CN106317463A - Citric acid plasticizer with flame retardance - Google Patents

Citric acid plasticizer with flame retardance Download PDF

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Publication number
CN106317463A
CN106317463A CN201610706480.2A CN201610706480A CN106317463A CN 106317463 A CN106317463 A CN 106317463A CN 201610706480 A CN201610706480 A CN 201610706480A CN 106317463 A CN106317463 A CN 106317463A
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China
Prior art keywords
acid
citric acid
plasticizer
source
glycerol
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Pending
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CN201610706480.2A
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Chinese (zh)
Inventor
倪玉英
包黎霞
倪念英
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Chengdu Miterui New Material Technology Co ltd
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Chengdu Miterui New Material Technology Co ltd
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Priority to CN201610706480.2A priority Critical patent/CN106317463A/en
Publication of CN106317463A publication Critical patent/CN106317463A/en
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • 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
    • C08K3/38—Boron-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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C08K5/34928—Salts
    • 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
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • 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
    • C08L27/00—Compositions 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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

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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)

Abstract

The invention discloses a flame-retardant citric acid plasticizer, which comprises a sodium hydroxide solution, glycerol, an acid source, toluene, a smoke suppression source, zinc borate, citric acid and a catalyst, wherein the weight part ratio of the acid source to the glycerol to the smoke suppression source to the zinc borate is (3-5): 1-6: 0.4-3: 0.3-1, wherein the molar part ratio of glycerol to toluene is 1: 8-12, and the mass part ratio of citric acid to glycerol is 1: 1-2. Wherein the acid source is one or more of ammonium polyphosphate, melamine phosphate and melamine polyphosphate; the smoke suppression source is one or more of magnesium hydroxide, aluminum hydroxide and zinc borate. Compared with the traditional citrate plasticizer, the invention solves the problem of easy precipitation on the premise of meeting the requirements of environmental protection and no toxicity, has flame retardance and expands the application range of the products.

