CN114805937B - Styrene-coated phosphorus-containing acid source particles and preparation method thereof - Google Patents

Styrene-coated phosphorus-containing acid source particles and preparation method thereof Download PDF

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Publication number
CN114805937B
CN114805937B CN202210489221.4A CN202210489221A CN114805937B CN 114805937 B CN114805937 B CN 114805937B CN 202210489221 A CN202210489221 A CN 202210489221A CN 114805937 B CN114805937 B CN 114805937B
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styrene
acid source
phosphorus
coated
particles
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CN114805937A (en
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彭昀成
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Qingyuan City Yicheng Flame Retardant Materials Co ltd
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Qingyuan City Yicheng Flame Retardant Materials Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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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)
  • Manufacturing Of Micro-Capsules (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention belongs to the field of flame-retardant materials, and discloses a styrene-coated phosphorus-containing acid source particle which consists of a phosphorus-containing acid source and a polymer layer coated on the surface of the phosphorus-containing acid source; the polymer layer is a linear polymer formed by free radical polymerization of 70-90wt% of styrene, 10-30wt% of maleic acid or maleic anhydride, and 0-5wt% of N-vinyl pyrrolidone. The particles are coated on the basis of a polymer material formed by styrene, unsaturated polycarboxylic acid and vinyl pyrrolidone, have good affinity with an acid source, can ensure sufficient fluidity in an ABS base material, and simultaneously, the invention also discloses a preparation method of the particles.

