CN100371386C - Polymer containing ultraviolet absorption group and titanium dioxide complex particle composition and method of preparing the same - Google Patents
Polymer containing ultraviolet absorption group and titanium dioxide complex particle composition and method of preparing the same Download PDFInfo
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- CN100371386C CN100371386C CNB2006100217235A CN200610021723A CN100371386C CN 100371386 C CN100371386 C CN 100371386C CN B2006100217235 A CNB2006100217235 A CN B2006100217235A CN 200610021723 A CN200610021723 A CN 200610021723A CN 100371386 C CN100371386 C CN 100371386C
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- polymkeric substance
- ultraviolet absorption
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Abstract
The invention discloses a polymer with ultraviolet absorption radical and titanium dioxide composite particle assemble material and preparing method, which comprises the following steps: making the 1-10% modification titanium dioxide and 50-100% de-ionized water for ultrasonic dispersion for 5-10 minutes at 150-200W; putting the serum and 5-25% monomer, 0.25-3 convergence emulsifier, 0.25-5% convergence ultraviolet absorbent, 0.01-1.5% evocating agent in the three-necked bottle with thermograph, blender and reflex condenser at 70-80DEG C for 3-6 hours; reducing the temperature and discharging port; precipitating by 1-10% calcium chloride aqueous solution; washing again and again with de-ionized water to wipe off unreacted emulsifier; drying at 60-70DEG C; getting polymer with ultraviolet absorption radical and titanium dioxide composite particle assemble material.
Description
Technical field
The present invention relates to a kind of polymkeric substance that contains ultraviolet absorption group and titanium dioxide complex particle composition and preparation method thereof, the preparation field that belongs to polymer composites, this complex particle composition have inorganic UV shield agent and the organic uv absorbers protective effect to UV-light.
Background technology
Polymer materials or plastics can variable colors under the sunlight long-term irradiation, become fragile, cracking or efflorescence, degraded takes place and lose its use properties.The method of polymkeric substance uvioresistant protection at present generally all is to add ultraviolet screening agent or UV light absorber respectively.
Ultraviolet screening agent, it is a kind of material that can reflect or absorb UV-light, usually mostly be some mineral dyes and filler as ultraviolet screening agent, common ultraviolet screening agent has (Yang Hongying such as silicon-dioxide, zinc oxide, titanium oxide, penning, Zhu Sukang, Donghua University's journal, 2003,29:8-13; Wang Yanhua, the Shanghai building materials, 2003,4:6-8).But these screeners are difficult to be implemented in homodisperse in the polymkeric substance, so use range is restricted because its high surface energy is easily assembled.
UV light absorber (UVA) is to use the earliest, the photostabilizer of consumption maximum, mainly is divided into five classes by chemical structure: 1. benzophenone, as UV-9, UV-214, UV-531, UV-1200 etc.; 2. benzotriazole category is as UV-P, UV-327, UV-326 etc.; 3. salicylate class is as BAD, TBS, OPS etc.; 4. triazines is as UV light absorber s-triazine etc.; 5. group-substituted acrylonitrile, as UV-317 etc. (Huang Maofu, dyeing and finishing science and technology, 2001,2:46-53).UV light absorber can absorb ultraviolet ray effectively, and converts it into harmless luminous energy form and discharge.To such an extent as to but thereby the small molecules UV light absorber is easy to gasify, volatilizees, is migrated to the work-ing life that the material surface loss has reduced material by solvent extraction.
Except using respectively separately ultraviolet screening agent and the UV light absorber, with both be added on simultaneously a kind of comparatively widely method that the opposing UV-light also is to use in the polymkeric substance (Liu pay win clever, Xiao Hanning etc., functional materials, 2004,35:495-500).The preparation organic compound selective ultraviolet blocking material of a kind of novel inorganic (Duan Xue, Li Lei, Sun Peng, Chinese patent, publication number CN1318595A, 2001) also can combine inorganic UV shield agent and organic uv absorbers.This method at first at high temperature prepares bimetal composite oxide, then organic uv absorbers is grafted on its surface and obtains the purpose product.What but this method obtained is the small molecules organic/inorganic composite material, preparation method's complexity, and conditional request is higher, and use range has limitation.
