CN101659759A - Organic-inorganic composite optothermal stabilizer, polyvinyl chloride prepared by using same and preparation method thereof - Google Patents
Organic-inorganic composite optothermal stabilizer, polyvinyl chloride prepared by using same and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic-inorganic composite optothermal stabilizer, a preparation method thereof and the application thereof in polyvinyl chloride. Main components of the organic-inorganiccomposite optothermal stabilizer include 2-hydroxyl-4-methoxyl-5-sulfoacid-benzophenone (BP-4), hydrotalcite (LDH), coupling agent and radical trapper. The preparation method of the optothermal stabilizer is as follows: firstly, proportionally putting the BP-4 and the LDH after roasting pretreatment into a reactor; adding water for preparing an aqueous solution; carrying out anion exchange reaction so as to obtain an organic-inorganic composite; and then, carrying out coupling and ultrasonic treatment on the composite so as to obtain the organic-inorganic composite optothermal stabilizer. A polyvinyl chloride product containing the stabilizer has greatly-improved photostability and obviously-improved hot workability.
Description
Technical field
The present invention relates to technical field of polymer, more particularly relate to be used for the optothermal stabilizer of polyvinyl chloride, and about the preparation method and the application of optothermal stabilizer.
Technical background
Polyvinyl chloride (PVC) material is easy to take place photodegradation under UV-irradiation, thereby causes its physics-chem characteristic to change, as darkens, and material becomes fragile and surperficial efflorescence etc., finally loses use value.The ordinary method of polymer materials anti-ultraviolet ageing is to add the organic ultraviolet photostabilizer of certain content in material body, as salol, O-hydroxyl-diphenyl ketone, adjacent hydroxyl and triazole and triazines etc.Though it is these photostabilizers have certain protection effect to polymkeric substance, still undesirable to the optical density of UV-light.And molecular weight is little, and is soluble in water, easily migration, and out of doors during life-time service, can be because of the surface volatilization, and run off gradually by liquid extracting such as rainwater, cause its light stabilization efficiency in material to reduce greatly.Seek and develop the focus that the novel photostabilizer with better light stabilising effect is still this area research.
2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone (2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid, be called for short BP-4) be a kind of anionic benzophenone light stabilizer, in the UV-light wave band, has stronger sorption than salol etc.But its less stable, when being heated to 140 ℃ of left and right sides, this stablizer can become brown liquid, and when being heated to 190 ℃, its thermal weight loss has reached 40%.When with add man-hour at 180 ℃ after PVC and other auxiliary agents mix, the PVC instant color-changing is degraded.Therefore, BP-4 is mainly used at present in the less demanding suntan lotion of thermal characteristics, frost, honey, emulsion, the wet goods sun care preparations.If want the UV light stabilizing agent as polyvinyl chloride, at first must solve its thermal stability problems with BP-4.
Hydrotalcite (Layered Double Hydroxides, be abbreviated as LDH) be the important anion type laminated compound of a class, the corresponding variation can take place thereby make structure and form with new negatively charged ion by the original negatively charged ion of displacement between ion-exchange means interposed layer in the control certain condition.
Utilize the controllability of this structure of hydrotalcite and composition, can prepare novel photostabilizer.As people such as Duan Xue the negatively charged ion of 5-benzotriazole-4-hydroxyl-3-isobutyl--Phenylsulfonic acid is inserted into nucleation/crystallization isolation method, with full back-mixing explosive type moment one-tenth nuclear technique synthetic hydrotalcite precursor (preparation method sees CN99119385.7) interlayer, prepared the intercalation configuration UV light stabilizing agent.This stablizer greater than 90%, and has good thermostability to the uv absorption rate of 280-370nm wave band.Can be used for polypropylene, polycarbonate, the photo-protection of materials such as acrylonitrile-butadiene-phenylethylene multipolymer and urethane.People such as He (Journal of Chemistry ofSolids, 2004,65,395-402) 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone (BP-4) is inserted by coprecipitation method synthetic hydrotalcite precursor, made hydrotalcite/BP-4 intercalation compound, solved the toxicity problem that BP-4 and skin directly contact effectively, but about the performance of this compound others and use and do not appear in the newspapers.The common ground of aforesaid method is the hydrotalcite precursor that all need adopt through the special methods preparation, and the preparation technology of complexity, the further use cost that promotes have greatly hindered this class photostabilizer and developed with promoting in industrial practical application.
