CN111675885A - PET (polyethylene terephthalate) light aging resistant and weather resistant master batch and preparation method thereof - Google Patents
PET (polyethylene terephthalate) light aging resistant and weather resistant master batch and preparation method thereof Download PDFInfo
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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Abstract
The invention relates to a PET light aging resistant and weather resistant master batch and a preparation method thereof, wherein the PET light aging resistant and weather resistant master batch comprises the following components in percentage by mass: 40-60% of resin carrier, 10-20% of light stabilizer, 15-25% of ultraviolet absorbent, 3-5% of dispersant, 5-15% of compatilizer, 0.5-2% of lubricant, 0.5-1.5% of anti-hydrolysis agent and 2-5% of antioxidant; in the technical scheme of the invention, a proper amount of hydrolysis resistant agent and antioxidant are added, so that the prepared PET photoaging-resistant master batch has good light stability and compatibility, can maintain good weather resistance under high-temperature, damp and hot conditions, and can be applied under severe environmental conditions.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a PET light aging resistant and weather resistant master batch and a preparation method thereof.
Background
PET is named as polyethylene terephthalate in Chinese, is a high polymer and is prepared by the dehydration condensation reaction of the polyethylene terephthalate. PET is a milky white or pale yellow, highly crystalline polymer with a smooth and glossy surface, excellent physical and mechanical properties over a wide temperature range, such as high strength, high elasticity, friction resistance, creep resistance, fatigue resistance, ductility, dimensional stability and good resistance to most chemicals. PET has ester bond, can be decomposed under the action of strong acid, strong base and water vapor, and has good organic solvent resistance and weather resistance. The disadvantages are slow crystallization rate, difficult forming and processing, high molding temperature, long production period and poor impact performance. The processability and physical properties of the glass fiber are improved by reinforcing, filling, blending and the like, so that the glass fiber has a remarkable reinforcing effect and the rigidity, heat resistance, chemical resistance, electrical properties and weather resistance of the resin are improved. Nowadays, with scientific development and technological progress, PET is increasingly replacing aluminum, glass, ceramics, paper, wood, steel and other synthetic materials due to its advantages of good heat resistance, chemical resistance, mechanical properties and electrical properties, especially good transparency, good insulation, lower production cost and higher application cost performance; with the development of PET, the family of PET is continuously expanding and growing. The application of PET is not limited to fibers any more, but further expands the fields of various containers, packaging materials, films, engineering plastics and the like. The fields of buildings, automobile industry, outdoor building materials, solar cell back plates and highway guardrails are developed vigorously in recent years.
The light stabilizer is an additive of high molecular products, which can shield or absorb the energy of ultraviolet rays, quench singlet oxygen and decompose hydroperoxide into inactive substances, etc., so that the possibility of photochemical reaction can be eliminated or slowed down, and the process of photoaging can be prevented or delayed under the radiation of light, thereby achieving the purpose of prolonging the service life of the high molecular products. The triazine ultraviolet resistant additive has high temperature resistance, extremely low volatility and difficult precipitation when the addition amount is high.
Disclosure of Invention
The invention provides a PET light aging resistant and weather resistant master batch and a preparation method thereof, aiming at overcoming the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the PET light aging resistant and weather resistant master batch comprises the following components in percentage by mass: 40-60% of resin carrier, 10-20% of light stabilizer, 15-25% of ultraviolet absorbent, 3-5% of dispersant, 5-15% of compatilizer, 0.5-2% of nucleating agent, 0.5-1.5% of lubricant, 1-2.5% of anti-hydrolysis agent and 2-5% of antioxidant.
As a modification of the present invention, the resin carrier is a PET resin; the granularity of the PET resin is 80-120 meshes.
As an improvement of the invention, the light stabilizer is one or a mixture of more of light stabilizer HALS-123, light stabilizer HALS-119, light stabilizer HALS-292 and light stabilizer HALS-611.
As an improvement of the invention, the ultraviolet absorbent is one or a mixture of more of an ultraviolet absorbent UV-360, an ultraviolet absorbent UV-1577, an ultraviolet absorbent UV-234 and an ultraviolet absorbent UV-328.
As an improvement of the invention, the dispersant is any one of polyethylene glycol, calcium stearate and trimethylolethane.
As an improvement of the invention, the compatilizer is any one of acetic acid-ethylene copolymer, maleic anhydride grafted styrene-ethylene butylene-styrene terpolymer and aluminum-titanium composite coupling agent.
