CN107033419A - A kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type - Google Patents

A kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type Download PDF

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Publication number
CN107033419A
CN107033419A CN201710287837.2A CN201710287837A CN107033419A CN 107033419 A CN107033419 A CN 107033419A CN 201710287837 A CN201710287837 A CN 201710287837A CN 107033419 A CN107033419 A CN 107033419A
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oxidant
preparation
particle diameter
flame retardant
diameter high
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CN201710287837.2A
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Inventor
曹宏生
王忠冬
熊畅
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Jiangsu Feiya Chemical Industry Co Ltd
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Jiangsu Feiya Chemical Industry Co Ltd
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Priority to CN201710287837.2A priority Critical patent/CN107033419A/en
Publication of CN107033419A publication Critical patent/CN107033419A/en
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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
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C08L13/02—Latex
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K5/01—Hydrocarbons
    • 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
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/136—Phenols containing halogens
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention discloses a kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type, comprise the following steps：1) deionized water and water immiscibility were communicated into high speed shear and water-based emulsion is made, wherein water immiscibility mutually includes primary antioxidant, auxiliary anti-oxidant and emulsifying agent；2) thickener, antifreezing agent, defoamer, fire retardant, fire retarding synergist and toughener are added in water-based emulsion；Each raw material accounts for emulsion type low-particle-diameter high-efficiency antioxidant total mass ratio：Primary antioxidant 10~40%, auxiliary anti-oxidant 10~30%, emulsifying agent 4~15%, thickener 0.5~4%, antifreezing agent 1~3%, defoamer 1~8%, fire retardant 3~7%, fire retarding synergist 4~9%, toughener 2~8%, remaining is deionized water；The present invention has following good effect：PBBs and PBDE are replaced using the environmentally friendly bromide fire retardant such as TDE, bromination triazine, brominated epoxy, tetrabromobisphenol A, it is very environmentally friendly.

