CN117024896A - Flame-retardant color master batch containing modified copolymer and preparation method thereof - Google Patents

Flame-retardant color master batch containing modified copolymer and preparation method thereof Download PDF

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Publication number
CN117024896A
CN117024896A CN202311123791.2A CN202311123791A CN117024896A CN 117024896 A CN117024896 A CN 117024896A CN 202311123791 A CN202311123791 A CN 202311123791A CN 117024896 A CN117024896 A CN 117024896A
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Prior art keywords
modified copolymer
flame
flame retardant
acrylic acid
modified
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CN202311123791.2A
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Chinese (zh)
Inventor
郑成锋
蓝晓锋
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Jiangmen Yangfan Industrial Co ltd
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Jiangmen Yangfan Industrial Co ltd
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Priority to CN202311123791.2A priority Critical patent/CN117024896A/en
Publication of CN117024896A publication Critical patent/CN117024896A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02Homopolymers or copolymers of hydrocarbons
    • C08J2325/04Homopolymers or copolymers of styrene
    • C08J2325/08Copolymers of styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K3/2279Oxides; Hydroxides of metals of antimony
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • C08K7/26Silicon- containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention discloses a flame-retardant color master batch containing a modified copolymer and a preparation method thereof, wherein the flame-retardant color master batch has the advantages of light weight, stable mechanical property, better compatibility among components, good flame-retardant property and the like, and comprises a modified copolymer carrier, pigment, a dispersing agent, a flame retardant and a filler; wherein the modified copolymer carrier is a product formed by free radical polymerization of a monomer obtained by coupling acrylic acid with diatomite and styrene. The product enhances the compatibility of diatomite and polymer through the coupling reaction of diatomite and acrylic acid, so that the components can form a system with strong interaction, thereby improving the mechanical property and colorability of the product.

