CN105802147A - Flame-retardant pbt material and preparation method thereof - Google Patents
Flame-retardant pbt material and preparation method thereof Download PDFInfo
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- CN105802147A CN105802147A CN201610231188.XA CN201610231188A CN105802147A CN 105802147 A CN105802147 A CN 105802147A CN 201610231188 A CN201610231188 A CN 201610231188A CN 105802147 A CN105802147 A CN 105802147A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a flame-retardant pbt material.The flame-retardant pbt material is prepared from, by weight, 10-13 parts of dibutyl phthalate, 0.5-0.7 part of lithium naphthenate, 4-6 parts of microencapsulation red phosphorus, 70-80 parts of caprolactam, 10-13 parts of attapulgite, 1-1.4 parts of zinc acetate, 2-3 parts of gamma-aminopropyl triethoxy silane, 18-20 parts of oxalic acid, 300-370 parts of polybutylene terephthalate, 2-3 parts of zinc borate, 1-2 parts of ricinoleic acid, 0.6-1 part of polysorbate 800, 2-3 parts of phthalic anhydride, 1-2 parts of ammonium octamolybdate, 3-4 parts of amino trimethylene phosphonic acid and 1-2 parts of molybdenum disulfide.The molybdenum disulfide, the zinc borate and the like are added, so that the flame retardant property of a finished product is effectively improved.
Description
Technical field
The present invention relates to field of material technology, particularly relate to a kind of fire-retardant pbt material and preparation method thereof.
Background technology
ZnO was widely studied in the last few years as a kind of photocatalyst-type anti-biotic agent, and it generates strong oxygen under photocatalysis
The active function groups of the property changed kills antibacterial.It has nontoxic, nonirritant, good stability, and difficult decomposition under high temperature, timeliness is long
For a long time, cheap, the advantage such as aboundresources, have broad application prospects；
The common carrier being presently used for loaded optic catalyst mainly has CNT (CNTs) and activated carbon, mesoporous material, Linesless charcoal
Black and zeolites etc. can obtain the nano-particle of size uniform by load, in turn ensure that functional nano-composites simultaneously
High stability.Nano-photocatalyst/porous mineral compound system, i.e. assembles Nano semiconductor photocatalyst or loads to mineral
In the hole of material or on surface, not only solve the agglomeration traits of nano-photocatalyst granule, reduce its consumption, also simultaneously
Utilize the high-specific surface area of porous mineral, strong characterization of adsorption to realize in water or the targeting enrichment of pollutants in air, urged by light
Agent is more effectively carried out light degradation；
Therefore nano-photocatalyst/porous mineral compound system can improve the disposal efficiency of catalysis material, reduces again
Its consumption and preparation cost, accomplished to have complementary advantages, and this support type composite had both remained the character of nano-particle itself,
Closed by the interface between nano-particle and matrix simultaneously, some new assembly effects can be produced again, make whole complex
System shows as distinctive synergistic enhancing effect, thus significantly improves the functional characteristic of material, but presently used carrier is the most all deposited
In the shortcoming such as expensive, surface activity point is low, therefore, research and develop a kind of novel carrier material and be the most increasingly subject to
The attention of scholars, find a kind of cheap, surface activity is high and the novel carriers of good stability seems the most necessary；
Polyamide due to its good mechanical property, barrier property, anti-wear performance, acid-proof alkaline and good processing characteristics,
Increasingly become indispensable material as engineering plastics and non-fibre material, its application relate to auto parts and components, cord fabric,
The fields such as tyre equatorial, electronic apparatus, household supplies, consumption becomes kinds most in polyamide product.But applying
Cheng Zhong, the polar group of polyamide 6 material makes it be prone to absorb moisture, causes dry state and low temperature impact strength is low, product
Easily there is the phenomenon such as plastic deformation, serious wear in product poor stability, friction, additionally, uses as mine engineering plastics, do not possess
Antistatic property, easily produces gas explosion etc., thus affects the stability of its product size, antiwear and friction reduction property and electrically
Can, which has limited its range of application；
Attapulgite, as a kind of natural nanometer fibrous clay mineral, has 2:1 type layer chain structure, in its crystal structure
There is a large amount of pore passage structure, and have that specific surface area is big, surface activity site is many, energy of adsorption
By force, excellent biocompatibility and the chemically and thermally feature such as stability, be a kind of economical and practical carrier material, giving birth to
The aspects such as thing, environment, new material have broad application prospects；Therefore it is an object of the invention to nano-photocatalyst with recessed
Convex rod stone is effectively combined, and is the most effectively distributed in polyamide, prepares a kind of novel composite.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of fire-retardant pbt material and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of fire-retardant pbt material, it is made up of the raw material of following weight parts:
Phthalic acid dibutyl ester 10-13, aphthenic acids lithium 0.5-0.7, microencapsulated powder oil 4-6, caprolactam 70-80, attapulgite
Soil 10-13, zinc acetate 1-1.4, gamma-aminopropyl-triethoxy-silane 2-3, ethanedioic acid 18-20, polybutylene terephthalate (PBT)
300-370, Firebrake ZB 2-3, castor oil acid 1-2, polyoxyethylene sorbitan monoleate 0.6-1, phthalic anhydride 2-3, ammonium octamolybdate 1-2, ammonia
Base trimethylene phosphonic 3-4, molybdenum bisuphide 1-2.
