CN112321900A - Bentonite for flame retardant and preparation method thereof - Google Patents

Bentonite for flame retardant and preparation method thereof Download PDF

Info

Publication number
CN112321900A
CN112321900A CN202011319990.7A CN202011319990A CN112321900A CN 112321900 A CN112321900 A CN 112321900A CN 202011319990 A CN202011319990 A CN 202011319990A CN 112321900 A CN112321900 A CN 112321900A
Authority
CN
China
Prior art keywords
bentonite
flame retardant
slurry
concentration
dispersant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011319990.7A
Other languages
Chinese (zh)
Inventor
俞铁明
张蕾
张怀婷
张有连
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZHEJIANG CHANGAN RENHENG TECHNOLOGY CO LTD
Original Assignee
ZHEJIANG CHANGAN RENHENG TECHNOLOGY CO LTD
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ZHEJIANG CHANGAN RENHENG TECHNOLOGY CO LTD filed Critical ZHEJIANG CHANGAN RENHENG TECHNOLOGY CO LTD
Priority to CN202011319990.7A priority Critical patent/CN112321900A/en
Publication of CN112321900A publication Critical patent/CN112321900A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • 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
    • C08K3/346Clay
    • 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
    • C08K5/00Use of organic ingredients
    • C08K5/02Halogenated hydrocarbons
    • 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
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/521Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl 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
    • C08K9/02Ingredients treated with inorganic substances
    • 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

Abstract

The invention discloses a preparation method of bentonite for a flame retardant, which comprises the following steps: (1) adding water into bentonite to prepare high-concentration slurry with the concentration of 3-20%; (2) heating the bentonite slurry to 40-80 ℃, and preserving heat for 24-48 hours; (3) adding water into the bentonite slurry for dispersion, and adding a dispersant; (4) heating to 40-80 deg.C, and stirring at high speed of 100-2000 rpm for 30-240 min; (5) dehydrating, drying and crushing to obtain the bentonite for the flame retardant. The bentonite of the invention keeps the special layered structure and dispersion form of the bentonite to the maximum extent, has the function of blocking heat and combustible gas generated during combustion, is easy to migrate and enrich in a matrix material, can effectively catalyze to form carbon, further strengthens the blocking function of the system by the carbon layer, and improves the flame retardance of the composite flame retardant material.

