CN108164752A - The PVC cable material fire retardant prepared based on nano combined intercalation technique - Google Patents

The PVC cable material fire retardant prepared based on nano combined intercalation technique Download PDF

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CN108164752A
CN108164752A CN201810078096.1A CN201810078096A CN108164752A CN 108164752 A CN108164752 A CN 108164752A CN 201810078096 A CN201810078096 A CN 201810078096A CN 108164752 A CN108164752 A CN 108164752A
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kaolin
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刘成旭
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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
    • 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
    • C08K3/34—Silicon-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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • 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
    • 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
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

Abstract

The invention discloses a kind of PVC cable material fire retardants prepared based on nano combined intercalation technique, are related to PVC cable material technical field, are made of the raw material of following parts by weight：25 35 parts of kaolin, 5 10 parts of zinc dimethacrylate, 15 parts of Diacetone Acrylamide, 5 10 parts of nano-silicon nitride, 15 parts of trihydroxymethylpropanyltri diglycidyl ether, 0.5 2 parts of isocyanuric acid three-glycidyl ester, 0.1 1 parts of titanate coupling agent, 0.05 0.5 parts of initiator, 50 100 parts of 95% ethyl alcohol, 50 100 parts of deionized water.The made fire retardant of the present invention belongs to low-smoke non-halogen flame-retardant agent, and flame retardant property prevents a large amount of additions of fire retardant from reducing the mechanical property of cable better than common fire retardant zinc borate, aluminium hydroxide, antimony oxide, while ensure to process the mechanical property of made cable at present.

Description

The PVC cable material fire retardant prepared based on nano combined intercalation technique
Technical field：
The present invention relates to PVC cable material technical fields, and in particular to a kind of PVC prepared based on nano combined intercalation technique Cable-material flame-retardant.
Background technology：
Wires and cables industry is the important mating industry of economic construction of China, is widely used in national economy every field, It is the second largest industry that automobile industry is only second in mechanical industry in occupation of the industry of Chinese electrician trade 1/4.PVC cable material It is the auxiliary agents such as addition inorganic filler, stabilizer, plasticizer, fire retardant, toughener, lubricant using polyvinyl chloride as basic resin, Particle is made, and then particle is processed into cable through mixture, kneading, extrusion.
Polyvinyl chloride resin can generate a large amount of smog and toxic corrosive gas when burning, smog is to cause people desperately in fire Primary risk factor, also serious delay rescue people's lives and properties opportunity.In order to reduce injury of the smog to human body, generally Fire retardant can be added in.The widely used halogen containing polymers of conventional flame retardant, once burning, raw smoke bigger, and hydrogen chloride can be generated Wait halogen gas.Therefore, other than flame retarding efficiency is high, low-smoke low-halogen is also the essential index of fire retardant.But city at present There are no a kind of cable products that can meet flame retarding efficiency height and low-smoke low-halogen requirement simultaneously on face.
Invention content：
The technical problems to be solved by the invention be to provide a kind of excellent fireproof performance and the feature of environmental protection it is strong based on nanometer PVC cable material fire retardant prepared by compound intercalation technique.
The technical problems to be solved by the invention are realized using following technical solution：
Based on PVC cable material fire retardant prepared by nano combined intercalation technique, it is made of the raw material of following parts by weight：
25-35 parts of kaolin, 5-10 parts of zinc dimethacrylate, 1-5 parts of Diacetone Acrylamide, nano-silicon nitride 5-10 Part, 1-5 parts of trihydroxymethylpropanyltri diglycidyl ether, 0.5-2 parts of isocyanuric acid three-glycidyl ester, titanate coupling agent 0.1- 1 part, 0.05-0.5 parts of initiator, 50-100 parts of 95% ethyl alcohol, 50-100 parts of deionized water.