Description

A kind of citric acid plasticizer with anti-flammability
Technical field
The present invention relates to a kind of plasticizer, be specifically related to a kind of citric acid plasticizer.
Background technology
Along with developing rapidly of Plastics Industry and textile and dyeing industry, the consumption of plasticizer dramatically increases.And present market Upper more common plasticizer is phthalate, and people were to healthy concern with to tradition phthalate in recent years Carrying out of plasticizer research, finds that air, water and soil earth or even food can be polluted by phthalic ester plasticizer, and Degradation speed is extremely slow in the environment, thus becomes the global environmental contaminants received much concern.It addition, in daily life people with The directly contact of plastic, phthalic ester plasticizer can enter human body by all means and cause in various degree Harm.
Citric acid ester plasticizer non-toxic and safe, is one of the first-selected environment-friendlyplasticizer plasticizer of domestic and international plastic industry, mainly Kind includes triethyl citrate (TEC), acetyl triethyl citrate (ATEC), tri-n-butyl citrate (TBC), acetyl Fructus Citri Limoniae Acid tri-n-butyl (ATBC), trioctyl lemon acid (TOC), ATOC (ATOC), citric acid tri-n-hexyl ester (THC), ATHC (ATHC), butyryl citric acid tri-n-hexyl ester etc..PVC is had excellent by citric acid ester plasticizer Good plasticization, its plasticization effect is suitable with DOP, DINP, can partly substitute DOP.But, the Fructus Citri Limoniae the most developed Esters of gallic acid (predominantly citric acid low-carbon alcohols esters, low-carbon alcohols system carbon number is straight chain and the branched-chain alcoho of 1～4) plasticizer exists The shortcoming that plasticizer is weak to migrate, volatility is high and Financial cost is high, it is impossible to be entirely applied to plasticizer industry.
Flame-retardant plasticizer is widely used in producing plastics and rubber industry, such as polrvinyl chloride revetment paper, conveyer belt, electric wire Deng, it is one of its primary raw material, current most domestic uses tricresyl phosphate as flame-retardant plasticizer, and not only cost is high, Primary plasticizer can't be replaced to use, affect range of application.
Summary of the invention
The technical problem to be solved is that citric acid ester plasticizer is weak to migrate and flame-retardant plasticizer application Scope is little, it is therefore intended that provide a kind of citric acid plasticizer with anti-flammability, introduces ether-ether key and solves citric acid ester type plasticising Agent is weak to migrate, and is simultaneously introduced fire retardant matter, improves the anti-flammability of plasticizer.
The present invention is achieved through the following technical solutions:
A kind of citric acid plasticizer with anti-flammability, including sodium hydroxide solution, glycerol, acid source, toluene, presses down Yan Yuan, boron Acid zinc, citric acid, catalyst, described acid source, glycerol, press down Yan Yuan, the ratio of weight and number of Firebrake ZB is 3 ~ 5:1 ~ 6:0.4 ~ 3: 0.3 ~ 1, and, the molfraction of glycerol and toluene than for 1:8 ~ 12, the mass fraction of citric acid and glycerol than for 1:1 ~ 2.Described acid source is one or more in APP, melamine phosphate, melamine polyphosphate；Described press down Yan Yuan For one or more in magnesium hydroxide, aluminium hydroxide, Firebrake ZB.
Further, a kind of citric acid plasticizer with anti-flammability, described acid source is melamine polyphosphate.
Further, a kind of citric acid plasticizer with anti-flammability, described in press down cigarette source be magnesium hydroxide.
Further, acid source, also known as dehydrant or carbonization accelerator, carbon source is also carbon forming agent, and it is to form foam carbonization The basis of layer, source of the gas is also named foaming source, is nitrogen-containing compound.Acid source decomposes generation dehydrant when heated, and it can be with carbon source shape Becoming ester, ester then dehydrated crosslinking forms charcoal, and the substantial amounts of non-flammable gases of source of the gas release simultaneously makes layer of charcoal expand.Thick layer of charcoal improves Polymer surfaces and the thermograde on layer of charcoal surface, make polymer surfaces temperature much lower compared with flame temperature, decrease polymerization Thing is degraded further and is discharged the probability of imflammable gas, has completely cut off the entrance of extraneous oxygen simultaneously, thus in considerable time In polymer can be played fire retardation.The generation of smog when smoke suppressant can not only reduce burning, it is also possible to in fire retardant Other components produce synergism, make flame retardant effect more preferable.
Further, in the present invention, carbon source is glycerol.
Wherein, APP, phosphorus content is up to 30%～32%, and nitrogenous is 14%～16%, raw smoke pole during burning Low, do not produce hydrogen halides.
Melamine phosphate, is a kind of environment-friendly type non-bittern combustion inhibitor, has the highest heat stability.
Melamine polyphosphate, not only can do acid source but also can do source of the gas, and performance is better than APP.
Tripolycyanamide is all that nitrogen content is the highest with dicyandiamide, can decompose generation nitrogen, can decompose when being heated during burning Produce a large amount of nitrogen and carbon dioxide.
All can discharge when magnesium hydroxide and aluminium hydroxide are heated and combine water, catabolic process can absorb substantial amounts of heat, point Solve the magnesium oxide generated and aluminium oxide is all good refractory material, the smog when steam that they release simultaneously can reduce burning Generation.
Firebrake ZB: Heat stability is good, toxicity is low, has the strongest smoke elimination effect, compounds respond well with other fire retardant, Smoke density during material combustion can be significantly reduced after interpolation.
A kind of citric acid plasticizer with anti-flammability, described catalyst is concentrated sulphuric acid, heteropoly acid, toluenesulfonic acid, strong acid One in type ion exchange resin.
Further, a kind of citric acid plasticizer with anti-flammability, described catalyst is strong acid ion exchange resin.
Wherein, concentrated sulphuric acid, it is commonly called as bad water, is a kind of highly corrosive strong mineral acid.Concentrated sulphuric acid has when concentration height Having strong oxidizing property, this is one of its difference maximum with common sulphuric acid or common concentrated sulphuric acid.It also has dehydration property, strong oxygen simultaneously The property changed, severe corrosive, difficult volatility, acid, water absorption etc..