Description

Bentonite for flame retardant and preparation method thereof
Technical Field
The invention belongs to the field of high polymer flame retardants, relates to a flame retardant component, and more particularly relates to bentonite for a flame retardant.
Background
The high polymer has the characteristic of being very easy to burn, and is very easy to cause fire. The oxygen index of the high polymers is mostly less than 20%. The combustion process produces a large amount of smoke and releases a lot of heat and toxic gases. Causing great loss to national economy, personal safety, environment and the like. Therefore, the flame retardant research of high polymers becomes one of the important research hotspots of the polymer material science, and receives high attention at home and abroad.
The bentonite is a clay material with a lamellar structure, and has good application potential in the field of flame retardance. Related research is also done by researchers in China. For example, a composite flame retardant containing modified nano-bentonite (No. CN 103788678B), discloses a composite flame retardant containing modified nano-bentonite, is prepared by adding the modified nano-bentonite into the flame retardant and adjusting the formula, has the advantages of low price, low smoke, small usage amount, good flame retardant effect, no toxicity, no pollution and the like, and is a composite flame retardant with good smoke suppression performance, good flame retardant performance, environmental protection and the like. A low toxicity flame retardant (application No. 201611108755.9) is provided. The components include bentonite, dicyclo hypophosphite, magnesium hydroxide, sodium bicarbonate, etc.
However, these studies do not relate to the morphology of the lamellar structure of bentonite and the effect of the lamellar structure on the flame retardancy and the physical properties of the polymer.
Disclosure of Invention
The invention aims to provide bentonite applied to the field of high polymer flame retardance and a preparation method thereof. The invention utilizes high-concentration, high-temperature and high-speed hydraulic stripping process to replace powder grinding process, so as to obtain the bentonite which is fully stripped and keeps complete lamellar structure.
The preparation method of the bentonite for the flame retardant is characterized by comprising the following steps:
(1) adding water into bentonite to prepare high-concentration slurry with the concentration of 3-20%;
(2) heating the bentonite slurry to 40-80 ℃, and preserving heat for at least 1 hour;
(3) dispersing the bentonite slurry in water, and adding a dispersant, wherein the addition amount of the dispersant is 0.1-1.0% of the amount of the bentonite; the concentration of the dispersed slurry is 1-5%;
(4) heating the bentonite slurry prepared in the step (3) to 40-80 ℃, and then stirring at a high speed at a rotating speed of 100-2000 rpm for 30-240 minutes;
(5) and (4) dehydrating, drying and crushing the bentonite slurry prepared in the step (4) to obtain the bentonite for the flame retardant.
Further, the high-concentration slurry in the step (1) has the concentration of 5-10%.
Further, the temperature in the step (2) is 60-80 ℃.
Further, in the step (3), the dispersant is sodium hexametaphosphate, sodium pyrophosphate, phosphate ester or high polymer dispersant.
Further, in the step (4), the temperature is 60-80 ℃, the stirring speed is 1500-2000 r/min, and the stirring time is 60-180 min.
The invention also provides bentonite for the flame retardant, which is prepared by the preparation method.
The invention also provides a high polymer flame retardant, which comprises the bentonite for the flame retardant prepared by the method.
The bentonite of the invention keeps the special layered structure and dispersion form of the bentonite to the maximum extent, has the function of blocking heat and combustible gas generated during combustion, is easy to migrate and enrich in a matrix material, can effectively catalyze to form carbon, further strengthens the blocking function of the system by the carbon layer, and improves the flame retardance of the composite flame retardant material.
The surface of the bentonite has active points with large activity, has unpaired electrons and can play a chemical role with high polymers. The polymer chains are adsorbed on the surface of the bentonite, and a plurality of points are chemically combined with the surface of the bentonite, so that the effect is called chemical adsorption, and the chemical adsorption is much larger than the simple physical adsorption. The chemical adsorption is characterized in that molecular chains are easier to move on the surface of the bentonite, but are not easy to separate from the bentonite. Thus, the high polymer and the bentonite form a strong bond capable of sliding, and the strength of the high polymer is increased.
The excellent barrier property of the bentonite enables the bentonite to gradually migrate to the surface of the material during combustion, the stability and the barrier property of the expanded carbon layer are improved, and the smoke release rate of the material is further reduced.
The bentonite for the flame retardant is compounded with the existing flame retardant for application, so that the flame retardant property of the high polymer can be obviously improved, and the physical property of the high polymer can be improved.
Detailed Description
Example 1
Example 1
100g of bentonite is taken and added with water to prepare high-concentration slurry with the concentration of 10 percent, the temperature is heated to 60 ℃, and the heat preservation is carried out for 24 hours. Then, water and 0.5g of a dispersant sodium hexametaphosphate were added, dispersed to a concentration of 4%, and heated to 80 ℃ and stirred at high speed for 60 minutes at a stirring speed of 1500 rpm. And after the reaction is finished, dehydrating, drying and crushing to obtain a finished product.
The prepared modified bentonite and halogen flame retardant chlorinated alicyclic hydrocarbon are uniformly added into ABS plastic.
The ABS plastic properties were tested as follows:
Figure BDA0002792561900000031
the results show that the oxygen index and GWIT of the flame retardant property index are improved after the modified bentonite is added; the strength index of the plastic is improved.
Example 2
1 ton of bentonite is added with water to prepare high-concentration slurry with the concentration of 8 percent, the temperature is heated to 70 ℃, and the temperature is kept for 48 hours. Then, water and 40kg of a phosphate ester dispersant were added, dispersed to a concentration of 5%, and heated to 70 ℃ and stirred at a high speed of 2000 rpm for 120 minutes. And after the reaction is finished, dehydrating, drying and crushing to obtain a finished product.
The prepared modified bentonite and phosphorus flame retardant ditolyl phosphate are uniformly added into PP plastic.
The PP plastic properties were tested as follows:
Figure BDA0002792561900000032
the results show that the oxygen index and GWIT of the flame retardant property index are improved after the modified bentonite is added; the strength index of the plastic is improved.
Example 3
1 ton of bentonite is added with water to prepare high-concentration slurry with the concentration of 5 percent, the temperature is heated to 80 ℃, and the temperature is kept for 36 hours. Then, water and 60 phosphate ester dispersant were added, dispersed to a concentration of 3%, and heated to 80 ℃ and stirred at high speed for 180 minutes at a stirring speed of 1500 rpm. And after the reaction is finished, dehydrating, drying and crushing to obtain a finished product.
The prepared modified bentonite, antimony flame retardant (antimony trioxide + tetrachlorophthalic anhydride) and halogen flame retardant are uniformly added into PE plastic.
The PE plastic properties were tested as follows:
Figure BDA0002792561900000041
the results show that the oxygen index and GWIT of the flame retardant property index are improved after the modified bentonite is added; the strength index of the plastic is improved.
It can be seen from the above examples that the bentonite for flame retardant of the invention, when used in combination with the existing flame retardant, can significantly improve the flame retardant property of the high polymer and can improve the physical properties of the high polymer.
Finally, the foregoing disclosure is directed to only certain embodiments of the invention. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.