The preparation method of a kind of described fire-retardant pbt material, comprises the following steps:
(1) by above-mentioned molybdenum bisuphide, ammonium octamolybdate mixing, joining in the deionized water of compound weight 30-40 times, magnetic force stirs
Mix 1-2 minute, add the 40-50% of above-mentioned polyoxyethylene sorbitan monoleate weight, rise high-temperature and be 50-60 DEG C, insulated and stirred 5-7 minute,
Flame-retardant emulsion a；
(2) above-mentioned attapulgite is calcined 1-2 hour at 300-350 DEG C, join acidifying 3-5 in the hydrochloric acid of 3-5mol/l little
Time, souring temperature is 20-35 DEG C, precipitation is washed 3-4 time, join in above-mentioned flame-retardant emulsion a after filtration, 100-200 rev/min
Stirring 17-20 minute, rise high-temperature and be 80-90 DEG C, insulated and stirred to water is done, and wears into fine powder, obtains activation attapulgite powder；
(3) take the 16-20% of above-mentioned ethanedioic acid weight, join in the dehydrated alcohol of its weight 25-30 times, stir；
(4) by above-mentioned zinc acetate, the mixing of aphthenic acids lithium, mixing is joined by weight 70-80 times, 46-50% ethanol solution
In, add above-mentioned activation attapulgite powder, ultrasonic 10-20 minute, drip the ethanol solution of above-mentioned ethanedioic acid, magnetic after dropping
Power stirs 3-4 minute, sucking filtration, is dried 3-5 hour by the product after sucking filtration at 110-116 DEG C, sends in Muffle furnace, at 600-
Calcine 1.7-2 hour at 640 DEG C, cooling, obtain zinc oxide load powder；
(5) remaining polyoxyethylene sorbitan monoleate is joined in the deionized water of its weight 100-130 times, under stirring condition, add amino
Trimethylene phosphonic, Firebrake ZB, magnetic agitation 2-3 minute, obtain flame-retardant emulsion b；
(6) above-mentioned zinc oxide load powder is joined in the dehydrated alcohol of its weight 60-70 times, add γ-aminopropyl three second
TMOS, rises high-temperature and is 80-90 DEG C, insulated and stirred 1.7-2 hour, and precipitation is washed 2-3 time, joined fire-retardant by sucking filtration
In emulsion b, 100-200 rev/min is stirred 19-20 minute, filters, and is vacuum dried 20-30 minute at being deposited in 50-60 DEG C,
Amino modified zinc oxide load powder；
(7) take the 10-16% of above-mentioned caprolactam weight, the 20-30% of residue ethanedioic acid weight, load with amino modified zinc oxide
Powder mixes, and adds the distilled water of compound weight 8-10 times, is sent in reactor, rises high-temperature and is 190-200 DEG C, insulation
React 3-4 hour, slowly cool to room temperature, be filtered to remove filtrate, precipitation is dried, grinds to form fine powder, obtain pre-polymerization modified oxidized
Zinc load powder；
(8) above-mentioned pre-polymerization modified zinc oxide load powder is mixed with remaining caprolactam, add compound weight 4-7 times
Distilled water, is sent in reactor, rises high-temperature and is 200-230 DEG C, adds remaining ethanedioic acid, insulation reaction 3-3.5 hour,
Discharging cools down, and is vacuum dried 1-2 hour at 50-60 DEG C, obtains polymeric modification zinc oxide load powder；
(9) being mixed with remaining each raw material by above-mentioned polymeric modification zinc oxide load powder, high-speed stirred is uniform, sends into twin screw and squeezes
Go out machine extrusion, through tie rod, cooling, pelletizing, dried, to obtain final product.