In addition, hydrotalcite is an inorganic materials, and is very poor with the consistency of polyvinyl chloride, directly is applied to this base polymer material, the mechanical properties decrease of polymer materials can occur causing because of being separated.
In view of this, research and develop out and have more high heat resistance, has more high-compatibility with organic high molecular compound, polrvinyl chloride product prepared therefrom has the optothermal stabilizer of higher light stability, mechanical property and good thermal processability energy, is that affiliated field technology worker faces problem jointly.
Summary of the invention
The purpose of this invention is to provide a kind of workable, preparation cost is low, the organic-inorganic composite optothermal stabilizer of high comprehensive performance and preparation method, be applied to polrvinyl chloride product simultaneously, in the hope of solving poor, volatile and poor, the problems such as the light stabilization efficiency is not high, poor heat stability of easy transport property, resistant to extraction of organic molecule photostabilizer, increase substantially the anti-ultraviolet ageing performance and the hot-work stability of goods with the organic substrate consistency.
Thought of the present invention, at first utilize hydrotalcite layers ionic interchangeability, by brand-new preparation method, 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone negatively charged ion (BP-4) directly is inserted into hydrotalcite layers, make a kind of organic-inorganic composition, make its premium properties that has two kinds of materials simultaneously concurrently, have high photo-protection efficient on the one hand, have low rate of migration and permanent stability on the other hand.Second step was that prepared mixture is carried out special processing, its thermotolerance reaches and the consistency of organic high molecular compound to improve, to satisfy the higher light stability of polrvinyl chloride product, mechanical property, reach the requirement of good thermal processability energy, reduce preparation and use cost simultaneously.
The concrete technical scheme that realizes above-mentioned purpose of the present invention is as follows:
The organic-inorganic composite optothermal stabilizer that is used for polyvinyl chloride (PVC), its raw material composition mainly contains 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone (BP-4), hydrotalcite (LDH), coupling agent and free radical scavenger, wherein the weight content ratio of hydrotalcite and 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone is 0.5～10, and the weight content of coupling agent and free radical scavenger is respectively the 0.2%-5% and the 0.5%-10% of talcum and 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone gross weight.
In technique scheme, described coupling agent is selected from titanate coupling agent and silane coupling agent, and is both a kind of in them, also two or more mixture in them; Described hydrotalcite is natural water talcum both, and also artificial hydrotalcite selects for use the natural water talcum to reduce production costs, and should preferentially select the natural water talcum for use; Described free radical scavenger is preferentially selected the compound that contains following structural unit for use:
R wherein
1For containing 1,1,2,2, the compound of-tetramethyl piperidine ring.
The preparation of above-mentioned organic-inorganic composite optothermal stabilizer mainly may further comprise the steps:
(1) will determine the 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone of proportional and insert reactor through the hydrotalcite that calcination process is crossed and add entry and be mixed with the aqueous solution, carry out anion exchange reaction (being intercalation) in 50～100 ℃, fully reaction is after separation, washing, drying make organic-inorganic composition;
(2) behind organic-inorganic composition that step (1) is made and the true quantitative coupling agent thorough mixing, place water or ethanol, add true quantitative free radical scavenger, apply ultrasonic irradiation, mixture and free radical scavenger are fully interacted, after filtration, washing, drying treatment make organic-inorganic composite optothermal stabilizer.
In the preparation method of above-mentioned organic-inorganic composite optothermal stabilizer, the described hydrotalcite of crossing through calcination process is in 300-800 ℃ of roasting 1-10 hour treated water talcum; Ultrasonic irradiation is pressed every cube of 5-250kW (5-250kW/m of material
3) shone 10-30 minute; Described frequency of ultrasonic is 20kHz; Described anion exchange reaction (being intercalation) reacted 10～50 hours down in 50～100 ℃.
By the polyvinyl chloride of above-mentioned organic-inorganic composite optothermal stabilizer preparation, its main ingredient constitutes, and counts with weight part:
100 parts of the polyvinyl chloride resins of 100phr
Organic-inorganic composite optothermal stabilizer 0.5-5
Dibasic lead phosphite 1-3
Lead sulfate tribasic 1-3
Stearic acid 0.3-1.
