CN109988293A - A kind of preparation method of high-temperature resistant fluorescent pigment - Google Patents
A kind of preparation method of high-temperature resistant fluorescent pigment Download PDFInfo
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- CN109988293A CN109988293A CN201711482977.1A CN201711482977A CN109988293A CN 109988293 A CN109988293 A CN 109988293A CN 201711482977 A CN201711482977 A CN 201711482977A CN 109988293 A CN109988293 A CN 109988293A
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- phthalic acid
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A kind of preparation method of high-temperature resistant fluorescent pigment, provide it is a kind of facilitate processing, improve the preparation method of durothermic fluorescent pigment.The following steps are included: S1, in a kettle 1,4 cyclohexanedimethanols of investment, are warming up to 90-120 DEG C；S2, zinc oxide, M-phthalic acid and terephthalic acid (TPA) are put into again, be dehydrated on one side, be slowly warming up to 200~230 DEG C on one side, keep the temperature 2-3h；S3, investment fluorescent dye, stirring vacuumize, cooling discharge after 1 hour；S4, ultra-fine grinding are made.Key reaction of the invention is the polycondensation reaction under zinc oxide catalysis of the hydroxyl with the carboxyl on M-phthalic acid and terephthaldehyde's acid molecule of 1,4 cyclohexanedimethanols, forms ester bond and water.It is compared with phthalic anhydride, M-phthalic acid and terephthalic acid (TPA) do not have ortho position steric effect, are easier to adequately be esterified, and obtain the resin of macromolecule, and residual small molecule is less, is not easily decomposed at high temperature, therefore temperature tolerance with higher.
Description
Technical field
The present invention relates to fluorescent pigment more particularly to a kind of high temperature resistant fluorescence for the note coloring of the plastics such as PE, PP, ABS
Pigment.
Background technique
Organic fluorescent pigment is generally made of fluorescent dye and vector resin, and wherein fluorescent dye provides fluorescence color development, is carried
Solid solution of the body resin as fluorescent dye provides the performances such as good coloring, heatproof, resistance to migration and solvent resistant.
Fluorescent pigment is used to need the melting injection temperature of short time tolerance plastics when high-temperature injection, at this temperature, glimmering
Delustering pigment cannot decompose discoloration.The injection temperature of common plastics is as follows:
| Plastics variety | Injection temperature |
| PS | 165 DEG C~230 DEG C |
| ABS | 220 DEG C~230 DEG C |
| PMMA | 220 DEG C~250 DEG C |
| PA | 270 DEG C~295 DEG C |
| PE | 230 DEG C~300 DEG C |
| PP | 220 DEG C~290 DEG C |
Currently used such fluorescent pigment is usually to use pentaerythrite, phthalic anhydride and benzoic acid dehydrating polycondensation gained resin
It is obtained through dyeing, since the ortho position steric effect of phthalic anhydride causes reaction that cannot thoroughly carry out, simultaneously because using benzoic acid
It is blocked, the benzoic acid of more small molecule is inevitably contained in product, decompose discoloration at high temperature, affect fluorescence
Color effect.
Summary of the invention
In order to overcome the problems, such as existing high-temperature resistant fluorescent pigment high-temperature discoloration, the present invention provides a kind of high-temperature resistant fluorescent pigments
Preparation method, the present invention use 1,4 cyclohexanedimethanols, M-phthalic acid and terephthalic acid (TPA) polycondensation reaction, prepare polyester
Resin obtains high-temperature resistant fluorescent pigment after fluorochromine as the vector resin of fluorescent pigment.This reaction on the one hand by
In replacing phthalic anhydride using M-phthalic acid, the not no steric effect at ortho position, esterification rapidly and, while blocking is binary
Acid is easier to be connected on molecular backbone, so that reactant small molecular is less, reaches purpose resistant to high temperature.
Technical scheme is as follows: the following steps are included:
S1,1,4 cyclohexanedimethanols are put into a kettle, be warming up to 90-120 DEG C；
S2, zinc oxide, M-phthalic acid and terephthalic acid (TPA) are put into again, be dehydrated on one side, slowly it is warming up to 200 on one side~
230 DEG C, keep the temperature 2-3h；
S3, investment fluorescent dye, stirring vacuumize, cooling discharge after 1 hour；
S4, ultra-fine grinding are made.