Description

Styrene-coated phosphorus-containing acid source particles and preparation method thereof
Technical Field
The invention belongs to the field of flame-retardant materials, and particularly relates to a styrene-coated phosphorus-containing acid source particle and a preparation method thereof.
Background
CN200580038977.1 discloses a composition comprising: (A) At least one halogen-free polymer that exhibits a total mass loss of at least about 7wt% when subjected to thermogravimetric analysis at a temperature of 370 ℃; (B) at least one acid source; (C) at least one carbon generating source; and (D) at least one blowing agent.
The polymer in the composition is derived from a mixture of monomers comprising (i) styrene and (ii) alkyl acrylate, and further, the copolymer is derived from a mixture of monomers comprising styrene and n-butyl acrylate, wherein the weight ratio of styrene to n-butyl acrylate is from 0.05:1 to 2:1.
An important application of the existing flame-retardant material is that the material is used in ABS material, acid source is mostly loaded in styrene, and particles of the acid source loaded by the styrene, other gas sources and carbon sources are added in the process of extrusion granulation of ABS to realize flame retardance. The coated acid source needs to ensure that the acid source does not contact the ABS during extrusion to destroy the ABS performance.
However, the problem with using a styrene substrate to support the acid source is: styrene does not completely encapsulate the acid source, resulting in an inability of the acid source to disperse effectively during extrusion of the substrate. In other schemes, melamine formaldehyde resin is used for coating, but the melamine formaldehyde resin can cause the acid source to be incapable of reacting to play a role in a higher temperature state.
Therefore, the technical problems to be solved in the scheme are as follows: how to improve the coating effect of the acid source, and meanwhile, particles formed by coating can be fully flowed and dispersed in the ABS base material so as to realize uniform distribution and efficacy exertion of the acid source in the ABS base material.
Disclosure of Invention
In view of the shortcomings and drawbacks of the prior art, a primary object of the present invention is to provide styrene-coated particles of a phosphorus-containing acid source, which are coated with a polymeric material based on styrene, an unsaturated polycarboxylic acid, and vinylpyrrolidone, and which have a good affinity for the acid source, while ensuring sufficient flowability in the ABS substrate.
It is another object of the present invention to provide a process for the preparation of the particles.
The specific scheme is as follows:
a styrene-coated phosphorus acid source-containing particle consists of a phosphorus acid source and a polymer layer coated on the surface of the phosphorus acid source;
the polymer layer is a linear polymer formed by free radical polymerization of 70-90wt% of styrene, 10-30wt% of maleic acid or maleic anhydride, and 0-5wt% of N-vinyl pyrrolidone.
The invention is not limited to the source of gas and/or carbon source being also encapsulated in the polymer layer to form an integrated system of acid source, source of gas, carbon source.
In the styrene-coated phosphorus-containing acid source particles, the phosphorus-containing acid source is red phosphorus or aluminum hypophosphite.
In the styrene-coated phosphorus-containing acid source particles, the weight ratio of the phosphorus-containing acid source to the linear polymer is 10-15:1.
Meanwhile, the invention also discloses a preparation method of the styrene-coated phosphorus-containing acid source particles, which comprises the following steps:
step 1: monomers consisting of styrene, maleic acid or maleic anhydride and N-vinyl pyrrolidone are reacted for 1 to 3 hours in the presence of an initiator, wherein the reaction temperature is 60 to 80 ℃;
step 2: adding a nonpolar organic solvent into the system in the step 1 to dilute and disperse, then adding a phosphorus-containing acid source, mixing, filtering and drying to obtain microsphere particles.
In the preparation method of the styrene-coated phosphorus acid source-containing particles, the non-aqueous polar organic solvent is methanol, ethanol or ethyl acetate; the dosage of the non-aqueous polar organic solvent is 2-5 times of the weight of the phosphorus-containing acid source.
In the preparation method of the styrene-coated phosphorus-containing acid source particles, the initiator is an oil-soluble initiator, and the amount of the initiator is 0.5-1wt% of the weight of the monomer.
In the preparation method of the styrene-coated phosphorus acid source-containing particles, the initiator is azobisisobutyronitrile or azobisisoheptonitrile.
Compared with the prior art, the invention has the beneficial effects that:
the particles are coated by a polymer material formed by styrene, unsaturated polycarboxylic acid and vinyl pyrrolidone, have good affinity with an acid source, and can ensure sufficient fluidity in an ABS base material.
The particle size of the master batch obtained by the treatment of the invention is about 10-30 mu m.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1
A preparation method of styrene-coated phosphorus-containing acid source particles comprises the following steps:
step 1: adding monomers consisting of styrene and maleic acid into 200g of ethanol solution, and reacting for 2 hours in the presence of an initiator at a temperature of 75 ℃; wherein, 80g of styrene and 20g of maleic acid; initiator 0.8g;
step 2: 3000g of ethanol is added into the system in the step 1 for dilution and dispersion, 1000g of aluminum hypophosphite is then added, and the mixture is filtered and dried to obtain microsphere particles.
Example 2
A preparation method of styrene-coated phosphorus-containing acid source particles comprises the following steps:
step 1: adding monomers consisting of styrene, maleic acid and N-vinyl pyrrolidone into 200g of ethanol solution, and reacting for 2 hours in the presence of an initiator at a temperature of 75 ℃; wherein, 80g of styrene, 15g of maleic acid and 5g of N-vinyl pyrrolidone; initiator 0.8g;
step 2: 3000g of ethanol is added into the system in the step 1 for dilution and dispersion, 1000g of aluminum hypophosphite is then added, and the mixture is filtered and dried to obtain microsphere particles.
Example 3
A preparation method of styrene-coated phosphorus-containing acid source particles comprises the following steps:
step 1: adding monomers consisting of styrene, maleic acid and N-vinyl pyrrolidone into 200g of ethanol solution, and reacting for 2 hours in the presence of an initiator at a temperature of 75 ℃; wherein, 80g of styrene, 17g of maleic acid and 3g of N-vinyl pyrrolidone; initiator 0.8g;
step 2: 3000g of ethanol is added into the system in the step 1 for dilution and dispersion, 1000g of aluminum hypophosphite is then added, and the mixture is filtered and dried to obtain microsphere particles.
Example 4
A preparation method of styrene-coated phosphorus-containing acid source particles comprises the following steps:
step 1: adding monomers consisting of styrene, maleic acid, maleic anhydride and N-vinyl pyrrolidone into 200g of ethanol solution, and reacting for 2 hours in the presence of an initiator at a temperature of 75 ℃; wherein, 70g of styrene, 25g of maleic anhydride and 5g of N-vinyl pyrrolidone; 1g of an initiator;
step 2: 4000g of ethanol is added into the system in the step 1 for dilution and dispersion, 1000g of aluminum hypophosphite is then added, and the mixture is filtered and dried to obtain microsphere particles.
Example 5
A preparation method of styrene-coated phosphorus-containing acid source particles comprises the following steps:
step 1: adding monomers consisting of styrene, maleic anhydride and N-vinyl pyrrolidone into 200g of ethanol solution, and reacting for 2 hours in the presence of an initiator at a reaction temperature of 75 ℃; wherein, 75g of styrene, 22g of maleic anhydride and 3g of N-vinyl pyrrolidone; 1g of an initiator;
step 2: 5000g of ethanol is added into the system in the step 1 for dilution and dispersion, 1300g of aluminum hypophosphite is then added, mixed, filtered and dried, and microsphere particles are obtained.
Example 6
A preparation method of styrene-coated phosphorus-containing acid source particles comprises the following steps:
step 1: adding monomers consisting of styrene, maleic acid and N-vinyl pyrrolidone into 200g of ethanol solution, and reacting for 2 hours in the presence of an initiator at a temperature of 75 ℃; wherein, 75g of styrene, 24g of maleic acid and 1g of N-vinyl pyrrolidone; 1g of an initiator;
step 2: 2000g of ethanol is added into the system in the step 1 for dilution and dispersion, then 1000g of aluminum hypophosphite is added, and the mixture is filtered and dried to obtain microsphere particles.
Comparative example 1
A preparation method of styrene-coated phosphorus-containing acid source particles comprises the following steps:
step 1: adding monomers consisting of styrene and crotonic acid into 200g of ethanol solution, and reacting for 2 hours in the presence of an initiator at a temperature of 75 ℃; wherein, 80g of styrene and 20g of crotonic acid; initiator 0.8g;
step 2: 3000g of ethanol is added into the system in the step 1 for dilution and dispersion, 1000g of aluminum hypophosphite is then added, and the mixture is filtered and dried to obtain microsphere particles.
Comparative example 2
A preparation method of styrene-coated phosphorus-containing acid source particles comprises the following steps:
step 1: adding monomers consisting of styrene, crotonic acid and N-vinyl pyrrolidone into 200g of ethanol solution, and reacting for 2 hours in the presence of an initiator at a temperature of 75 ℃; wherein, 80g of styrene, 15g of crotonic acid and 5g of N-vinyl pyrrolidone; initiator 0.8g;
step 2: 3000g of ethanol is added into the system in the step 1 for dilution and dispersion, 1000g of aluminum hypophosphite is then added, and the mixture is filtered and dried to obtain microsphere particles.
Performance testing
Test item 1: and (3) adding the flame-retardant master batch and PPO (polypropylene oxide) into the ABS, wherein the dosages of the flame-retardant master batch and the PPO are 75%, 20% and 5% as in the examples and the comparative examples, mixing and granulating to prepare modified particles, and adding the modified particles into an injection molding machine for injection molding to obtain the ABS fire cow material.
The ABS fire cow feed was tested for the following items: tensile strength, impact strength, IZOD notched impact strength.

