CN101817947A - Wideband ultraviolet absorber for polyolefin and preparation method thereof - Google Patents
Wideband ultraviolet absorber for polyolefin and preparation method thereof Download PDFInfo
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- CN101817947A CN101817947A CN201010139504A CN201010139504A CN101817947A CN 101817947 A CN101817947 A CN 101817947A CN 201010139504 A CN201010139504 A CN 201010139504A CN 201010139504 A CN201010139504 A CN 201010139504A CN 101817947 A CN101817947 A CN 101817947A
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- ultraviolet absorber
- polyolefin
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Abstract
The invention discloses a novel ultraviolet absorber having excellent absorption effect in wider ultraviolet band range (from 200nm to 420nm) and a preparation method thereof. The novel ultraviolet absorber mainly comprises the ingredients of: phenyl salicylates and derivatives thereof, and triazine or ortho-hydroxyazimidobenzene compounds. The preparation method of the novel ultraviolet absorber comprises the steps: adding and pre-fusing phenyl salicylates and derivatives thereof until white crystals are completely changed into viscous liquid, then adding azimidobenzene or triazine, sufficiently stirring and reacting at the temperature from 150 to 180 DEG C until two phases are completely fused to one phase, and preparing the wideband ultraviolet absorber by cooling and grinding. The wideband ultraviolet absorber according to the invention can be extensively applied to the light protection of polyolefin articles which are liable to photooxidative degradation, such as PVC, PS, PP and the like. Long-term retaining rate of the comprehensive property of the polyolefin articles containing the ultraviolet absorber during outdoor use is greatly enhanced.
Description
Technical field
The present invention relates to technical field of polymer, more particularly relate to be used for polyolefinic ultraviolet absorbers and preparation method thereof.
Technical background
Common polyolefine ultraviolet absorbers all has a common feature as benzophenone, triazines, azimidobenzene compounds etc., promptly has intramolecular hydrogen bond.The existence of this structure can make compound when being subjected to ultraviolet light irradiation, under the constant situation of electron spinning multiplicity, by non-radiative mode electronic excitation energy is converted to vibrational energy (S
1～～～～～→ S
0), thereby realization is to the protection of body material.
Dissimilar ultraviolet absorbers is because its molecular structure difference, is specific and limited to the absorption bands and the receptivity of UV-light, and this just causes the ultraviolet protection scarce capacity of single ultraviolet absorbers to material.For example: the absorption width of Octabenzone (UV531) commonly used is narrower, and only the ultraviolet light wave to 250nm-330nm has better absorption, and is to almost not effect of the UV-light in other frequency range, therefore very limited to the protection of base material.Seek have the ultraviolet absorbers of strong assimilation effect to be still this area problem to be solved is arranged in broad ultraviolet band scope.
Carrying out the photostabilizer of different structure rationally composite is an effective way that improves the light stabilization efficiency.As: L.Avar etc. have investigated hindered amine light stabilizer and have mixed the influence of back to the ultraviolet ageing behavior of polyacrylic ester type coating by a certain percentage with ultraviolet absorbers, find both compound aging progresses that can delay coating more effectively.After discovery hindered amine light stabilizer such as T.Kurumada and ultraviolet absorbers are composite; hindered amine as light stabilizer is subjected to the provide protection in early stage of ultraviolet absorbers; reduced the loss of hindered amines; and hindered amine makes ultraviolet absorbers avoid free radical to the capture ability of free radical to attack, and the long and is that the light stabilization efficiency strengthens.It is suitable that the greatest problem that this class has a composite existence between the stablizer of different photo-protection mechanism is that the consistency of performance and structure between auxiliary agent and matching are difficult to, the problem that usually exists partial properties to cancel out each other.
To have same stable mechanism, but the stablizer of different absorption bandses carries out the composite new focus of attention in affiliated field that becomes.At present the research of this respect report is few, and unique research report sees Y. Dobashi etc. the composite back of different structure ultraviolet absorbers (UVA-A and UVA-B) is found that both have certain collaborative reinforced effects.
The present invention is directed to the deficiency of existing research, with the ultraviolet absorbers is to select composite object, absorption peak characteristic according to each ultraviolet absorbers, utilize compounded technology, make at 290nm～420nm wave band and have the wideband ultraviolet absorber of remarkable synergistic enhancing effect, this has not only overcome compatibility, matching between different stable mechanism auxiliary agents, and the contradiction between the inconsistent property of partial action, and improved consistency with base material, can provide better photo-protection effect for polyolefine material.
Summary of the invention:
A kind of polyolefine ultraviolet absorbers that The present invention be directed to the deficiencies in the prior art and propose and preparation method thereof, limited to solve existing ultraviolet absorbers in the absorption frequency range and the intensity of ultraviolet region, can not cover the problem of ultraviolet region fully.
