CN102477167A - Application of organic polymer material complex used as light stabilizer - Google Patents
Application of organic polymer material complex used as light stabilizer Download PDFInfo
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- CN102477167A CN102477167A CN2010105534242A CN201010553424A CN102477167A CN 102477167 A CN102477167 A CN 102477167A CN 2010105534242 A CN2010105534242 A CN 2010105534242A CN 201010553424 A CN201010553424 A CN 201010553424A CN 102477167 A CN102477167 A CN 102477167A
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Abstract
The invention discloses an application of an organic polymer material complex used as a light stabilizer; the organic polymer material complex is used according to a routine using method of an addition-type light stabilizer; the beta-dione-rare earth complex is applied as an organic polymer material light stabilizer; the beta-dione-rare earth complex has a general chemical formula of REL3-x(OH)x.mH2O; in the formula, (1) RE is a combination of one or more than one of praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and ytterbium (Yb) with a random ratio, or mixed rare earth with above elements as main elements; (2) L represents an anion of beta-dione; (3) x=0-2, and m=0-3. The light stabilizer of the invention has the following advantages that: (1) the light stabilization efficiency is obviously superior to that of common ultraviolet ray absorbers; (2) the hear resistance is obviously higher than that of common ultraviolet ray absorbers and hindered amine light stabilizers, and is higher than that of stabilizers with a high molecular weight; (3) the tendency of a blooming phenomenon is extremely low.
Description
Technical field
The present invention relates to one type of application of adopting the organic polymer material title complex as photostabilizer.
Background technology
Most of organic polymer materials; Comprise plastics, chemical fibre, rubber, coating, paint, tackiness agent etc.; Be exposed to and photodegradation reaction can take place under the sight and wear out, show as variable color, tarnish, occur degradation outward appearance and physical and mechanical properties deterioration under crazing, erosion, be full of cracks and tensile strength, shock strength, extensibility and the electrical property.Therefore, the organic polymer material of outdoor use must carry out Photostabilised processing, and some is to the special sensitive polymers of ultraviolet ray, and like Vestolen PP 7052, even indoor application products also need be handled.The photoaging of organic polymer material can be inhibited through adding photostabilizer.That has developed at present is organic high
The molecular material photostabilizer mainly contains four types of photomask agent, UV light absorber, excited state quenchers and radical scavengers.The main compound type of photomask agent is mineral dye and fillers such as carbon black, white titanium pigment, zinc oxide: UV light absorber mainly is adjacent hydroxyaromatic compounds and some phenyl ring replacement p-Hydroxybenzoates such as O-hydroxyl-diphenyl ketone, o-hydroxy and triazole; Excited state quenchers mainly is the sulfur-bearing organic ligand title complex of nickel; Radical scavenger then mainly is hindered amine compounds such as hindered piperidine.The photostabilizer of these types obtains practical application in different fields.It's a pity that they all respectively have its a fly in the ointment: the photomask agent protection effect is good, price is low, but has opacifying property, is only applicable to opaque material; UV light absorber has extensive applicability, but photo-stability efficiency is general, meanwhile; Because of belonging to pure organic cpds; Also have shortcomings such as volatile, bloom, migration, extraction, the persistence that this has not only influenced its usefulness performance also causes contaminate environment simultaneously; Excited state quencher light stability is high, volatility is low, bloom and the little and anti-extraction of migration, but can decompose variable color during dirty big, the high temperature process of color depth, toxicity and ring, has antagonistic action with sulfur-containing additive; The radical scavenger look shallow, photo-stability efficiency is high; But it is, have antagonistic action, and the same with UV light absorber with acidic matrix, additive and surrounding material owing to have alkalescence; Because of belonging to pure organic cpds, also there are shortcomings such as volatile, bloom, migration, extraction.Therefore; Though just industriallization and obtain practical application of the photostabilizer of the above-mentioned type before in the seventies in 20th century; But constantly enlarge environment for use and worsen increasingly high technology and the economic performance requirement that (environmental pollution constantly strengthens the uv-radiation that the destruction of ozonosphere has caused arriving ground) proposes again day by day for adapting to polymer materials outdoor use field; Up at present, the development research of relevant photostabilizer is still being carried out very actively.Not only efficiently durable, suitability by force but also hygienic environment-protecting, stable performance, cost performance height be the target that the research and development of polymer materials