As an improvement of the invention, the nucleating agent is any one of polyolefin elastomer, sodium benzoate and polyethylene oxide; the lubricant is any one of stearic acid, calcium stearate and ethylene bisstearamide; the hydrolysis resistant agent is polycarbodiimide hydrolysis resistant agent.
As an improvement of the invention, the antioxidant is one or a mixture of several of hindered phenol antioxidant 1010 and phosphite antioxidant 168.
As an improvement of the invention, the preparation method of the PET light aging resistant and weather resistant master batch comprises the following steps:
(1) weighing the raw materials according to the proportion;
(2) adding the prepared mixture into a high-speed mixer, and stirring for 15-30 minutes at 95-150 ℃;
(3) feeding the mixed materials into a double-screw machine for melt blending, wherein the melting temperature is 260-275 ℃, and the rotating speed of the screws is 150-300 r/min;
(4) and extruding the mixed materials by a double-screw extruder, and then shearing, mixing, cooling, granulating and drying to obtain the PET light aging resistant and weather resistant master batch.
As an improvement of the invention, the rotating speed of the mixer in the step (2) is 860-1200 r/min; the length-diameter ratio of the twin-screw extruder in the step (4) is 40-48:1, and the temperature of each zone from the feeding section to the die surface is 260-275 ℃.
The hydrolysis resistance agent selected by the invention has the following action mechanism:
compared with the prior art, the invention has the following beneficial effects because the technology is adopted:
the invention discloses a PET light aging resistant and weather resistant master batch and a preparation method thereof.
Detailed Description
The present invention will be further illustrated with reference to the following specific embodiments.
Example 1:
the PET light aging resistant and weather resistant master batch comprises the following components in percentage by mass at normal temperature and normal pressure: 40% of PET resin, 15% of light stabilizer HALS-123, 25% of ultraviolet light absorber UV-360, 4% of calcium stearate, 1.5% of Stearic Acid (SA), 8% of acetic acid-ethylene copolymer (EVA), 2% of polyethylene oxide, 2.5% of polycarbodiimide anti-hydrolysis agent (UN-03) and 2% of compound of hindered phenol antioxidant 1010 and phosphite antioxidant 168. Wherein the mass ratio of the hindered phenol antioxidant 1010 to the phosphite antioxidant 168 is 1: 2.
the preparation method comprises the following steps: the components are proportioned according to the weight ratio, then the proportioned components are added into a high-speed mixer and mixed for 20 minutes at the mixing temperature of 100 ℃, the rotating speed of the mixer is 860 revolutions per minute, and the mixed materials are added into a double-screw extruder for melt blending, the melting temperature is controlled at 260 ℃, and the rotating speed of screws is 150 revolutions per minute; and (3) feeding the mixed materials into a double-screw extruder (the length-diameter ratio of the double-screw extruder is 40:1, and the temperature of each area from the feeding section to the die surface is 260-275 ℃) for extrusion, and then shearing, mixing, cooling, granulating, drying and packaging to obtain the PET light-aging-resistant weather-resistant master batch.
TABLE 1 DSC differential thermal analysis data of PET photoaging resistant weatherable masterbatch prepared in example 1
| Sample (I) | Tg/℃ | Tcc/℃ | Tm/℃ | Tmc/℃ | Xc/% |
| Pure PET | 78.87 | 156.51 | 253.95 | 166.75 | 27.19 |
| PET/master batch | 75.28 | 132.86 | 255.38 | 200.87 | 27.86 |
Example 2:
the PET light aging resistant and weather resistant master batch comprises the following components in percentage by mass at normal temperature and normal pressure: 60% of PET resin, 10% of light stabilizer HALS-119, 15% of ultraviolet light absorber UV-234, 3% of calcium stearate, 1% of Ethylene Bis Stearamide (EBS), 6% of acetic acid-ethylene copolymer (EVA), 2% of polyolefin elastomer POE, 1% of polycarbodiimide hydrolysis resistant agent (UN-03) and 2% of compound of hindered phenol antioxidant 1010 and phosphite antioxidant 168; wherein the mass ratio of the hindered phenol antioxidant 1010 to the phosphite antioxidant 168 is 1: 2.
the preparation method comprises the following steps: the components are proportioned according to the weight ratio, then the proportioned components are added into a high-speed mixer and mixed for 15 minutes at the mixing temperature of 150 ℃, the rotating speed of the mixer is 1000 revolutions per minute, and then the mixed materials are added into a double-screw extruder for melt blending, the melting temperature is controlled at 270 ℃, and the rotating speed of screws is 200 revolutions per minute; after being extruded by a double-screw extruder (the length-diameter ratio of the double-screw extruder is 45:1, and the temperature of each area from a feeding section to a die surface is 260 ℃ to 275 ℃), the PET light aging resistant and weather resistant master batch is obtained by shearing, mixing, cooling, granulating, drying and packaging.