The concrete technical scheme that realizes above-mentioned purpose of the present invention is as follows:
Wideband ultraviolet absorber for polyolefin, its component is formed and is mainly comprised: salol compounds or derivatives thereof 0.25-0.5phr, azimidobenzene compounds or compound in triazine class 0.5-0.75phr.In above-mentioned wideband ultraviolet absorber for polyolefin technical scheme, described salol compounds or derivatives thereof can be a kind of compound, also can be two or more compound; Azimidobenzene compounds or compound in triazine class can be a kind of compound equally, also can be two or more compound.
In above-mentioned wideband ultraviolet absorber for polyolefin technical scheme, preferentially select salol compounds and derivative thereof for use with following structure:
R wherein
1For H ,-C (CH
3)
3With-C
8H
17In a kind of.Preferentially select for use for the azimidobenzene compounds and to have following structure:
R wherein
2Be Cl; R
3For
In one of structure.Preferentially select for use for compound in triazine class and to have following structure:
R wherein
4, R
5And R
6Be respectively
Above-mentioned wideband ultraviolet absorber for polyolefin is taked following method preparation: with the salol compounds or derivatives thereof heating pre-fusion of proportional quantity, all change viscous liquid into until white crystal, add azimidobenzene compounds or compound in triazine class afterwards, abundant stirring reaction under 150～180 ℃, until the complete fusion of two-phase is a phase, and cooling is after grinding promptly makes wideband ultraviolet absorber.In the stirring reaction process, the ultraviolet absorbers of different structure forms a kind of new composite UV light stabilizing agent by interaction physics, chemistry.
In the preparation method of above-mentioned wideband ultraviolet absorber for polyolefin, the heating pre-fusion temperature of salol compounds or derivatives thereof is generally 130 ℃～150 ℃ scopes; After adding azimidobenzene compounds or compound in triazine class, the stirring reaction temperature is controlled at 150～180 ℃, and the reaction times is generally at 1～8 hour, and concrete time and temperature and concrete polymkeric substance are relevant; The stirring velocity of reaction is generally 50～300 rev/mins of scopes.
Experimental result shows, ultraviolet absorbers provided by the invention all effectively improves to the absorption intensity and the width of UV-light, add the polyolefine material that new ultra-violet light absorber provided by the invention makes, the polyolefine material that contains single ultraviolet absorbers relatively, light stability is improved obviously, and the mechanical property long-term retention rate obtains bigger raising.Cause the reason of above-mentioned phenomenon as follows:
The ultraviolet absorbers of different structure is different with intensity to the absorption frequency range of UV-light.By scientific and reasonable composite, can make a kind of new ultraviolet absorbers, its absorption width at ultraviolet region obviously increases, and absorption intensity also improves a lot, and the photo-protection ability of body material is improved greatly.Concrete protection effect is referring to embodiment.
Description of drawings
Accompanying drawing 1 is the ultraviolet absorption spectrogram of wideband ultraviolet absorber I of the present invention and adjacent hydroxyl salol of corresponding single ultraviolet absorbers and triazine 5.
Accompanying drawing 2 is ultraviolet absorption spectrograms of wideband ultraviolet absorber IV of the present invention and the adjacent hydroxyl salol of corresponding single ultraviolet absorbers and 2-(2-hydroxyl-3,5-dicumylphenyl)-azimidobenzene.
Can find out obviously that from Fig. 1 adjacent hydroxyl phenyl salicytate has two absworption peaks at 230nm～250nm and 280nm～320nm, and triazine 5 has the biabsorption peak at 330nm to 380nm. Prepared Novel broadband ultraviolet absorber I presents stronger wider absworption peak after both interworkings in 210nm～390nm scope. Similarly, can obviously find out the more adjacent hydroxyl phenyl salicytate of Novel broadband UV absorbers IV and 2-(2-hydroxyl-3,5-dicumylphenyl)-azimidobenzene from Fig. 2, the width of its ultraviolet absorption peak increases, and absorption intensity improves.
Concrete enforcement formula
Below be the present invention to be specifically described by embodiment.In following each embodiment, the umber of each component is parts by weight (phr).
Embodiment 1:
With the adjacent hydroxyl salol of 0.25phr heating and melting, all change viscous liquid into until white crystal, afterwards 0.75phr triazine 5 is joined in the viscous liquid, at 180 ℃ of about 4h of following stirring reaction, until the complete fusion of two class ultraviolet absorbers is a phase, cooling is after grinding promptly makes wideband ultraviolet absorber I.