Preparation method includes the following steps：
(1) kaolinic pretreatment：Kaolin is first heated to 150-200 DEG C of heat preservation calcining 0.5-2h, is again heated to 450-500 DEG C of heat preservation calcining 1-3h, takes out when naturally cooling to less than 70 DEG C；
(2) kaolinic intercalation polymeric：Zinc dimethacrylate, Diacetone Acrylamide are added in into 95% ethyl alcohol and is drawn Agent is sent out, and is heated to reflux state insulated and stirred 10-30min, adds kaolin after pretreatment, continues reflux heat preservation and stirs Mix 2-5h, centrifugal filtration, gained filter residue washs 2 times with absolute ethyl alcohol, most after dried in 55-60 DEG C of baking oven to constant weight to get Intercalation modifying kaolin；
(3) pretreatment of nano-silicon nitride：Nano-silicon nitride is heated to 500-550 DEG C of heat preservation and calcines 1-3h, it is naturally cold It is taken out when but to less than 100 DEG C；
(4) surface of nano-silicon nitride is modified：Nano-silicon nitride after pretreatment and trimethylolpropane tris are shunk Glycerin ether is sufficiently mixed, and is heated to 115-125 DEG C of insulated and stirred 0.5-2h with the heating rate of 5-10 DEG C/min, is added different Cyanuric acid three-glycidyl ester continues at 115-125 DEG C of insulated and stirred 0.5-2h, then cold with the cooling rate of 5-10 DEG C/min But 0.5-1h is stood to 0-5 DEG C of heat preservation, gained mixture is made micro mist through micronizer and is modified silicon nitride to get surface；
(5) preparation of fire retardant：Intercalation modifying kaolin is added in into deionized water, surface is modified silicon nitride and titanate esters Coupling agent, and reflux state insulated and stirred 0.5-2h is heated to, gained mixture is sent into spray dryer, dry gained particle Micro mist is made to get fire retardant through micronizer.
The kaolinic content of crystal is higher than 80% weight in the kaolin, and quartz is less than 0.5% weight, Fe2O3It is less than 1.0% weight, K2O and Na2The summation of O is less than 0.5% weight.
The average particle size of the nano-silicon nitride is in 25nm, and specific surface area is in 50m2/g。
The titanate coupling agent is selected from isopropyl three (isostearoyl base) titanate esters, isopropyl three (dioctylphosphoric acid ester) titanium One kind in acid esters, isopropyl three (dioctyl pyrophosphate) titanate esters.
The one kind of the initiator in azodiisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile.
The beneficial effects of the invention are as follows：The present invention is using intercalation polymeric method in the aggregated generation flame retardant type third of kaolin interlayer Olefin(e) acid resin, so as to significantly improve kaolinic flame retardant property；And surface is carried out to nano-silicon nitride using surface-modification method and is changed Property, and then enhance the flame retardant property of nano-silicon nitride；Recycle titanate coupling agent that intercalation modifying kaolin, surface are modified nitrogen SiClx fusion generation fire retardant, made fire retardant belong to low-smoke non-halogen flame-retardant agent, and flame retardant property is better than common fire retardant at present Zinc borate, aluminium hydroxide, antimony oxide, while ensure to process the mechanical property of made cable, prevent a large amount of addition drops of fire retardant The mechanical property of low cable.
Specific embodiment：
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below Specific embodiment is closed, the present invention is further explained.
Embodiment 1
(1) kaolinic pretreatment：25g kaolin is first heated to 150-200 DEG C of heat preservation calcining 2h, is again heated to 450- 500 DEG C of heat preservation calcining 2h, take out when naturally cooling to less than 70 DEG C；
(2) kaolinic intercalation polymeric：5g zinc dimethacrylates, 3g diacetones third are added in into 95% ethyl alcohol of 100g Acrylamide and 0.3g initiator azodiisobutyronitriles, and reflux state insulated and stirred 10min is heated to, it adds after pretreatment Kaolin, continue flow back insulated and stirred 2h, centrifugal filtration, gained filter residue is washed 2 times with absolute ethyl alcohol, most after 55-60 DEG C It is dried in baking oven to constant weight to get intercalation modifying kaolin；
(3) pretreatment of nano-silicon nitride：5g nano-silicon nitrides are heated to 500-550 DEG C of heat preservation and calcine 1h, it is naturally cold It is taken out when but to less than 100 DEG C；
(4) surface of nano-silicon nitride is modified：Nano-silicon nitride after pretreatment and 1g trimethylolpropane tris are contracted Water glycerin ether is sufficiently mixed, and is heated to 115-125 DEG C of insulated and stirred 0.5h with the heating rate of 5-10 DEG C/min, is added 0.5g isocyanuric acid three-glycidyl esters continue at 115-125 DEG C of insulated and stirred 1h, then with the cooling rate of 5-10 DEG C/min It is cooled to 0-5 DEG C of heat preservation and stands 0.5h, gained mixture is made micro mist through micronizer and is modified silicon nitride to get surface；
(5) preparation of fire retardant：Intercalation modifying kaolin is added in into 100g deionized waters, surface is modified silicon nitride and 0.5g titanate coupling agents isopropyl three (isostearoyl base) titanate esters, and reflux state insulated and stirred 1h is heated to, gained mixes It closes object to be sent into spray dryer, micro mist is made to get fire retardant through micronizer in dry gained particle.
