CN107841048A - A kind of polypropene composition of sensitization discoloration and its preparation method and application - Google Patents
A kind of polypropene composition of sensitization discoloration and its preparation method and application Download PDFInfo
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- CN107841048A CN107841048A CN201710021332.1A CN201710021332A CN107841048A CN 107841048 A CN107841048 A CN 107841048A CN 201710021332 A CN201710021332 A CN 201710021332A CN 107841048 A CN107841048 A CN 107841048A
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- sensitization discoloration
- polypropene composition
- melamine
- microcapsules
- sensitization
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of polypropene composition of sensitization discoloration, by weight, including following component：96.5~98.5 parts of acrylic resin；0.5~2.5 part of sensitization discoloration microcapsules；The core of the sensitization discoloration microcapsules is spiropyran compounds, wall material is melamine resin, wall material is polymerized by formaldehyde and melamine, formaldehyde/melamine mol ratio is 2.5/1 ~ 3/1, in the case where pH is 7.5 ~ 8.5 environment addition reaction is occurred into for melamine and formaldehyde first and obtains melamine methylol prepolymer, then light change material spiropyran compounds are dispersed in the sodium dodecyl sulfate aqueous solution of 0.2 1.0wt% concentration, finally melamine methylol prepolymer is added in above-mentioned solution, and solution is adjusted to pH and obtains microcapsule emulsion for 5.5 ~ 6.5, 80 90 DEG C of reaction 3h, washing, filter, sensitization discoloration microcapsules are obtained after drying.The polypropene composition of the sensitization discoloration is able to take the long-term illumination of sunshine, stably changes colour back and forth, and long-term weatherability is good, can be widely used in inner and outer decorative parts of automobile.
Description
Technical field
The present invention relates to plastics modification technology field, the polypropene composition and its system of a kind of sensitization discoloration are related specifically to
Preparation Method and application.
Background technology
With the increase of people's individual demand, it is desirable to the color of automotive part to switch to from the solid color of static state
The effect to change colour with the change of environment.Discoloration usually requires external environment factor effect, such as light and heat.If plastics are in light
In the presence of another color is changed into from a kind of color, become original color again again after lucifuge.
The A of the CN 105111768 and A of CN 103275509 describe a kind of chromoplastic material technical recipe, described discoloration modeling
Material is formed by plastic body, colour-changing agent, photochromic material, oxidant and combination of stabilizers, described photochromic material
It is spiro-pyrans class material.Under ultraviolet light, the C-O keys fracture open loop in colourless pyran structure, coloured isoquinoline is obtained
Quinoline isomers, isoquinolin can absorb visible ray and develop the color, and the fracture of C-O keys is completely reversibility in spiro-pyrans, removes ultraviolet lighting
After penetrating, open loop physical efficiency is returned to original spirane structure without developing the color, and is changed into original color, but during reversible change
Photochemistry side reaction can occur, so as to influence the cycle-index of reversible color, and when by strong light or heat-flash effect, spiro-pyrans
Fatiguability loses the ability of discoloration, can not change colour so as to fail.
The content of the invention
It is an object of the invention to provide can stably be changed colour back and forth by the long-term illumination of firmly sunshine, long-term weatherability
A kind of polypropene composition of good sensitization discoloration.
Another object of the present invention is to provide the preparation method of above-mentioned polypropene composition.
A kind of polypropene composition of sensitization discoloration, by weight, including following component：
96.5~98.5 parts of acrylic resin；
0.5~2.5 part of sensitization discoloration microcapsules；
The core of the sensitization discoloration microcapsules is spiropyran compounds, and wall material is melamine resin, melamine first
Urea formaldehyde is polymerized by formaldehyde and melamine.
Microcapsules preparation process of the present invention comprises the following steps：First by mol ratio be 2.5/1 ~ 3/1 formaldehyde and
Melamine occurs addition reaction in the case where pH is 7.5 ~ 8.5 environment and obtains melamine methylol prepolymer, and light then is become into material
Material spiropyran compounds are dispersed in the sodium dodecyl sulfate aqueous solution of 0.2 ~ 1.0wt% concentration, finally by methylol melamine
Amine prepolymer is added in above-mentioned solution, and solution is adjusted to pH and obtains microcapsule emulsion, 80-90 DEG C of reaction for 5.5 ~ 6.5
3h, washing, suction filtration, obtain sensitization discoloration microcapsules after drying.
The sensitization discoloration Microcapsules Size is 1~5 um.When Microcapsules Size is too big, microcapsule emulsion is unstable easily
Layering, microcapsule coated is poor, and the aberration that discoloration is uneven and discoloration is front and rear is larger, the polypropene composition of the sensitization discoloration
Can change colour back and forth number reduction；When Microcapsules Size is too small, dodecyl sodium sulfate dosage is too high, and residual is more, and smell is big,
Cost is high, and processing is not easy to disperse, and discoloration is uneven.When Microcapsules Size is 1 ~ 5 um, microcapsule coated is good, and particle diameter is big
It is small suitable, process good dispersion.