photostabilizer are pursued.Containing nickel complex once was the most popular field of photostabilizer development research, but after the eighties in 20th century, because its toxicity and problem of environmental pollution cause concern, relevant research is lowered the temperature rapidly.Study on the modification order that the substitute is UV light absorber and hindered amine as light stabilizer becomes active, and main research direction is: (1) polymer quantizes (comprising aggretion type and non-aggretion type), (2) reactivityization (but getting final product copolymerization or grafting), (3) intramolecularly multifunction, (4) hindered amine low alkalinityization.Polymer quantizes effectively to improve anti-volatilization, migration, the extractable of stablizer; Thereby can improve effectiveness persistence and safety in utilization: reactivityization more can realize " permanent " bonding of stablizer and polymeric matrix, thereby reaches photo-stability efficiency " permanent " performance; The intramolecularly multifunction can realize the intramolecularly synergy and effectively improve stable performance; The hindered amine low alkalinityization then can reduce it to tart susceptibility, thus but broadened application scope.Regrettably these modified measures also bring many new problems, and for example: high molecular weight products is owing to transport property and bad dispersibility in base material, and its light stability is usually not as the lower molecular weight kind; The more satisfactory method of use of reactive photostabilizer is that it is grafted to polymer surfaces, can significantly reduce consumption like this, but there is problem of environmental pollution in the grafting process, and the grafting layer is prone to made material forfeiture protection by abrasion; The intramolecularly multifunction can produce detrimentally affect to using at aspects such as thermostability, consistency, color and lusters under many situation; The light stability of hindered amine can decrease because of low alkalinityization.How being in harmonious proportion these contradictions has become the focus of relevant research to obtain best modified effect.According to relevant study, single with regard to technical feature optimization, well-designed is important terms of settlement with making up molecular structure, and for example the molecular weight with non-aggretion type and aggretion type high molecular weight products is controlled at respectively about 500～600 and 2700.But this causes these enforcement difficulty that just related to the modification technology of more complicated building-up process originally further to strengthen again, and cost improves, and product performance stability is restive.Maybe just because of these deficiencies these organic complex art economic performances that can reach with the polymer chemistry modification are improved and are unsatisfactory, therefore, though the patent of having delivered at present a lot (according to statistics, 1977～
In the period of 1996; The patent of relevant hindered amine as light stabilizer just has more than 1100); But the achievement that realizes suitability for industrialized production and better applied few (relatively success is several kinds of HMW hindered amines, like T'inuvin 622, Chimassorb 944 and Cyasorb UV-3346).This shows that the development photostabilizer also need be explored new approach.Bibliographical information is arranged recently, and some rare earth organic acid salt is used as the PVc thermo-stabilizer with certain light stabilising effect (japanese communique, clear 46.-40421), and some beta-diketone compound has light stabilising characteristic (Polym.Degrad.Stab., 1986,16 (2): 169～186) of UV light absorber to polymkeric substance.The present invention receives this inspiration and notices following favorable factor and beta-diketon one rare earth compounding used as the organic polymer material photostabilizer carry out system's further investigation and obtain:
(1) beta-diketone compound can form with rare earth and be insoluble in water and with organic medium the stable complex of certain affinity is arranged as containing the oxygen sequestrant;
(2) beta-diketon-rare earth compounding itself has similar a visible ultraviolet absorption characteristic and ability with the part beta-diketon;
(3) the rare-earth ion coordination number is high, and beta-diketon can make molecular weight obviously improve through forming rare earth compounding, thereby possibly have effectiveness enduring qualities such as higher anti-volatilization, migration, medium extraction;
(4) the nontoxic or low toxicity of rare earth ion and compound thereof;
(5) the rare earth sulfocompound is unstable, beta-diketon-rare earth compounding not can with sulfur-containing additive generation antagonistic action:
(6) beta-diketon-rare earth compounding is synthetic simple and easy, and productive rate is high, the nonstaining property waste discharge.
Summary of the invention
The objective of the invention is in order to overcome above-mentioned technical barrier; The application of one type of beta-diketon-rare earth compounding as photostabilizer is provided; Press the common method of use of addition type photostabilizer and use, said beta-diketon-rare earth compounding is as the application of organic polymer material photostabilizer.