The invention have the advantage that first attapulgite is calcined and acidification by the present invention, attapulgite can be increased
The silicone hydroxyl group on stone surface, gives attapulgite surface more negative charge, increases its absorbability to metal cation,
By the attapulgite in-situ precipitate of absorption Zn2+ ion is obtained presoma, obtain ZnO/ attapulgite composite wood by calcination
Material, with attapulgite as carrier, can improve the dispersibility of ZnO nanoparticle, it is thus achieved that have the composite of high antibacterial activity,
Attapulgite as layer chain silicate clay, the advantages such as tool specific surface area is big and lateral reactivity site is many, load nano-ZnO
After, considerably increasing the contact area of ZnO and microorganism, high adsorption activity based on attapulgite, antibacterial can be by antibacterial material
Material absorption is forming enrichment about so that ZnO nano granule is easier to directly contact with antibacterial, thus plays its antibacterial characteristics
Cause inactivation of bacteria, then this composite is participated in the pre-polymerization process of caprolactam, utilize caprolactam open-loop products
Aminocaproic acid reacts with the amino of composite material surface, makes composite material surface be grafted a certain amount of polyamide prepolymer aggressiveness, at it
Surface forms one layer of strong boundary layer；Participate in the polymerization process of polyamide the most again, due to the polyamides of composite material surface grafting
Amine performed polymer can participate in the ring-opening polymerisation of caprolactam, therefore, it is possible to form " micronetwork " structure with masterbatch as core, enters
And add intensity and the toughness of polyamide substrate material, and, beneficially composite is in the dispersion of polyamide substrate material；
Present invention adds molybdenum bisuphide, Firebrake ZB etc., effectively raise the fire resistance of finished product.
Detailed description of the invention
A kind of fire-retardant pbt material, it is made up of the raw material of following weight parts:
Phthalic acid dibutyl ester 10, aphthenic acids lithium 0.5, microencapsulated powder oil 4, caprolactam 70, attapulgite 10, zinc acetate 1,
γ aminopropyl triethoxysilane 2, ethanedioic acid 18, polybutylene terephthalate (PBT) 300, Firebrake ZB 2, castor oil acid 1, poly-mountain
Pear ester 800.6, phthalic anhydride 2, ammonium octamolybdate 1, ATMP 3, molybdenum bisuphide 1.