Organic-inorganic composite optothermal stabilizer provided by the invention has very excellent comprehensive performance, the principle that its excellent over-all properties produces is: hydrotalcite is after high-temperature roasting, impurity and small molecules volatile matter etc. are removed, and the hydrotalcite crystal is activated, and are beneficial to the ionic exchange.When in the aqueous solution, carrying out the carbanion in BP-4 and the natural water talcum fully being exchanged after certain hour fully reacts, make ideal BP-4/ hydrotalcite organic-inorganic composition with BP-4.By surperficial coupling processing, improve the consistency of mixture and polymeric matrix again.At last surface-treated mixture and free radical scavenger are issued the looks mutual effect in ultrasonication, obtained the organic-inorganic composite optothermal stabilizer of excellent combination property.
Application result shows, add the PVC material that organic-inorganic composite optothermal stabilizer provided by the invention makes, with respect to conventional art, the UV stable performance of material is improved obviously, the mechanical property long-term retention rate is improved, and hot-work stability also obviously improves.Its reason is:
1,2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone is inserted into hydrotalcite layers, combine hydrotalcite to the function of shielding of UV-light and 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone absorptive function to UV-light, make the photo-protection efficient of one package stabilizer obviously strengthen, and the adding of free radical scavenger also can be caught a part of free radical, has further improved the light stability of polymeric matrix.Simultaneously, the formation of intercalation configuration has reduced the easy leachability of BP-4, and the permanent stability of material are improved.
2, the adding of coupling agent has improved the consistency of mixture and polymeric matrix, is beneficial to the good distribution of organic and inorganic optothermal stabilizer in matrix, and is useful to the raising of mechanical property.
3, the adding passivation of free radical scavenger organic-inorganic composition and the matrix resin thermal destruction activation point that interacts and produce, consume living radical, improved the hot-work stability of the polyolefine material that contains this organic-inorganic composition.
Polyvinyl chloride by the organic-inorganic composite optothermal stabilizer preparation can be used for making various goods such as pvc pipe material, profiled material, sheet material, and the long-term retention rate of goods over-all properties can be greatly improved.
Specific embodiment
To closing embodiment the present invention is specifically described below, so that personnel's the understanding of the present invention of affiliated technical field.Be necessary what this particularly pointed out to be; embodiment is used for just that the present invention will be further described; can not be interpreted as limiting the scope of the invention; affiliated art skilled person; to improvement and adjustment that the present invention makes non-intrinsically safe, should still belong to protection scope of the present invention according to the invention described above content.
In the following embodiments, except that specifying, related per-cent all is weight percentage, and related umber is parts by weight (phr).
Provide organic-inorganic composite optothermal stabilizer embodiment below.
Embodiment 1:
With natural water talcum (LDH) about 8 hours of 300 ℃ of left and right sides roastings.The product of roasting and the 5phr 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone (BP-4) that take by weighing 5phr add in the 20phr water.Fully stir, reaction is about 40 hours about 80 ℃, with product filtration, washing, drying, obtains organic-inorganic composition, with the titanate coupling agent thorough mixing of this mixture and mixture weight 0.2%.To suspend in water through the organic-inorganic composition of coupling processing and the free radical scavenger of mixture weight 0.5%, apply ultrasonic irradiation about 10 minutes, frequency of ultrasonic is 20kHz, presses material 200kW/m
3Implement irradiation, with product filtration, washing, drying, obtain desired organic-inorganic composite optothermal stabilizer after ultrasonication finishes.Be designated as organic-inorganic composite optothermal stabilizer I.
Embodiment 2:
With artificial hydrotalcite (LDH) about 3 hours of 600 ℃ of left and right sides roastings.Taking by weighing 5phr product of roasting and 10phr 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone (BP-4) adds in the 25phr water.Fully stir, reaction is about 10 hours in about 100 ℃, with product filtration, washing, drying, obtains organic-inorganic composition.With this mixture and 3% titanate coupling agent and silane coupling agent (mass ratio is 1: 1) thorough mixing.To be suspended in the ethanol through the organic-inorganic composition and 5% free radical scavenger of coupling processing, applied ultrasonic irradiation about 20 minutes, frequency of ultrasonic is 20kHz, presses material 100kW/m
3Implement irradiation, with product filtration, washing, drying, obtain desired organic-inorganic composite optothermal stabilizer after ultrasonication finishes.Be designated as organic-inorganic composite optothermal stabilizer II.