Strongly acidic cation-exchange, mainly contains highly acid reactive group such as sulfonic group, and this ion exchange resin can To exchange all of cation.Using storng-acid cation exchange resin to make the catalyst of epoxidation reaction, product colour is shallow Much, and will not etching apparatus.
Further, glycerol has three oh groups, and glycerol is without the sweet clear and bright thick liquid of color and taste.Odorless.Have warm Sweet taste.National standard is referred to as glycerol, can absorb moisture, also can absorb hydrogen sulfide, Blausure (German) and sulfur dioxide from air.
Further, glycerol contains multiple hydroxyl, and cheap, it is possible to decomposes the acid reaction obtained with acid source and generates Ester, and the easy dehydrated crosslinking of ester generated becomes charcoal, thus flame retardant effect is preferable.
Toluene, achromaticity and clarification liquid.There is strong refractivity, can be with ethanol, ether, acetone, chloroform, Carbon bisulfide and ice second Acid is miscible, atomic is dissolved in water.
A kind of citric acid plasticizer with anti-flammability, sodium hydroxide solution, glycerol and acid source are joined containing In the stirred reactor of solvent toluene.Temperature of reactor is maintained at 100 ~ 120 DEG C, to remove water byproduct, generates the mixing of alcohol Thing；Being added by gained mixture in high-speed mixer, high-speed stirred, after 15 ~ 30 minutes, adds and presses down cigarette source and Firebrake ZB, and Its input air flow reducing mechanism will be pulverized, until product cut size D50 ＜ 5 microns, D97 ＜ 10 microns；There iing temperature control oil Bath, agitator, water knockout drum, reflux condenser four-hole bottle in add in citric acid, gained mixture and carry out being heated to 210 ~ 260 DEG C, stirring, after citric acid dissolves completely and mixs homogeneously with mixture, add catalyst, be heated to 200 ~ 230 DEG C；100 ~ 150 DEG C carry out acylation reaction, and obtained mixture obtains anti-flammability citric acid plasticizer after treatment；
Citric acid ester plasticizer is weak to migration, volatility height, and research shows, the plasticizer of molecular weight is in polymer collective In be easy to migrate.Its resistance to migration can be improved by improving the molecular weight of plasticizer.It addition, by containing ester The plasticizer of base introduces ehter bond, the compatibility and the pliability of resin can be improved, thus reach to improve the purpose that resin is flexible, Research shows, Etheric ester type plasticizer has good heat stability and low volatility.
Further, the hydroxyl of polyol is converted into the most preferably mechanism of side chain ether is known Williamson ether synthesis mechanism, it includes being reacted by hydroxyl and active metal or metal hydride or metal hydroxides Forming alkoxide, then alkoxide generates side chain ether with alkyl halide or alkylsurfuric acid reactant salt.
Further, for the polyol containing n hydroxyl of every mole, it is necessary to use the carboxylic acid less than n mole. Use n mole or each available hydroxyl of polyol may be caused all to be converted into side chain ester more than the carboxylic acid of n mole Base, leaves available oh group to follow-up Williamson etherificate synthetic reaction.Although for every mole containing n hydroxyl The polyol of base, the use carboxylic acid less than n mole, but in the reaction, the polyol molecule of relatively small fraction Hydroxyl can be completely converted into side-chain ester group, or do not have any one hydroxyl to be converted into side-chain ester group, but anti-at intermediate In should expecting, most polyol molecule will partial esterification, at least one hydroxyl remaining.Containing partial esterification chemical combination The intermediate reaction product of thing can carry out Williamson synthetic reaction and generate final product.
The present invention compared with prior art, has such advantages as and beneficial effect:
1, a kind of citric acid plasticizer with anti-flammability of the present invention, compared with tradition citric acid ester plasticizer, is meeting ring Protect nontoxic on the premise of, solve and easily separate out and migrate big problem；
2, a kind of citric acid plasticizer with anti-flammability of the present invention, has anti-flammability, expands the range of application of this series products.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with embodiment, the present invention is made Further describing in detail, the exemplary embodiment of the present invention and explanation thereof are only used for explaining the present invention, are not intended as this The restriction of invention.
Embodiment
A kind of citric acid plasticizer with anti-flammability of the present invention, melamine polyphosphate, glycerol, magnesium hydroxide, The ratio of weight and number of Firebrake ZB is 4:5:2.8:0.8, and, the molfraction of glycerol and toluene ratio for 1:11, citric acid with The mass fraction of glycerol than for 1:1.8,
(1) sodium hydroxide solution, glycerol and melamine polyphosphate are proportionally added into stirring containing solvent toluene Mix in reactor.Temperature of reactor is maintained at 100 ~ 120 DEG C, to remove water byproduct, generates the mixture of alcohol；
(2) adding in high-speed mixer by step (1) gained mixture, high-speed stirred, after 15 ~ 30 minutes, adds magnesium hydroxide And Firebrake ZB, and will its input air flow reducing mechanism be pulverized, until product cut size D50 ＜ 5 microns, D97 ＜ 10 microns are i.e. Can；
(3) in the four-hole bottle having temperature-regulated oil bath, agitator, water knockout drum, reflux condenser, institute in citric acid, step (2) is added Obtain mixture and carry out being heated to 210 ~ 260 DEG C, stirring, after citric acid dissolves completely and mixs homogeneously with mixture, add by force Acid-type ion-exchange resin, is heated to 200 ~ 230 DEG C；
(4) carrying out acylation reaction at 100 ~ 150 DEG C, obtained mixture distill through decompression, neutralize, washes, dehydrate, take off Anti-flammability citric acid plasticizer is obtained after chromogenic filter；
Above-described detailed description of the invention, has been carried out the purpose of the present invention, technical scheme and beneficial effect the most in detail Illustrate, be it should be understood that the detailed description of the invention that the foregoing is only the present invention, the guarantor being not intended to limit the present invention Protect scope, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done, should be included in this Within the protection domain of invention.

