CN105237971A - Novel composite light stabilizer - Google Patents
Novel composite light stabilizer Download PDFInfo
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- CN105237971A CN105237971A CN201510787201.5A CN201510787201A CN105237971A CN 105237971 A CN105237971 A CN 105237971A CN 201510787201 A CN201510787201 A CN 201510787201A CN 105237971 A CN105237971 A CN 105237971A
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- photostabilizer
- light stabilizer
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Abstract
The invention relates to a novel composite light stabilizer. The novel composite light stabilizer is prepared by compounding the following components in parts by weight: 65-50 parts of 2,2'-methylene bis[6-(benzotriazol-2-yl)-4-tert-octylphenol], 30-40 parts of ply(4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol-alt-1,4-butanedioic acid) and 5-10 parts of 2,2,6,6-tetramethyl-4-piperidinyl stearate. The novel composite light stabilizer has the advantages of favorable light stability, thermal stability and durability as well as good ageing resistance; due to the addition of ternary piperidyl stearate, the composite light stabilizer has a long-chain structure and favorable compatibility, so that the light stabilizer formed by a ternary compound system can be better compatible with a plastic product, the light stabilizing time is prolonged, and the condition that the service life of the novel composite light stabilizer is influenced by light stabilizer blind spots generated by local non-uniformity is avoided; in addition, the cost of piperidyl stearate is only about 40% of the price 362, so that the production cost is greatly reduced.
Description
Technical field
The invention belongs to photostabilizer studying technological domain, particularly the novel built type photostabilizer of ternary system.
Background technology
Under aerial oxygen, moisture and ultraviolet effect, polymer materials is degraded usually, cause physical strength to reduce, color tone change, or even polymer product is finally totally disrupted.People suppress degradation process by adding various stablizer, prevent the quality variation of polymer product.
The photostabilizer added in current room temperature polyethylene film mainly contains several as follows: the photostabilizer of the photostabilizer of hindered amine type, the photostabilizer of UV light absorber type, quencher type and anti-oxidant type.
The photostabilizer be most widely used in the market is generally the compound of triazines, hydroxyethyl piperidine alkoxide polycondensate and this two classes photostabilizer, as EP0448036A1, EP0319480A, US5,603,885 and US4,582, the photostabilizer compound mentioned in 785.Main hindered amine as light stabilizer HS-362 adopting the photostabilizer of compounded technology to have Beijin Tiangang Auxiliary Co., Ltd. to produce at present, it is latest generation compound highly effective energy high molecular photostabilizer, be applicable to polyethylene, the polyolefin articles such as polypropylene, especially for polyethylene and EVA mono-anti-, and two anti-plastic film for agricultural use effect is better.Define the polymerized hindered amine light stabilizer of being used widely at present, the stimulation of this photostabilizer to people is less, but in actual applications, photostabilizer HS-362 fast light, heat-resisting, aging is good not.
For above-mentioned phenomenon, China Patent No. is 200710198455.9 propose a kind of complex type light stabilizer and application thereof, described complex type light stabilizer, it comprises poly-{ [6-[(N-normal-butyl-2, 2, 6, 6-tetramethyl--4-piperylhydrazine)-imino-]-1, 3, 5-triazine-2, 4-bis-base] [2-(2, 2, 6, 6-tetramethyl-piperidyl)-secondary amino-hexa-methylene-[4-(2, 2, 6, 6-tetramethyl-sends pyridine base)-secondary amino]] with the compound of another kind of photostabilizer, described another kind of photostabilizer is selected from: triazines, benzophenone, benzotriazole or hindered amine light stabilizer.This complex type light stabilizer has excellent light, thermally-stabilised weather resistance, and ageing resistance is good, and production cost is lower; But its consistency is poor, can not be compatible in plastics well, thus affect the life-span of goods.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind ofly has the good and novel built type photostabilizer that consistency is good of excellent light stability, thermostability, weather resistance and ageing resistance.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of novel built type photostabilizer, and its innovative point is: described novel built type photostabilizer by weight, forms by following component is composite:
2,2'-methylene-bis (the tertiary octyl group of 4--6-benzotriazole phenol) 65 ~ 50 parts;
Poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) ester 30 ~ 40 parts;
2,2,6,6-tetramethyl--4-piperidine alcohols stearate 5 ~ 10 parts.