Table 2 DSC differential thermal analysis data of the PET weatherable master batch prepared in example 2 with light aging:
| sample (I) | Tg/℃ | Tcc/℃ | Tm/℃ | Tmc/℃ | Xc/% |
| Pure PET | 78.87 | 156.51 | 253.95 | 166.75 | 27.19 |
| PET/master batch | 76.46 | 133.31 | 258.46 | 200.25 | 28.56 |
Example 3:
the PET light aging resistant and weather resistant master batch comprises the following components in percentage by mass at normal temperature and normal pressure: 55% of PET resin, 10% of light stabilizer HALS-292, 15% of ultraviolet light absorber UV-1577, 3.5% of trimethylolethane, 1.5% of Ethylene Bis Stearamide (EBS), 9% of maleic anhydride grafted styrene-ethylene butylene-styrene terpolymer (SEBS-g-MA), 2% of polyethylene oxide, 1.5% of polycarbodiimide hydrolysis resistant agent (UN-03) and 2.5% of hindered phenol antioxidant 1010.
The preparation method comprises the following steps: the components are proportioned according to the weight ratio, then the proportioned components are added into a high-speed mixer and mixed for 30 minutes at the mixing temperature of 95 ℃, the rotating speed of the mixer is 1200 r/min, and the mixed materials are added into a double-screw extruder for melt blending, the melting temperature is 275 ℃, and the rotating speed of screws is 300 r/min; after being extruded by a double-screw extruder (the length-diameter ratio of the double-screw extruder is 48:1, and the temperature of each area from a feeding section to a die surface is 260 ℃ to 275 ℃), the PET light aging resistant and weather resistant master batch is obtained by shearing, mixing, cooling, granulating, drying and packaging.
Table 3 DSC differential thermal analysis data of the PET weatherable master batch prepared in example 3 for light aging protection:
| sample (I) | Tg/℃ | Tcc/℃ | Tm/℃ | Tmc/℃ | Xc/% |
| Pure PET | 78.87 | 156.51 | 253.95 | 166.75 | 27.19 |
| PET/master batch | 76.24 | 134.36 | 260.38 | 201.14 | 28.8 |
With the introduction of the master batch, the glass transition temperature of the material tends to be reduced, which shows that the gaps among PET molecular chains are increased, the energy threshold required by chain segment motion is reduced, and the material is easy to enter a high-elastic state.
Example 4:
comparative example:
the common PET anti-aging master batch comprises the following components in percentage by mass at normal temperature and normal pressure: 60% of PET resin, 10% of HALS-292, 15% of UV-1577, 8% of maleic anhydride grafted styrene-ethylene butylene-styrene terpolymer (SEBS-g-MA), 5% of polyethylene oxide and 2% of hindered phenol antioxidant 1010.
The preparation method comprises the following steps: the components are proportioned according to the weight ratio, then the proportioned components are added into a high-speed mixer to be mixed for 20 minutes at the mixing temperature of 135 ℃, the mixed materials are added into a double-screw extruder to be melted and blended, the melting temperature is controlled to be 260-275 ℃, and the materials are extruded by the double-screw extruder to be cooled, granulated and dried to obtain the product.
The master batches prepared in examples 1 to 3 and comparative example were added to PET pure resin in an amount of 3%, and the properties after secondary extrusion granulation were measured as follows:
and (3) detecting bubbles: a200 g sample of the master batch was taken to see if air bubbles were present.
Hydrolysis resistance test: drying the master batches, preparing sample strips at the same time, and calculating the strength retention rate according to different master batches in a constant temperature and humidity device with the temperature of 85 ℃ and the RH of 90% for 15 hours.
And (3) ultraviolet performance test: drying the master batch to prepare a standard color plate, and taking out the standard color plate after 200h under the condition that the ultraviolet wavelength is 340nm and the power is 40W 6 to measure the color difference value.
Testing thermal oxidation performance: and (3) drying the master batches, preparing a color plate, placing the color plate in a blowing oven at 180 ℃, placing the color plate for 10 hours, and observing whether the color plate is yellow or not.
The results of the performance measurements are shown in Table 4.