Wherein, 1,4 cyclohexanedimethanols, M-phthalic acid and terephthalic acid (TPA) polycondensation reaction, prepare polyester resin.
In polyester resin, the mass percent of 1,4 cyclohexanedimethanols is 40~45%, the quality hundred of M-phthalic acid
Score is 45~50%, and the mass percent of terephthalic acid (TPA) is 5~10%.
A kind of preparation method of high-temperature resistant fluorescent pigment, comprising the following steps:
S1,1,4 cyclohexanedimethanols are put into a kettle, be warming up to 100 DEG C；
S2, zinc oxide, M-phthalic acid and terephthalic acid (TPA) are put into again, are dehydrated on one side, be slowly warming up to 200 DEG C on one side,
Keep the temperature 2h；
S3, investment fluorescent dye, stirring vacuumize, cooling discharge after 1 hour；
S4, ultra-fine grinding are made.
Key reaction of the invention is the hydroxyl of 1,4 cyclohexanedimethanols on M-phthalic acid and terephthaldehyde's acid molecule
Carboxyl the polycondensation reaction under zinc oxide catalysis, form ester bond and water.It is compared with phthalic anhydride, M-phthalic acid and terephthaldehyde
Acid does not have ortho position steric effect, is easier to adequately be esterified, and obtains the resin of macromolecule, residual small molecule is less, at high temperature
It is not easily decomposed, therefore temperature tolerance with higher.
Specific embodiment
The invention will be further described with comparative example with reference to embodiments, but not limited to this.
Embodiment is raw materials used unless otherwise stated, is technical grade commercially available product.
A kind of preparation method of high-temperature resistant fluorescent pigment, comprising the following steps:
S1,1,4 cyclohexanedimethanols are put into a kettle, be warming up to 90-120 DEG C；
S2, zinc oxide, M-phthalic acid and terephthalic acid (TPA) are put into again, be dehydrated on one side, slowly it is warming up to 200 on one side~
230 DEG C, keep the temperature 2-3h；
S3, investment fluorescent dye, stirring vacuumize, cooling discharge after 1 hour；
S4, ultra-fine grinding are made.
Wherein, 1,4 cyclohexanedimethanols, M-phthalic acid and terephthalic acid (TPA) polycondensation reaction, prepare polyester resin.As
The vector resin of fluorescent pigment obtains high-temperature resistant fluorescent pigment after fluorochromine.
In polyester resin, the mass percent of 1,4 cyclohexanedimethanols is 40~45%, the quality hundred of M-phthalic acid
Score is 45~50%, and the mass percent of terephthalic acid (TPA) is 5~10%.
A kind of preparation method of high-temperature resistant fluorescent pigment, comprising the following steps:
S1,1,4 cyclohexanedimethanols are put into a kettle, be warming up to 100 DEG C；
S2, zinc oxide, M-phthalic acid and terephthalic acid (TPA) are put into again, are dehydrated on one side, be slowly warming up to 200 DEG C on one side,
Keep the temperature 2h；
S3, investment fluorescent dye, stirring vacuumize, cooling discharge after 1 hour；
S4, ultra-fine grinding are made.
1,4 cyclohexanedimethanol structural formulas are as follows:
M-phthalic acid structural formula is as follows:
Terephthalic acid (TPA) structural formula is as follows:
The key reaction of this synthesis is the hydroxyl of 1,4 cyclohexanedimethanols on M-phthalic acid and terephthaldehyde's acid molecule
Carboxyl the polycondensation reaction under zinc oxide catalysis, form ester bond and water.It is compared with phthalic anhydride, M-phthalic acid and terephthaldehyde
Acid does not have ortho position steric effect, is easier to adequately be esterified, and obtains the resin of macromolecule, residual small molecule is less, at high temperature
It is not easily decomposed, therefore temperature tolerance with higher.