Further, described 2, 2, 6, 6-tetramethyl--4-piperidine alcohols stearate obtains by the following method: to mechanical stirrer is housed, thermopair, dropping funnel adds the tetramethyl piperidine of 35 mass parts successively in dewatering unit four-hole bottle with being with, the methyl stearate of 57 mass parts and the octane of 135 mass parts, then reaction mixture is under agitation heated to backflow, be back to dehydration, be cooled to less than 100 DEG C again, catalyzer is added, methyl alcohol is constantly had to deviate from, migrate out methyl alcohol, about 4 little on return line without muddy, backflow terminates, heat up again and steam the octane of 30-40 mass parts, sampling gas-chromatography monitoring stearate acid is less than 1% for qualified, to meet the requirements of solution and cool to 90 DEG C, and add the water of 30 mass parts, and stir 1 hour, and leave standstill and within 30 minutes, separate lower layer of water, upper strata reflux dewatering, after dehydration is clean, then precipitation is to without flow, then negative pressure devolatilization is less than 0.5% qualified, obtains qualified finished product after essence filter.
The invention has the advantages that: novel built type photostabilizer of the present invention, it is good that it has excellent light stability, thermostability, weather resistance and ageing resistance, the complex type light stabilizer proposed with 200710198455.9 compares, add ternary piperidyl stearate and there is backbone, its good consistency, the photostabilizer of ternary built System forming is made better to be compatible in plastics, strengthen its light steady time, avoid the photostabilizer blind spot produced because local is uneven, thus cause the life-span affecting goods; And because piperidyl stearate cost is only about 40% (piperidyl stearate market value per ton about 2.8 ten thousand yuan, and photostabilizer per ton 362 price is at about 7.2 ten thousand yuan) of the price of 362, greatly reduce production cost.
Embodiment
The following examples can make the present invention of professional and technical personnel's comprehend, but therefore do not limit the present invention among described scope of embodiments.
2,2,6, the preparation of 6-tetramethyl--4-piperidine alcohols stearate: to mechanical stirrer is housed, thermopair, adds tetramethyl piperidine 35g, methyl stearate 57g and octane 135g in dropping funnel and band dewatering unit four-hole bottle successively, then reaction mixture is under agitation heated to backflow, be back to dehydration, then be cooled to less than 100 DEG C, catalyzer is added, methyl alcohol is constantly had to deviate from, migrate out methyl alcohol, about 4 little on return line without muddy, backflow terminates, heat up and steam the octane of 30-40g, sampling gas-chromatography monitoring stearate acid is less than 1% for qualified; To meet the requirements of solution and cool to 90 DEG C, and add the water of 30g, and stir 1 hour, and leave standstill and within 30 minutes, separate lower layer of water, upper strata reflux dewatering, after dehydration is clean, then precipitation is to without flow, then negative pressure devolatilization is less than 0.5% qualified, obtains qualified finished product after essence filter.
embodiment 1
The preparation of photostabilizer A1: get 2; 2'-methylene-bis (the tertiary octyl group of 4--6-benzotriazole phenol) 64g, poly-succinic (4-hydroxyl-2; 2; 6; 6-tetramethyl--1-piperidine ethanol) ester 28g and 2,2,6; 6-tetramethyl--4-piperidine alcohols stearate 8g drops in still; logical nitrogen protection, is first directly warming up to about 100, until solid materials in still molten clear after; unlatching is stirred between 105-115 and is incubated 1 hour; by in material press-in coolship, cool after 12 hours, block is added pulverizer and pulverize again after screening; code is installed good, warehouse-in by specified requirement.
embodiment 2
The preparation of photostabilizer A2: get 2; 2'-methylene-bis (the tertiary octyl group of 4--6-benzotriazole phenol) 50g, poly-succinic (4-hydroxyl-2; 2; 6; 6-tetramethyl--1-piperidine ethanol) ester 40g and 2,2,6; 6-tetramethyl--4-piperidine alcohols stearate 10g drops in still; logical nitrogen protection, is first directly warming up to about 100, until solid materials in still molten clear after; unlatching is stirred between 105-115 and is incubated 1 hour; by in material press-in coolship, cool after 12 hours, block is added pulverizer and pulverize again after screening; code is installed good, warehouse-in by specified requirement.