Description

Flame-retardant color master batch containing modified copolymer and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a flame-retardant color master batch containing a modified copolymer and a preparation method thereof.
Background
The color master consists of pigment or dye, carrier and additive, and is an aggregate prepared by uniformly loading extra amount of pigment into resin. The flame-retardant color master is a pigment preparation prepared by adding flame retardant and mixing with other components, and can be used for coloring and flame retarding materials such as plastics, rubber, textiles and the like. The carrier materials commonly used in the preparation of the flame-retardant masterbatch in the prior art are thermoplastic resins such as polyethylene or polypropylene, pigments are directly mixed with the carrier resins through mechanical stirring in the preparation process, the mixed colors have the phenomena of poor coloring effect and nonuniform colors, in order to realize the flame retardant property of the masterbatch, the flame retardant is directly added in the mixing process, the flame retardant is unevenly dispersed, the flame retardant properties of different parts of the masterbatch are different, the masterbatch carrier has poor compatibility with other components, and the mechanical property of a plastic product is also poor.
CN105647100a discloses a high-black high-brightness ABS flame-retardant masterbatch, its preparation method and application method, the main components of the masterbatch include ABS resin, high-gloss black seed, flame retardant synergist, processing aid and surface brightening agent, and the masterbatch has the characteristics of high surface glossiness, high blackness and good flame-retardant effect, but the masterbatch has poor compatibility among components, and problems of poor colorability, poor mechanical property and the like can occur.
Therefore, development of a flame-retardant color master batch which is more stable in structure, better in compatibility among components, low in cost and environment-friendly is needed.
Disclosure of Invention
Based on the defects in the prior art, the invention provides a flame-retardant color master batch containing a modified copolymer and a preparation method thereof, wherein the modified copolymer adopts hydroxylated diatomite as a raw material, the diatomite is soaked in acrylic acid for modification, hydroxyl contained on the surface of the diatomite and carboxyl in the acrylic acid undergo esterification reaction in the modification process to form modified acrylic acid, the surface property of the diatomite is changed, the dispersibility and stability of the diatomite in a polymer are improved, and the compatibility between the diatomite and a polyolefin carrier is increased. Subsequently, the modified acrylic acid is polymerized with styrene by free radicals to form a modified copolymer support. Finally, blending the modified copolymer carrier with other components to generate the flame-retardant color master batch containing the modified copolymer. The flame-retardant color master batch has the advantages of light weight, stable mechanical property, better compatibility among components, good flame-retardant property and the like.
The flame-retardant masterbatch containing the modified copolymer is prepared from the following components in parts by weight:
further, the dispersing agent is selected from one or more of polyethylene wax, stearic acid, paraffin wax and EBS.
Further, the flame retardant is selected from inorganic flame retardants or organic flame retardants.
Further, the filler is selected from talc.
Further, the pigment is selected from an organic pigment or an inorganic pigment.
An object of the present invention is to provide a method for preparing the flame retardant masterbatch comprising a modified copolymer, comprising the steps of:
s1, preparation of modified acrylic acid: soaking diatomite with hydroxylated surface in acrylic acid, heating by ultrasonic, and then washing to obtain the modified acrylic acid;
s2, adding a catalyst BPO into the modified acrylic acid and styrene under the nitrogen atmosphere, and heating for reaction to obtain the modified copolymer carrier;
s3, blending the modified copolymer carrier with the rest components, and feeding the mixture into a double-screw extruder for melt blending, and performing extrusion molding to obtain the flame-retardant color master batch containing the modified copolymer.
Further, the mass ratio of the acrylic acid to the hydroxylated diatomite is 10:0.1-0.3.
Further, in step S1, the heating temperature is 80-100 ℃.
Further, in step S3, the melting temperature is 200 ℃ to 220 ℃.
Further, in the step S2, the BPO is used in an amount of 0.1-0.5wt% of styrene.
The invention has the following beneficial effects: the modified copolymer carrier is prepared by coupling reaction of acrylic acid and diatomite, and then the product is formed by free radical polymerization of styrene, and the diatomite has the advantages of high porosity, light weight, good high temperature resistance and the like, is a good flame-retardant material, can effectively improve the interfacial binding force of the diatomite and a color master carrier material through the coupling reaction of the acrylic acid and the diatomite, can better enable the diatomite and the color master carrier material to be compatible, improves the specific surface area and the flame-retardant property of the modified copolymer carrier, and simultaneously enhances the mechanical strength of the flame-retardant color master.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following examples are set forth. The starting materials, reactions and workup procedures used in the examples are those commonly practiced in the market and known to those skilled in the art unless otherwise indicated.
The diatomite in the embodiment of the invention has the specification of 800 meshes and is purchased from Hebei Xinxu mineral limited company;
the dispersing agent in the embodiment of the invention is polyethylene wax, which is purchased from Qingdao Sauno chemical industry Co., ltd;
the flame retardant in the embodiment of the invention is antimony trioxide, and is purchased from the chemical industry limited company of Jinxin;
the filler in the embodiment of the invention is talcum powder and is purchased from Guangdong source epitaxy powder limited company;
the catalyst BPO provided by the embodiment of the invention is purchased from Guangzhou city edge creation chemical Co., ltd;
the pigments in the embodiment of the invention are Bayer iron oxide yellow 4920 and Bayer iron oxide red 4130, purchased from Shanghai refining and beautifying industry Co., ltd;
the parts referred to in the present invention refer to parts by weight unless specifically indicated otherwise.
Example 1
The flame-retardant masterbatch containing the modified copolymer is prepared from the following components in parts by weight:
flame retardant color concentrates containing the modified copolymers were prepared as follows:
s1, adding diatomite with hydroxylated surface and acrylic acid into a stirrer, soaking diatom ooze in acrylic acid (the mass ratio of the acrylic acid to the hydroxylated diatomite is 10:0.1), stirring at 80 ℃, simultaneously performing ultrasonic reaction for 4 hours, and repeatedly washing the crude product with a proper amount of water to remove unreacted raw materials and byproducts to obtain modified acrylic acid;
s2, placing the modified acrylic acid and styrene (modified acrylic acid: styrene=1:1, n/n) in a reaction kettle, introducing nitrogen, adding a catalyst BPO, controlling the dosage of the BPO to be 0.2wt% of the styrene, and reacting at 90 ℃ to obtain the modified copolymer carrier;
s3, adding 70 parts of modified copolymer carrier and 75 parts of Bayer iron oxide yellow 4920 into a mixer, stirring for 10min, then heating to 60 ℃, adding 5 parts of polyethylene wax and 10 parts of antimonous oxide, fully stirring for 40min, then adding 10 parts of talcum powder, stirring completely and uniformly, then adding into a double-screw extruder, heating to melt the copolymer (200-220 ℃), uniformly mixing, and extruding to obtain the flame-retardant masterbatch containing the modified copolymer.
Example 2
The flame-retardant masterbatch containing the modified copolymer is prepared from the following components in parts by weight:
flame retardant color concentrates containing the modified copolymers were prepared as follows:
s1, adding diatomite with hydroxylated surface and acrylic acid into a stirrer, soaking diatom ooze in acrylic acid (the mass ratio of the acrylic acid to the hydroxylated diatomite is 10:0.1), stirring at 80 ℃, simultaneously performing ultrasonic reaction for 4 hours, and repeatedly washing the crude product with a proper amount of water to remove unreacted raw materials and byproducts to obtain modified acrylic acid;
s2, placing the modified acrylic acid and styrene in a reaction kettle, introducing nitrogen, adding a catalyst BPO, controlling the dosage of the BPO to be 0.2wt% of the styrene, and reacting at 90 ℃ to obtain the modified copolymer carrier;
s3, adding 80 parts of modified copolymer carrier and 90 parts of Bayer iron oxide red 4130 into a mixer, stirring for 10min, then heating to 60 ℃, adding 7 parts of polyethylene wax and 15 parts of antimonous oxide, fully stirring for 40min, then adding 12 parts of talcum powder, stirring completely and uniformly, then adding into a double-screw extruder, heating to melt the copolymer (200-220 ℃), uniformly mixing, and extruding to obtain the flame-retardant masterbatch containing the modified copolymer.
Comparative example 1
The preparation method, the components and the parts by weight of the flame-retardant masterbatch are the same as those of the embodiment 1, and the only difference is that the modified acrylic acid is not added in the comparative embodiment 1, but common diatomite with the same parts by weight is used for replacing the modified acrylic acid.
Test example 1
The color concentrates prepared in example 1 and comparative example 1 were subjected to mechanical property test.
The tensile strength and flexural strength of the samples were measured by a universal material tester and tested according to astm d638 reference standards, and the results are shown in table 1.
Table 1 table of results of testing the mechanical properties of the color concentrates of example 1 and comparative example 1
As can be seen from Table 1, the average tensile strength and the average bending strength of the flame retardant masterbatch containing the modified copolymer prepared in example 1 of the invention are higher than those of comparative example 1, which shows that the flame retardant masterbatch prepared in example 1 has good mechanical properties, is obviously better than that of comparative example 1 with alternative components, and has good application prospect.