The acrylic resin is atactic copolymerized polypropene resin, under 230 DEG C, 2.16 kg loads, according to
ASTMD1238 is tested, and the melt flow rate (MFR) of atactic copolymerized polypropene resin is 10~30 g/10min.
The polypropene composition of the sensitization discoloration also includes 0.5-2 part auxiliary agents, and it is stable that the auxiliary agent is selected from antioxidant, light
One or more of mixtures in agent or lubricant.
The antioxidant is the mixture of Hinered phenols and phosphite ester kind antioxidant.
The light stabilizer is hindered amine light stabilizer.
One or several kinds of the lubricant in ethylene bis stearamide, erucyl amide, zinc stearate or silicone oil
Mixture.
Add after acrylic resin and sensitization discoloration microcapsules are mixed from the main spout positioned at double screw extruder one end
Enter in double screw extruder, the one or more of mixing additionally added if needed in antioxidant, light stabilizer or lubricant
Thing and above-mentioned acrylic resin and sensitization discoloration microcapsules add after being mixed together, and carry out melting mixing, and melting mixing temperature is
170~190 DEG C, extruding pelletization, obtain the polypropene composition.
A kind of polypropene composition of sensitization discoloration can be applicable to fascia, auxiliary fasia console, seat, door-plate, insurance
In thick stick or column.
Compared to the prior art, the present invention has the advantages that：
By the sensitization discoloration microcapsules from addition special construction, microcapsule wall material causes core light to become material not by sunshine
In ultraviolet damage, so as to effectively protect light become material, the long-term illumination of sunshine can be withstood, stably
Change colour back and forth, the discoloration of prepared polypropene composition is fast, and long-term weatherability is good.
Embodiment
The present invention is further illustrated below by embodiment, following examples are the preferable embodiment party of the present invention
Formula, but embodiments of the present invention are not limited by following embodiments.
Raw material
Acrylic resin, atactic copolymerized polypropene resin, J-570S, carefree Chemical Co., Ltd., at 230 DEG C, 2.16 kg are born
It is 28g/10min to test melt flow rate (MFR) according to ASTMD-1238 under lotus；
Sensitization discoloration powder, originate from Guangzhou crystalline substance color painting Science and Technology Ltd.；
Spiropyran compounds, N- ethoxy -3,3- dimethyl -6- nitroindoline quinoline spiro-pyrans, originate from Guangzhou Weng Jiang chemical reagent
Co., Ltd；
Toluene di-isocyanate(TDI), BASF AG；
Polypropylene glycol, PPG2000, Shandong Lanxing Dongda Chemical Co., Ltd；
Emulsifier tween 80, wide state YueShun Chemical Co., Ltd.s；
Dihydromethyl propionic acid, Guangzhou Xin Putai Chemical Co., Ltd.s；
Antioxidant, light stabilizer, lubricant, melamine, formaldehyde, dodecyl sodium sulfate pick up from commercially available.
The preparation of embodiment 1-10 sensitization discoloration microcapsules
In the case where weak pH is 7.5 ~ 8.5 environment addition reaction is occurred into for formaldehyde and melamine that mol ratio is 2.5/1 ~ 3/1 first
Melamine methylol prepolymer is obtained, light change material spiropyran compounds are then dispersed in the 12 of 0.2-1.0wt% concentration
In alkyl sulfonic acid sodium water solution, finally melamine methylol prepolymer is added in above-mentioned solution, and by solution adjust to
PH obtains microcapsule emulsion for 5.5 ~ 6.5,80-90 DEG C of reaction 3h, washing, suction filtration, obtains sensitization discoloration microcapsules after drying；Its
In, the mol ratio of formaldehyde and melamine is 2.5/1 in embodiment 1-2, the mol ratio of formaldehyde and melamine in embodiment 3-4
For 2.75/1, the mol ratio of formaldehyde and melamine is 3/1 in embodiment 5-10.
Above-mentioned sodium dodecyl sulfate aqueous solution concentration is 0.8wt%, and product is sensitization discoloration microcapsules A, and particle diameter is
0.5um,
Above-mentioned sodium dodecyl sulfate aqueous solution concentration is 0.7wt%, and product is sensitization discoloration microcapsules B, particle diameter 1um,
Above-mentioned sodium dodecyl sulfate aqueous solution concentration is 0.6wt%, and product is sensitization discoloration microcapsules C, particle diameter 2.5um,
Above-mentioned sodium dodecyl sulfate aqueous solution concentration is 0.5wt%, and product is sensitization discoloration microcapsules D, particle diameter 4um,
Above-mentioned sodium dodecyl sulfate aqueous solution concentration is 0.4wt%, and product is sensitization discoloration microcapsules E, particle diameter 5um,
Above-mentioned sodium dodecyl sulfate aqueous solution concentration is 0.3wt%, and product is sensitization discoloration microcapsules F, particle diameter 7um.