The preparation method of a kind of described fire-retardant pbt material, comprises the following steps:
(1) by above-mentioned molybdenum bisuphide, ammonium octamolybdate mixing, join in the deionized water of compound weight 30 times, magnetic agitation 1
Minute, add the 40% of above-mentioned polyoxyethylene sorbitan monoleate weight, rising high-temperature is 50 DEG C, and insulated and stirred 5 minutes obtains flame-retardant emulsion a；
(2) above-mentioned attapulgite is calcined 1 hour at 300 DEG C, join in the hydrochloric acid of 3mol/l and be acidified 3 hours, acidifying temperature
Degree is 20 DEG C, precipitation is washed 3 times, join in above-mentioned flame-retardant emulsion a after filtration, and 100 revs/min are stirred 17 minutes, rise high temperature
Degree is 80 DEG C, and insulated and stirred to water is done, and wears into fine powder, obtains activation attapulgite powder；
(3) take the 16% of above-mentioned ethanedioic acid weight, join in the dehydrated alcohol of its weight 25 times, stir；
(4) by above-mentioned zinc acetate, the mixing of aphthenic acids lithium, join mixing by weight 70 times, the ethanol solution of 46%, add
Above-mentioned activation attapulgite powder, ultrasonic 10 minutes, drips the ethanol solution of above-mentioned ethanedioic acid, magnetic agitation 3 points after dropping
Clock, sucking filtration, the product after sucking filtration is dried 3 hours at 110 DEG C, sends in Muffle furnace, calcine 1.7 hours at 600 DEG C, cold
But, zinc oxide load powder is obtained；
(5) remaining polyoxyethylene sorbitan monoleate is joined in the deionized water of its weight 100 times, under stirring condition, add amino trimethylene
Methylphosphonic acid, Firebrake ZB, magnetic agitation 2 minutes, obtain flame-retardant emulsion b；
(6) above-mentioned zinc oxide load powder is joined in the dehydrated alcohol of its weight 60 times, add γ aminopropyl-triethoxy
Silane, rising high-temperature is 80 DEG C, insulated and stirred 1.7 hours, and precipitation is washed 2 times, joined in flame-retardant emulsion b by sucking filtration, 100
Rev/min stirring 19 minutes, filter, will be deposited at 50 DEG C vacuum drying 20 minutes, obtain amino modified zinc oxide load powder；
(7) take the 10% of above-mentioned caprolactam weight, the 20% of residue ethanedioic acid weight, mix with amino modified zinc oxide load powder
Closing, add the distilled water of compound weight 8 times, be sent in reactor, rising high-temperature is 190 DEG C, and insulation reaction 3 hours is slow
Slow cool down, to room temperature, is filtered to remove filtrate, precipitation is dried, grinds to form fine powder, obtains pre-polymerization modified zinc oxide load powder；
(8) above-mentioned pre-polymerization modified zinc oxide load powder is mixed with remaining caprolactam, add the steaming of compound weight 4 times
Distilled water, is sent in reactor, and rising high-temperature is 200 DEG C, adds remaining ethanedioic acid, insulation reaction 3 hours, and discharging cools down,
It is vacuum dried 1 hour at 50 DEG C, obtains polymeric modification zinc oxide load powder；
(9) being mixed with remaining each raw material by above-mentioned polymeric modification zinc oxide load powder, high-speed stirred is uniform, sends into twin screw and squeezes
Go out machine extrusion, through tie rod, cooling, pelletizing, dried, to obtain final product.
Performance test:
Hot strength is 94.8MPa；
Notch impact strength (KJ/m2) 10.06；
Vertical combustion (1.6mm) FV-O；
The zinc oxide load powder wherein prepared is O.lg/L to colibacillary minimum inhibitory concentration.
Claims (2)
1. a fire-retardant pbt material, it is characterised in that it is made up of the raw material of following weight parts:
Phthalic acid dibutyl ester 10-13, aphthenic acids lithium 0.5-0.7, microencapsulated powder oil 4-6, caprolactam 70-80, attapulgite
Soil 10-13, zinc acetate 1-1.4, gamma-aminopropyl-triethoxy-silane 2-3, ethanedioic acid 18-20, polybutylene terephthalate (PBT)
300-370, Firebrake ZB 2-3, castor oil acid 1-2, polyoxyethylene sorbitan monoleate 0.6-1, phthalic anhydride 2-3, ammonium octamolybdate 1-2, ammonia
Base trimethylene phosphonic 3-4, molybdenum bisuphide 1-2.
