CN107383826A - A kind of preparation method of nano-calcium carbonate doped calcium light composite material - Google Patents

A kind of preparation method of nano-calcium carbonate doped calcium light composite material Download PDF

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Publication number
CN107383826A
CN107383826A CN201710600146.3A CN201710600146A CN107383826A CN 107383826 A CN107383826 A CN 107383826A CN 201710600146 A CN201710600146 A CN 201710600146A CN 107383826 A CN107383826 A CN 107383826A
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stirred
calcium carbonate
calcium
insulated
added
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张娟
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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
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C08G64/0225—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen
    • C08G64/0241—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a kind of preparation method of nano-calcium carbonate doped calcium light composite material, the present invention is by the tosca of surface organic processing to ammonification polycarbonate surface, the toughness and impact strength of finished-product material can be improved, the composite of the present invention is light, processing is readily transported, production cost can be effectively reduced.

Description

A kind of preparation method of nano-calcium carbonate doped calcium light composite material
Technical field
The invention belongs to Material Field, and in particular to a kind of preparation method of nano-calcium carbonate doped calcium light composite material.
Background technology
Phosphorus flame retardant has less toxic, low cigarette, pollutes small, advantages of environment protection in combustion, efficiently against The shortcomings that halogen containing flame-retardant, therefore phosphonium flame retardant is widely used in the fire-retardant of polymer, wherein, phosphate ester flame retardants are made It is widely studied for organic phosphorus flame retardant, the phosphate flame retardants of some liquid is because its raw material sources is extensive, cheap, Realize industrialization and marketization application.But there is big, poor compatibility of poor heat resistance, volatility etc. in the phosphate flame retardant of liquid Problem, therefore, the solid phosphate ester flame retardant for developing high phosphorus content and HMW are the inexorable trends of phosphorus flame retardant development；
Makrolon has good shock resistance, resisting heat distortion performance, and good weatherability, hardness are high, therefore suitable for production The various parts of car and light truck, it is concentrated mainly on illuminator, instrument board, heating plate, frost removal and poly- carbonic acid Bumper of ester alloy etc..According to developed country's data, makrolon use ratio in electric, auto manufacturing exists 40%- 50%, use ratio of the current China in the field only account for 10% or so, and electric and auto manufacturing is Chinese rapid The pillar industry of development, these following fields will be huge to the demand of poly- carbonic acid vinegar；
Makrolon is the high molecular polymer containing carbonate group in a kind of strand, is a kind of tough thermoplastic resin, The polytypes such as aliphatic, aromatic series, aliphatic-aromatic can be divided into according to the structure of ester group.Makrolon has HI high impact The advantages that intensity, use temperature range are wide, fatigue durability is good, tasteless odorless, is widely used in glazing, auto industry It is industrial with electronic apparatus.But aliphatic and the mechanical performance of aliphatic-aromatic makrolon are relatively low, it usually needs right Polycarbonate article carries out special processing, which has limited its application in terms of engineering plastics, improves the hardness of makrolon, It is set to have widely application to be particularly important；
But makrolon is there is also some defects, as processing characteristics is poor, poor flame retardant properties etc., these shortcomings all urgently improve；
Application number 201410678882.7, discloses a kind of toughened polycarbonate alloy and preparation method thereof, and its component presses quality Percentage matches：PC 40%- 60%, PBT 20%- 40%, compatilizer 1%- 4%, triphenyl phosphite 0.1%- 1.5%, Filler 5%- 15%, coupling agent 0.1%- 0.5%, impact modifier 5%- 10%, antioxidant 0.1%- 0.5%, lubricant 0.1%- 1%th, fire retardant 3%- 8%, powdered whiting particle is contained in the filler, it is by filler, polycarbonate-copolymerized extrusion, shape Into composite, the compatibility of filler and makrolon in the composite is poor, and the stability of finished product is poor.
The content of the invention
In view of the defects and deficiencies of the prior art, the present invention intends to provide a kind of nano-calcium carbonate doped calcium lightweight is answered The preparation method of condensation material.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of nano-calcium carbonate doped calcium light composite material, comprises the following steps：