Wherein, the kaolinic content of crystal is higher than 80% weight in kaolin, and quartz is less than 0.5% weight, Fe2O3It is less than 1.0% weight, K2O and Na2The summation of O is less than 0.5% weight；The average particle size of nano-silicon nitride exists in 25nm, specific surface area 50m2/g。
Embodiment 2
(1) kaolinic pretreatment：30g kaolin is first heated to 150-200 DEG C of heat preservation calcining 2h, is again heated to 450- 500 DEG C of heat preservation calcining 2h, take out when naturally cooling to less than 70 DEG C；
(2) kaolinic intercalation polymeric：8g zinc dimethacrylates, 3g diacetones third are added in into 95% ethyl alcohol of 100g Acrylamide and 0.5g initiator azodiisobutyronitriles, and reflux state insulated and stirred 15min is heated to, it adds after pretreatment Kaolin, continue flow back insulated and stirred 3h, centrifugal filtration, gained filter residue is washed 2 times with absolute ethyl alcohol, most after 55-60 DEG C It is dried in baking oven to constant weight to get intercalation modifying kaolin；
(3) pretreatment of nano-silicon nitride：10g nano-silicon nitrides are heated to 500-550 DEG C of heat preservation and calcine 2h, it is naturally cold It is taken out when but to less than 100 DEG C；
(4) surface of nano-silicon nitride is modified：Nano-silicon nitride after pretreatment and 2g trimethylolpropane tris are contracted Water glycerin ether is sufficiently mixed, and is heated to 115-125 DEG C of insulated and stirred 0.5h with the heating rate of 5-10 DEG C/min, adds 1g Isocyanuric acid three-glycidyl ester continues at 115-125 DEG C of insulated and stirred 2h, is then cooled down with the cooling rate of 5-10 DEG C/min 0.5h is stood to 0-5 DEG C of heat preservation, gained mixture is made micro mist through micronizer and is modified silicon nitride to get surface；
(5) preparation of fire retardant：Intercalation modifying kaolin is added in into 100g deionized waters, surface is modified silicon nitride and 0.5g titanate coupling agents isopropyl three (isostearoyl base) titanate esters, and reflux state insulated and stirred 1h is heated to, gained mixes It closes object to be sent into spray dryer, micro mist is made to get fire retardant through micronizer in dry gained particle.
Wherein, the kaolinic content of crystal is higher than 80% weight in kaolin, and quartz is less than 0.5% weight, Fe2O3It is less than 1.0% weight, K2O and Na2The summation of O is less than 0.5% weight；The average particle size of nano-silicon nitride exists in 25nm, specific surface area 50m2/g。
Embodiment 3
(1) kaolinic pretreatment：35g kaolin is first heated to 150-200 DEG C of heat preservation calcining 2h, is again heated to 450- 500 DEG C of heat preservation calcining 2h, take out when naturally cooling to less than 70 DEG C；
(2) kaolinic intercalation polymeric：10g zinc dimethacrylates, 3g diacetones third are added in into 95% ethyl alcohol of 100g Acrylamide and 0.5g initiator azodiisobutyronitriles, and reflux state insulated and stirred 15min is heated to, it adds after pretreatment Kaolin, continue flow back insulated and stirred 3h, centrifugal filtration, gained filter residue is washed 2 times with absolute ethyl alcohol, most after 55-60 DEG C It is dried in baking oven to constant weight to get intercalation modifying kaolin；
(3) pretreatment of nano-silicon nitride：10g nano-silicon nitrides are heated to 500-550 DEG C of heat preservation and calcine 2h, it is naturally cold It is taken out when but to less than 100 DEG C；
(4) surface of nano-silicon nitride is modified：Nano-silicon nitride after pretreatment and 2g trimethylolpropane tris are contracted Water glycerin ether is sufficiently mixed, and is heated to 115-125 DEG C of insulated and stirred 0.5h with the heating rate of 5-10 DEG C/min, adds 1g Isocyanuric acid three-glycidyl ester continues at 115-125 DEG C of insulated and stirred 2h, is then cooled down with the cooling rate of 5-10 DEG C/min 0.5h is stood to 0-5 DEG C of heat preservation, gained mixture is made micro mist through micronizer and is modified silicon nitride to get surface；
(5) preparation of fire retardant：Intercalation modifying kaolin is added in into 100g deionized waters, surface is modified silicon nitride and 0.5g titanate coupling agents isopropyl three (isostearoyl base) titanate esters, and reflux state insulated and stirred 1h is heated to, gained mixes It closes object to be sent into spray dryer, micro mist is made to get fire retardant through micronizer in dry gained particle.