Embodiment 2:
With the 0.5phr Whitfield's ointment right-the pre-heat fusing of octyl octylphenyl, all change viscous liquid into until white crystal, afterwards with 0.5phr2-(2-hydroxyl-3, the 5-dicumylphenyl)-benzotriazole joins in the viscous liquid, at 160 ℃ of about 3h of following stirring reaction, until the complete fusion of two class ultraviolet absorbers is a phase, and cooling is after grinding promptly makes wideband uv-absorbing agent II.
Embodiment 3:
With the 0.4phr Whitfield's ointment right-tertiary butyl phenyl ester preheating fusion, all change viscous liquid into until white crystal, afterwards 0.6phr2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorinated benzotriazole is joined in the viscous liquid, at 170 ℃ of about 5h of following stirring reaction, until the complete fusion of two class ultraviolet absorbers is a phase, cooling is after grinding promptly makes wideband uv-absorbing agent III.
Embodiment 4
With the pre-heat fusing of the adjacent hydroxyl salol of 0.5phr, all change viscous liquid into until white crystal, afterwards with 0.5phr2-(2-hydroxyl-3, the 5-dicumylphenyl)-benzotriazole joins in the viscous liquid, at 165 ℃ of about 2h of following stirring reaction, until the complete fusion of two class ultraviolet absorbers is a phase, and cooling is after grinding promptly makes wideband uv-absorbing agent IV.
Provide the fast light polyolefinic embodiment and the test result that contain ultraviolet absorbers of the present invention below.
Embodiment 1:
With mixing material (100phrPVC/2phr organo-tin het stabilizer/0.5phr stearic acid/0.5phr photostabilizer, wherein photostabilizer is new ultra-violet light absorber I, adjacent hydroxyl salol (Phe), a kind of in the triazine 5 (Tra)) in two rollers in 170 ℃ of about 8min of left and right sides rollers refining, under 180 ℃, be molded into the sheet material and the sheet material of desired thickness again, be made for test and use.To test test result such as following table behind the aging 480h of its accelerating ultraviolet:
Embodiment 2:
With mixing material (100phrPVC/2phr organo-tin het stabilizer/0.5phr stearic acid/0.5phr photostabilizer, wherein photostabilizer is new ultra-violet light absorber II, Whitfield's ointment is right-octyl octylphenyl (Phobe), 2-(2-hydroxyl-3, the 5-dicumylphenyl)-a kind of in the benzotriazole (UV234)) in two rollers in 170 ℃ of about 8min of left and right sides rollers refining, under 180 ℃, be molded into the sheet material and the sheet material of desired thickness again, be made for test and use.To test test result such as following table behind the aging 480h of its accelerating ultraviolet:
Embodiment 3:
In polypropylene, add 0.5phr new ultra-violet light absorber III respectively, or the 0.5phr Whitfield's ointment right-tertiary butyl phenyl ester (Phbe), or 0.5phr 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorinated benzotriazole (UV326), (processing temperature is respectively: 170 ℃ through the twin screw extruder extruding pelletization, 190 ℃, 200 ℃, 200 ℃), under 200 ℃, be molded into the sheet material and the sheet material of desired thickness again, be made for test and use.To test test result such as following table behind the aging 480h of its accelerating ultraviolet:
Embodiment 4:
In polystyrene, add 0.5phr new ultra-violet light absorber IV respectively, or the adjacent hydroxyl salol (Phe) of 0.5phr, or 0.5Phr2-(2-hydroxyl-3, the 5-dicumylphenyl)-benzotriazole (UV234), through the twin screw extruder extruding pelletization (processing temperature is respectively: 170 ℃, 190 ℃, 200 ℃, 200 ℃), under 200 ℃, be molded into the sheet material and the sheet material of desired thickness again, be made for test and use.To test test result such as following table behind the aging 480h of its accelerating ultraviolet:
Be necessary to be pointed out that at this; above embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in art can make some nonessential improvement to the present invention and adjustment is implemented according to the foregoing invention content.
Claims (6)
1. a wideband ultraviolet absorber for polyolefin is characterized in that the component composition of this absorption agent mainly comprises: salol compounds or derivatives thereof 0.25-0.5phr, azimidobenzene compounds or compound in triazine class 0.5-0.75phr.
2. according to claim 1 described wideband ultraviolet absorber for polyolefin, it is characterized in that described salol compounds and derivative thereof have following structure:
R wherein
1For H ,-C (CH
3)
3With-C
8H
17In a kind of.
3. according to claim 1 described wideband ultraviolet absorber for polyolefin, it is characterized in that described azimidobenzene compounds has following structure:
R wherein
2Be Cl; R
3For
In one of structure.