Description

A kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type
Technical field
The present invention relates to antioxidant production technical field, the preparation side of especially a kind of low particle diameter high-efficiency anti-oxidant of flame retardant type Method.
Background technology
Rubber, plastics, ABS, latex etc. are constantly widened as the important materials in daily life, its application field, but high Molecular material is either natural or synthesis, all easily occurs oxidation reaction, makes material colour fading, yellowing, hardening, cracking, funeral Loss of gloss is damp and transparent etc., and then causes the drop of the physical properties such as impact strength, anti-flexing intensity, tensile strength and elongation Low, influence is used.So it is most simple effective method that antioxidant is added in these materials.Original amines antioxidants is by conduct The general antioxidant of rubber-like has been used for many years, but is had certain pollution to environment due to it and easily product is changed colour, limitation Their applications in terms of light color article, high-grade product.So people now just gradually use phenolic antioxidant, particularly by Hinder phenols.Although phenolic antioxidant belongs to green antioxidant but its antioxidant effect is more single, so when in use often to be obstructed Phenolic antioxidant is primary antioxidant, is the method that auxiliary anti-oxidant is combined from monothioester or phosphite ester kind antioxidant.But Current antioxidant is extremely unstable, is easily burnt in the case where temperature is unstable, therefore, must just develop one kind The antioxidant of flame retardant type.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type, above-mentioned prior art is solved One or more in problem.
To solve the above problems, the technical scheme is that：A kind of preparation side of the low particle diameter high-efficiency anti-oxidant of flame retardant type Method, its innovative point is：Comprise the following steps：
1) deionized water and water immiscibility were communicated into high speed shear and water-based emulsion is made, wherein water immiscibility is mutually comprising master Antioxidant, auxiliary anti-oxidant and emulsifying agent；
2) thickener, antifreezing agent, defoamer, fire retardant, fire retarding synergist and toughener are added in water-based emulsion；It is described Each raw material accounts for emulsion type low-particle-diameter high-efficiency antioxidant total mass ratio：Primary antioxidant 10~40%, auxiliary anti-oxidant 10~30%, breast Agent 4~15%, thickener 0.5~4%, antifreezing agent 1~3%, defoamer 1~8%, fire retardant 3~7%, fire retarding synergist 4 ~9%, toughener 2~8%, remaining is deionized water；
It is characterized in that step 1) in, primary antioxidant, auxiliary anti-oxidant and emulsifying agent are first heated mixing under mechanical stirring Uniformly, being heated to temperature is, after 80~160 DEG C, and deionized water is added under 1500~2000 revs/min of high speed shear and is carried out Emulsify 2h~3h.
In some embodiments, primary antioxidant is paracresol and dicyclopentadiene butylation product.
In some embodiments, auxiliary anti-oxidant is trisnonyl phenyl phosphite, double 13 esters or thio of thio-2 acid In dipropionic acid dilauryl at least any one.
In some embodiments, emulsifying agent is AEO, APES, aliphatic acid polyoxy In vinyl acetate or aliphatic alcohol polyoxyvinethene phosphate at least any one.
In some embodiments, thickener be carboxymethyl cellulose, sodium carboxymethylcellulose or xanthans at least Any one.
In some embodiments, antifreezing agent is at least any one in ethylene glycol, propane diols, glycerine or ammonium sulfate Kind.
In some embodiments, defoamer is organic silicon defoamer.
In some embodiments, fire retardant is bromide fire retardant, and the bromide fire retardant is brominated triazine, decabrominated dipheny At least one of ethane, tetrabromobisphenol A and low molecule brominated epoxy.
In some embodiments, fire retarding synergist is the oxide of antimony.
In some embodiments, toughener is one kind in haloflex and high glue powder.
The present invention has following good effect：Use TDE, bromination triazine, brominated epoxy, tetrabromobisphenol A etc. Environmentally friendly bromide fire retardant replaces PBBs and PBDE, very environmentally friendly.
Embodiment
A kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type, comprises the following steps：
1) deionized water and water immiscibility were communicated into high speed shear and water-based emulsion is made, wherein water immiscibility is mutually comprising master Antioxidant, auxiliary anti-oxidant and emulsifying agent；
2) thickener, antifreezing agent, defoamer, fire retardant, fire retarding synergist and toughener are added in water-based emulsion；It is described Each raw material accounts for emulsion type low-particle-diameter high-efficiency antioxidant total mass ratio：Primary antioxidant 10~40%, auxiliary anti-oxidant 10~30%, breast Agent 4~15%, thickener 0.5~4%, antifreezing agent 1~3%, defoamer 1~8%, fire retardant 3~7%, fire retarding synergist 4 ~9%, toughener 2~8%, remaining is deionized water；
It is characterized in that step 1) in, primary antioxidant, auxiliary anti-oxidant and emulsifying agent are first heated mixing under mechanical stirring Uniformly, being heated to temperature is, after 80~160 DEG C, and deionized water is added under 1500~2000 revs/min of high speed shear and is carried out Emulsify 2h~3h.
In some embodiments, primary antioxidant is paracresol and dicyclopentadiene butylation product.
In some embodiments, auxiliary anti-oxidant is trisnonyl phenyl phosphite, double 13 esters or thio of thio-2 acid In dipropionic acid dilauryl at least any one；Emulsifying agent is AEO, APES, fat In sour polyoxyethylene ester or aliphatic alcohol polyoxyvinethene phosphate at least any one；Thickener is carboxymethyl cellulose, carboxylic In sodium carboxymethylcellulose pyce or xanthans at least any one；Antifreezing agent is in ethylene glycol, propane diols, glycerine or ammonium sulfate At least any one；Defoamer is organic silicon defoamer；Fire retardant is bromide fire retardant, and the bromide fire retardant is bromo three At least one of piperazine, TDE, tetrabromobisphenol A and low molecule brominated epoxy；Fire retarding synergist is the oxide of antimony； Toughener is one kind in haloflex and high glue powder.
The present invention has following good effect：Use TDE, bromination triazine, brominated epoxy, tetrabromobisphenol A etc. Environmentally friendly bromide fire retardant replaces PBBs and PBDE, very environmentally friendly.
Described above is only the preferred embodiment of the present invention, it is noted that to those skilled in the art, not On the premise of departing from the invention design, some similar modification and improvement can also be made, these also should be regarded as the present invention Protection domain within.

Claims (10)