At present, the method by emulsion polymerizing preparation compound/titanium dioxide complex particle use comparatively extensively (Zhang Liangjun, Cheng Julan, Zhao Zhongyu, coatings industry, 2003,33:1-4).But be to use conventional emulsifier to carry out letex polymerization and have following problems: poor stability (2) influenced film forming speed when (1) product was subjected to shearing force and high low temperature, and difficult recovery of residual emulsifying agent degraded, the water tolerance, chemical resistance and the glued membrane that cause environmental pollution (3) to influence glued membrane are prone to pin hole, and polymkeric substance mechanics, optical property are descended.(Zhang Hongtao, Ren Tianbin, bonding, 1999,20 (2): 26-28; Guyot A., Tauer K, Asua J.M, et al.Acta Polym, 1999,50:57-66).
Summary of the invention
The objective of the invention is to provide a kind of polymkeric substance that contains ultraviolet absorption group and titanium dioxide complex particle composition and preparation method thereof at the deficiencies in the prior art, be characterized in using Polymerizable Emulsifier, by letex polymerization inorganic UV shield agent and aggretion type organic uv absorbers are connected on the polymkeric substance with chemical bond-linking, make inorganic UV shield agent homodisperse in polymkeric substance, and prevent that organic uv absorbers from gasifying, volatilize, moving, and realized inorganic organic compound uvioresistant macromolecular material and preparation method thereof in polymkeric substance.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
Containing the polymkeric substance of ultraviolet absorption group and the recipe ingredient of titanium dioxide complex particle composition is:
1～10 part of modifying titanium dioxide
5～25 parts of monomers
0.25～5 part of aggretion type uv-absorbing agent
0.25～3 part of Polymerizable Emulsifier
0.01～1.5 part of initiator
50～100 parts of solvents
Wherein monomer is at least a in methyl methacrylate, butyl acrylate, methyl acrylate and ethyl propenoate, the vinylbenzene.
The aggretion type uv-absorbing agent is a benzophenone compound, and molecular structural formula is as follows:
X is
CH
2—CH＝CH
2。
Polymerizable Emulsifier is a maleic anhydride derivative sodium sulfonate, and molecular structural formula is as follows:
R is C
8～C
20Alkyl
Initiator is any in Potassium Persulphate, ammonium persulphate or the redox initiation system.
Solvent is water or ethanol.
The preparation method who contains the polymkeric substance and the titanium dioxide complex particle composition of ultraviolet absorption group:
(1) preparation of modifying titanium dioxide
Take by weighing titanium dioxide 1-10 part, coupling agent 0.01-1.5 part, solvent 10-50 part, TiO 2 particles is dispersed in the solvent that is dissolved with coupling agent, power is 150-200W ultra-sonic dispersion 5-10 minute, then slurries are transferred in the three-necked bottle that has thermometer, agitator and reflux exchanger, reacted 6-10 hour down for 40～70 ℃, after temperature 60-80 ℃ oven dry, grind and obtain the modifying titanium dioxide particle in temperature;
(2) contain the preparation of the polymkeric substance and the titanium dioxide complex particle composition of ultraviolet absorption group
With modifying titanium dioxide 1-10 part, deionized water 50-100 part, power is 150-200W ultra-sonic dispersion 5-10 minute, then with slurries and monomer 5-25 part, Polymerizable Emulsifier 0.25-3 part, aggretion type uv-absorbing agent 0.25-5 part, initiator 0.01-1.5 part joins and has thermometer, in the three-necked bottle of agitator and reflux exchanger, in temperature 70-80 ℃, reacted cooling discharge 3-6 hour, precipitate with the 1-10% calcium chloride water, and,, obtain to contain the polymkeric substance and the titanium dioxide complex particle composition of ultraviolet absorption group temperature 60-70 ℃ of oven dry down with deionized water repetitive scrubbing removal unreacted emulsifying agent.