Wherein, the kaolinic content of crystal is higher than 80% weight in kaolin, and quartz is less than 0.5% weight, Fe2O3It is less than 1.0% weight, K2O and Na2The summation of O is less than 0.5% weight；The average particle size of nano-silicon nitride exists in 25nm, specific surface area 50m2/g。
Reference examples 1
(1) kaolinic pretreatment：35g kaolin is first heated to 150-200 DEG C of heat preservation calcining 2h, is again heated to 450- 500 DEG C of heat preservation calcining 2h, take out when naturally cooling to less than 70 DEG C；
(2) kaolinic intercalation polymeric：10g zinc dimethacrylates, 3g diacetones third are added in into 95% ethyl alcohol of 100g Acrylamide and 0.5g initiator azodiisobutyronitriles, and reflux state insulated and stirred 15min is heated to, it adds after pretreatment Kaolin, continue flow back insulated and stirred 3h, centrifugal filtration, gained filter residue is washed 2 times with absolute ethyl alcohol, most after 55-60 DEG C It is dried in baking oven to constant weight to get intercalation modifying kaolin；
(3) pretreatment of nano-silicon nitride：10g nano-silicon nitrides are heated to 500-550 DEG C of heat preservation and calcine 2h, it is naturally cold It is taken out when but to less than 100 DEG C；
(4) surface of nano-silicon nitride is modified：Nano-silicon nitride after pretreatment and 2g trimethylolpropane tris are contracted Water glycerin ether is sufficiently mixed, and is heated to 115-125 DEG C of insulated and stirred 0.5h with the heating rate of 5-10 DEG C/min, adds 1g Isocyanuric acid three-glycidyl ester continues at 115-125 DEG C of insulated and stirred 2h, is then cooled down with the cooling rate of 5-10 DEG C/min 0.5h is stood to 0-5 DEG C of heat preservation, gained mixture is made micro mist through micronizer and is modified silicon nitride to get surface；
(5) preparation of fire retardant：Intercalation modifying kaolin, surface modification silicon nitride are added in into 100g deionized waters, and Reflux state insulated and stirred 1h is heated to, gained mixture is sent into spray dryer, and dry gained particle is through micronizer Micro mist is made to get fire retardant.
Wherein, the kaolinic content of crystal is higher than 80% weight in kaolin, and quartz is less than 0.5% weight, Fe2O3It is less than 1.0% weight, K2O and Na2The summation of O is less than 0.5% weight；The average particle size of nano-silicon nitride exists in 25nm, specific surface area 50m2/g。
Reference examples 2
(1) kaolinic pretreatment：35g kaolin is first heated to 150-200 DEG C of heat preservation calcining 2h, is again heated to 450- 500 DEG C of heat preservation calcining 2h, take out when naturally cooling to less than 70 DEG C；
(2) kaolinic intercalation polymeric：10g zinc dimethacrylates, 3g diacetones third are added in into 95% ethyl alcohol of 100g Acrylamide and 0.5g initiator azodiisobutyronitriles, and reflux state insulated and stirred 15min is heated to, it adds after pretreatment Kaolin, continue flow back insulated and stirred 3h, centrifugal filtration, gained filter residue is washed 2 times with absolute ethyl alcohol, most after 55-60 DEG C It is dried in baking oven to constant weight to get intercalation modifying kaolin；
(3) pretreatment of nano-silicon nitride：10g nano-silicon nitrides are heated to 500-550 DEG C of heat preservation and calcine 2h, it is naturally cold It is taken out when but to less than 100 DEG C；
(4) surface of nano-silicon nitride is modified：Nano-silicon nitride after pretreatment and 2g trimethylolpropane tris are contracted Water glycerin ether is sufficiently mixed, and is heated to 115-125 DEG C of insulated and stirred 2.5h with the heating rate of 5-10 DEG C/min, then with 5- The cooling rate of 10 DEG C/min be cooled to 0-5 DEG C heat preservation stand 0.5h, gained mixture through micronizer be made micro mist to get Surface is modified silicon nitride；
(5) preparation of fire retardant：Intercalation modifying kaolin is added in into 100g deionized waters, surface is modified silicon nitride and 0.5g titanate coupling agents isopropyl three (isostearoyl base) titanate esters, and reflux state insulated and stirred 1h is heated to, gained mixes It closes object to be sent into spray dryer, micro mist is made to get fire retardant through micronizer in dry gained particle.