Claims (10)

1. The flame-retardant color master batch containing the modified copolymer is characterized in that the components of the flame-retardant color master batch containing the modified copolymer comprise a modified copolymer carrier, pigment, dispersing agent, flame retardant and filler;
wherein the modified copolymer carrier is a product formed by free radical polymerization of a monomer obtained by coupling acrylic acid with diatomite and styrene.
2. The flame-retardant masterbatch containing a modified copolymer according to claim 1, wherein the flame-retardant masterbatch containing a modified copolymer comprises the following components in parts by mass: 70-80 parts of modified copolymer carrier; 70-90 parts of pigment; 4-7 parts of dispersing agent; 10-15 parts of flame retardant; 8-12 parts of filler.
3. The flame retardant masterbatch comprising a modified copolymer of claim 1 wherein said dispersant is selected from one or more of polyethylene wax, stearic acid, paraffin wax, EBS.
4. The flame retardant masterbatch comprising a modified copolymer of claim 1 wherein said flame retardant is selected from the group consisting of inorganic flame retardants and organic flame retardants.
5. Flame retardant masterbatch comprising a modified copolymer according to claim 1 wherein said filler is selected from talc.
6. The method for preparing a modified copolymer-containing flame retardant masterbatch according to any one of claims 1-5, characterized in that the method for preparing a modified copolymer-containing flame retardant masterbatch comprises the steps of:
s1, preparation of modified acrylic acid: soaking diatomite with hydroxylated surface in acrylic acid, heating by ultrasonic, and then washing to obtain the modified acrylic acid;
s2, adding a catalyst BPO into the modified acrylic acid and styrene under the nitrogen atmosphere, and heating for reaction to obtain the modified copolymer carrier;
s3, blending the modified copolymer carrier with the rest components, and feeding the mixture into a double-screw extruder for melt blending, and performing extrusion molding to obtain the flame-retardant color master batch containing the modified copolymer.
7. The method for preparing a flame retardant masterbatch comprising a modified copolymer of claim 6 wherein the mass ratio of acrylic acid to hydroxylated diatomaceous earth is 10:0.1-0.3.
8. The method for preparing a flame retardant masterbatch comprising a modified copolymer of claim 6 wherein in step S1 the heating is at a temperature of 80-100 ℃.
9. The method for preparing a flame retardant masterbatch comprising a modified copolymer of claim 6 wherein in step S3 the melting temperature is 200 ℃ -220 ℃.
10. The method for preparing a flame retardant masterbatch comprising a modified copolymer of claim 6 wherein in step S2 said BPO is used in an amount of 0.1-0.5wt% of styrene.
CN202311123791.2A 2023-09-01 2023-09-01 Flame-retardant color master batch containing modified copolymer and preparation method thereof Pending CN117024896A (en)

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Application Number Priority Date Filing Date Title
CN202311123791.2A CN117024896A (en) 2023-09-01 2023-09-01 Flame-retardant color master batch containing modified copolymer and preparation method thereof

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