Organic polymer material photostabilizer provided by the invention is the following beta-diketon-rare earth compounding of general formula:
REL
3-x(OH)
x.mH
2O
In the formula:
(1) RE is praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium
(Er), the arbitrary proportion of one or more in thulium (Tm), the ytterbium (Yb) combination or be master's mishmetal with above-mentioned element:
(2) L represents the negatively charged ion of the following beta-diketon of general formula:
RCOCHR
2COR
1
In the formula, R and Rl can be the same or different, and can be alkyl, haloalkyl, naphthenic base, aryl or heterocyclic radical separately, and R2 can be hydrogen, alkyl, haloalkyl, naphthenic base, aryl or heterocyclic radical;
(3)x=O～2，m=0～3。
In the chemical general formula of said beta-diketon-rare earth compounding, x=O.
In the chemical general formula of said beta-diketon-rare earth compounding, m=o.
In the chemical general formula of said beta-diketon-rare earth compounding, x=0, m=O.
Said beta-diketon is methyl ethyl diketone, benzoyl acetone, diphenylpropane-1,3-dione(DPPO), stearoyl benzoyl methane.
Said organic polymer material can be plastics, chemical fibre, rubber, coating, paint, tackiness agent.
Beta-diketon-rare earth compounding of using as the organic polymer material photostabilizer of the present invention can prepare by the method for bibliographical information.
Beta-diketon one rare earth compounding organic polymer material photostabilizer of the present invention can use by the common method of use of addition type photostabilizer.
Relevant research shows that beta-diketon-rare earth compounding of the present invention is used as the organic polymer material photostabilizer, has the following advantages at least:
(1) photo-stability efficiency obviously is superior to UV light absorber commonly used;
(2) thermotolerance is apparently higher than UV light absorber commonly used and hindered amine as light stabilizer, and is higher than its HMW kind:
(3) tendency of generation bloom phenomenon is minimum;
(4) not with sulfur-containing additive generation antagonistic action.
Embodiment
Below through concrete but non-restrictive example the present invention is further described.
Embodiment 1
Under the room temperature, 9.729 (0.06mo1) benzoyl acetone (HBA) is dissolved in 300ml.Absolute ethyl alcohol adds 60mL 1mol.L
-1Sodium hydroxide (0.06mol) aqueous solution mixes reaction, then, slowly drips 40mL 0.5mol.L
-1Samarium trichloride (SmCl
3, the 0.02mol) aqueous solution continued stirring reaction 1.5 hours.The deposition that reaction generates is through room temperature ageing filtration under diminished pressure after 24 hours, and filter cake can not checked cl ions with 1:1 aqueous ethanolic solution washing to filtrating with the acidifying silver nitrate solution, then, to constant weight, gets little yellow powdered product in 150 ℃ of constant pressure and dries.Through assay determination, the Sm of product, C, H content are respectively 22.89%, 57.18% and 4.97%, with chemical formula Sm (BA)
3(Sm, C, H cubage value are respectively 23.72%, 56.84%, 4.77%) conforms to.
Embodiment 2
Press compound method and the condition of embodiment 1, with SmCl
3In Sm replace with Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb respectively, can obtain consisting of RE (BA)
3The little yellow powdered product of (RE represents Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm or Yb).
Embodiment 3
Under the room temperature, 13.449 (0.06m01) diphenylpropane-1,3-dione(DPPO) (HDBM) is dissolved in the 300mL absolute ethyl alcohol, an, x.60mLlmolL
-1Sodium hydroxide (0.06t001) aqueous solution mixes reaction, then, slowly drips 40mL 0.5molL.Samarium trichloride (SmCl
3, the 0.02mo1) aqueous solution continued stirring reaction 1.5 hours.The deposition that reaction generates is through room temperature ageing filtration under diminished pressure after 24 hours, and filter cake can not checked cl ions with l:1 aqueous ethanolic solution washing to filtrating with the acidifying silver nitrate solution, then, to constant weight, gets light yellow powdery product in 150 ℃ of constant pressure and dries.Through assay determination, the Sm of product, C, H content are respectively 1 8.49%, 65.68% and 4.40%, and (Sm, C, H cubage value are respectively 1 8.33%, 65.89%, 4.42%) conforms to chemical formula Sm (DBM) 3.
Embodiment 4
Press compound method and the condition of embodiment 1, the Sm among the SmCl3 is replaced with Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb respectively, can obtain consisting of RE (DBM)
3The light yellow powdery product of (RE represents Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm or Yb).