contrast experiment's part
comparative example 1:
A: get 3 grams of above-mentioned photostabilizer A1,0.3 gram of tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester and four [methyl-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 2:1(weight ratio) and compound (B215, composite antioxidant), 1000 grams of polyethylene 2100TN00, controlling melt flow rate (MFR) (g/10min) is 0.25-0.35(Qilu Petrochemical), extruding pelletization 185 DEG C time, at 190 DEG C of condition lower sheetings, thickness is 0.2mm;
B: similarity condition is that photostabilizer becomes ZX-783(Suqian development Chemical Co., Ltd.);
C: similarity condition is that photostabilizer becomes photostabilizer HS-362(Beijin Tiangang Auxiliary Co., Ltd.)
Ageing device is U.S. ATLAS company Ci65 type ageing oven, and backboard temperature is 63 DEG C, does not spray water, 0.35W/m
2at340nm.
Measure carbonyl index with infrared spectrophotometer, the time of the carbonyl index arrival 0.1 of above-mentioned three kinds of light stabilizer combinations is respectively:
A2990 hour
B2620 hour
C2750 hour
By above-mentioned contrast, the carbonyl index of the light stabilizer combination under A condition arrive 0.1 time the longest, thus to stablize the resistance of aging of A1 the strongest for light.
Comparative example 2:
A: get the photostabilizer A2 in 2.5 grams of embodiments, 0.3 gram of 3,5-di-t-butyl-4 hydroxy-phenylpropionic acid octadecanol (1076, oxidation inhibitor), 1000 grams of polyethylene 2100TN00, melt flow rate (MFR) (g/10min) is 0.25-0.35(Qilu Petrochemical), extruding pelletization 185 DEG C time.At 190 DEG C of condition lower sheetings, thickness is 0.1mm;
B: similarity condition is that photostabilizer becomes photostabilizer B (CHIMASSORB944, from Ciba);
C: similarity condition is that photostabilizer becomes photostabilizer HS-362(Beijin Tiangang Auxiliary Co., Ltd.)
Ageing device is U.S. ATLAS company Ci65 type ageing oven, and backboard temperature 63 DEG C, do not spray water 0.35, W/m
2at340nm.
Measure carbonyl index with infrared spectrophotometer, the time of the carbonyl index arrival 0.1 of above-mentioned two kinds of light stabilizer combinations is respectively:
A3630 hour
B3250 hour
C3400 hour
By above-mentioned contrast, the carbonyl index of the light stabilizer combination under A condition arrive 0.1 time the longest, thus to stablize the resistance of aging of A2 the strongest for light.
heavy natural sunning
Photostabilizer succinic acid and 4-hydroxyl-2 by photostabilizer A1, photostabilizer 362, photostabilizer D(photostabilizer D, 2,6, the polymkeric substance of 6-tetramethyl--1-piperidine alcohols and poly-{ [6-[(N-normal-butyl-2,2,6,6-tetramethyl--4-piperylhydrazine)-imino-]-1,3,5-triazine-2,4-bis-base] [2-(2,2,6,6-tetramethyl-piperidyl)-secondary amino-hexa-methylene-[4-(2,2,6,6-tetramethyl-sends pyridine base)-secondary amino]] compound) carry out simultaneous test:
Anti-aging agricultural canopy film (PE)
Testing installation:
ZC-65 dual-screw pelletizer
The three-layer co-extruded blown film unit of SJ-65/30
Masterbatch technique: height stirs double-screw extruding pelletizing method and produces, technological temperature 185 DEG C
In film, the content of photostabilizer is 0.5%
To be exposed to the sun place: Jiangsu Province, China Nantong
To be exposed to the sun condition: 45 Du Chaonan, retort stand, without backboard
Be exposed to the sun in March, 2013 time opening
Specification: thickness 0.07mm
Actual be exposed to the sun 360 days after sampling analysis
Transverse breakage elongation retention (after 12 months)
Photostabilizer (A1) 86.2%
Photostabilizer (362) 80.8%
Photostabilizer (D) 85.8%
