adjoins the mass ratio 1:1 to mutter with azobenzene.
Auxiliary agent includes one of oxidant, compatilizer, age resister, light stabilizer or multiple combinations.
Embodiment 4
A kind of antiultraviolet polymer composite, by weight consisting of:
Photochromic agent inorganic photochromic agent therein is CaHfO3:La2O3。
In the modified photochromic agent of the polymethyl methacrylate, the photochromic agent accounts for the polymethylacrylic acid
The 1% of the modified photochromic agent total weight of methyl esters.
Organic photochromic agent is that spiral shell adjoins the composition muttered with azobenzene, and wherein spiral shell adjoins the mass ratio 1:1 to mutter with azobenzene.
Auxiliary agent includes one of oxidant, compatilizer, age resister, light stabilizer or multiple combinations.
Embodiment 5
A kind of antiultraviolet polymer composite, by weight consisting of:
Photochromic agent inorganic photochromic agent therein is CaHfO3:La2O3。
In the modified photochromic agent of the polymethyl methacrylate, the photochromic agent accounts for the polymethylacrylic acid
The 2% of the modified photochromic agent total weight of methyl esters.
Organic photochromic agent is that spiral shell adjoins the composition muttered with azobenzene, and wherein spiral shell adjoins the mass ratio 1:1 to mutter with azobenzene.
Auxiliary agent includes one of oxidant, compatilizer, age resister, light stabilizer or multiple combinations.
Embodiment 6
A kind of antiultraviolet polymer composite, by weight consisting of:
Photochromic agent inorganic photochromic agent therein is CaHfO3:La2O3。
In the modified photochromic agent of the polymethyl methacrylate, the photochromic agent accounts for the polymethylacrylic acid
The 1.5% of the modified photochromic agent total weight of methyl esters.
Organic photochromic agent is that spiral shell adjoins the composition muttered with azobenzene, and wherein spiral shell adjoins the mass ratio 1:1 to mutter with azobenzene.
Auxiliary agent includes one of oxidant, compatilizer, age resister, light stabilizer or multiple combinations.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And deformation, the scope of the present invention are extremely equally limited by appended claims.
Claims (7)
1. a kind of antiultraviolet polymer composite, which is characterized in that by weight consisting of:
The photochromic agent includes inorganic photochromic agent and organic photochromic agent.
2. antiultraviolet polymer composite according to claim 1, which is characterized in that the inorganic photochromic agent
For using CaHfO3 as the inorganic photochromic material of basis material, expression formula M1-XHfO3: xR, wherein M is alkaline-earth metal
One of Elements C a, Sr, Ba；X is the doping of R, 0≤x≤0.03；R is the rare earth element being doped in basis material, choosing
From one of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a variety of.
3. antiultraviolet polymer composite according to claim 1, which is characterized in that the inorganic photochromic agent
Mass ratio with the organic photochromic agent is 1:3.
4. antiultraviolet polymer composite according to claim 1, which is characterized in that the poly-methyl methacrylate
In ester modified photochromic agent, the photochromic agent accounts for the modified photochromic agent total weight of the polymethyl methacrylate
0.1%-5%.
5. antiultraviolet polymer composite according to claim 1, which is characterized in that the organic photochromic agent
Adjoin for spiral shell and mutters and azobenzene.
6. antiultraviolet polymer composite according to claim 1, which is characterized in that the auxiliary agent includes oxidation
One of agent, compatilizer, age resister, light stabilizer or multiple combinations.
7. antiultraviolet polymer composite according to claim 1, which is characterized in that the poly-methyl methacrylate
The preparation method of ester modified photochromic agent, comprising the following steps:
1) methyl methacrylate monomer and ethyl alcohol are added into reactor, makes the methyl methacrylate after stirring
It is dissolved completely in ethyl alcohol, inorganic colour-changing agent and organic colour-changing agent is added, continue to stir and be warming up to 60 DEG C -80 DEG C, add
Initiator B PO ethanol solution stops heating and continues to be kept stirring 1-2 hours, is gradually cooled to solid；
2) above-mentioned solid abrasive is obtained into the modified photochromic agent of polymethyl methacrylate at powder.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811219880.6A CN109370120A (en) | 2018-10-19 | 2018-10-19 | A kind of antiultraviolet polymer composite |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811219880.6A CN109370120A (en) | 2018-10-19 | 2018-10-19 | A kind of antiultraviolet polymer composite |
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| CN109370120A true CN109370120A (en) | 2019-02-22 |
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| CN201811219880.6A Pending CN109370120A (en) | 2018-10-19 | 2018-10-19 | A kind of antiultraviolet polymer composite |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629250A (en) * | 2004-10-20 | 2005-06-22 | 南开大学 | Organic photochromic composite nano materials and method for preparing same |
| CN104449658A (en) * | 2014-11-07 | 2015-03-25 | 广东工业大学 | Inorganic reversible photochromic material and preparation method thereof |
| CN105199273A (en) * | 2015-07-28 | 2015-12-30 | 苏州新区特氟龙塑料制品厂 | Formula of optically variable modified polytetrafluoroethylene |
-
2018
- 2018-10-19 CN CN201811219880.6A patent/CN109370120A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629250A (en) * | 2004-10-20 | 2005-06-22 | 南开大学 | Organic photochromic composite nano materials and method for preparing same |
| CN104449658A (en) * | 2014-11-07 | 2015-03-25 | 广东工业大学 | Inorganic reversible photochromic material and preparation method thereof |
| CN105199273A (en) * | 2015-07-28 | 2015-12-30 | 苏州新区特氟龙塑料制品厂 | Formula of optically variable modified polytetrafluoroethylene |
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Application publication date: 20190222 |