Embodiment 1
1,4 cyclohexanedimethanol 172g are added in the 500ML there-necked flask with blender, condenser, are slowly warming up to
100 ± 2 DEG C, zinc oxide 5g is put into, M-phthalic acid 200g, terephthalic acid (TPA) 28g are slowly warming up to 200~230 while stirring
DEG C heat preservation 2 hours, while not stopping to be dehydrated, put into fluorescent dye 7.8g, stirring starts to vacuumize after five minutes, discharge after 1 hour,
Ultra-fine grinding obtains high-temperature resistant fluorescent pigment.
Embodiment 2
1,4 cyclohexanedimethanol 180g are added in the 500ML there-necked flask with blender, condenser, are slowly warming up to
100 ± 2 DEG C, zinc oxide 5g is put into, M-phthalic acid 196g, terephthalic acid (TPA) 24g are slowly warming up to 200~230 while stirring
DEG C heat preservation 2 hours, while not stopping to be dehydrated, put into fluorescent dye 8g, stirring starts to vacuumize after five minutes, discharge after 1 hour, surpasses
It is finely divided to obtain high-temperature resistant fluorescent pigment.
The comparison of heat-resisting quantity.Above-mentioned fluorescent pigment and each 5g of commercially available high-temperature resistant fluorescent pigment are taken, high-temperature baking is placed in
10 minutes, observe pigment reduced gravity situations.Measurement result is shown in Table 1.
Table 1
| Baking temperature | Embodiment 1 | Embodiment 2 | It is commercially available |
| 220℃ | 0.72% | 0.65% | 2.48% |
| 250℃ | 2.13% | 1.76% | 8.17% |
From table 1 it follows that embodiment 1 and embodiment 2, under 220 DEG C of high temperature, weightlessness less than 1%, lose by commercial product
Again more than 2%；Embodiment 1 and embodiment 2 are under 250 DEG C of high temperature, and weightlessness 2% or so, commercial product weightlessness is more than 8%, this reality
It applies a product and is substantially better than commercial product.
Claims (4)
1. a kind of preparation method of high-temperature resistant fluorescent pigment, which comprises the following steps:
S1,1,4 cyclohexanedimethanols are put into a kettle, be warming up to 90-120 DEG C；
S2, zinc oxide, M-phthalic acid and terephthalic acid (TPA) are put into again, are dehydrated on one side, be slowly warming up to 200~230 DEG C on one side,
Keep the temperature 2-3h；
S3, investment fluorescent dye, stirring vacuumize, cooling discharge after 1 hour；
S4, ultra-fine grinding are made.
2. a kind of preparation method of high-temperature resistant fluorescent pigment according to claim 1, which is characterized in that wherein, 1,4 hexamethylenes
Alkane dimethanol, M-phthalic acid and terephthalic acid (TPA) polycondensation reaction, prepare polyester resin.
3. a kind of preparation method of high-temperature resistant fluorescent pigment according to claim 2, which is characterized in that in polyester resin
In, the mass percent of 1,4 cyclohexanedimethanols is 40~45%, and the mass percent of M-phthalic acid is 45~50%, right
The mass percent of phthalic acid is 5~10%.
4. a kind of preparation method of high-temperature resistant fluorescent pigment according to claim 1, which is characterized in that including following step
It is rapid:
S1,1,4 cyclohexanedimethanols are put into a kettle, be warming up to 100 DEG C；
S2, zinc oxide, M-phthalic acid and terephthalic acid (TPA) are put into again, be dehydrated on one side, be slowly warming up to 200 DEG C on one side, heat preservation
2h；
S3, investment fluorescent dye, stirring vacuumize, cooling discharge after 1 hour；
S4, ultra-fine grinding are made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711482977.1A CN109988293A (en) | 2017-12-29 | 2017-12-29 | A kind of preparation method of high-temperature resistant fluorescent pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711482977.1A CN109988293A (en) | 2017-12-29 | 2017-12-29 | A kind of preparation method of high-temperature resistant fluorescent pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109988293A true CN109988293A (en) | 2019-07-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711482977.1A Withdrawn CN109988293A (en) | 2017-12-29 | 2017-12-29 | A kind of preparation method of high-temperature resistant fluorescent pigment |
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| Country | Link |
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| CN (1) | CN109988293A (en) |
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2017
- 2017-12-29 CN CN201711482977.1A patent/CN109988293A/en not_active Withdrawn
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Application publication date: 20190709 |