4. according to claim 1 described wideband ultraviolet absorber for polyolefin, it is characterized in that described compound in triazine class has following structure:
R wherein
4, R
5And R
6Be respectively
5. the method for preparing the described wideband ultraviolet absorber for polyolefin of each claim in the claim 1 to 4, it is characterized in that the salol compounds or derivatives thereof heating pre-fusion of elder generation with proportional quantity, all change viscous liquid into until white crystal, add azimidobenzene compounds or compound in triazine class afterwards, abundant stirring reaction under 150～180 ℃, until the complete fusion of two-phase is a phase, and cooling is after grinding promptly makes wideband ultraviolet absorber.
6. the preparation method of wideband ultraviolet absorber for polyolefin according to claim 5 is characterized in that said reaction stirring velocity is 50～300 rev/mins.
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|---|---|---|---|
| CN2010101395043A CN101817947B (en) | 2010-04-06 | 2010-04-06 | Wideband ultraviolet absorber for polyolefin and preparation method thereof |
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|---|---|---|---|
| CN2010101395043A CN101817947B (en) | 2010-04-06 | 2010-04-06 | Wideband ultraviolet absorber for polyolefin and preparation method thereof |
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| CN101817947A true CN101817947A (en) | 2010-09-01 |
| CN101817947B CN101817947B (en) | 2012-07-25 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968646A (en) * | 2016-06-30 | 2016-09-28 | 襄阳南洁高分子新型材料有限公司 | Preparation method of ultraviolet-proof, short-wave and blue-light PVC preservative film |
| CN107057125A (en) * | 2017-05-18 | 2017-08-18 | 句容亿格纳米材料厂 | Modified salicylic acid aligns the preparation and its application in anti-light pollution plastics of octyl phenyl ester |
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| US3238138A (en) * | 1961-12-28 | 1966-03-01 | Union Oil Co | 2, 4, 6-triaryl-1, 3, 5-triazines in ultraviolet light absorption method and coatingcomposition |
| NO912574L (en) * | 1990-07-03 | 1992-01-06 | Rhone Poulenc Chimie | PIPERIDINYL COMPOUNDS AND THEIR USE AS ADDITIVES. |
| JP2000191917A (en) * | 1998-12-24 | 2000-07-11 | Fine Rubber Kenkyusho:Kk | Insecticidal resin composition and molding product using the same |
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| CN101367792A (en) * | 2008-10-13 | 2009-02-18 | 大连化工研究设计院 | Benzotriazole light stabilizer containing hindered amine group |
| CN101544803A (en) * | 2009-04-30 | 2009-09-30 | 四川大学 | Polyvinyl chloride ultraviolet stabilizer, polyvinyl chloride prepared from same and method for preparing same |
| CN101544782A (en) * | 2009-05-15 | 2009-09-30 | 北京化工大学 | Supermolecular structural 5,5'-methylene disalicylic acid intercalation ultraviolet absorption material and preparation method thereof |
-
2010
- 2010-04-06 CN CN2010101395043A patent/CN101817947B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3238138A (en) * | 1961-12-28 | 1966-03-01 | Union Oil Co | 2, 4, 6-triaryl-1, 3, 5-triazines in ultraviolet light absorption method and coatingcomposition |
| NO912574L (en) * | 1990-07-03 | 1992-01-06 | Rhone Poulenc Chimie | PIPERIDINYL COMPOUNDS AND THEIR USE AS ADDITIVES. |
| JP2000191917A (en) * | 1998-12-24 | 2000-07-11 | Fine Rubber Kenkyusho:Kk | Insecticidal resin composition and molding product using the same |
| CN101210105A (en) * | 2006-12-30 | 2008-07-02 | 上海普利特复合材料有限公司 | Illumination aging resisting polycarbonate/styryl resin composition and preparing method thereof |
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| CN101367792A (en) * | 2008-10-13 | 2009-02-18 | 大连化工研究设计院 | Benzotriazole light stabilizer containing hindered amine group |
| CN101544803A (en) * | 2009-04-30 | 2009-09-30 | 四川大学 | Polyvinyl chloride ultraviolet stabilizer, polyvinyl chloride prepared from same and method for preparing same |
| CN101544782A (en) * | 2009-05-15 | 2009-09-30 | 北京化工大学 | Supermolecular structural 5,5'-methylene disalicylic acid intercalation ultraviolet absorption material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968646A (en) * | 2016-06-30 | 2016-09-28 | 襄阳南洁高分子新型材料有限公司 | Preparation method of ultraviolet-proof, short-wave and blue-light PVC preservative film |
| CN107057125A (en) * | 2017-05-18 | 2017-08-18 | 句容亿格纳米材料厂 | Modified salicylic acid aligns the preparation and its application in anti-light pollution plastics of octyl phenyl ester |
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| Publication number | Publication date |
|---|---|
| CN101817947B (en) | 2012-07-25 |
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