Longitudinal fracture elongation retention (after 12 months)
Photostabilizer (A1) 77.4%
Photostabilizer (362) 70.2%
Photostabilizer (D) 79.6%
Transverse tensile strength retention rate (after 12 months)
Photostabilizer (A1) 89.1%
Photostabilizer (362) 82.2%
Photostabilizer (D) 86.35%
Longitudinal tensile strength retention rate (after 12 months)
Photostabilizer (A1) 90.6%
Photostabilizer (362) 81.1%
Photostabilizer (D) 79.3%
Practical application in plastic sheeting for farm use
Testing installation:
ZC-65 dual-screw pelletizer
The three-layer co-extruded blown film unit of SJ-90/30
Masterbatch technique: banburying method is produced, technological temperature 185 DEG C
In film, the content of photostabilizer is 0.6%
Button canopy place: Dongtai, specification: 3500 × 0.07mm
Actual button canopy sampling analysis after 360 days, obtains following data:
Transverse breakage elongation retention (after 12 months)
Photostabilizer (A1) 90.6%
Photostabilizer (362) 83.2%
Photostabilizer (D) 85.2%
Longitudinal fracture elongation retention (after 12 months)
Photostabilizer (A1) 83.2%
Photostabilizer (362) 74.8%
Photostabilizer (D) 76.5%
Transverse tensile strength retention rate (after 12 months)
Photostabilizer (A1) 85.3%
Photostabilizer (362) 83.2%
Photostabilizer (D) 84.5%
Longitudinal tensile strength retention rate (after 12 months)
Photostabilizer (A1) 78.9%
Photostabilizer (362) 77.6%
Photostabilizer (D) 78.2%.
Table 1 is ternary built photostabilizer of the present invention and binary built photostabilizer, the contrast of unitary photostabilizer in agricultural canopy film is applied.
Table 2 is ternary built photostabilizer of the present invention and binary built photostabilizer, the contrast of unitary photostabilizer in plastic sheeting for farm use practical application.
Table 3 is contrasts of ratio performance in ternary built photostabilizer of the present invention.
Table 1 ternary built photostabilizer of the present invention and binary built photostabilizer, the contrast of unitary photostabilizer in agricultural canopy film is applied
| Transverse breakage elongation retention | Longitudinal fracture elongation retention | Transverse tensile strength retention rate | Longitudinal tensile strength retention rate | |
| Photostabilizer 362 | 83.2% | 74.8% | 83.2% | 77.6% |
| Photostabilizer D | 85.8% | 79.6% | 86.35% | 79.3% |
| Photostabilizer A1 | 90.6% | 83.2% | 85.3% | 78.9% |
As can be seen from the above table, photostabilizer A1 is in agricultural canopy film application, transverse breakage elongation retention, longitudinal fracture elongation retention, transverse tensile strength retention rate and longitudinal tensile strength retention rate are all best, and thus the ageing resistance of ternary built photostabilizer is fine.
Table 2 ternary built photostabilizer of the present invention and binary built photostabilizer, the contrast of unitary photostabilizer in plastic sheeting for farm use practical application
| Transverse breakage elongation retention | Longitudinal fracture elongation retention | Transverse tensile strength retention rate | Longitudinal tensile strength retention rate | |
| Photostabilizer 362 | 83.2% | 74.8% | 83.2% | 77.6% |
| Photostabilizer D | 85.2% | 76.5% | 84.5% | 78.2% |
| Photostabilizer A1 | 90.8% | 84.3% | 86.9% | 79.9% |
As can be seen from the above table, photostabilizer A1 is in agricultural canopy film application, transverse breakage elongation retention, longitudinal fracture elongation retention, transverse tensile strength retention rate and longitudinal tensile strength retention rate are all best, and thus the ageing resistance of ternary built photostabilizer is fine.