Wherein, the kaolinic content of crystal is higher than 80% weight in kaolin, and quartz is less than 0.5% weight, Fe2O3It is less than 1.0% weight, K2O and Na2The summation of O is less than 0.5% weight；The average particle size of nano-silicon nitride exists in 25nm, specific surface area 50m2/g。
Reference examples 3
(1) kaolinic pretreatment：35g kaolin is first heated to 150-200 DEG C of heat preservation calcining 2h, is again heated to 450- 500 DEG C of heat preservation calcining 2h, take out when naturally cooling to less than 70 DEG C；
(2) kaolinic intercalation polymeric：10g zinc dimethacrylates, 3g diacetones third are added in into 95% ethyl alcohol of 100g Acrylamide and 0.5g initiator azodiisobutyronitriles, and reflux state insulated and stirred 15min is heated to, it adds after pretreatment Kaolin, continue flow back insulated and stirred 3h, centrifugal filtration, gained filter residue is washed 2 times with absolute ethyl alcohol, most after 55-60 DEG C It is dried in baking oven to constant weight to get intercalation modifying kaolin；
(3) pretreatment of nano-silicon nitride：10g nano-silicon nitrides are heated to 500-550 DEG C of heat preservation and calcine 2h, it is naturally cold It is taken out when but to less than 100 DEG C；
(4) surface of nano-silicon nitride is modified：By nano-silicon nitride after pretreatment, and with the heating of 5-10 DEG C/min Speed is heated to 115-125 DEG C of insulated and stirred 0.5h, adds 1g isocyanuric acid three-glycidyl esters, continues at 115-125 DEG C Then insulated and stirred 2h is cooled to 0-5 DEG C of heat preservation with the cooling rate of 5-10 DEG C/min and stands 0.5h, gained mixture is through ultra micro Pulverizer is made micro mist and is modified silicon nitride to get surface；
(5) preparation of fire retardant：Intercalation modifying kaolin is added in into 100g deionized waters, surface is modified silicon nitride and 0.5g titanate coupling agents isopropyl three (isostearoyl base) titanate esters, and reflux state insulated and stirred 1h is heated to, gained mixes It closes object to be sent into spray dryer, micro mist is made to get fire retardant through micronizer in dry gained particle.
Wherein, the kaolinic content of crystal is higher than 80% weight in kaolin, and quartz is less than 0.5% weight, Fe2O3It is less than 1.0% weight, K2O and Na2The summation of O is less than 0.5% weight；The average particle size of nano-silicon nitride exists in 25nm, specific surface area 50m2/g。
Reference examples 4
(1) kaolinic pretreatment：35g kaolin is first heated to 150-200 DEG C of heat preservation calcining 2h, is again heated to 450- 500 DEG C of heat preservation calcining 2h, take out when naturally cooling to less than 70 DEG C；
(2) kaolinic intercalation polymeric：10g zinc dimethacrylates, 3g diacetones third are added in into 95% ethyl alcohol of 100g Acrylamide and 0.5g initiator azodiisobutyronitriles, and reflux state insulated and stirred 15min is heated to, it adds after pretreatment Kaolin, continue flow back insulated and stirred 3h, centrifugal filtration, gained filter residue is washed 2 times with absolute ethyl alcohol, most after 55-60 DEG C It is dried in baking oven to constant weight to get intercalation modifying kaolin；
(3) pretreatment of nano-silicon nitride：10g nano-silicon nitrides are heated to 500-550 DEG C of heat preservation and calcine 2h, it is naturally cold It is taken out when but to less than 100 DEG C；
(4) preparation of fire retardant：Intercalation modifying kaolin, nanometer nitrogen after pretreatment are added in into 100g deionized waters SiClx and 0.5g titanate coupling agents isopropyl three (isostearoyl base) titanate esters, and reflux state insulated and stirred 1h is heated to, Gained mixture is sent into spray dryer, and micro mist is made to get fire retardant through micronizer in dry gained particle.