1. a kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type, it is characterised in that：Comprise the following steps：
1) deionized water and water immiscibility were communicated into high speed shear and water-based emulsion is made, wherein water immiscibility mutually includes main antioxygen Agent, auxiliary anti-oxidant and emulsifying agent；
2) thickener, antifreezing agent, defoamer, fire retardant, fire retarding synergist and toughener are added in the water-based emulsion；It is described Each raw material accounts for emulsion type low-particle-diameter high-efficiency antioxidant total mass ratio：Primary antioxidant 10~40%, auxiliary anti-oxidant 10~30%, breast Agent 4~15%, thickener 0.5~4%, antifreezing agent 1~3%, defoamer 1~8%, fire retardant 3~7%, fire retarding synergist 4 ~9%, toughener 2~8%, remaining is deionized water；
It is characterized in that the step 1) in, primary antioxidant, auxiliary anti-oxidant and emulsifying agent are first heated mixing under mechanical stirring Uniformly, being heated to temperature is, after 80~160 DEG C, and deionized water is added under 1500~2000 revs/min of high speed shear and is carried out Emulsify 2h~3h.
2. a kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type according to claim 1, it is characterised in that：It is described Primary antioxidant is paracresol and dicyclopentadiene butylation product.
3. a kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type according to claim 1, it is characterised in that：It is described Auxiliary anti-oxidant is at least any in trisnonyl phenyl phosphite, double 13 esters of thio-2 acid or dilauryl thiodipropionate It is a kind of.
4. a kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type according to claim 1, it is characterised in that：It is described Emulsifying agent is AEO, APES, polyoxyethylene carboxylate or AEO In phosphate at least any one.
5. a kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type according to claim 1, it is characterised in that：It is described Thickener be carboxymethyl cellulose, sodium carboxymethylcellulose or xanthans at least any one.
6. a kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type according to claim 1, it is characterised in that：It is described Antifreezing agent be ethylene glycol, propane diols, glycerine or ammonium sulfate at least any one.
7. a kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type according to claim 1, it is characterised in that：It is described Defoamer is organic silicon defoamer.
8. a kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type according to claim 1, it is characterised in that：It is described Fire retardant is bromide fire retardant, and the bromide fire retardant is brominated triazine, TDE, tetrabromobisphenol A and low molecule bromine Change at least one of epoxy.
9. a kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type according to claim 1, it is characterised in that：It is described Fire retarding synergist is the oxide of antimony.
10. a kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type according to claim 1, it is characterised in that：Institute It is one kind in haloflex and high glue powder to state toughener.
CN201710287837.2A 2017-04-27 2017-04-27 A kind of preparation method of the low particle diameter high-efficiency anti-oxidant of flame retardant type Pending CN107033419A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4341677A (en) * 1980-04-03 1982-07-27 Ppg Industries, Inc. Antioxidants and reinforced polymers and oil-in-water emulsions of antioxidants
US5196142A (en) * 1989-03-17 1993-03-23 Ciba-Geigy Corporation Aqueous antioxidant emulsions
WO2001023498A1 (en) * 1999-09-28 2001-04-05 Basf Aktiengesellschaft Method for the continuous production of stabilizer dispersions
JP2004224978A (en) * 2003-01-24 2004-08-12 Nippon A & L Kk Emulsion liquid of phenolic stabilizer and use thereof
CN101805458A (en) * 2010-04-07 2010-08-18 天津力生化工有限公司 Method for preparing emulsion composite antioxidant
CN102181072A (en) * 2011-02-24 2011-09-14 常州大学 Preparation method of emulsion antioxidant
CN102344581A (en) * 2011-06-14 2012-02-08 江苏飞亚化学工业有限责任公司 Preparation method of emulsion type low-particle-diameter high-efficiency antioxidant
CN102702995A (en) * 2012-05-28 2012-10-03 常州大学 Preparation method of aqueous emulsion type neoprene antioxidant system product

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4341677A (en) * 1980-04-03 1982-07-27 Ppg Industries, Inc. Antioxidants and reinforced polymers and oil-in-water emulsions of antioxidants
US5196142A (en) * 1989-03-17 1993-03-23 Ciba-Geigy Corporation Aqueous antioxidant emulsions
WO2001023498A1 (en) * 1999-09-28 2001-04-05 Basf Aktiengesellschaft Method for the continuous production of stabilizer dispersions
JP2004224978A (en) * 2003-01-24 2004-08-12 Nippon A & L Kk Emulsion liquid of phenolic stabilizer and use thereof
CN101805458A (en) * 2010-04-07 2010-08-18 天津力生化工有限公司 Method for preparing emulsion composite antioxidant
CN102181072A (en) * 2011-02-24 2011-09-14 常州大学 Preparation method of emulsion antioxidant
CN102344581A (en) * 2011-06-14 2012-02-08 江苏飞亚化学工业有限责任公司 Preparation method of emulsion type low-particle-diameter high-efficiency antioxidant
CN102702995A (en) * 2012-05-28 2012-10-03 常州大学 Preparation method of aqueous emulsion type neoprene antioxidant system product

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
包静严，齐泮仑，衣学飞等: "乳液型ABS抗氧剂的研制", 《塑料助剂》 *
吴文剑，王忠冬，吴开赟: "抗氧剂KY-616对顺丁橡胶的抗热氧老化作用及其与硫酯的协同抗氧化性能", 《合成材料老化与应用》 *

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Application publication date: 20170811