Claims (7)

1. The preparation method of the bentonite for the flame retardant is characterized by comprising the following steps:
(1) adding water into bentonite to prepare high-concentration slurry with the concentration of 3-20%;
(2) heating the bentonite slurry to 40-80 ℃, and preserving heat for 24-48 hours;
(3) dispersing the bentonite slurry in water, and adding a dispersant, wherein the addition amount of the dispersant is 0.1-1.0% of the amount of the bentonite; the concentration of the dispersed bentonite slurry is 1-5%;
(4) heating the bentonite slurry prepared in the step (3) to 40-80 ℃, and then stirring at a high speed at a rotating speed of 100-2000 rpm for 30-240 minutes;
(5) and (4) dehydrating, drying and crushing the bentonite slurry prepared in the step (4) to obtain the bentonite for the flame retardant.
2. The method according to claim 1, wherein the high consistency slurry in the step (1) has a consistency of 5 to 10%.
3. The method according to claim 1, wherein the temperature in the step (2) is 60 to 80 ℃.
4. The method according to claim 1, wherein the dispersant in the step (3) is sodium hexametaphosphate, sodium pyrophosphate, phosphate ester or a high polymer dispersant.
5. The process according to claim 1, wherein the temperature in the step (4) is 60 to 80 ℃, the stirring speed is 1500 to 2000 rpm, and the stirring time is 60 to 180 minutes.
6. The bentonite for flame retardant, which is produced by the production method according to any one of claims 1 to 5.
7. A high polymer flame retardant, characterized in that the high polymer flame retardant comprises the bentonite for flame retardant prepared by the preparation method of any one of claims 1 to 8.
CN202011319990.7A 2020-11-23 2020-11-23 Bentonite for flame retardant and preparation method thereof Pending CN112321900A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011319990.7A CN112321900A (en) 2020-11-23 2020-11-23 Bentonite for flame retardant and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011319990.7A CN112321900A (en) 2020-11-23 2020-11-23 Bentonite for flame retardant and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112321900A true CN112321900A (en) 2021-02-05