Wherein, the kaolinic content of crystal is higher than 80% weight in kaolin, and quartz is less than 0.5% weight, Fe2O3It is less than 1.0% weight, K2O and Na2The summation of O is less than 0.5% weight；The average particle size of nano-silicon nitride exists in 25nm, specific surface area 50m2/g。
Reference examples 5
(1) kaolinic pretreatment：35g kaolin is first heated to 150-200 DEG C of heat preservation calcining 2h, is again heated to 450- 500 DEG C of heat preservation calcining 2h, take out when naturally cooling to less than 70 DEG C；
(2) pretreatment of nano-silicon nitride：10g nano-silicon nitrides are heated to 500-550 DEG C of heat preservation and calcine 2h, it is naturally cold It is taken out when but to less than 100 DEG C；
(3) surface of nano-silicon nitride is modified：Nano-silicon nitride after pretreatment and 2g trimethylolpropane tris are contracted Water glycerin ether is sufficiently mixed, and is heated to 115-125 DEG C of insulated and stirred 0.5h with the heating rate of 5-10 DEG C/min, adds 1g Isocyanuric acid three-glycidyl ester continues at 115-125 DEG C of insulated and stirred 2h, is then cooled down with the cooling rate of 5-10 DEG C/min 0.5h is stood to 0-5 DEG C of heat preservation, gained mixture is made micro mist through micronizer and is modified silicon nitride to get surface；
(4) preparation of fire retardant：Kaolin after pretreatment is added in into 100g deionized waters, surface is modified silicon nitride With 0.5g titanate coupling agents isopropyl three (isostearoyl base) titanate esters, and it is heated to reflux state insulated and stirred 1h, gained Mixture is sent into spray dryer, and micro mist is made to get fire retardant through micronizer in dry gained particle.
Wherein, the kaolinic content of crystal is higher than 80% weight in kaolin, and quartz is less than 0.5% weight, Fe2O3It is less than 1.0% weight, K2O and Na2The summation of O is less than 0.5% weight；The average particle size of nano-silicon nitride exists in 25nm, specific surface area 50m2/g。
Embodiment 4
It is prepared by fire retardant：Be utilized respectively embodiment 1-3, reference examples 1-5 prepares fire retardant, and set respectively with zinc borate, The reference examples 6, reference examples 7, reference examples 8 of aluminium hydroxide, antimony oxide as fire retardant.
It is prepared by CABLE MATERIALS：According to 1 dispensing of table, it is sent into double screw extruder after all raw materials are sufficiently mixed, extruder Temperature setting for 150-160 DEG C of an area, 160-170 DEG C of 2nd area, 160-180 DEG C of 3rd area, 160-180 DEG C of 4th area, head temperature 170 DEG C, rotating speed 30r/min, be molded to obtain sheet material.
The performance of made CABLE MATERIALS is measured, measurement result is as shown in table 2.
1 cable composition of raw materials of table
Raw material Dosage/g Raw material Dosage/g
The degree of polymerization 1300~3000PVC resins 55 Chlorinated paraffin 5
Diisononyl phthalate 12 Fire retardant 5
Hollow glass micro mist 10 Barium stearate 1.5
Activated Calcium carbonate 5 Calcium zinc stabilizer 1
Epoxidized soybean oil 5 UV-531 0.5
2 cable performance measurement result of table
Group Tensile strength/MPa Elongation at break/% Oxygen index (OI)/% Smoke density (nonflame)
Embodiment 1 28 221 52 243
Embodiment 2 32 228 53 238
Embodiment 3 30 225 55 227
Reference examples 1 27 219 50 251
Reference examples 2 25 212 48 262
Reference examples 3 22 203 44 283
Reference examples 4 18 187 39 305
Reference examples 5 15 161 36 336
Reference examples 6 22 184 43 294
Reference examples 7 25 175 41 287
Reference examples 8 21 178 41 275
The basic principles, main features and the advantages of the invention have been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent thereof.