（1）2,6 xylenols, anhydrous Aluminum chloride mixing are taken, is stirred, rise temperature is 100-105 DEG C, adds POCl3, Insulated and stirred 200-320 minutes, it is 47-50 DEG C to reduce temperature, adds 3-4 times of compound weight, 76-80% ethanol solution In, insulated and stirred 1-2 hours, temperature is reduced to normal temperature, 10-15mol/l phosphoric acid solution is added dropwise, is stirred after being added dropwise equal It is even, filtering, precipitation is washed, air drying, obtains carboxyphosphonic acids ester；
（2）Above-mentioned carboxyphosphonic acids ester is taken, is added in the absolute ethyl alcohol of 13-20 times of its weight, stirs, adds 3- aminopropans Ethyl triethoxy silicane alkane, the insulated and stirred 16-20 hours at 50-55 DEG C, ethanol is distilled off, air drying, obtains ammonification phosphoric acid Ester；
（3）Carbonic ester, above-mentioned ammonification phosphate, dry toluene, stannous octoate are mixed, stirred, is put into dry gather Close in pipe, be passed through argon gas, tube sealing under vacuum, be placed in insulation reaction 20-25 hours in 120-130 DEG C of oil bath, product is cooled down, It is added in chloroform, stirs, sequentially add ice methanol, ice n-hexane, stands, vacuum at 40-45 DEG C will be deposited in Dry 2-3 days, obtain ammonification makrolon；
（4）It is 1-2 to take mol ratio:1-2 calcium carbonate, calcium oxide mixing, it is added to the deionized water of 40-50 times of compound weight In, stir, add stearic acid, rise temperature is 80-90 DEG C, and insulated and stirred to water is done, and cooling, obtains stearic acid modified carbonic acid Calcium；
（5）Above-mentioned ammonification makrolon is taken, is mixed with stearic acid modified calcium carbonate, is added to the anhydrous of 3-4 times of compound weight Ethanol, rise temperature are 50-60 DEG C, insulated and stirred 1-2 hours, filtering, precipitation are washed, 2-3 is dried at 90-100 DEG C of vacuum Hour, cooling, produce the nano-calcium carbonate doped calcium light composite material；
Described 2,6 xylenols, anhydrous Aluminum chloride, POCl3,10-15mol/l phosphoric acid solution, the ethoxy of 3- aminopropyls three Base silane, carbonic ester, dry toluene, stannous octoate, chloroform, ice methanol, ice n-hexane, calcium carbonate, stearic weight Than for 4-5：3-4：3-5：20-30：2-3：110-130：50-60:4-5:20-30:30-40:10-16：10-16:2-3.
Advantages of the present invention：
For the present invention with 2,6 xylenols, POCl3 for raw material, anhydrous Aluminum chloride is catalyst, by phosphatizing treatment, obtains carboxylic Base phosphate, then itself and APTES are reacted, obtain phosphoramidate, be then blended with carbonic ester Polymerization, obtains ammonification makrolon, and then itself and resin acid modified calcium carbonate is blended, obtains nano-calcium carbonate doped calcium lightweight composite wood Material；
The present invention is by the tosca of surface organic processing to ammonification polycarbonate surface, it is possible to increase finished-product material it is tough Property and impact strength, composite of the invention are light, are readily transported processing, can effectively reduce production cost.
Embodiment
Embodiment 1
A kind of preparation method of nano-calcium carbonate doped calcium light composite material, comprises the following steps：
（1）2,6 xylenols, anhydrous Aluminum chloride mixing are taken, is stirred, rise temperature is 105 DEG C, adds POCl3, insulation Stirring 320 minutes, it is 50 DEG C to reduce temperature, is added in 3 times of compound weight, 80% ethanol solution, insulated and stirred 2 hours, Temperature is reduced to normal temperature, 10mol/l phosphoric acid solution is added dropwise, is stirred after being added dropwise, filters, precipitation is washed, normal temperature Dry, obtain carboxyphosphonic acids ester；
（2）Above-mentioned carboxyphosphonic acids ester is taken, is added in the absolute ethyl alcohol of 13 times of its weight, stirs, adds 3- aminopropyls Triethoxysilane, insulated and stirred 16 hours at 50 DEG C, ethanol is distilled off, air drying, obtains ammonification phosphate；
（3）Carbonic ester, above-mentioned ammonification phosphate, dry toluene, stannous octoate are mixed, stirred, is put into dry gather Close in pipe, be passed through argon gas, tube sealing under vacuum, be placed in insulation reaction 20 hours in 120 DEG C of oil bath, product is cooled down, is added to In chloroform, stir, sequentially add ice methanol, ice n-hexane, stand, will be deposited at 40 DEG C and be dried in vacuo 2 days, obtain Ammonification makrolon；
（4）It is 1 to take mol ratio:1 calcium carbonate, calcium oxide mixing, are added in the deionized water of 50 times of compound weight, stir Uniformly, stearic acid is added, rise temperature is 80 DEG C, and insulated and stirred to water is done, and cooling, obtains stearic acid modified calcium carbonate；
（5）Above-mentioned ammonification makrolon is taken, is mixed with stearic acid modified calcium carbonate, is added to the anhydrous second of 3 times of compound weight Alcohol, rise temperature are 50 DEG C, insulated and stirred 1 hour, filtering, precipitation are washed, dried 2 hours at 90 DEG C of vacuum, cooling, produced The nano-calcium carbonate doped calcium light composite material；
Described 2,6 xylenols, anhydrous Aluminum chloride, POCl3,10mol/l phosphoric acid solution, 3- aminopropyl triethoxies Silane, carbonic ester, dry toluene, stannous octoate, chloroform, ice methanol, ice n-hexane, calcium carbonate, stearic weight ratio For 4：3：3：20：2：110：50:4:20:30:10：10:2.