The preparation of the sensitization discoloration microcapsules of comparative example 4
Spiropyran compounds are added in three-necked flask, are slowly dropped into 20ml toluene di-isocyanate(TDI)s（TDI）, 10ml poly- the third two
Alcohol, 1.5ml emulsifier tweens 80,23ml acetone, low speed 200r/min stir 10min, after reacting 30min at 46 DEG C, add two
Hydroxymethyl propionic acid（DMPA）, 60 DEG C, high-speed stirred 1500r/min are warming up to, reaction 30min or so, cool drying, is pulverized
Last shape, obtain the sensitization discoloration microcapsules G that particle diameter is 2.5um.
The preparation of the polypropene composition of embodiment 1-10 and the sensitization discoloration of comparative example 4：
It is formulated, is added after acrylic resin, antioxidant, light stabilizer, lubricant and sensitization discoloration microcapsules are mixed double by table 1
In screw extruder, melting mixing is carried out, melting mixing temperature is 170~190 DEG C, extruding pelletization, obtains the polypropylene group
Compound, composition is then molded into colour table, for testing its discoloration.
The preparation of the polypropene composition of comparative example 1-3 sensitization discolorations：
It is formulated by table 1, twin-screw is added after acrylic resin, antioxidant, light stabilizer, lubricant and sensitization discoloration powder are mixed
In extruder, melting mixing is carried out, melting mixing temperature is 170~190 DEG C, extruding pelletization, obtains the polypropene composition,
Then composition is molded into colour table, for testing its discoloration.
Performance test methods
（1）Color after the color before observation colour table illumination, sunshine irradiate 30 days by visual observation, to observe poly- third in the present invention
Can ene compositions by the discoloration back and forth that stablize after illumination；
（2）Determined by model Color-Eye 7000a color difference meter before colour table solar irradiation and after sunshine irradiates 30 days
L, a, b and Δ E, Lab colour model is by illumination L and tri- key elements of a about color, b composition, L represent illumination, quite
In brightness, a represents the scope from carmetta to green, and b is represented from yellow to blue scope, without sunshine in lower section table 1
Colour table color after irradiating 30 days uses L1、a1、b1Represent, the color after sunshine irradiates 30 days uses L2、a2、b2Table
Show, aberration Δ E=((L before and after discoloration2-L1)2+（a2-a1)2+(b2-b1)2)1/2；
（3）Melt flow rate (MFR), 230 DEG C, under 2.16 kg loads, tested according to ASTMD-1238.
The embodiment 1-10 of table 1 and comparative example 1-4 each group distribution ratio（Parts by weight）And each the performance test results
Continued 1
As can be seen from Table 1, the polypropene composition prepared by embodiment is continuing when adding sensitization discoloration microcapsules
Colour table aberration Δ E of the solar irradiation after 30 days is small, and can become original color again during removal illumination, and adds not entering in comparative example
The sensitization discoloration powder or polyurethane of row microcapsule coated are the polypropene composition continuous light of the sensitization discoloration microcapsules of wall material
Aberration Δ E after 30 days is big, can not become original color again when removing illumination, fail.
Claims (10)
- A kind of 1. polypropene composition of sensitization discoloration, it is characterised in that by weight, including following component：96.5~98.5 parts of acrylic resin；0.5~2.5 part of sensitization discoloration microcapsules；The core of the sensitization discoloration microcapsules is spiropyran compounds, and wall material is melamine resin.
- 2. the polypropene composition of a kind of sensitization discoloration according to claim 1, it is characterised in that the sensitization discoloration is micro- Capsule manufacturing process comprises the following steps：In pH it is 7.5 ~ 8.5 first by formaldehyde and melamine that mol ratio is 2.5/1 ~ 3/1 Addition reaction occurs under environment and obtains melamine methylol prepolymer, is then dispersed in light change material spiropyran compounds In the sodium dodecyl sulfate aqueous solution of 0.2 ~ 1.0 wt% concentration, finally melamine methylol prepolymer is added to above-mentioned In solution, and it is 5.5 ~ 6.5 to obtain microcapsule emulsion that solution, which is adjusted to pH, 80-90 DEG C of reaction 3h, washing, after filtering, drying Obtain sensitization discoloration microcapsules.
- 3. the polypropene composition of a kind of sensitization discoloration according to claim 1, it is characterised in that the sensitization discoloration is micro- Capsule grain diameter is 1~5 um.