Claims (6)

1. the PVC cable material fire retardant prepared based on nano combined intercalation technique, which is characterized in that by the original of following parts by weight Material is made：
25-35 parts of kaolin, 5-10 parts of zinc dimethacrylate, 1-5 parts of Diacetone Acrylamide, 5-10 parts of nano-silicon nitride, 1-5 parts of trihydroxymethylpropanyltri diglycidyl ether, 0.5-2 parts of isocyanuric acid three-glycidyl ester, titanate coupling agent 0.1-1 Part, 0.05-0.5 parts of initiator, 50-100 parts of 95% ethyl alcohol, 50-100 parts of deionized water.
2. the PVC cable material fire retardant according to claim 1 prepared based on nano combined intercalation technique, feature are existed In preparation method includes the following steps：
(1) kaolinic pretreatment：Kaolin is first heated to 150-200 DEG C of heat preservation calcining 0.5-2h, is again heated to 450-500 DEG C heat preservation calcining 1-3h, taken out when naturally cooling to less than 70 DEG C；
(2) kaolinic intercalation polymeric：Zinc dimethacrylate, Diacetone Acrylamide and initiation are added in into 95% ethyl alcohol Agent, and reflux state insulated and stirred 10-30min is heated to, kaolin after pretreatment is added, continues the insulated and stirred that flows back 2-5h, centrifugal filtration, gained filter residue is washed 2 times with absolute ethyl alcohol, most after drying in 55-60 DEG C of baking oven to constant weight to get slotting Layer modified kaolin；
(3) pretreatment of nano-silicon nitride：Nano-silicon nitride is heated to 500-550 DEG C of heat preservation calcining 1-3h, is naturally cooled to It is taken out at less than 100 DEG C；
(4) surface of nano-silicon nitride is modified：By nano-silicon nitride after pretreatment and trimethylolpropane tris glycidol Ether is sufficiently mixed, and is heated to 115-125 DEG C of insulated and stirred 0.5-2h with the heating rate of 5-10 DEG C/min, adds isocyanide urine Sour three-glycidyl ester is continued at 115-125 DEG C of insulated and stirred 0.5-2h, is then cooled to the cooling rate of 5-10 DEG C/min 0-5 DEG C of heat preservation stands 0.5-1h, and gained mixture is made micro mist through micronizer and is modified silicon nitride to get surface；
(5) preparation of fire retardant：Intercalation modifying kaolin is added in into deionized water, surface is modified silicon nitride and titanate esters coupling Agent, and reflux state insulated and stirred 0.5-2h is heated to, gained mixture is sent into spray dryer, and dry gained particle is through super Micro mist is made to get fire retardant in atomizer.
3. the PVC cable material fire retardant according to claim 1 or 2 prepared based on nano combined intercalation technique, feature It is：The kaolinic content of crystal is higher than 80% weight in the kaolin, and quartz is less than 0.5% weight, Fe2O3Less than 1.0% Weight, K2O and Na2The summation of O is less than 0.5% weight.
4. the PVC cable material fire retardant according to claim 1 or 2 prepared based on nano combined intercalation technique, feature It is：The average particle size of the nano-silicon nitride is in 25nm, and specific surface area is in 50m2/g。
5. the PVC cable material fire retardant according to claim 1 or 2 prepared based on nano combined intercalation technique, feature It is：The titanate coupling agent is selected from isopropyl three (isostearoyl base) titanate esters, isopropyl three (dioctylphosphoric acid ester) metatitanic acid One kind in ester, isopropyl three (dioctyl pyrophosphate) titanate esters.
6. the PVC cable material fire retardant according to claim 1 or 2 prepared based on nano combined intercalation technique, feature It is：The one kind of the initiator in azodiisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile.
CN201810078096.1A 2018-01-26 2018-01-26 The PVC cable material fire retardant prepared based on nano combined intercalation technique Pending CN108164752A (en)

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Application publication date: 20180615