Claims (5)

1. a citric acid plasticizer with anti-flammability, it is characterised in that include sodium hydroxide solution, glycerol, acid source, first Benzene, press down Yan Yuan, Firebrake ZB, citric acid, catalyst, described acid source, glycerol, press down Yan Yuan, the ratio of weight and number of Firebrake ZB be 3 ~ 5:1 ~ 6:0.4 ~ 3:0.3 ~ 1, and, the molfraction of glycerol and toluene ratio for 1:8 ~ 12, the quality of citric acid and glycerol Portion rate is 1:1 ~ 2；
Described acid source is one or more in APP, melamine phosphate, melamine polyphosphate；
The described cigarette source that presses down is one or more in magnesium hydroxide, aluminium hydroxide, Firebrake ZB.
A kind of citric acid plasticizer with anti-flammability the most according to claim 1, it is characterised in that described acid source is three Poly cyanamid Quadrafos.
A kind of citric acid plasticizer with anti-flammability the most according to claim 1, it is characterised in that described in press down cigarette source and be Magnesium hydroxide.
A kind of citric acid plasticizer with anti-flammability the most according to claim 1, it is characterised in that described catalyst is One in concentrated sulphuric acid, heteropoly acid, toluenesulfonic acid, strong acid ion exchange resin.
A kind of citric acid plasticizer with anti-flammability the most according to claim 4, it is characterised in that described catalyst is Strong acid ion exchange resin.
CN201610706480.2A 2016-08-23 2016-08-23 Citric acid plasticizer with flame retardance Pending CN106317463A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574750A (en) * 2020-06-05 2020-08-25 淮南安信泰科技有限公司 Citric acid mixed fat plasticizer and preparation method thereof

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CN105820375A (en) * 2016-05-23 2016-08-03 徐州猎奇商贸有限公司 Composite flame retardant

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574750A (en) * 2020-06-05 2020-08-25 淮南安信泰科技有限公司 Citric acid mixed fat plasticizer and preparation method thereof

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