The contrast of ratio performance in table 3 ternary built photostabilizer of the present invention
| Transverse breakage elongation retention | Longitudinal fracture elongation retention | Transverse tensile strength retention rate | Longitudinal tensile strength retention rate | |
| Embodiment 1 A1 | 90.6% | 83.2% | 85.3% | 78.9% |
| Embodiment 2 A2 | 90.8% | 84.3% | 86.9% | 79.9% |
As can be seen from the above table, photostabilizer A1 is compared with photostabilizer A2, transverse breakage elongation retention, longitudinal fracture elongation retention, transverse tensile strength retention rate and longitudinal tensile strength retention rate are relatively lower, thus the optimum compound proportion of novel photostabilizer is 2,2'-methylene-bis (the tertiary octyl group of 4--6-benzotriazole phenol): poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) ester: 2,2,6,6-tetramethyl--4-piperidine alcohols stearate=50:40:10.
The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (2)
1. a novel built type photostabilizer, is characterized in that: described novel built type photostabilizer by weight, forms by following component is composite:
2,2'-methylene-bis (the tertiary octyl group of 4--6-benzotriazole phenol) 65 ~ 50 parts;
Poly-succinic (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidine ethanol) ester 30 ~ 40 parts;
2,2,6,6-tetramethyl--4-piperidine alcohols stearate 5 ~ 10 parts.
2. novel built type photostabilizer according to claim 1, it is characterized in that: described 2, 2, 6, 6-tetramethyl--4-piperidine alcohols stearate obtains by the following method: to mechanical stirrer is housed, thermopair, dropping funnel adds the tetramethyl piperidine of 35 mass parts successively in dewatering unit four-hole bottle with being with, the methyl stearate of 57 mass parts and the octane of 135 mass parts, then reaction mixture is under agitation heated to backflow, be back to dehydration, be cooled to less than 100 DEG C again, catalyzer is added, methyl alcohol is constantly had to deviate from, migrate out methyl alcohol, about 4 little on return line without muddy, backflow terminates, heat up again and steam the octane of 30-40 mass parts, sampling gas-chromatography monitoring stearate acid is less than 1% for qualified, to meet the requirements of solution and cool to 90 DEG C, and add the water of 30 mass parts, and stir 1 hour, and leave standstill and within 30 minutes, separate lower layer of water, upper strata reflux dewatering, after dehydration is clean, then precipitation is to without flow, then negative pressure devolatilization is less than 0.5% qualified, obtains qualified finished product after essence filter.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029149A (en) * | 2007-04-02 | 2007-09-05 | 广东华南精细化工研究院有限公司 | Efficient heat-resisting polyolefine composite light stabilizer, its production and use |
| CN103274994A (en) * | 2013-06-17 | 2013-09-04 | 南通市振兴精细化工有限公司 | Preparation method of 2, 2, 6, 6-tetramethyl-piperidinooxy stearate |
| CN103724947A (en) * | 2012-10-15 | 2014-04-16 | 中纺投资发展股份有限公司 | Thermoplastic polyether ester elastomer white compound with excellent weather resistance |
| CN104271655A (en) * | 2012-04-04 | 2015-01-07 | 塞特克技术公司 | Stabilized polyolefins having increased agrochemical and uv resistance and methods of use |
| CN104937024A (en) * | 2013-01-25 | 2015-09-23 | 株式会社Adeka | Resin composition |
-
2015
- 2015-11-17 CN CN201510787201.5A patent/CN105237971A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029149A (en) * | 2007-04-02 | 2007-09-05 | 广东华南精细化工研究院有限公司 | Efficient heat-resisting polyolefine composite light stabilizer, its production and use |
| CN104271655A (en) * | 2012-04-04 | 2015-01-07 | 塞特克技术公司 | Stabilized polyolefins having increased agrochemical and uv resistance and methods of use |
| CN103724947A (en) * | 2012-10-15 | 2014-04-16 | 中纺投资发展股份有限公司 | Thermoplastic polyether ester elastomer white compound with excellent weather resistance |
| CN104937024A (en) * | 2013-01-25 | 2015-09-23 | 株式会社Adeka | Resin composition |
| CN103274994A (en) * | 2013-06-17 | 2013-09-04 | 南通市振兴精细化工有限公司 | Preparation method of 2, 2, 6, 6-tetramethyl-piperidinooxy stearate |
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Application publication date: 20160113 |