The present invention has following advantage:
1, by letex polymerization inorganic UV shield agent and organic uv absorbers are connected on the polymkeric substance with chemical bond-linking, can make inorganic UV shield agent homodisperse and prevent that organic uv absorbers from gasifying, volatilize, moving in polymkeric substance in polymkeric substance.
2,, make product stability when being subjected to shearing force and high low temperature improve by using Polymerizable Emulsifier; Can not produce residual emulsifying agent, the protection environment; Water tolerance, the chemical resistance of glued membrane are improved, polymkeric substance mechanics, optical property are strengthened.
3, adopt letex polymerization, method is simple, and cost is low, helps suitability for industrialized production.
Description of drawings
Fig. 1 is P (St-M12-BPMA)/TiO
2The infrared spectrogram of composite particles
Fig. 2 removes TiO in the composite particles
2After P (St-M12-BPMA) (a) and P (St-M12) uv absorption spectra (b)
Fig. 3 is P (St-M12-BPMA)/TiO
2The thermogravimetric curve of composite particles
Experimental result shows, in the infrared spectrogram of Fig. 1 at 1726cm
-1The place finds the charateristic avsorption band of carbonyl in the emulsifying agent, 1624cm
-1The place finds the charateristic avsorption band of ketone carbonyl in the uv-absorbing agent, 1493cm
-1, 1449cm
-1The place finds cinnamic charateristic avsorption band, 500-600cm
-1Neighbouring is Ti-O stretching vibration absorption peak.P in the uv absorption spectra of Fig. 2 (St-M12-BPMA) absorption band occurs at 285nm and 333nm, is the characteristic absorbance of uv-absorbing agent.The thermogravimetric curve of Fig. 3 proves that further polymkeric substance/titanium dioxide is the composite particles of chemical bond combination, and this part polymkeric substance relative mass content is 513.87%.
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not explain and be limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1:
With titanium dioxide 1g, silane coupling agent 0.05g, ethanol 10g adds beaker, power is 200W ultra-sonic dispersion 10 minutes, then slurries are transferred to and have thermometer, in the three-necked bottle of agitator and reflux exchanger, in 70 ℃ of reactions of temperature 6 hours, after 80 ℃ of oven dry of temperature, grind and obtain the modifying titanium dioxide particle, with modifying titanium dioxide particle 1g, deionized water 50g, power is 200W ultra-sonic dispersion 5 minutes, then with slurries and vinylbenzene (St) 9g, Polymerizable Emulsifier maleic anhydride derivative sodium sulfonate (M12) 0.5g, aggretion type uv-absorbing agent 2-hydroxyl-4-(3-methacrylate based-2-hydroxyl propoxy-) benzophenone (BPMA) 0.45g, initiator 0.045g, join and have thermometer, in the three-necked bottle of agitator and reflux exchanger, 80 ℃ of temperature, reacted 6 hours, cooling discharge, precipitate with 5% calcium chloride water, and remove the unreacted emulsifying agent with the deionized water repetitive scrubbing, in 70 ℃ of oven dry down of temperature, acquisition contains the polymkeric substance and the titanium dioxide complex particle composition of ultraviolet absorption group, with products therefrom in Soxhlet extractor through trichloromethane backflow extracting 10 days, remove homopolymerization P (St-M12-BPMA), in 70 ℃ of oven dry down of temperature, carry out examination of infrared spectrum respectively then, ultra-violet absorption spectrum test and thermogravimetic analysis (TGA) test.