Claims (7)

1. A styrene-coated phosphorus-containing acid source particle, characterized in that: the coating consists of a phosphorus acid source and a polymer layer coated on the surface of the phosphorus acid source;
the polymer layer is a linear polymer formed by free radical polymerization of 70-90wt% of styrene, 10-30wt% of maleic acid or maleic anhydride, and 0-5wt% of N-vinyl pyrrolidone.
2. The styrene coated phosphorus acid source containing particles of claim 1 wherein: the phosphorus acid source is red phosphorus or aluminum hypophosphite.
3. The styrene coated phosphorus acid source containing particles of claim 1 wherein: the weight ratio of the phosphorus-containing acid source to the linear polymer is 10-15:1.
4. A process for the preparation of styrene coated particles of a phosphorus acid source according to any one of claims 1 to 3, wherein: the method comprises the following steps:
step 1: monomers consisting of styrene, maleic acid or maleic anhydride and N-vinyl pyrrolidone are reacted for 1 to 3 hours in the presence of an initiator, wherein the reaction temperature is 60 to 80 ℃;
step 2: adding a nonpolar organic solvent into the system in the step 1 to dilute and disperse, then adding a phosphorus-containing acid source, mixing, filtering and drying to obtain microsphere particles.
5. The method for preparing styrene-coated phosphorus-containing acid source particles according to claim 4, wherein: the non-aqueous polar organic solvent is methanol, ethanol or ethyl acetate; the dosage of the non-aqueous polar organic solvent is 2-5 times of the weight of the phosphorus-containing acid source.
6. The method for preparing styrene-coated phosphorus-containing acid source particles according to claim 4, wherein: the initiator is an oil-soluble initiator, and the dosage of the initiator is 0.5-1wt% of the weight of the monomer.
7. The method for preparing styrene-coated phosphorus-containing acid source particles according to claim 6, wherein: the initiator is azobisisobutyronitrile or azobisisoheptonitrile.
CN202210489221.4A 2022-05-05 2022-05-05 Styrene-coated phosphorus-containing acid source particles and preparation method thereof Active CN114805937B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107667143A (en) * 2015-03-25 2018-02-06 英力士苯领集团股份公司 The method for preparing the thermoplastic polymer composition with the optimization degree of cross linking
CN113174089A (en) * 2021-05-26 2021-07-27 兰州大学 Polystyrene nano-microsphere coated red phosphorus flame retardant and preparation and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10347012A1 (en) * 2003-10-07 2005-05-25 Clariant Gmbh Phosphorus-containing flame retardant agglomerates
DE102005013957A1 (en) * 2005-03-26 2006-09-28 Clariant Produkte (Deutschland) Gmbh Phosphorus-containing thermally stabilized flame retardant agglomerates

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107667143A (en) * 2015-03-25 2018-02-06 英力士苯领集团股份公司 The method for preparing the thermoplastic polymer composition with the optimization degree of cross linking
CN113174089A (en) * 2021-05-26 2021-07-27 兰州大学 Polystyrene nano-microsphere coated red phosphorus flame retardant and preparation and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
苯乙烯马来酸酐共聚物化学改性研究进展;徐健;余红敏;;化学研究(第05期);97-102 *

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