TABLE 4 Master batch Performance test Table
| Bubbles in the master batch | Strength retention ratio | Color difference value | Yellow stain | |
| Example 1 | Is free of | 82% | 5.56 | Is free of |
| Example 2 | Is free of | 85% | 7.60 | Is free of |
| Example 3 | Is free of | 81% | 6.55 | Is free of |
| Comparative example | Is provided with | 26% | 3.54 | Light yellow |
In later-stage material processing, the master batch prepared by the invention can improve the transparency of the product, has good film strength and prevents PET from hydrolysis. The polyester fiber prepared from the master batch not only can prolong the service life, but also can maintain the processing performance and the shock resistance of the material, and the master batch has no harmful effect on human bodies, is green and sanitary, and is simple and convenient to prepare.
The above-mentioned embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the scope of the present invention should be defined by the claims, and equivalents including technical features of the claims, i.e., equivalent modifications within the scope of the present invention.
Claims (10)
1. The PET light aging resistant and weather resistant master batch is characterized by comprising the following components in percentage by mass: 40-60% of resin carrier, 10-20% of light stabilizer, 15-25% of ultraviolet absorbent, 3-5% of dispersant, 5-15% of compatilizer, 0.5-2% of nucleating agent, 0.5-1.5% of lubricant, 1-2.5% of anti-hydrolysis agent and 2-5% of antioxidant.
2. The PET photoaging-resistant weather-resistant master batch as claimed in claim 1, wherein: the resin carrier is PET resin; the granularity of the PET resin is 80-120 meshes.
3. The PET photoaging-resistant weather-resistant master batch as claimed in claim 1, wherein: the light stabilizer is one or a mixture of more of light stabilizer HALS-123, light stabilizer HALS-119, light stabilizer HALS-292 and light stabilizer HALS-611.
4. The PET photoaging-resistant weather-resistant master batch as claimed in claim 1, wherein: the ultraviolet absorbent is one or more of ultraviolet absorbent UV-360, ultraviolet absorbent UV-1577, ultraviolet absorbent UV-234 and ultraviolet absorbent UV-328.
5. The PET photoaging-resistant weather-resistant master batch as claimed in claim 1, wherein: the dispersing agent is any one of polyethylene glycol, calcium stearate and trimethylolethane.
6. The PET photoaging-resistant weather-resistant master batch as claimed in claim 1, wherein: the compatilizer is any one of acetic acid-ethylene copolymer, maleic anhydride grafted styrene-ethylene butylene-styrene terpolymer and aluminum-titanium composite coupling agent.
7. The PET photoaging-resistant weather-resistant master batch as claimed in claim 1, wherein: the nucleating agent is any one of polyolefin elastomer, sodium benzoate and polyoxyethylene; the lubricant is any one of stearic acid, calcium stearate and ethylene bisstearamide; the hydrolysis resistant agent is polycarbodiimide hydrolysis resistant agent.
8. The PET photoaging-resistant weather-resistant master batch as claimed in claim 1, wherein: the antioxidant is one or a mixture of more of hindered phenol antioxidant 1010 and phosphite antioxidant 168.
9. The preparation method of the PET light aging resistant and weather resistant master batch is characterized by comprising the following steps:
weighing the raw materials according to the proportion;
adding the prepared mixture into a high-speed mixer, and stirring for 15-30 minutes at 95-150 ℃;
feeding the mixed materials into a double-screw machine for melt blending, wherein the melting temperature is 260-275 ℃, and the rotating speed of the screws is 150-300 r/min;
and extruding the mixed materials by a double-screw extruder, and then shearing, mixing, cooling, granulating and drying to obtain the PET light aging resistant and weather resistant master batch.
10. The preparation method of the PET photoaging-resistant weather-resistant master batch according to claim 9, wherein the preparation method comprises the following steps: the rotating speed of the mixer in the step (2) is 860-1200 r/min; the length-diameter ratio of the twin-screw extruder in the step (4) is 40-48:1, and the temperature of each zone from the feeding section to the die surface is 260-275 ℃.
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| CN113232340A (en) * | 2021-03-24 | 2021-08-10 | 浙江大东南股份有限公司 | Preparation method of white hydrolysis-resistant anti-aging BOPET (biaxially-oriented polyethylene terephthalate) back plate film |
| CN115216125A (en) * | 2022-07-29 | 2022-10-21 | 宿迁联宏新材料有限公司 | Special anti-broken PET spinning weather-resistant master batch and preparation method thereof |
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| CN118530570A (en) * | 2024-07-26 | 2024-08-23 | 苏州宝丽迪材料科技股份有限公司 | High-weather-resistance master batch for color polyester and preparation method and application thereof |
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Application publication date: 20200918 |