Embodiment 2:
With titanium dioxide 10g, silane coupling agent 1.5g, ethanol 50g adds beaker, power is 200W ultra-sonic dispersion 10 minutes, then slurries are transferred to and have thermometer, in the three-necked bottle of agitator and reflux exchanger, reacted 10 hours down for 70 ℃ in temperature, after 60 ℃ of oven dry of temperature, grind and obtain the modifying titanium dioxide particle, with modifying titanium dioxide particle 10g, deionized water 100g, power is 200W ultra-sonic dispersion 10 minutes, then with slurries and methyl methacrylate 25g, Polymerizable Emulsifier maleic anhydride derivative sodium sulfonate 3g, aggretion type uv-absorbing agent 2-hydroxyl-4-allyloxy benzophenone 5g, initiator 1.5g, join and have thermometer, in the three-necked bottle of agitator and reflux exchanger, in 80 ℃ of temperature, reacted 6 hours, cooling discharge precipitates with 10% calcium chloride water, and removes the unreacted emulsifying agent with the deionized water repetitive scrubbing, in 70 ℃ of oven dry down of temperature, obtain to contain the polymkeric substance and the titanium dioxide complex particle composition of ultraviolet absorption group.
Embodiment 3:
With titanium dioxide 1g, silane coupling agent 0.01g, ethanol 10g adds beaker, power is 150W ultra-sonic dispersion 10 minutes, then slurries are transferred to and have thermometer, in the three-necked bottle of agitator and reflux exchanger, reacted 6 hours down for 40 ℃ in temperature, after 70 ℃ of oven dry of temperature, grind and obtain the modifying titanium dioxide particle, with modifying titanium dioxide particle 1g, deionized water 50g, power is 150W ultra-sonic dispersion 5 minutes, then with slurries and methyl acrylate 5g, Polymerizable Emulsifier maleic anhydride derivative sodium sulfonate 0.25g, aggretion type uv-absorbing agent 2-hydroxy-4-methyl acryloxy benzophenone 0.25g, initiator 0.01g, join and have thermometer, in the three-necked bottle of agitator and reflux exchanger, in 80 ℃ of temperature, reacted 3 hours, cooling discharge precipitates with 1% calcium chloride water, and removes the unreacted emulsifying agent with the deionized water repetitive scrubbing, in 60 ℃ of oven dry down of temperature, obtain to contain the polymkeric substance and the titanium dioxide complex particle composition of ultraviolet absorption group.
Embodiment 4:
With titanium dioxide 8g, silane coupling agent 0.4g, ethanol 32g adds beaker, and power is 180W ultra-sonic dispersion 8 minutes.Then slurries are transferred to and have thermometer, in the three-necked bottle of agitator and reflux exchanger, reacted 8 hours down for 60 ℃ in temperature, after 75 ℃ of oven dry of temperature, grind and obtain the modifying titanium dioxide particle, with modifying titanium dioxide particle 8g, deionized water 90g, power is 180W ultra-sonic dispersion 5 minutes, then with slurries and vinylbenzene 10g, methyl methacrylate 10g, Polymerizable Emulsifier maleic anhydride derivative sodium sulfonate 1.8g, aggretion type uv-absorbing agent 2-hydroxy-4-methyl acryloxy benzophenone 1.2g, initiator 0.2g joins and has thermometer, in the three-necked bottle of agitator and reflux exchanger, in 80 ℃ of temperature, reacted cooling discharge 4 hours, precipitate with 8% calcium chloride water, and,, obtain to contain the polymkeric substance and the titanium dioxide complex particle composition of ultraviolet absorption group in 65 ℃ of oven dry down of temperature with deionized water repetitive scrubbing removal unreacted emulsifying agent.
Claims (4)
1. a polymkeric substance and titanium dioxide complex particle composition that contains ultraviolet absorption group is characterized in that the recipe ingredient of this complex particle composition is by weight:
1～10 part of modifying titanium dioxide
5～25 parts of monomers
0.25～5 part of aggretion type uv-absorbing agent
0.25～3 part of Polymerizable Emulsifier
0.01～1.5 part of initiator
50～100 parts of solvents
Wherein monomer is at least a in methyl methacrylate, butyl acrylate, methyl acrylate and ethyl propenoate, the vinylbenzene; The aggretion type uv-absorbing agent is a benzophenone compound, and molecular structural formula is as follows:
Or
Or CH
2-CH=CH
2
Polymerizable Emulsifier is a maleic anhydride derivative sodium sulfonate, and molecular structural formula is as follows:
R is C
8～C
20Alkyl;
By letex polymerization inorganic ultraviolet light screener and aggretion type uv-absorbing agent are connected on the polymkeric substance with chemical bond-linking.