Embodiment 3:
With natural water talcum (LDH) about 3 hours of 800 ℃ of left and right sides roastings.Taking by weighing 10phr product of roasting and 2phr 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone (BP-4) adds in the 25phr water.Fully stir, reaction is about 50 hours in about 50 ℃, with product filtration, washing, drying, obtains organic-inorganic composition.With this mixture and 5% silane coupling agent thorough mixing.To suspend in water through the organic-inorganic composition and 10% free radical scavenger of coupling processing, applied ultrasonic irradiation about 30 minutes, frequency of ultrasonic is 20kHz, presses material 50kW/m
3Implement irradiation, after ultrasonication finishes,, obtain desired organic-inorganic composite optothermal stabilizer product filtration, washing, drying.Be designated as organic-inorganic composite optothermal stabilizer III.
Provide the embodiment and the test result of the polyvinyl chloride that contains optothermal stabilizer provided by the invention below.
Embodiment 1:
Respectively with 0.5phr light (heat) stablizer, the 1phr dibasic lead phosphite, the 2phr lead sulfate tribasic, 0.5phr stearic acid adds the polyvinyl chloride resin (PVC-SG8 of 100phr, former chemical plant, sky, Yibin) in, in double roll mill,, under about 180 ℃, be molded into the PVC of institute material again, be made for test and use in 170 ℃ of mixing about 8min in the left and right sides.
Light (heat) stablizer refers to 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone, hydrotalcite and organic-inorganic composite optothermal stabilizer of the present invention respectively.1# is for adding the PVC sample of 0.5phr 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone; 2# is for adding the PVC sample of 0.5phr hydrotalcite; 3# is for adding the PVC sample of 0.5phr organic-inorganic composite optothermal stabilizer I of the present invention.Test result sees the following form 1.
Table?1
Embodiment 2:
Respectively with 1phr light (heat) stablizer, the 1phr dibasic lead phosphite, the 2phr lead sulfate tribasic, 0.5phr stearic acid adds the polyvinyl chloride resin (PVC-SG8 of 100phr, former chemical plant, sky, Yibin) in, in double roll mill,, under about 180 ℃, be molded into required PVC material again, be made for test and use in 170 ℃ of mixing about 10min in the left and right sides.
Light (heat) stablizer refers to 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone, hydrotalcite and organic-inorganic composite optothermal stabilizer of the present invention respectively.1# is for adding the PVC sample of 1phr 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone; 2# is for adding the PVC sample of 1phr hydrotalcite; 3# is for adding the PVC sample of 1phr organic-inorganic composite optothermal stabilizer II of the present invention.Test result sees the following form 2.
Table?2
Embodiment 3:
Respectively with 3phr light (heat) stablizer, the 1phr dibasic lead phosphite, the 2phr lead sulfate tribasic, 0.5phr stearic acid adds the polyvinyl chloride resin (PVC-SG8 of 100phr, former chemical plant, sky, Yibin) in, in double roll mill,, under about 180 ℃, be molded into required PVC material again, be made for test and use in 170 ℃ of mixing about 10min in the left and right sides.
Light (heat) stablizer refers to 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone, hydrotalcite and organic-inorganic composite optothermal stabilizer of the present invention respectively.1# is for adding the PVC sample of 3phr 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone; 2# is for adding the PVC sample of 3phr hydrotalcite; 3# is for adding the PVC sample that the 3phr present embodiment prepares sample organic-inorganic composite optothermal stabilizer I.Test result sees the following form 3.
Table?3
* degraded rapidly can't prepare sample
Embodiment 4:
Respectively with 5phr light (heat) stablizer, the 1phr dibasic lead phosphite, the 2phr lead sulfate tribasic, 0.5phr stearic acid adds the polyvinyl chloride resin (PVC-SG8 of 100phr, former chemical plant, sky, Yibin) in, in double roll mill,, under about 180 ℃, be molded into required PVC material again, be made for test and use in 170 ℃ of mixing about 10min in the left and right sides.
Light (heat) stablizer refers to 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone, hydrotalcite and organic-inorganic composite optothermal stabilizer of the present invention respectively.1# is for adding the PVC sample of 5phr 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone; 2# is for adding the PVC sample of 5phr hydrotalcite; 3# is for adding the PVC sample of 5phr organic-inorganic composite optothermal stabilizer II of the present invention.Test result sees the following form 4.