- A kind of 4. polypropene composition of sensitization discoloration according to claim 1, it is characterised in that the acrylic resin For atactic copolymerized polypropene resin, under 230 DEG C, 2.16 kg loads, tested according to ASTMD1238, atactic copolymerized polypropene tree The melt flow rate (MFR) of fat is 10~30 g/10min.
- 5. the polypropene composition of a kind of sensitization discoloration according to claim 1, it is characterised in that the sensitization discoloration Polypropene composition also includes 0.5-2 part auxiliary agents, the one kind or several of the auxiliary agent in antioxidant, light stabilizer or lubricant Kind mixture.
- A kind of 6. polypropene composition of sensitization discoloration according to claim 1, it is characterised in that the antioxidant be by Hinder the mixture of phenols and phosphite ester kind antioxidant.
- 7. the polypropene composition of a kind of sensitization discoloration according to claim 1, it is characterised in that the light stabilizer is Hindered amine light stabilizer.
- 8. the polypropene composition of a kind of sensitization discoloration according to claim 1, it is characterised in that the lubricant is selected from One or several kinds of mixtures in ethylene bis stearamide, erucyl amide, zinc stearate or silicone oil.
- A kind of 9. preparation method of the polypropene composition of sensitization discoloration described in claim any one of 1-8, it is characterised in that Comprise the following steps：From the main feeding positioned at double screw extruder one end after acrylic resin and sensitization discoloration microcapsules are mixed Mouth is added in double screw extruder, is additionally added if needed one or more of in antioxidant, light stabilizer or lubricant Mixture and above-mentioned acrylic resin and sensitization discoloration microcapsules add after being mixed together, and carry out melting mixing, melting mixing temperature Spend for 170~190 DEG C, extruding pelletization, obtain the polypropene composition.
- 10. a kind of polypropene composition of sensitization discoloration described in claim any one of 1-8 is in fascia, secondary instrument Application in plate, seat, door-plate, bumper or column.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710021332.1A CN107841048B (en) | 2017-01-12 | 2017-01-12 | A kind of polypropene composition of sensitization discoloration and its preparation method and application |
| PCT/CN2018/071537 WO2018130117A1 (en) | 2017-01-12 | 2018-01-05 | Photochromic polypropylene composite, preparation method for same, and applications thereof |
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| CN201710021332.1A CN107841048B (en) | 2017-01-12 | 2017-01-12 | A kind of polypropene composition of sensitization discoloration and its preparation method and application |
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| CN110578258A (en) * | 2019-07-01 | 2019-12-17 | 绍兴墨织韵纺织科技有限公司 | Preparation process of photochromic polypropylene yarn fabric |
| CN110885500B (en) * | 2019-12-03 | 2022-02-08 | 上海日之升科技有限公司 | High-transparency polypropylene resin capable of optically changing color and preparation method thereof |
| CN114075371B (en) * | 2020-08-19 | 2023-07-28 | 中国石油化工股份有限公司 | Temperature-sensitive polyester, film and preparation method thereof |
| CN112107089B (en) * | 2020-09-16 | 2023-01-03 | 浙江理工大学 | Preparation method of healthy bracelet capable of displaying safe sun exposure time based on ionic liquid hydrogel |
| CN112358722B (en) * | 2020-12-11 | 2022-08-09 | 上海金发科技发展有限公司 | Polyamide composite material and preparation method and application thereof |
| CN114316424B (en) * | 2021-11-22 | 2023-08-25 | 金发科技股份有限公司 | Transparent weather-proof PP/PS composite material and preparation method thereof |
| CN116640382B (en) * | 2023-06-06 | 2024-08-30 | 成都金发科技新材料有限公司 | Spraying-free material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101225296A (en) * | 2008-02-01 | 2008-07-23 | 北京服装学院 | Method for preparing photochromic micro-encapsulation |
| CN104059294A (en) * | 2014-06-24 | 2014-09-24 | 张剑升 | Ultraviolet photochromic material, and product and application thereof |
| CN105524399A (en) * | 2015-12-29 | 2016-04-27 | 银禧工程塑料（东莞）有限公司 | A 3D printing polymer material and a preparing method thereof |
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| EP2907845A4 (en) * | 2012-10-12 | 2016-07-27 | Ccs Inc | Sealant composition for electrical and electronic parts, coating material for electrical and electronic parts, and led device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225296A (en) * | 2008-02-01 | 2008-07-23 | 北京服装学院 | Method for preparing photochromic micro-encapsulation |
| CN104059294A (en) * | 2014-06-24 | 2014-09-24 | 张剑升 | Ultraviolet photochromic material, and product and application thereof |
| CN105524399A (en) * | 2015-12-29 | 2016-04-27 | 银禧工程塑料（东莞）有限公司 | A 3D printing polymer material and a preparing method thereof |
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| CN107841048B (en) | 2019-11-26 |
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