Family

ID=74322082

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011319990.7A Pending CN112321900A (en) 2020-11-23 2020-11-23 Bentonite for flame retardant and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112321900A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5391228A (en) * 1990-12-21 1995-02-21 Southern Clay Products, Inc. Method for preparing high solids bentonite slurries
JP2005015692A (en) * 2003-06-27 2005-01-20 Daicel Polymer Ltd Flame retardant resin composition
CN102604441A (en) * 2012-03-21 2012-07-25 山东理工大学 Organic bentonite for composite flame retardants and preparation process thereof
CN104130562A (en) * 2014-07-28 2014-11-05 江苏嘉铂新材料有限公司 Nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic and preparation method thereof
CN110357118A (en) * 2019-08-29 2019-10-22 苏州中材非金属矿工业设计研究院有限公司 A kind of bentonite prepares the low energy consumption production technology of inorganic gel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5391228A (en) * 1990-12-21 1995-02-21 Southern Clay Products, Inc. Method for preparing high solids bentonite slurries
JP2005015692A (en) * 2003-06-27 2005-01-20 Daicel Polymer Ltd Flame retardant resin composition
CN102604441A (en) * 2012-03-21 2012-07-25 山东理工大学 Organic bentonite for composite flame retardants and preparation process thereof
CN104130562A (en) * 2014-07-28 2014-11-05 江苏嘉铂新材料有限公司 Nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic and preparation method thereof
CN110357118A (en) * 2019-08-29 2019-10-22 苏州中材非金属矿工业设计研究院有限公司 A kind of bentonite prepares the low energy consumption production technology of inorganic gel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李鑫: "低品质膨润土提质改性技术研究", 《硅酸盐通报》 *

Similar Documents

Publication Publication Date Title
Kong et al. Ultrathin iron phenyl phosphonate nanosheets with appropriate thermal stability for improving fire safety in epoxy
CN109943099B (en) Flame retardant based on modified alpha-zirconium phosphate and preparation method thereof
CN109897273B (en) Composite flame retardant graft-modified EVA (ethylene-vinyl acetate) foam material and preparation method thereof
CN110591156B (en) Zirconium phosphate flame retardant modified based on graphitized carbon nitride composite intercalation and preparation method thereof
Shi et al. Co-MOF@ MXene hybrids flame retardants for enhancing the fire safety of thermoplastic polyurethanes
CN107474247B (en) Preparation method of phosphorus-nitrogen synergistic water-soluble polymer flame retardant
CN103554598B (en) The preparation method of halogen-free flameproof high density polyethylene(HDPE)/ethylene-vinyl acetate copolymer
CN104211955A (en) Halogen-free flame-retardation nylon 6 montmorillonite nanocomposite and preparation method thereof
Huang et al. Flame retardant polypropylene with a single molecule intumescent flame retardant based on chitosan
CN114855298A (en) Flame-retardant smoke-inhibiting polylactic acid fiber and preparation method thereof
CN108641190A (en) A kind of preparation method of novel flame redundant material
CN106496920B (en) low smoke density ABS resin and preparation method thereof
Ma et al. Nacre-inspired intumescent flame retardant bridging network for intelligent fire warning and prevention
CN111607219B (en) Low-smoke thermoplastic polyurethane elastomer composite material and preparation method thereof
CN112321900A (en) Bentonite for flame retardant and preparation method thereof
CN115716985B (en) Halogen-free flame-retardant polyurethane elastomer and preparation method thereof
CN107674303B (en) Modified kaolin flame-retardant synergist and preparation method and application thereof
CN106519421A (en) Flame-retardant composite sheet and preparation method thereof
CN110183779B (en) Application of carboxymethyl cellulose cerium as flame retardant in high molecular polymer material
Lian et al. A novel bio-based PAbz@ PBA maize structure for improving fire protection, toxic gas suppression and mechanical performance of intumescent flame-retardant epoxy coatings
Lian et al. A green organic-inorganic PAbz@ ZIF hybrid towards efficient flame-retardant and smoke-suppressive epoxy coatings with enhanced mechanical properties
WO2023060571A1 (en) Bio-based macromolecule modified nano zirconium phosphate flame retardant and fire-proof coating prepared by using same
CN105621440A (en) Preparation method and application of metal modified MCM-41 molecular screen
CN115160646B (en) Modified kaolinite and preparation method thereof
CN106750936B (en) Rare earth-iron-boron and expansion type flame retardant cooperative flame retardant PP composite material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210205