2. the preparation method of a fire-retardant pbt material as claimed in claim 1, it is characterised in that comprise the following steps:
(1) by above-mentioned molybdenum bisuphide, ammonium octamolybdate mixing, joining in the deionized water of compound weight 30-40 times, magnetic force stirs
Mix 1-2 minute, add the 40-50% of above-mentioned polyoxyethylene sorbitan monoleate weight, rise high-temperature and be 50-60 DEG C, insulated and stirred 5-7 minute,
Flame-retardant emulsion a；
(2) above-mentioned attapulgite is calcined 1-2 hour at 300-350 DEG C, join acidifying 3-5 in the hydrochloric acid of 3-5mol/l little
Time, souring temperature is 20-35 DEG C, precipitation is washed 3-4 time, join in above-mentioned flame-retardant emulsion a after filtration, 100-200 rev/min
Stirring 17-20 minute, rise high-temperature and be 80-90 DEG C, insulated and stirred to water is done, and wears into fine powder, obtains activation attapulgite powder；
(3) take the 16-20% of above-mentioned ethanedioic acid weight, join in the dehydrated alcohol of its weight 25-30 times, stir；
(4) by above-mentioned zinc acetate, the mixing of aphthenic acids lithium, mixing is joined by weight 70-80 times, 46-50% ethanol solution
In, add above-mentioned activation attapulgite powder, ultrasonic 10-20 minute, drip the ethanol solution of above-mentioned ethanedioic acid, magnetic after dropping
Power stirs 3-4 minute, sucking filtration, is dried 3-5 hour by the product after sucking filtration at 110-116 DEG C, sends in Muffle furnace, at 600-
Calcine 1.7-2 hour at 640 DEG C, cooling, obtain zinc oxide load powder；
(5) remaining polyoxyethylene sorbitan monoleate is joined in the deionized water of its weight 100-130 times, under stirring condition, add amino
Trimethylene phosphonic, Firebrake ZB, magnetic agitation 2-3 minute, obtain flame-retardant emulsion b；
(6) above-mentioned zinc oxide load powder is joined in the dehydrated alcohol of its weight 60-70 times, add γ-aminopropyl three second
TMOS, rises high-temperature and is 80-90 DEG C, insulated and stirred 1.7-2 hour, and precipitation is washed 2-3 time, joined fire-retardant by sucking filtration
In emulsion b, 100-200 rev/min is stirred 19-20 minute, filters, and is vacuum dried 20-30 minute at being deposited in 50-60 DEG C,
Amino modified zinc oxide load powder；
(7) take the 10-16% of above-mentioned caprolactam weight, the 20-30% of residue ethanedioic acid weight, load with amino modified zinc oxide
Powder mixes, and adds the distilled water of compound weight 8-10 times, is sent in reactor, rises high-temperature and is 190-200 DEG C, insulation
React 3-4 hour, slowly cool to room temperature, be filtered to remove filtrate, precipitation is dried, grinds to form fine powder, obtain pre-polymerization modified oxidized
Zinc load powder；
(8) above-mentioned pre-polymerization modified zinc oxide load powder is mixed with remaining caprolactam, add compound weight 4-7 times
Distilled water, is sent in reactor, rises high-temperature and is 200-230 DEG C, adds remaining ethanedioic acid, insulation reaction 3-3.5 hour,
Discharging cools down, and is vacuum dried 1-2 hour at 50-60 DEG C, obtains polymeric modification zinc oxide load powder；
(9) being mixed with remaining each raw material by above-mentioned polymeric modification zinc oxide load powder, high-speed stirred is uniform, sends into twin screw and squeezes
Go out machine extrusion, through tie rod, cooling, pelletizing, dried, to obtain final product.
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| CN201610231188.XA CN105802147A (en) | 2016-04-14 | 2016-04-14 | Flame-retardant pbt material and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444717A (en) * | 2008-12-05 | 2009-06-03 | 江苏工业学院 | Method for preparing concavo-convex rod soil/zinc oxide nanometer composite material |
| CN102952327A (en) * | 2011-08-25 | 2013-03-06 | 上海杰事杰新材料(集团)股份有限公司 | Resin composite material and its preparation method and use |
| CN104448299A (en) * | 2013-09-24 | 2015-03-25 | 骏马化纤股份有限公司 | In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof |
-
2016
- 2016-04-14 CN CN201610231188.XA patent/CN105802147A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444717A (en) * | 2008-12-05 | 2009-06-03 | 江苏工业学院 | Method for preparing concavo-convex rod soil/zinc oxide nanometer composite material |
| CN102952327A (en) * | 2011-08-25 | 2013-03-06 | 上海杰事杰新材料(集团)股份有限公司 | Resin composite material and its preparation method and use |
| CN104448299A (en) * | 2013-09-24 | 2015-03-25 | 骏马化纤股份有限公司 | In-situ-polymerized halogen-free flame-retardant nylon 6/attapulgite nano composite material and preparation method thereof |
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Application publication date: 20160727 |