2. according to described polymkeric substance and the titanium dioxide complex particle composition that contains ultraviolet absorption group of claim 1, it is characterized in that initiator is any in Potassium Persulphate, ammonium persulphate or the redox initiation system.
3. according to described polymkeric substance and the titanium dioxide complex particle composition that contains ultraviolet absorption group of claim 1, it is characterized in that solvent is water or ethanol.
4. according to the described preparation method who contains the polymkeric substance and the titanium dioxide complex particle composition of ultraviolet absorption group of one of claim 1～3, it is characterized in that this method may further comprise the steps:
(1) preparation of modifying titanium dioxide
Take by weighing titanium dioxide 1-10 weight part, coupling agent 0.01-1.5 weight part, solvent 10-50 weight part, TiO 2 particles is dispersed in the solvent that is dissolved with coupling agent, power is 150-200W ultra-sonic dispersion 5-10 minute, then slurries are transferred in the three-necked bottle that has thermometer, agitator and reflux exchanger, reacted 6-10 hour down for 40～70 ℃, after temperature 60-80 ℃ oven dry, grind and obtain the modifying titanium dioxide particle in temperature;
(2) contain the preparation of the polymkeric substance and the titanium dioxide complex particle composition of ultraviolet absorption group
With modifying titanium dioxide 1-10 weight part, deionized water 50-100 weight part, power is 150-200W ultra-sonic dispersion 5-10 minute, then with slurries and monomer 5-25 weight part, Polymerizable Emulsifier 0.25-3 weight part, aggretion type uv-absorbing agent 0.25-5 weight part, initiator 0.01-1.5 weight part joins and has thermometer, in the three-necked bottle of agitator and reflux exchanger, in temperature 70-80 ℃, reacted cooling discharge 3-6 hour, precipitate with the 1-10% calcium chloride water, and,, obtain to contain the polymkeric substance and the titanium dioxide complex particle composition of ultraviolet absorption group temperature 60-70 ℃ of oven dry down with deionized water repetitive scrubbing removal unreacted emulsifying agent.
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| CN102330338A (en) * | 2011-07-29 | 2012-01-25 | 苏州卡奇特纺织有限公司 | Ultraviolet resisting agent for acrylic fabric |
| CN104788725B (en) * | 2015-03-25 | 2017-11-07 | 合肥工业大学 | A kind of light stabilizer for having ultraviolet screener and absorption function concurrently and preparation method thereof |
| CN105733036A (en) * | 2016-03-28 | 2016-07-06 | 王社兵 | High-strength aging-resistant mine cable |
| CN107459842B (en) * | 2017-08-03 | 2019-09-06 | 西藏亚吐克工贸有限公司 | The dedicated titanium dioxide process of papermaking |
| CN108002543B (en) * | 2017-11-30 | 2020-07-31 | 天津大学 | Application of acinetobacter to degradation of ultraviolet absorbent PBSA |
| CN113861711A (en) * | 2021-09-14 | 2021-12-31 | 浙江亚厦装饰股份有限公司 | Wood-plastic composite section with low aging and fading speed and preparation method thereof |
| CN114716627A (en) * | 2022-03-14 | 2022-07-08 | 东莞市迪彩塑胶五金有限公司 | High-molecular UV absorbent for outdoor non-woven fabric and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408762A (en) * | 2001-09-25 | 2003-04-09 | 兰化胶乳研制中心 | Inorganic nano particle-high molecular composite material and its preparing method and use |
| CN1552764A (en) * | 2003-12-19 | 2004-12-08 | 上海交通大学 | Method for preparing uvioresistant polyester by nanometer titania in situ |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1408762A (en) * | 2001-09-25 | 2003-04-09 | 兰化胶乳研制中心 | Inorganic nano particle-high molecular composite material and its preparing method and use |
| CN1552764A (en) * | 2003-12-19 | 2004-12-08 | 上海交通大学 | Method for preparing uvioresistant polyester by nanometer titania in situ |
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