Claims (1)
1. adopt the application of organic polymer material title complex as photostabilizer, it is characterized in that: the common method of use of pressing the addition type photostabilizer is used, and adopts the application of beta-diketon-rare earth compounding as the organic polymer material photostabilizer,
(1) chemical general formula of said beta-diketon-rare earth compounding is:
REL
3-x(OH) x.mH
2In the O formula:
1) RE be in praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), the ytterbium (Yb) one or more arbitrary proportion combination or be master's mishmetal with above-mentioned element;
2) L represents the negatively charged ion of the following beta-diketon of general formula:
RCOCHR2COR
1
In the formula, R and R
1Can be the same or different, can be alkyl, haloalkyl, naphthenic base, aryl or heterocyclic radical separately, and R2 can be hydrogen, alkyl, haloalkyl, naphthenic base, aryl or heterocyclic radical;
3)x=O～2，m=O～3;
(2), in the chemical general formula of said beta-diketon one rare earth compounding, x=O;
(3), in the chemical general formula of said beta-diketon one rare earth compounding, m=0;
(4), in the chemical general formula of said beta-diketon one rare earth compounding, x=O, m=0;
(5), said beta-diketon is methyl ethyl diketone, benzoyl acetone, diphenylpropane-1,3-dione(DPPO), stearoyl benzoyl methane;
(6), said organic polymer material can be plastics, chemical fibre, rubber, coating, paint, tackiness agent.
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| CN2010105534242A CN102477167A (en) | 2010-11-22 | 2010-11-22 | Application of organic polymer material complex used as light stabilizer |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105462339A (en) * | 2015-12-28 | 2016-04-06 | 广西师范学院 | Application of compound solution of beta-cyclodextrin and rare earth Tb complex in micro-contact printing |
| CN105462343A (en) * | 2015-12-28 | 2016-04-06 | 广西师范学院 | Application of compound solution of beta-cyclodextrin and rare earth Dy complex in microcontact printing |
| CN105462342A (en) * | 2015-12-28 | 2016-04-06 | 广西师范学院 | Gamma-cyclodextrin and rare earth Tb complex and application of gamma-cyclodextrin and rare earth Tb complex in microcontact printing technique |
| CN105504958A (en) * | 2015-12-28 | 2016-04-20 | 广西师范学院 | Application of alpha-cyclodextrin and rare-earth Dy complex composite solution in micro-contact printing |
| CN109880444A (en) * | 2019-01-31 | 2019-06-14 | 湖南诺诚光伏科技有限公司 | A kind of preparation method of EVA packaging adhesive film surface covering |
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2010
- 2010-11-22 CN CN2010105534242A patent/CN102477167A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105462339A (en) * | 2015-12-28 | 2016-04-06 | 广西师范学院 | Application of compound solution of beta-cyclodextrin and rare earth Tb complex in micro-contact printing |
| CN105462343A (en) * | 2015-12-28 | 2016-04-06 | 广西师范学院 | Application of compound solution of beta-cyclodextrin and rare earth Dy complex in microcontact printing |
| CN105462342A (en) * | 2015-12-28 | 2016-04-06 | 广西师范学院 | Gamma-cyclodextrin and rare earth Tb complex and application of gamma-cyclodextrin and rare earth Tb complex in microcontact printing technique |
| CN105504958A (en) * | 2015-12-28 | 2016-04-20 | 广西师范学院 | Application of alpha-cyclodextrin and rare-earth Dy complex composite solution in micro-contact printing |
| CN105504958B (en) * | 2015-12-28 | 2018-09-21 | 广西师范学院 | Using gamma-cyclodextrin and rare earth β-diketone complex complex composite solution micro-contact printing application |
| CN105462343B (en) * | 2015-12-28 | 2018-09-21 | 广西师范学院 | Using beta-cyclodextrin and rare earth β-diketone complex complex composite solution micro-contact printing application |
| CN105462339B (en) * | 2015-12-28 | 2018-09-21 | 广西师范学院 | Using beta-cyclodextrin and rare earth Tb complexs composite solution micro-contact printing application |
| CN105462342B (en) * | 2015-12-28 | 2018-11-02 | 广西师范学院 | Gamma-cyclodextrin and rare earth Tb complexs and its application in microcontact printing techniques |
| CN109880444A (en) * | 2019-01-31 | 2019-06-14 | 湖南诺诚光伏科技有限公司 | A kind of preparation method of EVA packaging adhesive film surface covering |
| CN109880444B (en) * | 2019-01-31 | 2021-05-04 | 湖南诺诚光伏科技有限公司 | Preparation method of EVA packaging adhesive film surface coating |
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Application publication date: 20120530 |