Claims (1)

1. a kind of preparation method of nano-calcium carbonate doped calcium light composite material, it is characterised in that comprise the following steps：
（1）2,6 xylenols, anhydrous Aluminum chloride mixing are taken, is stirred, rise temperature is 100-105 DEG C, adds POCl3, Insulated and stirred 200-320 minutes, it is 47-50 DEG C to reduce temperature, adds 3-4 times of compound weight, 76-80% ethanol solution In, insulated and stirred 1-2 hours, temperature is reduced to normal temperature, 10-15mol/l phosphoric acid solution is added dropwise, is stirred after being added dropwise equal It is even, filtering, precipitation is washed, air drying, obtains carboxyphosphonic acids ester；
（2）Above-mentioned carboxyphosphonic acids ester is taken, is added in the absolute ethyl alcohol of 13-20 times of its weight, stirs, adds 3- aminopropans Ethyl triethoxy silicane alkane, the insulated and stirred 16-20 hours at 50-55 DEG C, ethanol is distilled off, air drying, obtains ammonification phosphoric acid Ester；
（3）Carbonic ester, above-mentioned ammonification phosphate, dry toluene, stannous octoate are mixed, stirred, is put into dry gather Close in pipe, be passed through argon gas, tube sealing under vacuum, be placed in insulation reaction 20-25 hours in 120-130 DEG C of oil bath, product is cooled down, It is added in chloroform, stirs, sequentially add ice methanol, ice n-hexane, stands, vacuum at 40-45 DEG C will be deposited in Dry 2-3 days, obtain ammonification makrolon；
（4）It is 1-2 to take mol ratio:1-2 calcium carbonate, calcium oxide mixing, it is added to the deionized water of 40-50 times of compound weight In, stir, add stearic acid, rise temperature is 80-90 DEG C, and insulated and stirred to water is done, and cooling, obtains stearic acid modified carbonic acid Calcium；
（5）Above-mentioned ammonification makrolon is taken, is mixed with stearic acid modified calcium carbonate, is added to the anhydrous of 3-4 times of compound weight Ethanol, rise temperature are 50-60 DEG C, insulated and stirred 1-2 hours, filtering, precipitation are washed, 2-3 is dried at 90-100 DEG C of vacuum Hour, cooling, produce the nano-calcium carbonate doped calcium light composite material；
Described 2,6 xylenols, anhydrous Aluminum chloride, POCl3,10-15mol/l phosphoric acid solution, the ethoxy of 3- aminopropyls three Base silane, carbonic ester, dry toluene, stannous octoate, chloroform, ice methanol, ice n-hexane, calcium carbonate, stearic weight Than for 4-5：3-4：3-5：20-30：2-3：110-130：50-60:4-5:20-30:30-40:10-16：10-16:2-3.
CN201710600146.3A 2017-07-21 2017-07-21 A kind of preparation method of nano-calcium carbonate doped calcium light composite material Pending CN107383826A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108671895A (en) * 2018-05-14 2018-10-19 集美大学 A kind of more gaps absorption organic volatile nano calcium carbonate composite material and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101469123A (en) * 2007-12-25 2009-07-01 比亚迪股份有限公司 Plastic alloy and preparation thereof
CN102898802A (en) * 2012-09-21 2013-01-30 常熟市凯力达蜂窝包装材料有限公司 Polycarbonate alloy material filled with flame-retardant silicate minerals
CN103540113A (en) * 2012-07-16 2014-01-29 东北林业大学 Method for improving mechanical properties of polypropylene carbonate (PPC) through calcium carbonate filled modification

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101469123A (en) * 2007-12-25 2009-07-01 比亚迪股份有限公司 Plastic alloy and preparation thereof
CN103540113A (en) * 2012-07-16 2014-01-29 东北林业大学 Method for improving mechanical properties of polypropylene carbonate (PPC) through calcium carbonate filled modification
CN102898802A (en) * 2012-09-21 2013-01-30 常熟市凯力达蜂窝包装材料有限公司 Polycarbonate alloy material filled with flame-retardant silicate minerals

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108671895A (en) * 2018-05-14 2018-10-19 集美大学 A kind of more gaps absorption organic volatile nano calcium carbonate composite material and preparation method thereof

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