Table?4
* degraded rapidly can't prepare sample
Embodiment 5:
Respectively with 5phr light (heat) stablizer, the 1phr dibasic lead phosphite, the 2phr lead sulfate tribasic, 0.5phr stearic acid adds the polyvinyl chloride resin (PVC-SG8 of 100phr, former chemical plant, sky, Yibin) in, in double roll mill,, under about 180 ℃, be molded into required PVC material again, be made for test and use in 170 ℃ of mixing about 10min in the left and right sides.
Light (heat) stablizer refers to 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone, hydrotalcite and organic-inorganic composite optothermal stabilizer of the present invention respectively.1# is for adding the PVC sample of 5phr 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone; 2# is for adding the PVC sample of 5phr hydrotalcite; 3# is for adding the PVC sample of 5phr organic-inorganic composite optothermal stabilizer III of the present invention.Test result sees the following form 5.
Table?5
* degraded rapidly can't prepare sample
Embodiment 6:
Respectively with 1phr light (heat) stablizer, the 1phr dibasic lead phosphite, the 2phr lead sulfate tribasic, 0.5phr stearic acid adds the polyvinyl chloride resin (PVC-SG8 of 100phr, former chemical plant, sky, Yibin) in, in double roll mill,, under about 180 ℃, be molded into required PVC material again, be made for test and use in 170 ℃ of mixing about 10min in the left and right sides.
Light (heat) stablizer refers to 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone, hydrotalcite and organic-inorganic composite optothermal stabilizer of the present invention respectively.1# is for adding the PVC sample of 1phr 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone; 2# is for adding the PVC sample of 1phr hydrotalcite; 3# is for adding the PVC sample of 1phr organic-inorganic composite optothermal stabilizer III of the present invention.Test result sees the following form 6.
Table?6
Claims (10)
1. organic-inorganic composite optothermal stabilizer, it is characterized in that the raw material composition mainly contains 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone, hydrotalcite, coupling agent and free radical scavenger, wherein the weight content ratio of hydrotalcite and 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone is 0.5～10, and the weight content of coupling agent and free radical scavenger is respectively the 0.2%-5% and the 0.5%-10% of talcum and 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone gross weight.
2. organic-inorganic composite optothermal stabilizer according to claim 1 is characterized in that described coupling agent is selected from titanate coupling agent and silane coupling agent.
3. organic-inorganic composite optothermal stabilizer according to claim 1 is characterized in that described hydrotalcite is the natural water talcum.
4. organic-inorganic composite optothermal stabilizer according to claim 1 is characterized in that described free radical scavenger is the compound that contains following structural unit:
R wherein
1For containing 1,1,2,2, the compound of-tetramethyl piperidine ring.
5. the method for preparing the described organic-inorganic composite optothermal stabilizer of one of claim 1 to 4 is characterized in that mainly may further comprise the steps:
(1) will determine the 2-hydroxyl-4-methoxyl group-5-sulfonic acid benzophenone of proportional and insert reactor through the hydrotalcite that calcination process is crossed and add entry and be mixed with the aqueous solution, carry out anion exchange reaction in 50～100 ℃, fully reaction is after separation, washing, drying make organic-inorganic composition;
(2) behind organic-inorganic composition that step (1) is made and the true quantitative coupling agent thorough mixing, place water or ethanol, add true quantitative free radical scavenger, apply ultrasonic irradiation, mixture and free radical scavenger are fully interacted, after filtration, washing, drying treatment make organic-inorganic composite optothermal stabilizer.
6. organic-inorganic composite optothermal stabilizer preparation method according to claim 5 is characterized in that described hydrotalcite calcination process is in 300-800 ℃ of roasting 1-10 hour.
7. organic-inorganic composite optothermal stabilizer preparation method according to claim 5 is characterized in that described ultrasonic irradiation is by material 5-250kW/m
3Shone 10-30 minute.
8. organic-inorganic composite optothermal stabilizer preparation method according to claim 7 is characterized in that described frequency of ultrasonic is 20kHz.
9. organic-inorganic composite optothermal stabilizer preparation method according to claim 5 is characterized in that described anion exchange reaction reacted 10～50 hours down in 50～100 ℃.
10. by the polyvinyl chloride of the described organic-inorganic composite optothermal stabilizer preparation of one of claim 1 to 4, it is characterized in that main ingredient constitutes, and counts with weight part:
Polyvinyl chloride resin 100
Organic-inorganic composite optothermal stabilizer 0.5-5
Dibasic lead phosphite 1-3
Lead sulfate tribasic 1-3
Stearic acid 0.3-1.
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